1 15 20 https://www.nal.usda.gov/exhibits/speccoll/files/original/fb48d3ea7ea29be668eab3fa32f2280d.pdf a6c5c192f7198d1e59bf0621b99f34f4 PDF Text Text Item D Number 02422 Author Corporate Author Report/Article TRta Abstracts on Environmental Fate and Levels of TCDD in Seveso Journal/Book Title Year 000 ° Month/Day Color D Number of hiagee 10 DeecrbtOII NOtBS Several abstracts are included in this item. Friday, October 05, 2001 Page 2422 of 2422 �ENVIRONMENTAL FATE AND LEVELS Laboratory Investigation for Microbiological ,; Degradation of 2, 3, 7, 8-Tetrachlorodibenzo- f p-Dioxin in Soil Added of Organic Compost I. A. D. L. S. A. V. G. G. - Cainoni di Mjccio Pontecorvo Vergori Cerquiglini Monteriolo di Do:nenico Silano Viviano Zapooni M. Philippi R. Hu'tter .- Sylvia Cerlesi ' \- ' J- - Sylvia Cerlesi 2, 3, 7, 8-TCDD Levels and Distribution in the Environment at Seveso after the ICMESA ' Accident on July 10th, 1976 Studies on Microbial Metabolism of TCDD under Laboratory Conditions I ' /. Geometrical Distribution of TCDD on the Surface Layer around ICMESA. An Analytical Description of the Main Features and the Different Approaches in the Different Mapping Procedures Analysis of the TCDD-Distribution as a Function of the Underground Depth for Data Taken in 1977 and 1979 in Zone A at Seveso (Italy) F H.K. Wipf E. Homberger N. Neuner U.B. Ranalder W. Vetter J.P. Vuilleuniier HICDD-levels in Soil and Plant Samples from the Seveso Area A. di Domenico G. Viviano G. Zapponi Environmental Persistence and Mobility of 2, 3, r 7,8-TCDD at Seveso • i" D.J. Mallet • - • R.J. Norstrom Tetrachlorodioxins (TCDD) in Great Lakes Herring Gull Eggs , ' A.L. Young C.E. Thalken Long-Term Field Studies.of a Rodent Population 'JI continuously Exposed to TCDD > V-« .- ^\-.'•• > . / L �ISTITUTO SUPERIORE D! SANITA 1 VIALE REGINA ELF.NA. 299 - - ... - 00101 ROMA Telcorimml: ISTISAN - Romi LABORATORIO DI TOSSICOLOGIA T.I.XRMOTI ISTISAN LABORATORY INVESTIGATION FOR MICROBIOLOGICAL DEGRADATION OF 2,3,7,8-TETRACHLORODIBENZO-p-DIOXIN IN SOIL ADDED OF ORGANIC COMPOST. ' - (l.Camoni, A.Di Muccio, D.Pontecorvo and L.Vergori. Istituto Superiore di Sanita, Viale Regina Elena, 299 -Roma) An experimental investigation having the aim of studying and/or assessing the effectiveness of proposed methods for microbiological degradation of 2,3,7,8-tetra= chlorodibenzo-p-dioxin (TCDD) in polluted soil of Seveso (Italy) has been carried out. Microorganisms' activity on the degradation process of TCDD in soils has been investigated by means of two different laboratory experiments in v/ich an organic compost was used to provide a large number of microorganisms. The experiments were developped along the following lines: . " i) Samples of soil taken in the "Zone A" of Seveso (Italy) containing.an average of 0,1 mg/Kg TCDD were analyzed in absence and in presence of the compost; ii) Samples of TCDD free soil, to wich TCDD was added at level of 0,1 mg/Kg, were also analyzed in absence and in presence of the'compost. In these samples also peptone was added. During the experiment, all the samples, contained in beakers, were stored in a non temperature-conditioned room (temperature between"+5°C and +28°C) and were protected * from direct sunlight. At regular intervals, 25 ml of distilled water were added to each sample to keep the soil moistened. Samples were analyzed over a period of 480 days • at-. 1 rir rftriKi ncr i n t e r v a l s . �Under the adopted conditions, both the experiments showed a reduction of TCDD content of about 25% in 480 days. Statistical evaluations of the experimental data emphasize that the observed decay is significant, but it is not related to the addition of the compost and peptone,' wich does not seem to exert any appreciable influence. Chemical analyses of TCDD were carried out by gaschromatography-mass published method. fragmentography using our previously �S. CERQUIGLINI MONTERIOLO, A. DI DOMENICO, V. SILANO, G. VIVIANO, G. ZAPPONI, ISTITUTO SUPERIORE DI SANITA1, ROME, ITALY 2,3,7,8-TCDD LEVELS AND DISTRIBUTION IN THE ENVIRONMENT AT SEVESO AFTER THE ICMESA ACCIDENT ON JULY 10th, 1976 Environment contamination at Seveso after the industrial accident involving the emission of a TCDD-containing toxic cloud was assessed by analyzing representative samples of different matter in the environment (soil, water, silt, dust particles, plant and animal tissues). TCDD levels in the soil surface layer ranged from <0.75 to %20 x 103 yg/m2. The territory involved was divided into three zones on the basis of soil contamination levels. TCDD levels were highest in Zone A whereas Zones B and R exhibited <50 and <5 yg/m2 levels, respectively. Vertical distribution of TCDD in the soil has been studied. A sharp decrease in TCDD levels was observed as depths increased. TCDD was also monitored in suspended and settleable air particulates using high-volume samplers or dustfall jars. TCDD levels in these samples ranged from 0.06 to 2.14 ng/g of dust for dustfall jar specimens and from 0.17 to 0.050 ng/g of dust for suspended particulates. No TCDD was detected in drinking, surface, or ground water samples (method sensitivity: in the ppt range). Traces of TCDD in the ppt range were occasionally found in the silt analyzed at the end of 1976 and early 1977. Maps were given to show territorial distribution of TCDD over the area concerned. 0 �M. PHILIPPI, R. MUTTER, INSTITUTE OF MICROBIOLOGY, SWISS FEDERAL INSTITUTE OF TECHNOLOGY, CH-8092 ZURICH, SWITZERLAND STUDIES ON MICROBIAL METABOLISM OF TCDD UNDER LABORATORY CONDITIONS Extensive measurements on the^behaviour of TCDD in soiil under natural conditions' or in the laboratory^"J suggested a half-life o appr. 1 year. litions laboratory " of It was postulated, that soil microorganisms may contribute to the assumed decay. In aquatic ecosystems no metabolism of TCDD was observed or at least a half-life of 600 days . Laboratory experiments gave indications, that some microorganisms might be able to attack TCDD to a limited extent . As a consequence of the Seveso accident (July 10, 1976) we initiated a programme to study under laboratory conditions the microbial metabolism of TCDD by pure or mixed cultures in liquid nutrient media and in nutrient enriched moist soils. The study was performed in closed systems at 28 C. 0,5 - 1 ppm of C-labelled TCDD (sp.ec.act. appr. 100 mCi/ mmole) was added to the cultures. Analysis was performed with TLC plates and with a RadioGC-System (Packard Instruments; GC model 427, Radiosystem 894); C0? was captured in 0,1 KOH. .; No strong microbial metabolism of TCDD could be detected, even after prolonged incubation of up to 1 year in liquid media or in soil samples. The extractability of TCDD from .the samples decreased often considerably » with prolonged incubation, simulating a decay. This difficulty has also been observed by other investigators ' ' . Careful and repeated extractions of the samples with various solvents increased the recovery of TCDD. Furthermore selective extraction of impurities present in the C-TCDD samples used suggested sometimes a metabolism of TCDD; but complete balances excluded this possibility. Our present data do not exclude a very slow metabolism of TCDD in the range of 1-2 % within 1 year by some of our strains. . • 1. Young, A.L., C.E. Thalken, E.L. Arnold, J.M. Cupello, and L.G. Cockerham, Report USAFA-TR-76-18, US Air Force Academy, Colorado 1976, 41 p. 2. Kearney, P.C., E.A. Woolson, and C.P. Ellington, Environm.Sci.Technol. 6_, 1017 (1972) . . ' • ' , 3. . Kearney, P.C., A.R. Isensee, C.S. Helling, E.A. Woolson, and J.R. Plimmer, Adv.Chemistry Series No. 120, 150 (1973) 4. ' . . ' Isensee, A.Rt and G.E. Jones, Environm.Sci.Techno!. 9_, 667 (1975) " ' " - ' . / 5. . Ward, C.T. and F. Matsumura, Arch.Environm.Contam.Toxicol. _7_, 349 (1978) 6. Matsumura, F. and H.J. Benezet, Environm.Health Perspect., September, 1973, p. 253 . �SILVIA CERLESI UFFICIO SPECIALE BELLA REGIONS LOMBARDIA-SEVESO (COMO) GIACOMO BRESSI, ELIO CALLIGARICH ISTITUTO NAZIONALE DI FISICA NUCLEARE, SEZ. DI PAVIA-PAVIA FABIO BOSSI, SERGIO P. RATTI ISTITUTO DI FISICA NUCLEARE DELL'UNIVERSITA' DI PAVIA GEOMETRICAL DISTRIBUTION OF TCDD ON THE SURFACE LAYER AROUND ICMESA. AN ANALYTICAL DESCRIPTION OF THE MAIN FEATURES AND .THE DIFFERENT APPROACHES IN THE DIFFERENT MAPPING PROCEDURES, Abstract A chemical plant failure 13 miles north of Milan (Italy) has spread an amount of 2, 3, 7, 8-Tetrachloro-di—benzo-pdioxin (TCDD) on a large'and heavily populated area. The data accumulated in different instants have been analyzed to give an overall geometrical description of the contamination due to the accident. The analysis of the data ma;de available shortly after the accident,, as a res.ult of an approximately equal-distan- * ce grid/has allowed the determination of the line of maximum contamination and has provided a number of indications usefull to program a 1979 campaigne based on a different grid. �SILVIA CERLESI UFFICIO SPECIALE DELLA REGIONE LOMBARDIA-SEVESO (COMO) GIACOMO BR1-SSI, ELIO CALLIGARICH ISTITUTO NAZIONALE DI FISICA NUCLEARE, SEZ. DI PAVIA-PAVIA FABIO BOSSI, SERGIO P. RATTI ISTITUTO DI FISICA NUCLEARE DELL 1 UNIVERSITA 1 DI PAVIA ANALYSIS OF THE TCDD-DISTRIBUTION AS A FUNCTION OF THE UNDERGROUND DEPTH FOR DATA TAKEN IN 1977 AND 1979 IN ZONE A AT SEVESO (ITALY). . Abstract . The TCDD distribution as a function of the depth below ground has been investigated on the data provided by two monitoring campaigns during 1977 and 1979 respectively. In spite of non trivial fluctuations, all the data can be reduced to an unique analytical form describing the distr^L butions up-•••to-- the maximum depth at which measurements have been done (1.5 m) with very reasonable statistical confidence level (^90%). The shape of the empirical distribution (a conical form) describing the data of the 1977 campaign remains the same also for the data of the 1979-campaign and may give an approximate indication of the TCDD penetration in the soil as a function of'time. �TCDD-lcvels in soil and plant samples from the Seveso area H.-K. Wipf, E. Homberger, N. Neuner, U.B. Ranalder, W. Vetter and J.P. Vuilleumier Givaudan Research Laboratories, CH-8600 Dubendorf, Switzerland * * * Soil and vegetation samples have been collected in the Seveso area from 1976 through 1979 and analyzed subsequently. In 1976, immediately after the incident, TCDD-concentrations in plant material reached the order of 1 ppm in the zone of highest contamination. In the following years, when there was no direct contact of the newly grown vegeta-tion with the accidentally released aerosol cloud, TCDD-levels in plants dropped by several orders-of magnitude. In 1977, even in the most contaminated part of Zone A with soil concentrations in the order of 10 ppb (ca. I'OOO ug/m2) no traces of TCDD were found in the flesh of applec, pears and peaches ncr in coin cobs and kernels (detection lim-, it 1 ppt). Traces of TCDD were detected, however, in the skin of the fruit and in the sheaths of the corn cobs. This strongly suggests that the contamination arises 'from local dust and not from plant uptake. Our studies of TCDD-distribution in carrots grown in heavily contaminated soil confirm the absence of a significant uptake of TCDD by plants. No measurable amounts of TCDD have been detected in any of ples (even carrots) collected in the scarcely contaminated through 1979. This is in accordance with the very low soil safety-zone, ranging in 1979 from not measurable (< 1 ppt) ty of the area to ca. 10 ppt in a few localized spots. 5/5/80 the vegetation samZone R from 1977 residues in this in the vast majori- �A. DI DOMENICO, G. VIVIANO, G. ZAPPONI, ISTITUTO SUPERIORE DI SANITA1, ROME, ITALY ENVIRONMENTAL PERSISTENCE AND MOBILITY OF 2,3,7,8-TCDD AT SEVESO TCDD levels were determined at 44 soil sites in Zone A during three surveys carried out at different times (1, 5 and 17 months) after the ICMESA accident. The data obtained provide statistically significant (p<0.01) evidence that the geometric mean of TCDD levels dropped to about one-half in the unworked soil of Zone A in the first 5 months after the accident. Following this period, no further decreases in TCDD levels were detected. Available data are consistent with the hypothesis that TCDD presence in the Seveso environment diminishes with time, and at a rate which also decreases with time. The same pattern seems to apply for TCDD soil penetration. From one calculation it appears that one month after the accident, TCDD half-life was about 1 year, whereas 17 months after the accident, it was estimated to be >10 years. �Tctrachlorodioxins (TCDD) in Great Lakes Herring Gull Eggs An intensive assessment of TCDD in the Great Lakes ecosystem has been completed using pools of 10 randomly selected Herring Gull eggs collected in 1979 from each of 2 colonies on the 5 Great Lakes (see map). These are the 10 monitor colonies of the Wildlife Contaminants Surveillance program which have been utilized by the Canadian Wildlife Service and the International Joint Commission Great Lakes Water Quality Board to monitor trends in persistent organochlorine contaminants (e.g., PCB's, mirex, DDE) in the Great Lakes aquatic ecosystem. Additional pooled samples were analyzed from colonies on the Niagara River, chosen for its proximity to the Hooker Chemical dumping site at Bloody Run, and Fighting Island in the Detroit River, which exhibited the highest organochlorine residues of any Herring Gull sample collected in 1979. Eggs collected from Scotch Bonnet Island (central Lake Ontario) in 1973 were also analyzed as a retrospective search for TCDD in L. Ontario samples. Chicks which hatched from this colony exhibited chick edema disease symptomatic of contamination by several toxic organochlorines, including hexachlorobcnzene and hexachlorodioxins. No tetrachlorodioxin isoners have been detected at or above a concentration of 10 ng/kg (parts per trillion) in these samples. The Great Lakes aquatic ecosystem has been exposed to TCDD via the atmosphere and via direct discharge. There is, however, no evidence of bioaccumulation into Great Lakes Herring Gull eggs. Herring Gulls are at the top of the food chain and have been shown to accumulate extremely high levels in eggs (50 times those in fish) of other organochlorine contaminants such as PCBs and mirex. It follows that: (1) Herring Gulls do not bioaccumulate TCDD and/or (2) levels of TCDD in the aquatic food web (i.e., fish) are extremely low. ' The first hypothesis is supported by the short half-life of TCDD in rats (12 and 15 days for males and females, respectively) relative to persistent PCB isomers (84 days for hexachlorobiphenyl). Chlorinated dibenzofurans are similar in structure and toxicity to dioxins. A CWS study showed that chlorinated dibenzofurans were eliminated much more rapidly than PCBs when fed to mallard ducks. The latter hypothesis is supported by the instability of TCDD to UV irradiation, the irreversible adsorption of TCDD to particulate matter in air, soil, water, and sediment, and the apparent inefficiency of bioaccumulation of TCDD from food by fish. • DOUGLAS J. HALLETT*, ROSS J. NORSTROM, Canadian Wildlife 'Service, National Wildlife Research Centre, Ottawa, Ontario, K1A OE7, FRANCIS I. ONUSKA, and MICHAEL E. COMBA, Inland Waters Directorate, National Water Research Institute, Burlington, Ontario. � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 095 Folder The folder containing the original item. 2422 Series The series number of the original item. Series IV Subseries IV Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Abstracts on Environmental Fate and Levels of TCDD in Seveso Subject The topic of the resource ecological fate soil testing biodegradation animal testing Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 077 Folder The folder containing the original item. 1981 Series The series number of the original item. Series III Subseries IV Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Date A point or period of time associated with an event in the lifecycle of the resource January 27 1984 Title A name given to the resource Transcript of Proceedings: Royal Commission on the Use and Effects of Chemical Agents on Australian Personnel in Vietnam, 27 January 1984 Subject The topic of the resource Australian Royal Commission Hearings herbicide toxicology ecological fate biodegradation ao_seriesIII https://www.nal.usda.gov/exhibits/speccoll/files/original/ceebbe46b74c9e2cd15069e0b531d0a5.pdf d3c965717fe075ecae65e8f0cabf431b PDF Text Text Item ID Number Q0626 Author 2A5-T Working Group, U.S. Environmental Protection A RBpOrt/ArtiClB TitlG 2,4,5-T Position Document 1 Journal/Book Title Year 1979 Month/Day March ^ Color Number of Images 152 DOSCriptOn NotOS Alvin L- Young filed this item under the category "Human Exposure lo Phenoxy Herbicides and TCDD" Tuesday. February 20, 2001 Pago 626 of 680 �PB80-212665 2,i|,5-T: Position Co cum en t 1 ( U . S . ) E n v i r o n m e n t a l Protection Agency A r l i n g t o n , VA Special Pesticide R e v i e w Div 15 Mar 79 U.S. DEPARTMENT OF COMMERCE National Technical Information Service �2,4,5-T: Position Document 1 2,4,5-T Working Group U.S. Environmental Protection Agency REPRODUCED BY NATIONAL TECHNICAL INFORMATION SERVICE U.3. DEPARTMENT OF COMMERCE SPRINGFIELD. VA. 22161 �NOTICE THIS D O C U M E N T H A S S E E N R E P R O D U C E D F R O M T H E BEST C O P Y F U R N I S H E D U S B Y THE SPONSORING AGENCY. A L T H O U G H IT IS R E C O G N I Z E D THAT C E R T A I N PORTIONS ARE I L L E G I B L E , IT IS BEING R E L E A S E D IN THE INTEREST 0? MAKING A V A I L A B L E AS MUCH INFORMATION AS POSSIBLE. �50272-101 I'.«!EPOKT DOCUMENTATION j »• "EPORT NO. G E J!^ _ _._.._1 3. Recipient's Accession No. • • ••'._. '- ... .... •,& o J r/ • o > < 5 _L . 4. Title and Subtitle 5. Report Date 2,4,5-T: Position Document I JJZ15/Z2 7. Author(s) 3. Performing Organization Rept. No. 9. Performing Organization Name and Address 10. Project/Task/Work Unit No. Special Pesticide Review Division Environmental Protection Agency Crystal Mall rf2 Arlington, VA 11. Contract(C) or Grant(G) No. (G) 13. Sponsoring Organization Name and Address 13. Type of Report & Period Covered Environmental Protection Agency 401 M St. SW Washington, DC 20460 14. 15. Supplementary Notes 16. Abstract (Limit: 200 words) Preliminary Risk Assessment: Examination of possible unreasonable risks associated with uses of pesticide and a gathering of all available information to determine whether or not this or any other risk does exist. Initiates literature search and evaluates risk data. Limited information on exposure to forecast extent of risk. 17. Document Analysis a. Descriptors 0504,0606,0703 t>. Identifiers/Open-Ended Terms c. COSATI Field/Group .8. Availability Statement Unlimited 19. Security Class (This Report) -Unc-l-ass-tfied- Page) 20. Security Class (This 21. No. of Pages 22. Price Unclassified (SeeANSI-Z39.18) See Instructions on Reverse OPTIONAL FORM 272 (4-77) (Formorly NTIS-3S) Department of Cammerce �2,4,5-T: I. II. III. Position Docunent 1 _P_age Background.. 1 A. Chemical/Physical Characteristics... 1 B. Manufacturing Process and Contaminants... 1 C. Formulation and Class .5 D. Registered Uses and Production 5 E. Metabolism in Experimental Systems....... 7 F-, Environmental Fate 10 (1) Persistence: Soils 10 (2) Persistence: Water 12 (3) Transport 15 (4) Bioaccumulation 15 G. Residues 19 (1) Soil...... 19 (2) Water „ 20 (3) Air 23 (4) Animals 24 (5) Plants 27 (6) Humans 29 (7) Animal Products 32 (8) Food... 37 (9) Human Exposure Via Industrial Accidents 38 H. Tolerances 42 I. Pesticide Episode Reports System-(PERS).. 43 Regulatory History 45 Summary of Scientific Evidence Relating to Rebuttable Presumption A. Oncogenic Effects.... (1) 2,4,5-T (a) Effects of Dietary 2,4,5-T «0.05 ppm TCDD) on Rodents..., (b) Effects of Subcutaneous Injection and Oral Administration of 2,4,5-T (30 ppm TCDD) on Rodents (2) TCDD (a) Oncogenic Effects of Low Levels of TCDD on Rodents (b) Effects Closely Related to Oncogenicity in Test Animals... (3) Preliminary Epidemiological Studies 3. Other Chronic or Delayed Toxic Effects... (1) Pesticide-free TCDD (a) Studies in which TCDD Produced Teratogenic and/or Fetotoxic Effects in Mice .. .. -i- 50 50 51 51 54 56 56 62 64 66 68 68 �Page (b) Studies in Which TCDD Produced • Teratogenic and/or Fetotoxic Effects in Rats' (c) Summary ......... ........ (2.) 2,4,5-T (TCDD Contamination Ranging From Undetectable co 30 ppm) ,,^ (a) Teratogenic and Fetotoxi'c"" Ef• fects in Rodents (b) Adverse Reproductive Effects in Other Mammalian Test Systems (c) Adverse Effects in Avian Species . . . (d) Studies in Avian Species in Which Adverse Effects Were Not Observed (e) Summary c,. (3) Exposure Analysis.... ..... .... (a) Oral Exposure. (b) Dermal Exposure.. . f.. . (i) Spray Applicator: Backpack Sprayer (ii) Spray Applicator: Tractor-mounted, Low-boots. Spray Equipment (iii) Aerial Application: Exposed Population Directly Beneath Spray Plane..«„.... (c) Inhalation Exposure: Aerial Application (d) Cumulative Exposure IV. 74 79 80 30 93 99 101 101 101 102 105 105 t08 110 113 116 Studies Relating to Posssibe Adverse Effects.. 118 A. Mutagenicity 118 (1) 2,4,5-T 118 (a) Positive Study 118 (b) Negative Studies 119 (2) 3. TCDD . 121 (a) Positive Studies < 121 (b) Negative Studies 123 (3) Chromosomal Damage 124 Toxicity to Huaans: TCDD 125 (1) Chloracne 125 (2) Porphyria eucanea tarda and £-An±no-levulinic Acid Synthetase..„ 127 References. 129 -ii- �2,4,5-T: POSITION DOCUMENT 1 I. BACKGROUND A. Chemical/Physical Characteristics •— The herbicide commonly known as 2,4,5-T (chemical name, 2,4,5-Trichlorophenoxyacetic Acid) has an empirical formula of CgH5Cl,0,. The pure acid form occurs as white crystals and has a molecular weight of 255.49, ing point is 156.6°C. The melt- Its solubility in water is 278 parts per million (ppm) at 25°C; it is also soluble in acetone, ethanol, ether, and alkaline solutions (1). The esters of 2,4,5-T are formulated to be emulsifiable in water and soluble in most oils, while its amine salts are soluble in water but insoluble in petroleum oils (2, 3)« B» Manu fac turi ng_ Process a,r.d Contaminants 2,4,5-T is produced commercially by a process using 1,2,4,5-tetrachlorobenzene as the starting material which is reacted with aiethanol and sodium hydroxide under high temperature and high pressure to give the sodium salt of 2,4,5-trichlorophenol (2,4,5-TCP).-X 2,4,5-TCP is the subject of a separate Rebuttable' Presumption Against Registration (RPAR) Position Document. It is discussed in this document because both it and its contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) may be present in some commercial 2,4,5-T and in 2,4,5-T samples used in animal experiments. -1- �This product is reacted with chloroacecic acid under mildly alkaline conditions. Sulfuric acid (H SO.) is then added to the product of this step to produce-2,H,5-T. The acid form of 2,4,5«T can be readily reacted with a variety of alcohols to produce a large selection of eaters and with o amines to produce aoine salts (3). During the first step in the manufacturing process of 2,4,5-1, if temperature and pressure are not carefully controlled, highly toxic contaminants, polychlorinated dibenzo-p-dioxins, may be formed in large quantities. The particular dioxin formed is dependent on the chlorophenols present (4). The term dioxin doss not apply to any one compound but to a group of related substances, which are distinguished by the number and orientation of chlorine atoms they contain* Dioxin toxicity also varies with the position and numbers of chlorines attached to the phenol rings. In the 2,4,5-T manufacturing process an' especially toaeic dioxin, 2,3,7»8«tetrachloradibenzG»p-dioxin (TCDD), is formed when the reaction temperature is excessive (8, 9, 10, 11, 12), most commonly at temperatures above 160°C. Halogens at the 2, 3» and 7 positions are known to produce toxic dioxins (13). In the case of TCDD X the chlorine atoms �are attached at the 2, 3, 7, and 3 positions which are considered the most toxic positions possible (It). The dioxin contaminant in 2,4,5-T is of particular.concern because of -its extremely high toxicity, and because of the apparent inability of manufacturers to produce 2,4,5-T 2/ without the contaminant, TCDD ( ) 7. TCDD occurs as a white crystalline solid. 99*5$ decomposed at 800°C. TCDD has the following It is solubility in various solvents at 25°C (7). • Solvent Acetone Benzene Dimethylsulfoxide Methanol Water Solubility (wt. per cent) 0*011 0.057 <0.01 0.001 0.00000002 (0.2 ppb) It has been recognized for quite some time that chlorinated dibenzo-p-dioxins occur as possible byproducts (contaminants) in the manufacturing of chlorinated phenols (15). The formation of TCDD during production of 2,4,5-TCP was demonstrated by Kimmig and Schulz (16). TCDD was obtained from the pyrolyzing of 2,4,5-TCP by Higginbotham £/ Since manufacturers are unable to produce 2,4,5-T without TCDD, all references to 2,4,5-T in this document refer to 2,4,5-T contaminated with some level of TCDD. -3- �et al. (11). They noted that the specific dioxin formed depended on the chlorophenol pyrolyzed. Kearney et al* (17)» however, reported that TCDD is historically associated with any pesticide derived from 2,4,5-TCF. A number of researchers (12, 18, 19, 20, 21) have reported on the formation of TCDD by thermal decomposition of tha sodium salt of 2,4,5-TCP under alkaline conditions during the manufacturing process. Since 1950, most of the chemical industry has known that large quantities of TCDD may be formed as a byproduct of tha 2,4,5-TCP manufacturing aot carefully controlled. process if tha procedures are At one time 2,4,5-T was produced which contained between 30 to 40 ppra of TCDD (7, 22, 55). Between 1968 and 1969, one manufacturer had a 90S decrease in the amount of TCDD present in the 2 $ 4»5~T it produced. Different manufacturers produced 2,4,5-T with different TCDD contents (17). After concern arose in 1969 about the extremely toxic effects of TCDD, manufacturing methods were changed and carefully controlled by manufacturers. By 1971 industry had reduced TCDD content in commercial samples of 2,4,5-T to less than 1 ppa (9, 23. 24), Current U.S. manufacturing specifications require 2,4,5-T presently being sold to -4- �contain less than 0.1 ppn TCDD (7), Several countries now produce commercial 2,4,5-T containing less than 0,05 TCDD (25). ppm "' C. Foraulatlori and Class "' 2,4,5-T is classed and used as a selective herbicide, especially fop brush control (2). It is formulated in many forms of salts and esters which are available as emulsifiable concentrates containing 2, 4, or 6 pounds actual acid equivalent per gallon and as oil soluble concentrates with 4 or 6 pounds active ingredient (AI) per gallon. The most commonly used formulations are the low volatile esters (26). 2,4,5-T also occurs in registrations mixed with 2,4-D, Dicamba, Picloram, Silvex, and 2-(2-methyl-4-chlorophenoxy) propionic acid D» (27). Registered Uses and Production 2,4,5-T has been produced as a registered pesticide in the United States since 1948, According to EPA records, approximately 122 companies hold Federal registrations and formulate 424 registered products; eleven companies have former state registrations-* and formulate 21 products. Pesticide products formerly registered under state pesticide registration laws and shipped or distributed for sale solely within intrastate commerce are subject to Federal pesticide regulations under 40 CFR Section I62.17(a). Application has been made to obtain Federal registration for intrastate use of these products. For a list of trade names under which 2,4,5-T is marketed, see the registrant/product list attached to this document, -5- �Section 7(c) of FIFRA requires manufacturers and frsrmulstors to submit to EP& information on production, sales, and distribution. Under FIFPA sections 7(c) and 10, this information may not be made available to the public. A confidential memorandum containing this informa- tion has been se"t to th* Deputy Assistant Administrator for ^esticides (28). The Pesticide Review (29) reported that, 1 1,626,C-"0 pounds of 2,-*,5-T acid, esters, and salts were produced, in the United States in 1969 and 12,335,000 pounds 1570. The Pesticide Review (29) also reported that the United States imported 738,907 pounds of 2,4,5-T during 19"l chrcugh 197-J-.1/ Of this total 155,342 pounds were imported in 1974. This vas down from ne-.rly 392,000 pound' ..'. 1973 h"t up from the 'S-year average of 148,000 pounds. While. TUie Pesticide Peview (29) does not report export, ^'iqure? for 2,4,5-T alone, it does report, exports of 2,4~c and 2,4,T-T together. Export of 2,4-D and 2,4,5-T was reported at 6.8 million pounds in 1972; 21 million pounds in 1973; and almost 22 million pounds in 1974, A great deal of variability exists in reports on usage of 2,4,5-T. Agricultural end-use data obtained from the National Study of Agricultural, Governmental, and Industrial Uses of Pesticides, conducted by this Agency (30) , indicated the following uses of 2,4,5-T in the United States in 1974. 4/ The ls»vel of TCDO in the imported 2,4,5-T was not reported„ �1 . pounds AI" Cron 1 aa-cliecRangeland and Pastures I 968,000 16,000 Rice^/ 1 | Nurserv Crop " 1 12,000 1 200 * Turf and Ornamentals ! 1 8 Blueberries— 1 i1 Estimated total use 1 996,0.00 in agriculture for 1974 1 % total acriculture 97.24 1.54 1.20 0.02 — 100.00 a/ The Agency has looked at effects on aquatic organisms representative of species likely to be exposed from application of the triethylamine formulation of 2,4,5-T tc rice. The calculated concentration of this formulation in a 6-inch layer of water at the highest recommended use rate is 0.9 ?pm. The LC-50 bioassay values for bluegill and catfish are well above this l*vel (ranginc from a 24-hour LC-50 of 53 ppm for oluegill to a 96-hour LC-50 of >72 ppm for~bluec.il! and channel catfish). Rainbow trout, which cannot be considered "representative of the organisms liksly to be exposed" in ti" * geographic area? where rice is grown, . have a 96-hour LC-50 ranging from 0.7 to 0.07 ppm. o/ Thj.-^ is no longer a recistered use. In addition, this survey reported that 324,491 pounds of active 2,4,5-T were used by federal and state agencies and 659,463 pounds by industry. Other sources have reported usages for 1974 as follow: rights-of-way, 4 million pounds; rangeland, 1.5 to 2.3 million pounds; rice, 220,000 pounds; and forestry, 5n,000 pounds. 3. Metabolism in _?.xperi^enta 1 Systems Several studies have demonstrated that 2,4,5-TC? is the primary degradation product or metabolite formed in the breakdown of 2,4,5-T, by either physical or biological -7- �mechanisms.- Crosby and "-Tone (31) found thac 2,4,5-1'C? was- one of the- ,?ajor decomposition oroodcts in the pr.otcde» composition of 2,4,5—t in. watar. Sharpee (32) four.d thac microbial degradation "of. 2,4,2-T in cwliuca, soil, and acuatic scosystems resulted in the formation of small amounts of 2,4,5-TC?. -/a- �Shafik et ai. (33) dosed Sprague-Dawley rats by gavage with 2,4,5-T at 50, 5, 0.05, three days. and 0.005 ag/kg for Two rats were dosed at each level. The authors found that,, at 0.005 mg/kg, excretion of 2,4,.fL-7 in urine was complete two days after the final dose. They also found 2,4,5-TCP excreted as a aetabolite in tfta urine of rats given 50 sag/kg, but no detectable 2,4,5-TCP was found at the two lowe-st dos-e levels. A hydroxylated trichlorophenoxyacatzo aeid and a hydroxylated trichlorophenol were identified, by unconJMrasd aass spectrornetric analysis, as possibly being two additional metabolites of 2,4,5—T. Grunow et al. (3"4) "studied seven sale Wistar rata fed a single 2., 4,5-T dose at 50 ag/kg body weight. They found that the daily renal excretion of free 2,4?5-T was, in general, at its aaxiaua on the second day after feeding. After seven days, free 2,4,5-T in the urine decreased to a value below 2% for ail aniaala. In addition to 2,4,5-T excreted in the free fora, the authors found it to be excreted as derivatives which could be converted into 2,4,5-T by acid hydrolysis. They were able to identify one of these as NC2,4,5-trichlorophanoxyacetyl) glycins. Grunow and 3ohme (35), in a study using Wistar rats . and NMRI sice, fed doses of 2,4,5-T at 200 zg/kg body Height. These authors isolated N(2,4,5-trichlorophenoxy -8- �acetyl) taurins as a metabolite of 2,4,5-T, in addition to the metabolites named above. . Clark et al. (36) found residues of 2,4,5-TC? in the muscle, li.ver, and kidney of sheep which were fed rations containing 2,000 pom of 2,4,5-T for 28 days. The 2,4,5-T used in this study had a purity of 99$ and contained no detectable dioxir. (detection limit: 0.5 ppn). Leng (37) conducted a feeding study during 1969 and 1570, in which dairy and beef cattle and sheep were given 2,4,5-T at levels from 10 to 2,000 ppm in the total diet for intervals of two to four weeks at each level tested. The author reported that no residues «0.05 ppn) occurred in ailk or cream of cows ingesting 10 no 30 p.pm 2,4,5-T. At 100.ppm 2,4,5-T in the diet, traces of 2,4,5-TCP (0.06 appeared in ailk and cream. ppm) When given high levels of 2,4,5-T, equivalent to 300 and 1,000 ppa in the total diet, residues of 2,4,5-T and 2,4,5-TC? ranged from 0.05 ppm in the milk of individual cows, to 0.5 •• . Fitzgerald et al. (38), studying the degradation of 2,4,5-T in woody plants, reported that colcrinetric analysis suggested, and chromatog^aphic analyses confirmed, that the n-butyl ester of 2,4,5-T is degraded in sweet gua (Liouidacbar stvrasi f lua) and southern red oak f Quergu_a falcata) to yield 2,4,5-TC?, -9- �F» Environsental (1) Pep3i9ter.g9_i_ _ Soil a Soil surface and foliage are ths major recipients of phenoxy herbicides (39) whether applied by ground spray t systems or froa aircraft.. Once 2,4,5~T reaches the soil it may be degraded chemically or biologically, volatilized and moved to other areas, absorbed on soil colloids or in organic natter, or leached to depths or locations where it cannot be absorbed by plant roots (4?). Morris st al. (176) reported on the persistence of 2,4,5-T in a Pacific Northwest forest. The authors found that six months after application of 2,4,5-T at 2.24 kg/ha (2 pounds/acre), the level of herbicide in the forest" floor declined 90J; after one year, less than 0.02 remained in the forest floor. kg/ha The authors found little leaching of 2,4,5-T from ths forest floor into soil, and no residues were found deeper than 15 cm (aaxisuffi residue found was 0.08 ppm) despite rainfall of 2'* ca the first month and 70 cm the first three months after application. Morris et al. (176) .stated that the rapid disappearance of 2,4,5-T fron the forest floor suggests abundant aierobial activity. Morris (401 reported microbial ac- tivity to be important in the disappearance of 2 t 4,5-T from forest-floor material in the laboratory, -10- �Wiese and Davis (41) found that, in an agricultural soil, 2,4,5-T remained in the upper six inches even after application of 4.5 inches of water over a short period of time. Helling et al. (39) found that 2,4,5-T is relatively mobile in sandy soils but that movement decreases as organic content increases. Thus 2,4,5-T is moderately mobile in clay soils and only slightly mobile in muck (42). loshido and Castro (43) studied the degradation of 2,4-D, 2,4,5-T, and Picloram in two Philippine soils under upland and submerged conditions. The authors found the degradation of 2,4,5-T to be rapid in Maahas clay. Slightly more 2,4,5-T residues were recovered in submerged than in upland Maahas soil. In Luisiana soil under submerged conditions, 2,4,5-T degraded rapidly in eight weeks after a four-week lag period, while it degraded gradually under upland conditions, with only about 40$ of.the 2,4,5-T recovered after 12 weeks. Morton et-al. (-44}, -using technical grade 2,4,5-T labeled in the carbcxyl position with carbon-14, found that its apparent half-life averaged 1.6 weeks in green tissues of native grasses at College Station and Spur, Texas, and 1.7 weeks in litter tissue. The authors stated that the -11- �amount and frequency of rainfall were conducive both to leaching and microoial decomposition of the herbicide, and to growth of sideoats gramma plants, all of which were factors contributing to rapid reduction of herbicide concentrations. • • — When considering the persistence of 2,4,5-T, the persistence of its manufacturing contaminant, TCDD, must also be considered. Helling et al« (39) found that TCDD was not photodeeoasposed on soil. TCDD was found to be immobile in Norfolk and Lakeland sandy loams, Hagerstown silfcy clay loam, Barnes clay loam, and Celeryviile muck, and was not leached further into soil by rainfall or irrigation.* During surface erosion of soil,, however, lateral transport of TCDD could occur. The persistence of TCDD in Lakeland loamy sand and Hagerstown silty clay loam at 1, 10, and 100 ppm was studied by Kearney et al. (46) for 360 days. After one year these researchers recovered 56 and 63$ of the originally applied TCDD in Hagarstown and Lakeland soils, respectively. Helling et al. (39) observed that TCDD's persistence was predictable since it is insoluble in water. (2) Ptr31 s t 9r,cq ;... Water Current information indicates that, although some 2,4,5-T may enter streams flowing through or adjacent to -12- �areas being sprayed, residue levels in streams .will be very low. Morris (4?) reported the results of an intensive study of stream contamination from spray projects on range and forest lands in Oregon which showed that peak concentrations of phenoxy herbicides seldom exceeded 0.1 ppm and that herbicide residues persisted for only a few hours in nearly all streams, Norris (47) speculated, however, that applica- tion of herbicides to marshy areas may result in high-level, long persistence of chemical residues in nearby streams. The Report of the Advisory Committee on 2,4,5-T to the Administrator of the Environmental Protection Agency (48) stated that all available data indicated that the amount of 2,4,5-T entering water is small and does not persist long. It is adsorbed on clay or absorbed by biota - within a matter of days* Phenoxy chemicals entering water may be lost by volatilization, degradation, adsorption on sediment, adsorption by biota, and dilution as additional'stream water passes through the site. Almost all authorities agree that there is adsorption on bottom sediment (48, 49, 50). I Kenaga (51) stated that esters of 2,4,5-T in most kinds of water, except highly acidic waters, are usually hydrolyzed within a matter of days. -13- When the 2-ethylhexyl �ester of 2,4,5-T was applied to water In the laboratory at a concentration of 1 ppm for an hydrolysis study, 58$' remained after 4 hours; 33J. after 8 hours; and 1?$. after 16 hours. Trichell et ai. (52), studying the las.s of herbicides in runoff water, found 2 ug/ml of 2,4,3-T in runoff water 24 hours after it was applied at 2»24 kg/ha^ after which 1*3 cm of rainfall wag simulated on sod-covered plots of 3? slope. Pour months after application, concentrations of 2*4>5-T in runoff water had diminished to 0.04 us/ml* Edwards and Glass (53) monitored runoff and percolation of 2,4,5-T at Coshocton, Ohio, for 14 months following application of 11.2 kg/ha of 2,4,5-T and found that 5.5 g/ha, or over Q.05* of the herbicide, was lost from the treated area. Most of the 2,4,5-T was removed, in runoff water during the first four months after application, and more than half of the loss occurred the first month after treatment. Kearney et al* (46) concluded that contamination of underground water supplies with TC'DD seemed very unlikely, since vertical movement of TCDD did not occur in a wide range of soil types. The fact that no leaching occurred, however, would not preclude runoff loss when soil erosion is significant (39). -14- �(3) Transport lasnaea and Jones (54) measured uptake of TCDD from soil by two crop species. Oats (Avena gativa,-) and soybeans (Glvcine max) were grown in Lakeland sandy 1-oam soil treated with 0.06 pprn TCDD. The concentration of TCDD in soil was approximately 4,000 times greater than the amount that would be deposited in soil from an application of 2,4,5-T (with 1 ppm TCDD) at a rate of 2 pounds/acre in the top 1/3 inch of the soil surface. The tops of these plants were harvested at intervals to maturity. Mature oats and soybean tops contained less than 1 part per billion (ppb) TCDD. TCDD was detected (with a detection limit of 1 ppb) in mature oat grain, while no TCDD was found in the bean of soybeans. The authors concluded that soil uptake of TCDD by plants was highly unlikely, since little or no TCDD was taken up by oats or soybeans under the conditions of this experiment ( 4) (54). 33,oaocurnu 1 at; 1,on Woolson et al. (55) conducted a study to determine if TCDD residues could be detected in bald eagle (Kaliaectas leucoceshalus) tissue extracts, as a representative of the top of a food chain. Center (U.S. Scientists at the Patuxent Wildlife Department of the Interior, Laurel, Maryland) collected, and furnished to these researchers, 19 bald eagle -15- �carcasses from Alaska, Maine, North Dakota, Wisconsin, Michigan, Minnesota, Arkansas, Illinois, Missouri, Maryland, Virginia, Iowa, New York, New Jersey, and Florida between 1966 and 1971. These states were selected as. sampling sites in order to provide a widely dispersed—sample population! The eagle tissues were prepared and extracted as described by Mulhearn et ai» (56).. Woolson et ai. (55) detected no dioxin residues at a level of 0,05 ppm TCDD, the lower Unit of detection for* moat pesticides in tissue samples run by t'ha Patuxent Wildlife Research Center at that time. The authors stated that fchs non-detection of dioxin residues could imply that, thers was no dioxin build-up in the food, chain; that the build-up was less than the [then] current detectable level of 0.05 ppm [50 ppb]; that the eagles examined were not contaminated although other samples might be; or that other species could feed on a different food chain to accumulate dioxins, laensee and Jones (57) exposed several organisms in a model aquatic ecosystem to 1 *C-labeled TCDD for up to 31 days to determine the distribution and bioacumulation potential in the aq-uatic environment. Soil containing from 0.0001 to 7.15 ppm adsorbed 1 4C-TCDD was placed in aquaria, containing eight snails (Phvsa sp»), a few strands of algae C.Qigjj,_o_go_n_j.UH eardiacum) t and 10 al of old aquarium water -16- �containing various diatons, protozoa, and rotifers. Fifteen duckweed fLesna n^inor) plants were also- added to one aquarium, Samples of daphnids were taken for analysis at 30 days, and two mosquito fish (Gambusia a f f i p. 1 3) were added to each tank. Three days later all of the organisms were removed for analysis, and two fingerling channel catfish (I c t a 1 ur us punetatus) were'added to each tank and exposed for six days. The authors stated that all organisms in both treatment and control tanks prospered during this exposure period, indicating that TCDD was not toxic at the concentrations used* TCDD accumulated in all organisms. highest TCDD concentration At the (7.45 ppm) algae accumulated 6,690 i 960 ppb TCDD; snails, 1,820 ± 170 p p b ; daphnids, 10,400 ± 480 -ppb; and Gambusia, 1,380 ± 220 ppb. were not analyzed for TCDD residues. Catfish At the second highest TCDD concentration (3.17 ppm), however, catfish accumulated 720 ± 130 ppb TCDD. The authors stated that accumulation in all of the test organisms from soil containing 0.1 ppb TCDD is important since this concentration approaches the concentration which would occur under normal field use of 2,4,5-T. The authors concluded that the data suggested that under certain circumstances (discharge of storm runoff from -17- �recently treated rangeland into a small pond), water-eroded surface soil or debris 0137 contain enough TCDD for measurable residues (parts per thousand [ppt] quantities) to accumulate in fish or other aquatic organisms* However, the authors speculated that TCDD, orginating from 2 S 4,5-T applications, discharged into large lakes, streams, or estuaries would probably become sufficiently diluted so that no measurable accumulation would occurA3 part of a broad study to determine whether 2,J|,5-T use leads to TCDD accumulation in the environment, Shadoff et al. (58) collected samples of fish, stud,, water, and human milk from areas in Texas and Arkansas. The Texas samples of water, mud, catfish, and walleyed pike were collected from the San Angelo Reservoir, an impoundment of the North Concho River. The authors stated that chis watershed has large acreages that have been sprayed with 2,4,5-T at 0*3 pounds/acre (2,4,5-T acid equivalent) for brush control, These researchers also obtained six samples of human milk; from mothers residing in the genera!! area of the San Angslo Haservoir-. la—addition, bass from a 125-ac.re pond in the heart of the Arkansas rice-growing area were collected. Water from this pond is used to flood rice fields treated with the equivalent of 1.25 pounds/acre of 2,4,5-T acid, four to eight weeks prior to flooding. -18- The water is �later drawn off the fields and pumped back into the pond for re-use. In addition, the pond is suppl-enented by water from wells and by water collected as run-off from surrounding rice fields during the rainy season. The authors stated that this cycle had been in use (including the proper use of 2,4,5-T) for 18 years up to the time of their study* The authors stated that no TCDD was detected in the tissues sampled, using a Gas Chromatography-Mass Spectrometry procedure with a detection limit which averaged less than 10 ppt. No evidence was found that TCDD is accumulating in the environment from the use of 2,4,5-T described in this study* G, (1) Residues Soil - ' - Woolson et al. (55) studied Lakeland sandy soil to determine if TCDD residues could be detected in soil receiving exceedingly large application of 2,4-D and 2,4,5-T. The heaviest rate of 2,4,5-T application was 947 pounds/acre applied aerially during 1962 through 1964, while the lightest rate was 160 pounds/acre applied aerially during 1968 and 1969. During this period, it was not uncommon for commercial samples of 2,4,5-T to contain levels of 30 to 40 ppm TCDD. -19- �The authors were able to detect small amounts of 2,4,5-T in the soil samples. They observed that the residue level decreased with time after application and stated that leaching and microbial decomposition could account for this decrease. Using a detection limit of 1'ess than 1 ppb, the authors did not detect any TCDD at any depth in 36-inch core samples of the .soil, (2) JUiAC In October 1965f the U*S» Geological Survey initiated a limited program of pesticide monitoring on 11 waterways in the western United States (59)» The streams, representing agricultural areas where the probability of observing pesticide residues would be greater, included the Missouri, Brasos, Yellowstone, Sacramento, Colorado, Arkansas, Yakiiaa, Rio Grajxde, and Snake Rivers* Pesticides chosen for analysis JLncluded the insecticides aldrin, ODD, DDE, DDT, dieldrin, endrin, heptaehior, heptachlor epoxide, and lindane, and the herbicides 2,4-D, 2,4,5-T, and silvex. The autnors reported that no herbicide was found at any tiae at any station during"the first year of the sampling program. The lower limit of sensitivity (detection) was 5 ppt* Manigold and Schulze (60), reporting on the results af the U*S* Geological Survey stream monitoring prograo for -20- �the two-year period October 1966 to September 1968, observed that beginning in August 1967 2,4-D, silvex, and 2,4,5-T had been detected frequently* 320 samples and ranged from 2,4,5-T was found in 28 of the 0*01 to 0.07 ppb.. The authors stated that the established criteria permitted 100 -us/liter (ppb) for herbicides. These authors reported that the analytical procedures were changed from the preceding report to use Law's sample clean-up procedure, which permits routine detection of pesticides at 0.005 ug/liter in most waters* Norris (47) observed that peak concentrations of phenoxy herbicides seldom exceeded 0,1 ppm in streams contaminated from spray projects on range and forest lands in Oregon. Lawson (61) studied 2,4,5-T residues in storm runoff from three small watersheds in Arkansas* Two watersheds, one cleared and the other partially cut, were sprayed with t-he _isooctyl ester of 2,4,5-T, A third watershed, adjacent to the two treated ones, was used as a control. Spraying was done in September 1971, June 1972, and July 1973* either to control woody sprouts and broadleaf vegetation or just to provide herbicide application for monitoring. The cleared watershed was treated with 4 pounds acid equivalent per acre and the partially cut site with 2 pounds/acre* -21- �In water samples taken after the first runoff-producing storm in October 1971| Lawson (61) detected an average of 2,1 ppa 2,4,5-T from the cleared watershed and 1*0 ppm from the partially cut site. Maximua amounts detected were 2«2 and 1.3 ppo for the two areas. No 2,4,5'-" was detected 0 from the control site. Only tracs amounts (less than Q.2 ppm) were detected from each of the two treated sites after the next runoffproducing storms in November 1971, None was detected from the control. In approximately 90 samples taken after storms during the period December 1971 through September 1973, no 2,4,5-T was detected by Lawson (61) in the runoff from the treated or control water sheds. Since TCDD is immobile in soil (39) and soluble in water at only 0,2 ppb (7), contamination the possibility of ground water is virtually nonexistent (46), TCDD could be present in runoff when soil erosion is significant (39)> and thus TCDD contamination of water bodies could occur, A recent National Academy of Sciences report on drinking water stated that 2,4,5-T and TCDD have never been detected in drinking water; the limit of detection was in -22- �the parts per trillion. However, the report did project the toxicity of 2,4,5-T and TCDD, their acceptable daily intake, and suggested no-adverse-effect levels (62)» (3) Air Prior to 1970, phenoxy herbicides were widely used for early posteniergence control of weeds in wheat* Johnson (63) reported that air samples collected during spring and summer in the state of Washington where these crops are grown contained as much as 0*06 ug/m' 2,4-0 and 2,4,5-T. Assuming -£h.a±—a—aan inhales about 30 a^ of air per day, the authors estimated that exposure to 0*06 ug/m would amount to inhalation of 1*8 ug phenoxy herbicide/day or 0.025 ug/kg of body weight per day for a 70 kg man. Ambient air monitoring for pesticides in predominantly agricultural areas of 28 states was conducted by the National Air Monitoring Program in calendar years (C¥) 1970 through 1972 using ethylene glycol impinger type samples. Table 1 records ±Jia-.a-ciitJinuatic mean of residues of 2,4,5-T detected in this program (64). -23- �Table 1. Air Monitoring Data for 2,4,5-T in 28 Stats Monitoring Programs (T.Q70 to lQ7g) 1 ! Name of 2,4,5-T Sster ! State or Citv Won i tor ^d For i Louisana Isopropyi eater • [Montana jNew Mexico {Idaho Ullino is 3GEE I Oregon i Tennessee i Tennessee Isooctyi sstsr lOklahosia ND s NOG Detected, •3 i ng/m 3 • ! ng/m 3 | ng/m CY 1Q70 ! C? 1071 ! CY 1^72 ND v ND ND ND 1.1 ND ND ND ND ND . .JfD 3.6 0.5 ND 2.7 1.9 ! ! ! i ! ! ! ! 14,6 0,8 1.0 1.7 ND ND ND ND JUL . : Phenoxy acetic acids are relatively strong acids, and animals rapidly excrete them unchanged in their urine (36) « In. their study- of the fate of atraaina, kuron, silvex, and 2 t 4,5-T in the dairy cow, St. John et al. (65) found that dairy cows given 2,4,5-T and silvex in their feed at. 5 ppiii for four days, completely eliminated both 2,4,5-T and sflvex as soluble salts in the urine two days after dosing stopped. Zlellnski and Fishbein (66) treated fsnia.Ie C573L/6 mice with a single subcutaneous injection of 100 sag/kg body weight of 2,4,5-T in diaethylaulfoxide solution. They sacrificed the animals at various intervals after injection and analyzed in JL2ia *°r 2,4,5-7. The amounts recovered as percentage of the amount injected indicated decreasing levels at the following time intervals after dosing: at 0 hours, 77.1 ± 5.0 J j at 16 hours, 56.9 * 4.2*; and a,b 2]l hours 23.7 *, 3.6£» -24- �In a preliminary report of a two-year chronic toxicity feeding study, Dow Chemical USA (110)'reported the following residue data for rats fed indicated TCDD doses: 24,000 ppt in liver and 8,100 ppt in-fat of females ingesting 2,200 ppt/day; 5,100 ppt in liver-and 1,700 ppt in fat of females ingesting 220 ppt/day; and 540 ppt in t liver and fat of females ingesting 22 pp.t/day« The pre- liminary report gives no residue data for treated males, or for controls of either sex. Piper et al. (6?) studied the fate of 2,4,5-T following oral administration to rats and dogs. Four groups of three male and three female Sprague-Dawley rats (Spartan strain) and two male and two female adult beagle dogs were given single doses of 14 . C-labeled 2,4,5-T. by intubation at 5, 50, 100, and 200 mg/kg body weight in rats and 5 mg/kg body weight in dogs* The authors combined data obtained for males and females since the pharmacokinetics of 2,4,5-T were essentially the same in each sex* In this study, the clearance half-life for 5 mg/kg 2,4,5-T from dog plasma was 77.0 hours; in rats the half-life was 4,7 hours at 5 mg/kg and 4.2 hours at 50 mg/kg. At doses of 100 and 200 mg/kg body weight, the clearance half-life for rats increased to 19.4 and 25*2 hours, showing that the -25- �pharmacokinetics of 2,4,3-T varies with dose as well as with species. The authors suggested that the half-life values at 100 and 200 mg/kg body weight indicated that these doses may have exceeded the excretory capacity of the rats. Zitlco (68) assayed chlorinated dibenzodioxin residues in aquatic animals, but was unable to detect these compounds (detection limit: 0,04 ug/g [ppmj for TCDD) in any of several aquatic animals from Canadian locations. had selected Tbe author species from high trophic levels of the aquatic food web to measure cumulative pesticide contamination, More recently, using improved analytical methods for detection of dioxin at ppt levels, Baughman and Meselson (69) found mean TCDD levels ranging from 18 ppt to 810 ppt in fish and crustaceans taken from Vietnamese rivers in August and September 1970. TCDD levels tended to be higher in fish. from interior rivers than in those from seacoast locations. In comparison, 3aughman and Meselson found less than. 3 ppt T-CDD in fish obtained in a market in Cape Cod s Massachusetts. In another study, Matsumura and Bensset (70) placed TCDDcoated sand directly in an aquarium containing brine shriap, mosquito larvae, and fish (silverside). TCDD pickup was low in fish (2 ppb) and brine shrimp (157 ppb) under the experimental conditions. But mosquito larvae, which are bottom -26- �feeders, showed a surprisingly high rate of pickup (4,150 ppb). The authors concluded that TCDD'was not likely to accumulate in as many biological systems as DDT because of TCDD's low solubility in water and lipids, as well as its low partition coefficient in lipids, • (5) Plants Clark et al» (36) reported that, when herbicides are applied to rangeland, the levels of phenoxy herbicides available for ingestion by grazing livestock depend upon the nature and degree of cover, the rate and mode of application, time after application, and climate conditions. Studies by Morton et al. (44) showed that residues on grass immediately after application of 2,4,5-T are not likely to exceed 100 to 150 ppm for each pound of actual herbicide applied, per acre, Leng (37) stated that herbicide residues in or on plants declined rapidly, with a half-life of one to two weeks, due to photodecomposition by sunlight, wash-off by rain, metabolism by plants, and dilution from growth of plants, 2,4,5-T was applied to grass in four states at an application rate of U pounds/gallon, 3 gallons/acre; initial residues immediately after treatment in California averaged 684 ppm (or 57 ppm/pound applied per acre); 1,668 -27- �ppo (or 139 ppm/pound) in Michigan; 1,464 ppm (or 122 ppm/pound) in North Carolina-; and 1,332 ppm OP (111 ppm/pound) in Texas, After two weeks, residues in the four locations averaged 26 to 34 ppm/pound per acre. After_l6 weeks* all residues had declined to an, average 3 ppm/pound applied per acre* Baur et al. (7!) treated grass species indigenous to Victoria County, Texas, with 2 pounds/acre 2,4S5-T esterOne month after appl.tea.tion the concentration averaged 4,060 ng/g (ppb) for 2,4,5-T acid and 2,890 ng/g (ppb) for 2,4,5-T aster* Six months after application the concentra- tion averaged 60 and 170 ng/g (ppb) for 2,4,5-T acid and ester, respectively. Gotsendaner and Hummel (72)^ described a 1969 study in which a 2,4,5-T propylene glycol butyl ether ester formulation was sprayed on Texas grass at an application r'-arte equivalent to 1,2 pounds of 2,4,5-T per acre; this rate was 6 to 24 times the usual rate applied to grazing lands for- brush control. At this time, manufacturing specifications 5J Studies submitted by registrants as part of petitions for residue tolerances are classified confidential, pending outcome of litigation in U.S. District Court, -28- �for no detectable TCDD in 2,4,5-T used a method sensitive to 1 ppn. The authors found that residues of TCDD decreased rapidly from about 500 ppt TCDD within one day of application, to about 35 ppt TCDD after four weeks, and about 15 ppt TCDD after 16 weeks. The TCDD decrease roughly paralleled the loss of 2,4,5-T from the same grass. (6) Humana Matsumura (73) studied 2,4,5-T in the blood and urine of human male volunteers who had ingested the chemical. After ingesting 150 mg (2.2 mg/kg), the plasma concentration of 2,4,5-T in one subject reached a peak of 21«1 ug/ml after four hours. A linear, semi-logarithmic concentration-time curve (a gradient of -0.065) four hours post-treatment indicated first order elimination and absorption kinetics. In a second part of this study, Matsumura gave two male volunteers single oral doses of 100 mg 2,4,5-T, Urine samples were collected over 72 hours. About 45? of the original dose was found in urine collected during the first 24 hours after treatment; 60$ had been recovered 36 hours after treatment; and after 72 hours, more than 80$ of the original dose of 2,4,5-T had been recovered. Gehring et al. (74) also studied the fate of 2,4,5-T following oral administration to man. -29- Five male volunteers, �ages 31 to 58 years, each ingested a single 5 ag/kg oral dose of analytical grade 2,.4»5-T, with a purity greater than 99J and less than the detectable level (0,05 ppm) TCDD, directly or as a slurry in milk. Blood, uri.ne, and fsees were collected at intervals for up to ingestion. 96 hours after Essentially all (88.5 ± 5*1$) of the 2,4,5-T ingested by these subjects was excreted unchanged in the urine after 96 hours* The plasma 2,4,5-T concentration increased rapidly following ingestion and after 7 hours reached a peak of approximately 57 ug/ml, after which the plasma contained 65S of the 2,'4,5-T in the body, of which 99$ was bound reve-ra-iM,y -to protein* Kohli et al, (75) also studied absorption and excretion of 2,4,5-T in man. Eight male volunteers, age 25 to 35 years, received a single oral dose (2, 3 f or 5 mg/kg) analytical grade 2,4,5«T with a purity greater clian 994« Urine was collected up to 96 hours, and blood samples ware collected up to 168 hours, 2,4,5-T was detected in some two-hour urine samples, indicating rapid excretion of the compound. More than half of the 2,4,5-T was excreted in the urine in the first 48 hours, although small quantities were still being excreted at 96 -30- hours. �2,4,5-T appeared in all plasma samples after one hour 2,4,5-T ingestion, indicating rapid absorption* Maximum concentration (approximately 25 ug/ml for the 5 mg/kg dose) was reached between 7 and 24 hours after ingestion and began to decline at a first-or_der rate after 32 hours. These investigators concluded that 2,4,5-T was readily absorbed from the gastrointestinal tract, that it was eliminated unchanged in the urine, and that the half-life for plasma clearance was 18,8 ± 3»1 hours-. These authors pointed out that, in general, higher recoveries were reported by Gehring et al. (74) who used an electron capture detector, instead of the flame-ionization detector used in their study. The National Hunan Monitoring Program for Pesticides, through its cooperative arrangement with the Health and Nutritional Examination Survey II (Hanes II project), is currently analyzing human urine samples for silvex, 2,4,5-T, and 2,4,5-TC? (64). in 1979, The survey is scheduled for completion but some extremely tentative results are available. No quantifiable 2,4,5-T residues have been detected in the first 400 samples; however, trace amounts «10 ppb) have been found in a few samples. Dougherty and Piotrowska (177) reported on screening of human urine for environmental contamination with toxic -31- �residues by negative chemical ionization mass spectrometry, The procedure is baaed on solvent extraction with minimal clean-up followed -by examination with negative chemical ionization mass spsetronetry 1'or organochlorine residues and related compounds with masses greater than 130 daltons* Urine for the screening procedure was obtained froa students at Florida State University (25 dorm residents; 21 football team members; and 11 swimming team members)* The authors reported that kh« limited survey of human urines Indicates contamination of the subjects with 2,4,5-T, pentachlorophenol, other polychlorophenoxy acids, and numerous unknown compounds* The authors indicated that 2,4,5-T was found in 36* (9/25) of the dora residents; 24J (5/21) of the football team; and 9i (1/11) of the swimming team* -The authors attempted to- define the source of the contamination by applying the same screening procedure to environmental substrates and suggested the food chain, (beef fat in the case of 2,4»5-T) as one significant source of the contamination. (7) ftnimal Products Sooner el_aJL*.. (.iSX^aw^Y^yad beef fat from cattle grazing on land where 2,4,5-T had been applied to determine if TCDD was present in this tissue* None of the 2,4,5-T samples used were available for analysis for TCDD content* -32- �The authors did not know whether ths samples were produced before 1972 (when maximum allowable TCDD content was 1 ppm) or after 1972 (when maximum allowable TCDD content was 0.1 ppni). None of the 16 samples from Sugarland, Texas, Missouri, and Oklahoma showed TCDD residues when analyzed by a gas chromatography-nass spectrometry detection technique (detection limits: 3 to 6 ppt). Three of the eight samples from Mertson, Texas, where animals had grazed for 30 days in a fenced pasture sprayed in its entirety with 2,4,5-T, gave . positive responses at the detection limit of 3 to 4 ppt TCDD. In another surveillance study, Mahle et al* (77) analyzed milk from_ cows, grazing on grass treated with 2,4,5-T in accord with normal agricultural practices. Twenty-five samples were collected from different farms in Oklahoma, Arkansas, and Missouri; these areas were selected as representative of those where 2,4,5-T is used to control broadleaf weeds and brush in pasture and rangeland. Milk purchased in Midland, Michigan, an area where 2,4,5-T is not used, provided control samples. Based on gas chromatography-njass spectrometry data (detection limit: 1 ppt), the authors-=-3-tatedr tirat- control samples were indistinguishable from the samples from treated areas and concluded that TCDD was not present. -33- �The residue levels reported in animal products in the studies cited below were obtained in laboratory feeding studies and not from animals grazing on pastures * and rangelands treated at dosage rats.? recommended on registered product labels. Nevertheless» residues obtained in these feeding studies could occur in the environment and at these sane levels since animals grazing on forage plants immediately after treatment at recommended rates of application could ingest 2,4,5-T in amounts similar to those fed In the studies. Leng (37) found no residues greater than 0.05 ppm in mi-tk or cream of cows ingesting 10 to 30 ppm. 2,4,5-T. At 100 ppm 2,4,5-T in the diet, traces of 2,4,,5-TCP (0.06 ppia) were found in milk and cream. When the diet contained high �levels of 2,4,5-T, equivalent to 300 and 1,000 ppm in the total diet, residues of 2,4,5-T and 2,4,5-TCP ranged from 0.15 to 0,5 ppn in milk of individual cows. Leng (37), reporting on residues in nveat and meat byproducts, stated that calves slaughtered after ingesting 300 ppn 2,4,5-T in the total diet contained average residues of 0.12 to 0.28 ppm in muscle, fat, and liver, and 3»3 ppn in kidney. Animals fed 900 to 2,000 ppm 2,4,5-T in the total diet and slaughtered without withdrawal had proportionally higher average residues in tissue* detected (detection limit: No residues were 0*05 ppm) in most tissues when animals were given untreated feed for one week after they had been on the highest levels (1,800 and 2,000 ppm) of 2,4,5-T for four weeks. Residues of 2,4,5-T declined rapidly in tissues as soon as animals started to eat untreated feed. Clark and Palmer (78) found 0.08 ppm 2,4,5-T in omental fat of each of two sheep given four oral doses of either 0.15 or 0,75 mg/kg of the propylene glycol butyl ester of 2,4,5-T. „ They.also . found 368 ppm 2,4,5-T in kidneys of animals killed by four daily 250 tag/kg doses of a 2,4,5-T ester. Clark et al. (36) found 2,4,5-T no higher than 0,05 ppm in muscle or fat of sheep held one week on untreated -35- �feed* Residues of the metabolite 2,4,5-TC? wer-e not detected in the fat of any of the animals* They also found that the 2,4,5-T level in liver and kidneys was less, than 0.05 ppm after the. animals were on untreated feed fan., seven, days* Leng (79) found Low levels of 2,4,5-T in muscle and fat of calves receiving 300 to 900 ppm 2,4,5-T in the diet and much higher residues in tissues of animals fed 1,800 pptB 2,4,5-T for 28 days.. Calves fed 300 ppra 2,4,5-T showed 0.12 and 0*28 ppm 2,4,5-T in muscle and fat, respectively. Calves fed 900 ppm showed 0*24 and 0.33 ppm in muscle and fat, respectively. And at 1,800 ppm in the diet, calves showed 1*2 and 2*0 ppm in muscle and fat, respectively. In this same study, Lang found relatively low residues of 2,4,5-T in Liver at feeding levels of 300 and 900 ppm (0.2 and 1.0 ppm, respectively) and sharply increased residues ~(7»9 ppm) as 1,800 ppm, indicating that the threshold level may have been exceeded at this higher dosage level* Residues of 2,4,5-T in kidney appeared to be proportional to the level in the diet. Eighty-five samples of beef fat were analyzed for TCDD content under the auspices of the EPA Dioxin Implementation Plan (see Section II). .36- These beef fat �samples included 18 samples from control areas; and 67 samples from areas previously trea.ted with 2,4,5-T» None of the 18 control samples had detectable amounts of TCDD at a detection limit of 10 ppt. Of the 67 samples from areas previously exposed to 2,4,5-T, one showed a * positive TCDD level of 60 ppt; two appeared to have TCDD at 20 ppt; and five may have had TCDD levels which ranged from 5 to 10 ppt. The values for these five samples were at or below the limits of detection of 10 ppt. Forty-three beef liver samples were analyzed and showed no TCDD residues at a detection limit of 10 ppt* (8) Food Evidence that very little 2,4,5-T.gets into 'food is seen in results of Market Basket Surveys conducted by the Food and Drug Administration (FDA), Of the 134 total diet samples involving 1,600 food composites (Market Basket Survey) analyzed from 1964 through April 1969, only three contained 2,4,5-T. Two were dairy products containing 8 to 13J fat with 0.008 and 0,19 ppm in the fat. A single meat, fish, and poultry composite from Boston consisting of 17 to 23% fat was found to contain 0,003 ppn 2,4,5-T on a fat basis (81, 82, 83, 84). FDA Market Basket Survey samples from 1969 through July 1974 showed no 2,4,5-T residues (detection limit: -37- 0.02 �ppn) in 155 total diet samples involving 1,869 food composites (85, 86, 87, 88, 89). (9) ffuaan r Sx303urq via Industrial Accidents There have been a nuaber of industrial accidents during manufacture of chlorinated phenols that have resulted in human exposure to TCDD. Whiteside (90) reported on a 19 J <9 -sxp.1 osian at a, chemical'plant producing 2,4,5-T in Nitro, West Virginia. The release of intermediate chemicals led 1:0 228 cases of chloracne among exposed woriears, Wh.itesidss stated that symptoms of affected workers included skin eruptions, shortness of breath, intolerance to cold, palpable and tender liver, loss of sensation in extremities, damage to peripheral nerves, fatigue, nervousness, irritabilityt insomnia, loss of libido, and vertigo* Goldmann (91) reported on a 1953 accident at a 2»4,5-TC? production plant in Germany, Temperature and pressure rose explosively in the autoclave, forming previously unknown, very toxic chlorinated hydrocarbonsj 42 persons contracted serious cases of dermatitis, in which 14 persons suffered consequent damage to internal organs, and seven persons experienced disturbances of the nervous system. �A similar accident occurred in Amsterdam in 1963 when an explosion in a 2,4,5-T factory resulted 'in 50 workers contracting chloracne (90). In 1954, 31 workers in a Hamburg, Germany, chemical plant producing 2,4,5-T from technical 2,4,5-TCP contracted chloracne (10, 16, 92) and suffered the physical and psychological symptoms associated with it (93). Kimaig and Schulz (10) extensively investigated the workers' conditions and conducted experiments treating the skin of a rabbit's ear with chemicals to which workers had been exposed. These researchers tentatively identified the causative agent of the chloracne as TCDD. Bauer et al. (15) conclusively identified TCDD as the cause of chloracne. ' •- In 1964 workers in a 2,4-D and 2,4,5-T plant in the United States developed chloracne (93, 94). Eleiberg 3-fr-al. -(94) found evidence of porphyria cutanea tarda (PCT) of varying degrees of severity in 11 out of 29 workers. PCT had never before been described as related to chloracne, nor had it been ascribed to industrial exposure in the United States. The authors stated that either the finished chemicals or some intermediate were responsible for both diseases. The Fine Chemicals Unit of Coalite and Chemical Products Limited located at Bolsover, Derbyshire, in England had been producing 2,4,5-TCP for nearly three years without -39- �incident whsn an explosion occurred at midnight on April 23, 19684 As a result of this exothermal reaction', TCDD had accidentally been produced* Workers at this plant were accid.ental.ly exposed to TCDD, and 79 cases of chloracne were recorded,- many of them severe (9, 95) » 9 Beginning in May 1971 an accidental poisoning episode occurred in the United States that affected humans, horses, and other animals. The exposure was related to the spraying of waste oil, contaminated with TCDD, on riding arenas to control dust. Three days after spraying, sparrows and other birds were found dead on the arena floor. Of 85 horses exercised withdn the arena, 62 became ill, and 48 died* The first horse died on June 20, 1971. continued to die as late as January 1974, Horses Human illnesses were less severe, but did include one case of hemorrhagia cystitis in a 6-year-old girl who frequently played in the arena* Analysis showed the arena contained 31.8 to 33*0 ug/g TCDD (96, 97, 162). Beale et al» (98) presented follow-up information on the 6-year-old girl involved in this accidental poisoning. These authors stated that the girl's symptoms resolved in three to four days and did not recur. Results of a repeat voiding cystogram three months later appeared normal. Cystoscopy at this time did, however, demonstrate nuaarous punctate haemorrnagic areas in the bladder, especially in -40- �the region of the trigone. Five years later, an investiga- tion showed that this girl had grown normally;- results of a physical examination, including a detailed neurological examination, were normal. Cystogram and liver-function tests wer'e also normal, as was the urinary -excretion of uroporphyrins, coproporphyrins, and thyroid function, On July 10, 1976, an accident at the ICMSSA chemical plant in the Seveso Region of Italy released 2 to 10 pounds of TCDD over a wide area (90, 99, 100). Hundreds of animals died, many area residents reported skin disorders, and an area of 110 hectares was evacuated (101). Reports of the • immediate symptoms and indications of many long-term effects are just becoming available. Seveso inhabitants initially experienced numerous, burn'like skin lesions which gradually receded; Whiteside (90) believed this type of lesion was probably due to direct contact with the sodium hydroxide and phenolic components of the fallout. Two and a half months after the explosion, however, children and young people in the zone most affected by the fallout developed symptoms of true chloracne, a sign of dioxin poisoning, on their faces, arms, and bodies* By November 1976, 28 people had developed confirmed cases of chloracne, and the number rose to 38 by December 1976; one year later, the number of confirmed cases of chloracne was 130. �A number of Seveso women were pregnant at the tiae of the accident, Whiteside (90) reported that the number of legal and illegal abortions performed, after the accident probably totalled 90* Results of 3 survey by an epidemological commission showed that 3,33 babies were delivered in the two months following the accident and that there were 51 spontaneous abortions as distinct from induced abortions (approximately double the rate of spontaneous abortions previously reported for the area)* Whiteside (90) reported that eight cases of birth abnormalities have been noted to date among babies born to women in the Seveso area who were pregnant at the tiae of the explosion* Physicians in the Seveso area have had difficulty relating this directly to the explosion, however, since this incidence of birth abnormalities was not disproportionate to the usual incidence of abnormal births* H• Tolerances There are no tolerances established for 2,4,5-T in or on food crops. Likewise, no tolerances have been set specifically for TCDD in or on food crops. However, 40 CFR Section 180,302 does establish a tolerance of 0.05 ppm for hexachlorophene on cotton seed (a nonhuman dietary food item), with a stated limitation that the technical grade • 42- �hexachlorophene used in the formulation shall not contain nore than 0»1 ppm TCDD. The limitation does not constitute a tolerance (102)» I. Pesticide Spjlsode Reports SvBteci (PER?) EPA's Pesticide Episode Response Branch of the Office of Pesticide Programs maintains a Pesticide Episode Reports System (PERS) which collects reports of pesticide exposure affecting humans, domestic animals, livestock, and wildlife (103), According to their records, there were 96 episodes from 1966 to April 1977 involving 2,4,5-1% Many of these 96 episodes recorded effects in more than one area of the environment. Plant damage was reported 60 times, effects on humans 16 times, water contamination 14 times, effects on domestic animals and soil contamination 7 times each, general environmental contamination 3 times, and fish kills and complaints against use of 2,4,5-T twice each. There was substantial evidence in 13 of the 96 episodes linking 2,U,5-T to the episode's effects; there was circumstantial evidence in 20 of the -episodes for involvement of 2,4,5-T; there was insufficient evidence in 62 of the episodes to prove or disprove involvement of 2,4,5-T; and one episode had no verification status listed. -43- �Of the 13 episodes for which there wag substantial evidence linking 2,4,5-T to the episode's effects, two involved humans (including one suicide); 2,4-D was also involved in both episodes. Three episodes involved plant damage from drift of herbicides; 2,4,5-T residues were found in plant samples in two episodes; 2,4-D was also involved in one of these episodes. Two episodes involved fish kills resulting from accidental spills into streams, with 2,4-D involved in both incidents? in one of these episodes, 6,000 fish (902 Juvenile salmon) were killed; residues of both 2»4-D and 2,4,5-T were found in these fish. Two incidents involved soil contamination when two warehouses were destroyed by a tornado and fire: many other pesticides were involved in both instances. Two episodes involved •domestic animals; in one, 24 cows died after herbicide application. Arsenic residues were found in two cows, and arsenic contamination of the herbicide mix was suspected* In the other instance, 8 cows drank water contaminated with 2,4>5-T; residue levels of G.03 and 0,02 ppm were found in the milk five and eight days, respectively, after the incident. dumped. Two hundred and forty gallons of milk were One incident involved water contamination as a result of a warehouse fire; many other pesticides were also involved* -44- �II. REGULATORY HISTORY 2,4,5-T was developed during World War-II and was first registered as a pesticide on March 2, 1948 (3). Since then, it has been the subject of several Federal regulatory actions.• — On April 13, 1966, the United States Department of Agriculture (USDA) and the Food and Drug Administration (FDA) published an announcement in the Federal Register abolishing the "No Residue and Zero Tolerance" concepts as scientifically untenable* Future registrations would be granted on the basis of either "Negligible Residue" or "Permissible Residue," Industry was given until December 31, 1967, to comply by obtaining tolerances for residues of 2,4,5-T in all treated food, feed products, and byproducts (in addition no registrations would be continued beyond December 31, 1970)• Following this action, a series of Pesticide Registration (PR) Notices were issued over several years, extending certain "no residue" and "zero tolerance" registrations beyond the December 31, 1967, deadline for obtaining residue tolerance. (These and all following PR Notices are cited in Reference 104.) Among uses of 2,4,5-T extended beyond the deadline were uses on pasture grasses and rangeland; on apples (Mclntosh), blueberries (low bush), cereal grains (undesignated), rice, and sugarcane; and in lakes and ponds. -45- �PR Notice 70-3 issued by the USDA on March 10, 1970, identified data needs for certain compounds* .'2,4,5-T was identified as one of the compounds requiring further teratogenic studies. PS Notice 70-11 published on April 20, 1970, suspended. 2,4,5-T products bearing certain directions for use* The suspended uses were all uses in lakes, ponds,' or on banks? and liquid formulations for use around the j recreation areas, and similar PB Notice 70-13 issued by the Q'SDA on May 1, 1970, cancelled 2,4,5-T products bearing certain directions for use. The cancelled use.s- were all granular 2,4,5-T formulations for use around the. home, recreational areas, and. similar sites; and all 2,4,5-T uses on food crops intended for human consumption. All registrants were advised of these actions, and two of the 2»4,5-T registrants, Dow Chemical and Hercules Incorporated, excercised their right undsr Section 4(e) of the Federal Insecticide, Fungicide, and Rodenticide Act (FIFHA) [? H.S,C. 135 et seq»] to petition for referral of the cancellation (rics use only) to an Advisory Committee, As provided by Section 4(c) of FIF3A (1964 amendment), a nine-member \dvisory Committee of scientists was appointed -46- �to consider all relevant facts, submit a report and recommendations regarding registration for certain uses of 2,4,5-T, and state the reasons or bases for these recommendations. Their report was submitted to the Administrator of the Environmental Protection Agency on May 7, 1971 (48)« The Committee recommended that use of 2,4,5-T be permitted in forestry, range land, and rights-of-way providing that the limit of 0.1 pom of contamination with TCDD be set for all future production of 2,4,5-T; that 2,4,5-T be applied no more than once a year at any one site; and that 2,4,5-T be applied with proper caution so that it will not contaminate other areas where it may come into contact with humans. The Committee also recommended that this action be reviewed again when existing deficiencies in information " about possible magnification of TCDD in the food chain have been rectified by specific research. In the meantime, PR Notice 70-22, published by the USDA on September 28, 1970, addressed the presence of chiorodioxin contaminants in economic poisons. This notice seated that the USDA had determined that certain toxic chlorodioxins (such as TCDD) may be present as contaminants in the basic materials used in formulating 2,4,5-T and silvex. The notice also stated that the presence of such -47- �ehlorodioxins constituted a possible hazard to man since they had been found to be extremely toxic to laboratory animals, and that appropriate regulatory action would be taken under provisions of FIFHA since products containing chlorodioxins are considered to be in violation of FIFRA.~" t Dow Chemical obtained an injunction against EPA in July 1972, enjoining further administrative action against 2,4,5-T* The United States Court of Appeals for the Eighth Circuit overturned the injunction in 1973» and administrative proceedings were allowed to go forward, On July 20, 1973, a notice of intent to hold public hearings on _aJL,l uses of 2,4,5-T was filed with the SPA Hearing Clerk under Section 6(b)(2) of FIFHA, as aaended 1972* Ail federally approved uses of 2,4,5-T were to be explored in a public hearing scheduled for April. 1974, following completion of an intensive monitoring prograas for detecting dioxin in. the ppt ranga (38 ?R 19869, July 2.9 > 1973)* On May 10, IS?4, the information hearing was expanded to include all insecticides and herbicides having 2,4,5-TCP in their manufacturing process. These included silvex, srbon, and ronnel, as well as 2,4,5-T and 2,4,5-TC?, all of which may contain TCDD* -48- �On June 24, 1974, EPA withdrew cancellation and information-gathering proceedings initiated against 2,4,5-T and related compounds because of its inability to monitor food for TCDD residues with the necessary analytical precision.. Although the 2,4,5-T notice of .hearing, was withdrawn, the Agency stated that it "will continue its TCDD residue aonitoring program and will take such further action as it deens appropriate once the results of the monitoring project are available" (39 FR 24050 June 28, 1974). On July 25-26, 1974, the Agency held a Dioxin Planning Conference in Washington, D.C., primarily for those parties having an interest in the withdrawn 2,4,5-T/dioxin hearings, to address data analy-sis-and retrieval (in the areas of analytical methodolgy, toxicology, and monitoring) with emphasis on analytical methodology for TCDD at the ppt level. As a result, the Agency established a Dioxin Implemen- tation Plan (DIP) intended to identify a preferable analytical methodology to monitor human and environmental samples for TCBD. On-going TCDD studies under the DIP include: an analytical method validation study to produce statistically defensible data; monito'ring for residues in human milk in the Pacific northwest; additional beef fat residue studies; -49- �additional technical pesticide residue studies; and an environmental monitoring program for TCDD residues in soil, water, and biota. III. S U M M A R Y OF SCIENTIFIC EVIDENCE H£JLA.IIKS.JLfl. g E$y T; tAB L 5 P RSS UM PTI0 N The following adverse effects of 2,4,5-T and/or TCBD have been found to exceed the criteria for issuance of a rebuttable presumption as stated in Section 162,11 of the Code of Federal Regulations ( CFB 40) » Because of industry's apparent inability to produce 2,4,5-T without TCDD contamination, none. oT the studies cited are for pure 2,4,5-T. The effects of TCDD must also be considered when assessing 2,4,5-T by the Agency's risk, criteria, A ». Q n o_o g 3 n i e S f f e c 13 — i 40 CFH Section 162.11(a) (3) (ii> U) provides that a .rebuttable presumption shall arise "if a pesticide's ingredient(s),«,(i)nduces oncogenic effects in experimental mammalian species or in man as a result of oral, inhalation or dermal exposure...." Section I62.3(bb) defines the tern oncogenic as "the property of a substance or a mixture of substances to produce or induce benign or malignant tumor formation in living animals.* -50- �The studies summarized below indicate that 2,4,5-T containing less than 0.05 ppm TCDD and/or TCDD alone have oncogenic effects in two mouse strains and one rat strain. Since 2,4,5-T, as currently formulated, contains TCDD (at a • maximum amount of 0*099 ppa), a rebuttable presumption against the registration of 2,4,5-T products has arisen because of the oncogenic effect of 2,4,5-T and its contaminant, TCDD. (1) (a) 2,4.5-T Effects of Dietary 2.H.5-T f<0.0? oqn T'CDD) on Rodents In their bioassy of 2,4,5-T for carcinogenicity in mice, Muranyi-Kovacs et al* (105) administered 2,4,5-T (containing <0.05 ppm TCDDJ^to inbred C3Hf and XVII/G mice. The mice were given 100 mg/liter of 2,4,5-T in the drinking water for two months beginning at six weeks of age. During the succeeding 15 to 20 months, the mice were given 2,4,5-T mixed in the diet at a concentration of 80 ppm ad j^lbitum. ' In C3Hf mice, 48S of the treated females (12/25) and 55J of the treated males (12/22) developed tumors, compared with control values of 21* (9/44) and 49J (21/43), respectively (Table 2), The differences between the number of tumors observed and the number expected were significant for female mice at all sites (p < 0.03) and for the combined sexes & This TCDD level is less than the 0.1 ppm TCDD currently found in most commercial formulations (see Section 1,3). -51- �(p < 0.01). For non-incidental tumors, the differences were significant for each sex and the combination; no significant differences were found in incidental tumors. 8/ Ho other strain-sex combination yielded statistically significan-t values OQ6). Rare types of tumors, not seen in the control animals, were observed in the treated C3Hf i 1 I j 1 [ [Strain females. Table 2. Oncottenic Effects of ?.4.5-T on Mice^ i Dietary! Mean Mice with Leukemia i i Level | Survi- and Lung and Liver } Tyao **3 ' Incidence- of .Tuaors i val Time, 5 (Sex No/Tataj. No /! *. Total f Lune ! L iv— i L«uk«n«a I Ot Jdazal ! C3HF ! M 630 22 I 2 ! 21/43 149 19 I -~ I 1511Js/ 80 i 1 ! '2/22 2 I 113 ! — ! 10 I (55 680 9/44 12,1 i 1 F 3 i t | 0 ! 5 ! 9 ! | 1 ii i 1 i 1 1 1 80 ! ! US n ! - ! 620 n ! i i & 12/25 IZTII/G I M 521 . 178 25/32 4 i |V 0 i 27 i 22 i i j 80 ! 16 1 14 i 15/20 i i ~ 1 1 1 tl 533 175 ii ! o 24 I 20 | - ! 2,1/40 2 1 2 0 I i f 569 153 i i i i 1 , | 184 ! ! f 80 ! 641^'' ! 16 16/19 i/ Data from Muranyi-Kovacs (105). I/ Estimated daily oral doge a 12 mg/kg body weight. I/ Effective number of mice are mice surviving longer than 300 days or developing a tuaor safore 300 days of age. i/ Pleomorphic salivary gland tumor. j/ Fibrosarcoma; one hyparplastic urinaz*y bladder and one aypsrplastic forestomach not Included. y One ostsogenic sarcoma; two sarcomas; two cutaneous tumors; one cervical tumor. I/ Forestomach uumor. I/ Urinary bladder papilloma; two hyperplastic lesions of urinary bladder not included. o ! I is ! L/ Two hemangiomas. I/' p < 0.01 compared with controls. S/ p < 0.001 compared with controls. £/ The i n v e s t i g a t o r s f o u n d no s i g n i f i c a n t s e x - r e l a t e d differences. £/ I n c i d e n t a l t u m o r s are t u m o r s discovered at n e c r o p s y of an animal w h i c h d i e d f r o m some o t h e r c a n c e r ; n o n incidental t u m o r s are t u m o r s d i a g n o s e d d u r i n g l i f e or which caused the d e a t h of the a n i m a l . -52- �A decrease in survival time for nice with tumors was noted in both male and female treated C3Hf mice' when compared with controls. C3Hf treated male mice survived an average of 51V days compared with 630 days for control male mice. According to the evaluation by EPA's Carcinogen Assessment Group [GAG] (106), this difference was significant (p <0.001), Treated female C3Hf mice survived 620 days compared with 630 days for control females. Chemically induced oncogenic effects typically show long latency periods. The finding of reduced longevity among treated animals as compared with controls complicates the assessment of the potential oncogenic effects of 2,4,5-T. In XVII/G mice, 84$ of the treated females (16/19) and 75J of the treated males (15/20) developed tumors, compared with control values of 53$ (21/40) and 78* (25/32), respectively. An increase in survival time for mice with tumors over controls was noted among the XVII/G .treated animals. There was an average survival time of 533 days for treated male mice compared with 521 days for control male mice. Treated females survived 641 days compared with 569 days for control females. According to CAG (106), the difference was significant (p < 0.01) in females. -53- �(b) Effects of Subcutaneous In.1eoti.on and Oral Administration of 2.U.5-T MO OOP 7CDD) on Rodents Innes at al. (107) studied the tuaorlgenicity of 2f4,5-T, containing about 30 ppm TCDD, in two hybrid strains of nice, designated as "Xw and "Yn, after oral or subcutaneous administration of the maximum tolerated dose (Table 3)« The testing was performed at Bicmstics Research Laboratories, under contract from the National Institutes of Health* Results of the studies were calculated comparing; treated groups with matched and pooled control s,-^ In the subcutaneous study, mice were given a single injection of 21.5 ag/Jcg of 2,4,5~T in a dimethyl sulfaxide (DMSO) solution at approximately 18 months of age* Seventeen percent (3/18) of the treated "Y1* males developed pulmonary adenomas, compared with 1J (1/7'D of the matched controls and 3% (4/122) of the pooled controls. This increased incidence of pulmonary adenomas was significant relative to both control groups Cp s 0.024 matched and p s- 0*04 pooled] (106), In the oral study, 21.5 ag/kg of 2,4,5-T in gelatin was administered daily by stomach tube, beginning at seven £/ Because this was a large scale screening- study, several control groups were used. No significant differences were found among these groups. .54- �days of aget After weaning, 60 ppm of 2,4,5-T was mixed in the diet and provided a,d libitum until the end of the study at approximately 18 months* Gross and histological examinations were made of all major organs and visible lesions; thyroid glands were not examined* According to CAG's evaluation (106), there were no significant differences between 2,4,5-T treated and control groups of mice with respect to tumors at specific sites or total number of tumor-bearing animals* 1 1 {Dose 1 (Strain : x ! i ! ! ii i ! 1 ! i iI ! ! !. M i 0 ! (matched) 1 0 | pooled) ( ! 60 F ! 0 ! (matched) ! 0 i (pooled) : i ! i SOY ! ( DTJta) Table 3. Tuners in Mice Ingesting ! L Mice wLth Specific _Jumors - . Mice with T':aors Reticulum Cell Tumor Type Pumonary I No/Total No % i_Sarcona ! Adenoma & Carcinoma Heostoma ! 0. 2 5/15 3 ! 33 I ! 50 M i 0 ! (matched) ! 0 i( pooled) ! 60 F i 0 I (matched) ! 0 i (pooled) ! 60 - I 22/79 28 5 5 8 : 6/18 2/18 33 11 1 1 1 1 4 8/87 9 1/81 3/18 6 17 4 __ _ 3 1 3 16/90 18 1 3/18 1/T5 "" 17 7- 2 1 7/82 9 3 2/18 11 1 ! 10 — — 3 ! —^ ! ii I 5 : i 1 i — ! i 1 i ~ ! — -55- I ! 1 i -- | �(2) TCPD ( a. ) OncoggnjLo g/'fects of Low L e v e l s of TCDIX Van Miller at al. (109) recently reported the results of a two-year feeding study with male Sprague-Dawley rats. Tan groups of ten animals per group were fed ground chow containing 0t 1, 5, 90, or 500 ppt (s 10~ gram TCDD/graa -9 food), an.d I, 5, 50, 500, or 1,000 ppb ( = 10 gram TCDD/gram food) TC&D, Food intake. (10 i 4 g/day) was significantly lower in . rats ingesting the three highest dose levels (50, 500, or 1,000 ppb TCDD) than in controls (21 ± 2 g/day), and none of the rats in these three groups gained weight after the start of the experimental diet. All rats receiving these thrae doge levels died between the second and fourth week of treatment*, On the other hand, food intake for rats on other doss levels was similar to controls (2,0 .* 2 g/day). Weight gain was significantly less only for rats given 5 ppb TCDD (391 *. 54 g) as compared to controls (531 A ^ g)» -56- In these �seven groups only one animal died before the 30th week, and that death occurred in the 500-ppt group at the 17th week. In the 5- and 1-ppb groups, all animals died'by the 90th week of the experiment. Table 4 shows the mortality figures for all groups. Table 4. Mortality in Rats Ingesting Various -Levels of TCDD ! ii i No, Rats Dead ! t i ?irfs Blatu i at QSth Wee IfA/j i i i 68 (60$) i i 6/10 i i i Ii\ l p p t i// 86 2/10 (20$) I j i ! 5 pp t ii 33 1 4/10 (40$) !so ppt* 4/10 (40$) i 69 7 .'500 pp-f 5/10 (50$) 17 1 ^L' 10/10 (100$ Ii 1 ppb H / 31 t 10/10 (100$ ) ! i 5 ppb 31 17 10/10 (100$ 1 50 ppb 3 i j/ ' i 10/10 (100$) ! ISOO ppb 2 •) 10/10 MOO* ) ! ll .000 ool5 Surviving animals sacrificed at 95 weeks. Control group. Di et contained no TCDD. Approximate weekly dose was 0 .0003 ug/kg body wt Approximate weekly dose was 0 » 001 ug/kg body wt. Approximate weekly dose was 0 •0 1 ug/kg body wt. Approximate weekly dose was 0* 1 ug/kg body wt. Approximate weekly dose was 0 •4 ug/kg body wt. Approximate weekly dose was 2 •0 ug/kg body wt. Approximate weekly dose was 2 4 ug/kg body we. Approximate weekly dose was 2 40 ug/kg body wt. Approximate weekly dose was 500 ug/kg body wt. 1p ! i i iii i &/ Ji/ Q_ / g/ ,§./ £/ JL/ Jl/ i/ JL/ Jt/ -57- > 1 ) ! i �Laparotomi93 were performed on all rats surviving through ths 65th week, and all tunor3 observed were biopsied. Rats were maintained on these diets until the ?8th week and were then placed on the control diet. were killed at 95 weeks. Surviving animals Complete necropsies were done at death or sacrifice, and tissue samples were microscopically examined. Special staining methods were used to "aid IB the diagnosis of neoplasms." Tunsorigenic and toxic effects were ooserved in the six lowest dose groups. in rats The overall incidence of neoplasms in the six experimental groups was 38$ (23/60), compared with 0$ (0/10) in ;the control group. is statistically significant (106). The difference Neoplastic nodules and cholangiocarcinomas of the liver were observed in 40? (4/10) of the rats ingesting 5 Ppb TCDDj two aniaals had both neoplastic nodules of the liver and cholangiocarcinomas. One rat (10J) in the 1 ppb group had hepatic carcinoma compared to none of the controls. Hepatic tumors were not found in other dose groups (Table 5). 1 Tablq 5. .Liver Tumors in Rats Ingesting ----^ Hats Wish i Hats With i Hats W i t h Neoplastic ! Cholangio- ! Nodules plus JL, Nodules ! ca**e ' TOES 3 !Carc -i no sis Dose (oob) \ Mo . J *» Mo. ! 1 ! No. \ ", ! i 0 1 « 0/10 i 0 i 0/10 i 0 i 0/10 ! 0 ! 0/10 i 0 ! 1/10 ! 10 i 1 / 1 Q i 1 0 i 1 7 i £./! U/ 1Q ! 11 Q-* ! 2/10 ! 20~/! J»/ JiJ ^a? i a/ Data from Van Miller (109). i/ Two animals had both neoplastic nodules of the liver and cholangiocaruinoisaST -58- �Tumors developed in 46J (23/50) of the rats ingesting 5, 50, or 500 ppt and 1 or 5 ppb TCDD, compared to none (0/10) in the control rats. Van Miller et al» noted that "nineteen (57J) Fsle - Agency calculation is 54$ (19/35)] of the animals that died in the six groups fed subacute levels of ICDD had neoplastic alterations." observed in the ear duct, kidney, and liver. Carcinomas were Three retriperi- toneal histiocytomas were described as metastasizing to the "lungs, kidney, liver, and skeletal musculature." According to CAG's evaluation (106), statistically significant increases in tumors at all sites were found in rats fed 5, 500, 1,000, and 5,000 ppt as- aoopared with control animals (psO.-05) [Table 6], Three of the ten deaths which occurred in the 5.ppb dose group were attributed to aplastic anemia. One animal in the 500-ppt group had a severe liver infarction, Dow Chemical USA (110) has provided EPA with a preliminary report of a study of TCDD's chronic toxic effects in Sprague-Dawley rats. Groups of 50 rats of each sex were fed 0,1, 0.01, or 0.001 ug TCDD/kg body weight daily for two years* To provide these dose levels, the concentrations of TCDD in the diet were approximately 2,200, 210, and 22 ppt. Eighty-six animals of each sex were used as controls. Dow (110) reported "discernible increases" in the incidence of hepatocellular carcinomas of the liver and of squamous cell carcinomas of the lung, hard palate/nasal -59- �Table 6. Total Tuaorg i n _ H a t s Ingesting TCDD-^ i i i Rats With | b/ ! Tumors I Tumors i Dose 1 Benign y.alizaanc Total ! Mo, * 1 i 0 i 1 Ppt 5 .PPt i 50 ppt !500 ppt 1 PPb i t^ £Bb ! i i 0 0 1 1 2. i I 2 ! ! ! i ! ! 0 0 5 1 2 ! o I o/io ! o/ro i ! ! 0*A/ 1 Q% ! I o ! 6A/ ! 5/10 sor7 I i & \ 3/10 30? ! 1 x/ \ 4* i 4/10 7 ! h/ i & 40 % \ ! J*" ! 4/io 5 7 I ? ! 10^ ! 7/10 QJL. u. Data, from Van Miller (109). £,/ £,/ Rats administered 50,, 500, and 1,000 ppb were all dead within four weeks. £/ Forty male rats used as controls for another study that were received at the same time and kept under identical conditions did not have neoplasms when killed at 18 months, i/ One rat had ear duct carcinoma and lymphocytic leukemia* The following tumor types were each observed in one rat: adenocarcinomas (kidney), malignant histiocytoma (retroperitoneal), angiosarcoma (skin), and Leydig cell adenoma (testis) A/ Three rats died with aplastic anemia. £/ The following tumor types were each observed in one rat: fibrosarcoma (muscle), squamous cell tumor (skin), and astrocytoma (brain). &/ The following tumor types were each observed, in one rat; fibroma (striated muscle), carcinoma (skin), sclerosing saminoma (testis), and adenocarcinoma (kidney), JL/ One rat had a severe liver infarction, i/ One rat had cholangiocareinoma and malignant histioeytoraas (retriperitoneal)* The following tumor types were each observed in one rat: angiosarcoma (skin), glioblastoma (brain), and malignant histiocytoma (retropsritioneal), j / One rat had squamous cell tumor (lung) and neoplastic . nodule (liver). Two rats had cholangiocareinoma and neopiastic nodule (liver)* Three rats had squaaious cell tumors (lung). One rat had neoplastic nodule. ( 0 8 -60- �turbinates, and tongue in rats at 0*1 ug/kg. reported decreased incidences of They also pituitary, uterine, mammary gland, pancreatic, and adrenal gland tumors at this dose level. Bow also reported that this dose level produced increased mortality, decreased body weight gain, and changes in blood chemistry values which Hepatocellular nodules and suggested severe toxicity* alveolar hyperplasia were observed in the 0.01 ug/kg group* A squamous cell carcinoma of the hard palate was observed in one female receiving this dose; Dow considered this unrelated to TCDD treatment because a similar iumor_occurred in "other concurrent studies," At 0.001 ug/kg there were no "discernible effects in male rats and an increased incidence of [reversible] swollen hepatocytes in female rats," Dow's preliminary report does not include control data, quantitative data on tumor incidence, or statistical analyses* CAG has not evaluated this s.tudy. describes the available tumor information. Table 7 Dow has submitted the final report for this study, which CAG is currently reviewing. -61- �Table 7« Tumors in Sprague-Dawley Rats Ingesting ! ! Dos-9 I ua/kc/da v ppt ! Tumors 0 ! •n<w «n «» 22 ! « m*w«» 10.001 10.01 i 210 i Hepatooellular Nodules 1 Squamous Cell Carcinoma-^ | ! ! i i Alveolar Hyperplasia : o I • 1 1 J lo.i 1_ 2,220 ! Bepatoceilular Carcinoma* i i i SLayanous Cell parci,noca-^ A/ Data from Dow Chemical USA (110), a preliminary report, JjL/ Hardpalate squamous cell carcinoma observed in only on* female rat* £/ Observed only in females, i/ Squamous cell carcinoma observed in lungs, hardpalate/nasal turbinate, or tongue. (b) gffeeta Cloaelv Related, to Oncoger.igi':? in Teat Many chemically non-reacfcive carcinogens are anzymatically converted to biologically active carcinogens, Th.e enzyme aryl hydrocarbon hydroxylase (AHH) is strongly implicated in this process (112). For example, the incidence of b-ronchiagenic carcinomas in humans C113) and mouse sarcomas induced by 3-methyl-cholanthr5n.e (11^) have been related to the level of inducibility of AHH (99). Kouri e"t--al. (114) studied AHH induction in human lymphocyte cultures by TCDD» The authors stated, "TCDD itself is not a potent carcinogen in mice; however, the synargistic action of TCDD with S-methylcholanthrene (MC) produces cancer in different strains of aice in direc" -62- �proportion to the degree of elevation of the induced hydroxylase activity and associated cytochrome p^^SO content," Their study showed a positive correlation between basal enzyme activity and enzyme levels maximally inducible by either TCDD or MC, They also found that TCDD is about 40 to 60 times more potent than MC as an inducer of hydroxylase activity in cultured human lymphocytes* These authors further suggested that, because of the relatively high levels of TCDD in certain parts of the .world, TCDD may also present considerable long-term risk because of possible synergisa in chemically initiated oncogenesis, in addition t-o short-term risks posed by its toxic and teratogenic properties. The implication of TCDD in AHH inducibility has also been reported by Poland and Glover (115, 116) and Poland et al. (117). In their studies on chick embryo livers, Poland and Glover (115) found that all dioxins which are potent inducers have halogens- at three of the four lateral ring positions and at least one nonhalogenated carbon atom, Poland and Glover (116) compared the po- tency of TCDD as an inducer of hepatic AHH with that of MC, the most commonly employed inducing agent. They stated that analysis of the data by a computer program for bioassay showed that TCDD was 28,640 times as potent -63- �as HC on a molar basis. (The 95? confidence interval of the potency ratio is 2.07 to 3.95 X 10 ») precision, A , was 0.18. The index of Poland et al. (117) suggested that a hepatic cytosol species which binds TCDD is the receptor for the induction of hepatic aryl hydrocarbon hydroxyiase, Allen et al* (118) conducted a study in which female rhesus monkeys were fed diets containing 500 ppt TC'DD for nine months. Anemia, throanbocytopenia, and leukopenia wsra the most debilitating changes. The altered lymphopoiesis could be associated with immune suppression. The authors reported widespread hypertrophy, hyperplasia, and metaplasia in the epithelium of monkey's exposed to TCDD, and related this to data showing increased tumor frequency in TCDD fed rats. (3) g£_g 1 ia_in_aj*_v Snji d ea i a1 o gj a a 1 S_t ud_j. a 3, Two epidemiolgical studies lend support to a finding of increased, tunorigenicity due to 2,^,5-" exposure., The English summary of a Swedish paper by Hardeil (108) stated that "there were seven cases of malignant mesenchyaiai tumors in [87] persons [who had besu] exposed to 2,4,5-T over a -64- �period of 10-20 years," In five of the cases, exposure had been direct and comparatively massive. The'latent period of. 10 to 20' years is in agreement with that assumed 'for chemical carcinogenesis. The statistical distribution of 7 of the 87 patients deviated from the national average with a dominance of tumors in males. Tung (120) reported an elevated incidence of primary liver cancers among Vietnamese following the wide application of "Agent Orange" as a defoliant during the years 1961 to .1962. "Agent Orange" is composed of equal parts 2,4,5-T and 2,4-D (2,4-dichiorophenoxyacetic acid) and is contaminated with TCDD, During 1962 to 1968, 10* (791/7911) of all cancers were Liver cancers, compared with 3? (159/5442) during 1955 to 1961* The latent period involved is shorter "than that normally assumed for chemical carcinogenesis; the possibility of a shorter latent period for some chemicals, however, cannot be eliminated. Neither of these studies is sufficient to be the basis of any firm conclusions concerning a causal connection between 2,4,5-T and cancer. But in view of the results obtained in experimental animals, they warrant noting. -65- �The Working Group concludes that there is sufficient evidence to indicate that 2,4,5-T, containing TCDD at levels as low as.0.05 ppm, and TCDD alone can produce oncogenic effects in mammalian species. Since 2,4,5-T, as . currently formulated, contains TCDD Cat a maximum amount of 0*099 ?pa»)» a rebuttable presumption against registration of 2,4,5-T products has arisen because of the oncogenic effects of 2,4,5-T and TCDD, B« 01her Chr o n 1 c or_ 0a 1 a_ved .Toxic.. 5f feat a 40 CFR Section 162*ll(a)(3)(ii)(B) provides that »a rebuttable presumption shall arise if a pesticide's ingredient(s)«,,(p)roduces any other chronics or delayed toxic effect in test animals at any dosage up to a level, as determined by the Administrator, which is substantially higher than that to which humans can reasonably be anticipated to be exposed, taking into account ample margins of safety.1* This section reflects concern that chronic exposure to "chemicals may result in injury to the reproductive system and/or the fetus and provides that a rebutcable presumption shall a-ris-e-frf chronic chemical exposure in test animals produces such results. The studies summarized below show that 2,4,5-T containing 0,5 ppm or less TCCD produces teratogenic and/or fetotoxic effects in mice at 30 mg/kg, in rats at 100 mg/kg, in hamsters at 40 mg/kg, and in birds at 1 rag/kg. -66- Other �studies show that pestioide-fres TCDD is fetotoxic and/op teratogenic at doses as low as 0.125 ug TCDD/kg in rats and 0.1 ug TCBD/kg -in mice. Specifically, these studies show that exposure to TCDD and/or 2,4,5-T containing TCDD during pregnancy is associated with statistically significant increases in the incidence of cleft palate, kidney anomalies, skeletal and intestinal tract anomalies, and embryonic resorption. (Maternal toxicity has also bee-h observed in many of these studies, primarily in the form of reduced weight gain and increased liver-to-body weight ratio. Whenever it has appeared particularly relevant, details have been cited in the individual studies*) The Working Group has concluded from these studies that 2,4,5-T containing TCDD, 2,4,5-T without detectable dioxin, and TCDD alone produce fetotoxic and teratogenic —-e-ffects Tn mammals. The Working Group has also concluded that an ample margin of safety does not exist for the —population at risk (women of child-bearing age) for dermal and inhalation exposure and for cumulative oral, dermal, and inhalation..ejcposure to both 2,4,5-T and/or TCDD* For these reasons, the Working Group recommends issuance of a rebuttabls presumption based on the fetotoxic and teratogenic effects of 2,4,5-T and/or TCDD. .67- �(1) 1^,3jleide-fpg3 TCDD A Bionetics Research Institute study on 2,4,5-T •provided the first indication that TCDD adversely affected mammalian development (123). In this study, detailed with later confirming studies in Section III.B.(2) below, 2,4,5-T significantly increased the frequency of cleft palate, kidney anomalies, and fetal mortality in the litters of treated dasa,. The 2,^,5-T used in this study contained approximately 30 ppo TCDD, Subsequent studies, detailed in this section, using pesticide-free TCDD have established that TCDD alone produces these effects, and that the TCDD contaminant may be the principal chemical determinant ...of the fetotoxic and tsratogenic effects in mammals exposed to the pesticide 2>4,5-T. (a) — - " 3Jbud i »_3_ J.n which T C 0 D Produced, £e_r_aJio.s_en_i ?. "and/or Fetotoxic _S?_f ecta _ i_r\. M,ice Courtney and Moore (128) studied TCDD 1 3 embryotoxic and teratogenic effects in three mouse strains (Table 8). Test animals were administered 1 or 3 ug TCDD/kg body weight subcutaneously in solutions of 100$ dimethylsulfoxide (DMSO) on days 6 to 15 of gestation. the control. strains. DMSO was administered as TCDD produced cleft palaces in all three At 3 ug/kg, 30J (3/10) of the CD-I litters had fetuses with cleft palates compared to 0$ (0/9) of the controls; 71* (5/7) of the C57BL/6 litters had cleft palates -68- �at 3 ug/kg as compared to Q% (0/23) of the controls; and 22% (2/29) of the DBA/2 litters had cleft palates, as compared to OJ (0/23) of the controls. The authors also found a marked increase in the incidence of kidney anomalies in all strains. On-e especially sensitive strain, C573L/6, developed kidney anomalies in 100? (7/7) of the litters as compared to 9J (2/23) in the controls. Maternal liver-to-body weight ratio was significantly increased in the inbred strains, C57BL/6 and DBA/2, but not in the randomly bred CD-1 mice, TCDD had no effect on fetal mortality, fetal weights, or maternal weights at the doses administered. Table 8. Teratogenic Effects of TCDD in Mice and ! Litters Affected/Live Litters ; Average ?eti^ses Affected/Live Litters I Strain!Dose (ug/kg) i Cleft Palate Kidney Anomalies Cleft Palate i Kidney Anomalies i ! « * 1 ! * i i Mouse i ICD-1 !O(DMSO) i 0/9 0 11 0 ! 1/9 3/9 0/9 33 1 i i 56 51 i 1/9 11 2/9 22 ! 4.6/9 5/9 100 1/10 10 16.5/10 65 10/10 ! V10 I 1 4 0 ! 1/23 i DBA/2 ! O(DMSO) i 0/23 0 0/23 3/23 13 ! 2/2Q 22 8/Q 8P 1/Q 11 11.8/Q 20 1 1 4 IC573L/1 O(DMSO) i 0/23 0 2/23 0/23 0 ! 1/23 9 16 ! ! 5/7 71 9.6/7 ! V7 43 7/7 100 i i ! JBai ! 0 0 0 ! 0/9 0 ! CD iO(DMSO) ! 0/9 0/9 0/9 i i 0.5 ! 0/6 67 0/6 0 ! 1.8/6 •50 0 4/6 Data from Courtney and Moore (128). In another study in which six dioxins were administered subcutaneously and orally to CD-1 mice, Courtney (133) found TCDD to be the most fetotoxic and teratogenic of the dioxin compounds, by either route of exposure at all dose levels tested (Table 9). -69- On days 7 to 16 of gestation, �TCDD was administered orally at 25 to 400 ug/kg body weight and subcutaneously at 25 to 200 ug/kg. Mortality per littler increased with the dose and reached 97$ (oral) and 76$ (subcutaneous) in the litters administered TCDD, as compared with a mortality of 6 and 14J in the oral and subcutaneous control grovips, respectively. The most common anomalies observed were cleft palates and malformed kidneys. All of the fetuses in the 200 and 400 ug/kg (oral) and 200 ug/kg (subcutaneous) groups exhibited cleft palates as compared to 0$ of the controls. Of the fetuses in the 200 ug/kg (oral) group, 100$ had kidney malformations as compared to 1$ of the ..controls-. Other anomalies observed were hydrocephalus, open eye, and club foot. Edema and pstechiae were also- observed in fetuses administered the high doses. Table a. ?qtotoxlc and. Teratogenie Effects of TCDD. is __CD-1 -Ml; ijjyjpr^aai^, Average ?J . i.rjcqaiieg /Total Fetysesi Dose Sidney ! Club Abnormal Clsft , Foot (ug/kg Route of Ad- $ Average Fecal Fetuses Palate Anomalies ! * ?•*? dav) Morsalitv/Litter Lpe** Lit~sr _! j Oral 6 34 4,6 25 . 3 3 Oral 50 8.1 72 , r 19 13 14 100 Oral 66 71 13 8.3 14 Oral 100 200 100 ._a.7 Q7 400 Oral 0,4 100 "50 11 Subcutaneous 36 82 25 6,7 53 Subcutaneous 50 56 58 5.0 17 79 Subcutaenous 0 72 100 95 3.5 85 200 75 Subcutaenous 100 Jfl. 4 1 Oral 6 0.3 0 15J [anisols ieora oil . (0.1 al) s/ •1t DMS SCT' 0.2 a/ Data from Courtney (133). i/ DMSO s diaethylsulfoxide. -70- �Moore et al. (17*0 also found that TCDD caused fetotoxic and teratogenic responses in C57BL/6 mice at 1 us/kg administered on days 10 through 13_.°f gestation. Compared with Q% incidence (0/27) in the control litters, 94J (15/16) of the treated litters exhibited kidney anomalies, and 19$ (3/16) had cleft palates. At 3 ug/kg, the incidence of these anomalies was 100$ (14/14) and 86} (12/14), respectively. Neubert and Dillman (127) tested the embryotoxic and teratogenic effects of TCDD in NMRI mice (Table 10), In one test, pregnant mice were given varying doses of TCDD (0,3 to 9 ug/kg) by intubation on days 6 to 15 of gestation. At 9 ug/kg, 1002 (3/3) of the viable litters had resorptions; 67J (6/9) of all litters had total resorptions* Oil control values were 32 and Oj for litters with resorptions and litters with total resorptions, respectively. Cleft palate was observed in all of the litters and -82J of the fetuses at 9 ug/kg; comparable oil control values were 6 and 0,7?, respectively. Statistically significant (p < 0.01) proportions of the fetuses evidenced" cleft palate at 3, 4,5, and 9 ug/kg (3, 13, and 82J, respectively) when compared with the oil control. -71- �Tabls 10. Embryotoxic and Teratogenic Effects of TCDD on NMHI Mio-»-a-/ ! Litters A f f e c t e d / V i a b l e Liters ! 1 Dos*k/| Hesorptions 1 Cleft Palace j ( Ufli/Hff) ! 9 \ *• « ! * 24 o- ! 23/951 6 i i 6/95 ! oil i 21/651 32 6 ! 1/65 0 ! 0.3 ! - 7/13! 51 ! 0/13 i 3.0 ! 16/24! 67 ! 7/24 29 ! 6/12 ! 1.5 ! 5/12! 12 50 i 9.0 ! 3/3 i 100 100 I 3/3 |9.0 I 3/ i. i 50 8* ! 5/8 Data from Neubert and Dillsan (127). Jl/ All doses administered on days 6 to 15, except second 9.0 ug/kg dose which was administered on days 9 to 13. In this study, a single oral dose of 45 ug/kg TCDD on day 6 produced resorption in 1GO/S of the viable litters; 23 ug/kg on day 10 led to 50$ resorptions. Seventy-one per cent of the viable litters had embryos with cleft palate when 45 ug/kg was given as a single dose on day II. Control values were 2 4J for litters with resorption and 6% for litters with cleft palates. Smith et al. (135) administered 0.001, 0.01, 0.1, 1.0, and 3.0 ug TCDD/kg body weight per day to CF-1 mice by gavage from days 6 through 15 of gestation (Table II). The percentage of resorptions per iaplantation was significantly higher in treated aice than in the controls only in the 1.0 ug/kg group. Cleft palate occurred in 71% of the litters treated at 3.0 ug/kg and in 21$ of the litters treated at 1.0 ug/kg; bilateral dilated renal peivises occurred in 28? -72- �of the litters treated at 3.0 ug/kg, and in 5J of the litters treated at 1.0 ug/kg. No significant increase in either cleft palate or dilated renal pelvis was observed at 0%1, 0.01, or 0,001 ug/kg. None (0/34) of th.e. control litters had. cleft palate or abnormal kidneys.— atogenio Effects of TCPD in CF-1 Mice3/ {Incidence of Cleft Litters With [Litters With Dilated! ! Palate in Litters Resorbed Fetuses! Renal Pelvis per \ j Dose Irjer Live L*'•£or>g oer L-'ve Litters ! L Litters ive ii j a ft ! % # ! it tiusZlssJ I £ ' * i 0 ! 0/34 i 0 i 0/34 ! 0 25/34 I 74 30/41 i 73 0.001 ! 2/41 | 5 0 1 ! 0/41 i i 0.01 ! 0/19 i 0 0 17/19 i 89 ! 0/19 ! i ! 0.1 ! 1/17 i 6 ! 0/17 0 16/17 i 94 ! 13/19 | 95 1.0 I 4/19 i J1& i 1/19 ! 5 3,0 MO/14 ! * 11/14 ! 78 ! 4/14 I ?$^ JL/ Data fron Smith et al, ( 135). Jl/ Statistically different from controls by the Fishers exact probability test (p < 0,05). 1 1 Neubert et al. (175) estimated the ED-50 for cleft palate in fetuses to be 40 ug TCDD/kg per day (Table 12). The no-effect-level during days 6 to 15 of gestation was estimated to be 2 ug/kg per day for NMRI mice. No pronounced fetal mortality was observed when 3 ug TCDD/kg body weight was administered on days 6 to 15 of pregnancy. Table 12. j Occurrence of Cleft Palate in Offspring of Mice Fed T ! Affected Litters/Total Litters Dose 5 Cleft Palates per * Strsin (uz/ks) LTotal Fetuses SxaEip«d # 0 CD-1 0 0/29 <0.3 ^0 ? ? V10 <1 DBA 0 0 0/23 4 ? 2/P 22 0 NMRI 10/160 6 0.7 3 9 7/?U 20 <1 0 C57B1 0 0/23 20 5/7 •? 71 Data from Neubert et al. (175K -73- �(b) Studies in Which TCDD Produced,Tqratogenie ar\d or Fetofcoxic Effects jLn Hats Sparschu et al» (129) administered TCDD to SpraguaDawley rats by gavaga at 0.03» 0,125, 0.5, 2..Q, and 8.0 ug/kg per day on days 6 through 15 of gestation (Table 13), Intestinal hemorrhages were observed in 14$ (18/127) of the fetuses at 0,125 574 (4/7) ug/kg; 36$ (36/99) at 0,5 ug/kg; and at 2.0 ug/kg? none (0/246) of the control fetuses had intestinal hemorrhages. At 8.0 ug/kg per day, all fetuses (100$) were resorbed as compared to 20$ (63/309) in the controls. and 2 ug/kg. Fetal weights wars depressed afc 0+125, 0,5, This .effect_was statistically significant (p <0.05) in ail groups except females at 0,5 ug/kg* Ho adverse effects were noted in the fetuses whose mothers were fad 0,03 ug/kg. Tha authors concluded that TCDD induced a high level of maternal and fetal toxicity and that 0.03 ug/kg per day was the no-effect~laval for fatal a.nd embryotojcic effects in rats. Table 13, ' Intestinal Hemorrhages in Offspring _of -Soragua - Daw lev Rats E 2 i .. Fetuses Affected/- Litters Affecred/Dose Fetuses Txaained "kitt^ps Sxasined (ug/kg 4 iDer dav) 4 \ t JL_ 0 (conQ/24 ! 0 0 0/246 trol) i 0 0/10 i 0 0,03 0/115 14 7/10 ! 70 0,125 18/127 36 10/12 i 83 36/99 0.5 2.0 2/4 ! 50 4/7 57 i i 8,0 ; — ..— — Data from Sparschu at ai. (129). -74- �Khera and Ruddick (6) studied the perinatal effects of TCDD in Wistar rats. In one test, rats were orally administered 0.125* 0.25, 0.5, and 1.0 ug TCDD/kg per day on days 6 through 15 of gestation (Table 14). Visceral lesions were observed at 0.25 ug/kg and above; slight decreases in fetal weight were also seen. Postnatal effects of prenatal exposure to TCDD were studied by allowing offspring of treated dams to be reared by untreated dams until weaning* Reduced survival, body weight gain, and reproductive ability in the progeny were observed after maternal treatment with 0.5 and 1*0 ug/kg* No fetotoxic effects were observed at 0*125 ug/kg. In a second experiment, rats were treated orally with 1, 2, 4, 8, and 16 ug TCDD/kg body weight per day on days 6 through 15 of gestation. TCDD treatment reduced fetal weight, and the number of live fetuses per litter, and produced visceral lesions in 50J (3/6) of the 1,0 ug/kg fetuses and 43J (3/7) of the 2*0 mg/kg fetuses, as compared to none (0/10) in the controls. The incidence of skeletal anomalies was comparable to that in the controls at all dose levels. Doses of 1 ug/kg or more produced maternal toxicity; 4 ug/kg or more produced 100J eiabryomortality. The authors concluded that oral treatment of pregnant Wistar rats with 0,25 ug (or more)/kg per day on days 6 to 15 of gestation adversely effected rat development. -75- �11. TqratogeniG Effects of TCDD in Wiatar Rats3/ Fetuses with Mic ro!Fetuses with iAvg. Fetal!Skeletal Anomalies/- scopic Visceral ! Dose ! Avg* >} Liv? j Weight i Total 4 Examined • Lesions/Total # Examined ! (uff/kz) ' Fetuses/Litter 1 (zrsms) I •t 1 * ! -JL , . j !T*st 1 ! ! i c 10.7 I On- ! I 4.82 ! 5/107 0 0/13 i, ._. {treated! 1 i { j i control i i I Treated! 18 0/11 i 11.0 0 ! 4,51 ! 21/116 j! I j ! i ! control! ! 0.125 ! ! 0.25 ! i 0.5 i ! i.o ! {Test 2 ! ! On- ! ! treated j i control i i Treated! i control i i 1.0 i ! 2.0 ! i 4.0 ! ! 8.0 i I 116,0 i j * 10.6 j i 4.64 i 3/121 4.79 i 6/109 4*46 ! 10/105 1JILJ. 6/81 10,9 10.5 i — 5LJL- 1 ! i 11.5 9.8 6.5 6.0 Q 0 p i i 2 6 10 0/38 1/33 3/31 1 4.68 ! 8/116 ! i 2SL 0/10 ir 0 9 12 3/6 3/7 i ! 50 43 ! J i S ! 1 In a/ Data from Khers and Huddick (6); treated controls given anisole-corn oil. j. j. 0 10 4,77 ! 9/89 1 4.17 ! 7/80 3.31 j 7/57 i 1 i 3 10 0 0/10 ! I i ff : I ! \ 1 i i ViO •» i i i i Courtney and Moore (128) administered TCDD to CD rats subcutaneous.!/ in solutions of 100$ DMSO on days 6 through 15 of gestation (Table 8). control, DMSO was administered as the Sidney anomalies were found in four of the six litters (67J) whose dams were administered 0.5 ug/kg as compared to 0% (0/9) in the controls. TCDD did not affect fetal mortality, fetal weight, or cleft palaces in the fetuses. Dow Cnanieal USA (110) conducted a three-generation reproductive study on Sprague-Dawley rats continuously fad the equivalent of 0,001, 0.01, or 0.1 ug TCDD/kg per day. -76- �A preliminary report cites reduced fertility and litter survival in f rats as the reasons for discontinuing the 0.1 ug/kg dose level; significantly reduced fertility was also observed at 0.01 ug/kg. "Clearly evident" indications of toxicity at 0.01 ug/kg among f and f litters included smaller litter size at birth, plus decreased survival and growth of neonates. Dilated renal pelvis was observed in each of the three f rats at 0.1 ug/kg which survived to adulthood. Increased frequency of this anomaly was also seen among weanlings at lower doses; however a doserelated or generational correlation could not be made* In summary, Dow concluded that "the reproductive capacity of rats ingesting TCDD was clearly affected at dose levels of 0.01 and 0.1 ug/kg per day, but not at 0.001 ug/kg per day , through three successive generations." The pre- liminary report did not include the numerical data necessary for Agency evaluation. Analysis will continue as these become available. -77 & 78- �Adverse reproductive effects due to TCDD.have also been observed in hamsters and chickens. Gastrointestinal hemorrhage was noted in hamster fetuses after .administration of TCDD at 0.5 ug/kg per day on days 6 to 10 of gestation (48; 62). Buu' Hoi et al, ( 1 1 1 ) established that 0.02 ug/kg TCDD caused teratogenic effects in chic-k embryos. Bowes et al» (137) and Verrett (136) confirmed these results. They found abnormalities in the beaks, eyes, and feet of chick embryos after TCDD exposure. (c) Summary Studies have established that TCDD is fetotoxic and teratogenic at doses as low as 0.125 ug/kg in rats (129) and at 0*3 ug/kg in mice (127); preliminary data from Dow (110) indicates that TCDD may have effects at 0.01 ug/kg in rats. Cleft palate and kidney anomalies have been observed in rats, mice, and hamsters. No fetotoxic or teratogenic effects have been observed at doses of 0,03 ug/kg in rats (129) and 0,1 ug/kg in mice (135). Table 15 lists the no-effect-levels in rats and mice for teratogenicity from TCDD, -79- Preceding page blank �Table 15^.. He—Ef feot-L«»v«l3 for Tqratagqnesia from TCDD (Route of Ad-INo-Effect-Leveli • Species I sini31 ration ! tig/kg, per dav ! Rsfsrsnc•? gaj i Suboutaneousi <0.5 iCourtney and Moore (128) ! Oral i 0,125 iKhera and Ruddick (6) ! Oral I 0.03 iSparschu at al* (129) House i Subcutaneous! <1«0 ! Courtney and Moore (128) ! Oral i ~<0.3 SNeubert and Dillaan (127) [__ Oral_______!_ Q_jJ_ ! Sqith, *.\ al .__L ' S )_____ Li. ( 2 ) gt^t^-T, (TCDD Contamination Ranging Froa Undet_aet_abl_e_ C a ) T e r atogqnic arid Fata t o x i e 5 f f e.c, tA^ in,. S o <i e nfca C«surtn«y at al* (123) developed the first evidence that a. 2»4,5«T pesticide product wag teratogenic and fetotoxic (Table 16) ,-ifi/ The 2,4,5-T used in this study contained approximately 30 ppm TCDD, The pesticide was administered daily either orally or subcutaneously on days 6 to 14 of gestation in C573L/6 mice, days 6 to 15 in ASH mice, and days 1C to 15 in Sprague-Dawley rats. Subcutaneous adminis- tration of 1.13 Kg/kg body weight resulted in significant increases in the incidence of cleft palate and cystic kidneys— ' in the embryos of both strains of mice, and fetal mortality in the C57BL/6 mice. Oral administration of Results of this study were published by the Department of Health, Education, and Welfare (121) and by Clegg (122)* J_l/ In a recent report on studies measuring renal alkaline phosphatase in fetal mice, Highman at al. (45) attributed the increased incidence of "cystic kidneys" in the offspring of 2,4,5-T treated animals to retarded d e v e l o p m e n t , rather than true teratogenesis. Reduction in fetal weight and increased incidence of claft palate were also observed among the fetuses of treated dams. -80- �Table 16. Teratogqnic Svaluatior: of in Mies'* ! ! • Per Litter .'• Avg. # Live Abnormal! % Fetuses ! ! ! Abnormal {Route of i ! Fetuses Fetuses i with. Fetal Mouse iAdminisiDose \t Lit% i Cleft Cystic Mortality Litters j i i Palate. Kidnev Strain !r rat ion J (nis:/k*:) Iters i £/ C57BL/6 | ! ! i 1 Nontreated! !— i 72 11 i <1 5,8 26 38 Control i Subcutaneous ! jy i 106 12 ! <1 2 425.5 29 1 41 14 { 0 Control ! Stomach tube! sJ \ 32 7,1 15 0 Treated 'Subcutaneous! 21,5^ ! 6 12 I 0 50 7.7 3 Treated ! Subcutaneous ! 1 1 S.O^ } 1 8 4.4 42 57-^ I 22^1 41^ B6*/ ! Treated Treated ! Stomach tube! 46. 4^ ! 6 I ! V! ! Stomach tube! 113. O*1 ! 12 1 1 • 1 1 / AKR* i ! Nontreated! i i ! — Control Treated i Stomach tube! &/ \ 12 1 1 y, / I i Subcutaneous! 1 13, O1*- ! 14 Treated 'Stomach tube! 1 13,0* • / / / / / £/ i 58 i Subcutaneous! I 5,1 6.1 7.7 31 ! 0 8 ! 0 7 i/ |2 1/ 7 9 t ?0J/ j i i t i i 2 i/ ? 8 1 7 48 4^ 7 36 23 11 7 0 60^ 100" 100^ 71 30 1 ^ 0 t ! Control 1 37^! 1 1 C57BL/6jt/ ! ! ! Nontreated! ! — ! 8 Control i Subcutaneous! £/ i 10 Treated ' Subcutaneous! 11 3, O*1 I 10 ii ii ii 3317 2 8.5 4,8 ' 72 4/1 7 5 ! <l 4 0 i <1 ! 0 7.1 6,9 8.8 6.9 29JL/ |2& 5.7 ^i^r- \ \ | i/ ji \ ' 16 0 1 at "55**• 0 42** 19 24 15 9 23i i X\ 0 71-i/» t 100^ Contained approximately 30 ppm TCDD. Data from Courtney et al, (123), Treated from day 6 through 14 of pregnancy. Killed on day 18 of gestation* Treated from day 9 through 17 of pregnancy. Killed on day .18 of gestation. Treated from day 6 through 15 of pregnancy. Killed on day 19 of gestation. / Dose, 100 ul DMSO per mouse. / Dose, 100 ul honey solution (honey to water, 1:1) per mouse. / Administered as a solution of 2,4,5-T in 100* DMSO in a volume of 100 ul per mouse. ./ 2,4,5-T was suspended in a honey solution (honey to water, 1:1) in a volume of 100 ul er mouse. / p s 0,01, . / p s 0,05, -81- �the same dose caused increased incidence of cleft palate and .fetal mortality in both strains and cystic kidneys in C573L/6 mice, Courtney et al. also reported increases in liver-to-body weight ratios in fetal laice, These investigators also found that il.6> 10, or 46.4 mg/kg 2,4,5-T given orally to Sprague-Dawley rats produced kidney anomalies and other embryatox.ie effects at all levels (Table 17). The occurrence of hesnorragic gastrointestinal tracts in rat fetuses was also reported* Roll (125) found embryotoxic and taratogenic effects in HMRI mice after prenatal exposure to 2,4,5-T containing 0,05 ± 0.02 ppm dioxin (Table 18). 2,4,5-T at 20 to 130 »g/kg body weight was administered orally to the dams on each of days 6 to 15 of gestation. At 90 or 130 mg/kg, the percentage of resorptions and/or dead fetuses was markedly increased relative to the controls; however, maternal toxic effects were also observed at these dose Statistically significant, doss-rslated reductions in fetal^weight were observed at 20 aig/kg and above. JL2/ Although the LD-50 for female NMHI mice had been previously determined to be 778 rag/kg, an increased aar-ernal mortality rate was seen at 130 mg/kg and weight gain was depressed at doses above 60 mg/kg (125)* -82- �Table 17. Tgra'toggric Evaluation of 2.4.5-T a ' / in J_ 1 Avg. Per Litter i . * Live! Abnormal!? Fetu ses Fetuses i Fetuses i with: % iEnlar-" Cystic ' j Kidney Fetal i Route of ! Iged Abnormal Test # Lit-! ! Renal iAdminisiDose Mortality Litters I Animal !trat3,on ! fae/ke) ters ! I Pelvis ii iii i 1 i ____ ' _.. .. 11 Sontreated i 0 7 ! 9.9 ! 9 ! 9 43 14 ! Control 1 j Stomach tube! £J i 12 8,7 ! 12 57 Treated ! Stomach tube! 4.6^X 8 i 21 88 8.2 ! 36s'7 I 18 12 X X 7 ' ! Stomach tube! 10.0* Treated 30^ 86 2^ 8 7.1 I 46* ! 17 7 i ! ! *.i Vi / ' w w Treated 67 2*7 Istonach tube / Contained approximately 30 ppm TCDD. / Data from Courtney et al. (123)» / Treated from day 10 through 15 of pregnancy. Killed on day 20 of gestation. / Dose, 200 ul honey solution (honey to water, 1:1) per rat» / 2,4,5-T was suspended in a honey solution (honey to water, 1:1) in a volume of 200 ul er rat, / p = 0.01. / p = 0,05. • • / The sample size was possibly too small to show a significant difference, i i i r i I Table 18. Snbrvotoxie Effects of 2.H.5-7 in WIPI Mice3-7 i iHesorptions and/or i Fetal i Cleft Palate ! Dose Implantations .!_. Dead Fetuses iweiaht 3g/kSL rser Preenancv'No. /Total No.! 1 Kjrrarns) No./V-iabl e No! I ! 0 10.1 ! 19/332 i 5.7! 1.23 ! 1.9! 6/313 20 6/3U 9.8 ! 30/3W ! 8,7! 1.09 ! U9I i 6.2 i 9.5 ! 22/248 ! 8.9! 1.06 1 4/226 35 60 ! 9.8! 9.9 ! 15/208 ! 7.2! 1.05 19/193 39/258 9.8 i 35/293 in. 9! 0.86 115.1! 90 I48.8J no q.6 ! 1P1/?1fi I60.U! 0.7^ 61/125 / Data from Roll (125). -83- �Cleft palate increased among fetuses exposed to 35 ag/kg or more and was significant when compared with control values. Skeletal retardation effects, manifested as insufficient ossification, were also observed. The teratogenic jjo-sffect lev®!, in mice for this 2,4,5-T was Considered to be 20 rag/kg. Later studies with a specially prepared sample of 2,4,5-T with no detectable amounts of dioxin (detection limit? <0«02 ppm) confirmed these results in mice (125, 126)* By contrast, daily oral administration of 25 to ^50 Eg/kg of* either the dioxin-free or commercial grade 2,4S5-T «0.1ppm dioxin) did not produce teratogsnic effects in FV 49 rats (126). Neubert and Dillman (127) also studied the effects of 2,4»5-T in SMRI mice, using three samples containing either (A) less than 0«02 ppm dioxin, (3) 0*05 ± 0«02 ppm dioxin (provided by Dr. Roll), or (C) an unknown amount of dioxin (Table 19).. (125). their results confirmed those obtained by Ro.Xl 2,4,5-T was administered to the dams orally in rape-seed oil on each of days 6 through 15 of gestation at 8 to 120 mg/kg body weight. The average number of resorptions was significantly higher than the oil control at 60, 90, and 120 ag/kg of sample (A), and 90 ag/kg of samples (3) and (C). Total resorption of one litter was observed in four of the groups (30, 45, 60, and 90 mg/kg) treated with sample (A) and in -84- �three of the litters treated with 90 mg/kg of sample (B); none was seen in the controls. Fetal weight was significantly depressed in all treated groups compared with the oil control, t • The percentage of fetuses with cleft palate was significantly higher than the control group in all 2,4,5-T groups treated with 45 mg/kg or more. In the group treated with 120 mg/kg 2,4,5-T containing <0.02 ppm dioxin, 54* (7/13) of the litters and 11? (16/145) of the fetuses exhibited cleft palate compared with oil control values of 6* (4/65) and 0.7* (5/669), respectively. These investigators also tested the butyl ester of 2,4,5-T and found similar effects. In experiments combining 2,4,5-T and TCDD, potentiation of teratogsnic effects was observed. Sixty mg/kg of 2,4,5-T (sample A) combined with 0.3 ug/kg TCDD increased cleft palate frequency among fetuses from 5 to 14J, la this study no cleft palates were observed among fetuses treated only with 0.3 ug/kg TCDD. -85- �1 \ \ Treatment 1 ! 'iDioxin i {Content! Dose i — !_ ! None SOU control! — 1Q. ggbrygtoyla 5ffqgga of ! Resnortion (.9ES) J_ 1$ Litters!? RES/Iaplan- i HES/Slngle i Fetal' ! with HES Station Sites ! Litter w/RES!Weight 1 f£) i .ff)! ! ! ! 0.4 ml! ia,4,5-T (A) ! <0.02 ,' 3.0 I i ! I 1 i ! 24 ! 32 ! 4 4 [ i 0,6 0.5 35 3 I 0,4 ! i J15.0 ! 38 ! 5 i ! i I i J30.0 'i45.0 J60.0 J90.0 ! 120.0 i 56 | ! ! 55 63 ! ! 7 6 11 ! ! 53 54 i ! 8 10 s t 0,8 1 I 0.6 1^* ! ! ! ! 1.28*1 ! 1.30 ! [ 1.27*! 1 I ! j Cleft Palate (C?) . i % LituersiJ Fecuses w^th Cp !'J"* 5jL- C? 1.«*| | U09*! 1 0.98^1 I 1.01*1 I.T* ! 1.02*1 1.3* 0,,6 1 0'.9S*I i 1.11*1 1 U11*| 0 i i 6 ! <7 1 "a 11 j | 16 !' 20 j 35 54 I | 12,4,5-T (B) ! 0.05 I30.0 i 44 ! 22 I 1 ! J60.0 i 37 ! 7 i 0.4 71 i t 1 b/ | 0.99*! 36 uo i 8 I90.0 ! i i i TI i .™Jl:L. „ J J ,.**„.. IjUflflLL. 72_ . . L . !2.4.«?-T (C1 I'jnknow. !<30.0 Data from Meubert and DlUaan (12,7); 2,4,5-T sample (b) raoairad from Roli (125). .JJ/ p i 0,01. ! 71 i I Bags at al« ( i ; ( 2 ) injected MMHI oics« subeutanaously with 50 and 110 as/Kg 2 , 4 , 5 - t «1.0 ppo <J.loTin) on each of days 6 through 14 of gestation. At 110 mg/kg» 2 , 4 , 5 - T was t«sratogenia, causing fatal death, c l e f t p a l a t g , and other anomalies. Courtney and Moors (128) studied the e f f a c e s of 2,4,5-? in CD-1 random-bred aice, two strains of inbred aiee, DBA/2J and C57BL/6J, and CD rats ( T a b l e 2 0 ) . ,36- 0.6' 0.7 <T 1 1 3* fe/ ..Jj/ 11* 2 9^ J" Z-J* . �Tabl1* 29. p"lb"votoxi| c Effects of Analytical and Technical 2.1.5-T* Kidnev i.noaalles i l l ! ! ! Cleft Palate (C?)! i i ! \% Fetal ! Fetal iJ LittersU CP per[J Litters!* Affected Fetuses i , I i Doss [Mortality [Weight [Affected [Affected [Affected iper Affected !SD«ey9s!Co=Dound! (E2/kz) Iner Litter! (zrana) ! iL-'ttsr ! IL'tter ! CD-I i ! i 1 I t i 1 Mouse [ i i 1 ! i ! I lExpt. 1 [ DMSO ! 6.6 0 0 ! 0 I 0 ! ! 1.35 ! — j 6.6 i ! 1.26 I 0 0 1 0 ! 0 ! 12,4,5-T 1 [(Tech.) ! i I ! 1 i I i 0 i 1..00 i 12,4,5-T ! 7.5 33 I 3.0 ! [(Tech.) ! ! I ! : i so ; j 100 : i j I l2,4,5-T 1 SfTeeh.) ! lEzpt. 2! DMSO i 150^1 1 ^^^ I !2,4,5-T I 100 j 1 ! KAnalv.V, I lExpt. 3! DMSO [ —- i 1 U,4,5-T I 100 I J KTach.) ! i | !2,4,5-T i 100 i i [(Analy.)i i 1 i [ 12,4,5-T ! 125 ! i '! IfAnalv.)! i DBA/2 i DMSO i — i ! Mouse 12,4,5-7 1 1 1 !(T-eh.) ! !C57B1/6[ DMSO I ! I Mouse 12,4,5-T ! ! 1 | i ! ((Tech.) f 100 ( i CD Rat! Sucrose I — i [ 10 ! !2,4,5-T ! 1 [(Tech.) ! i 1 i2»4,5-T i 21.5 i i ii [(Tech.) ! I I 12,4,5-T i 46.4 [1 [(Tech.) ! ! i i 100 i 1 ! i i 80.0; 8.8 9.6 8.4 10.7 11.6 12.9 • 26.1 27.0 10.3 15. Q 3.4 1.8 1.4 3.8 y| |2,4,5-T ! 51.7 52.1 t : ! 0.91 !j ! o : i 100 I j 5.3 ! 0 ii 0.73 /! i 89 : 1.09 : I o.85*/i j j i I ; 0 I 4.4 | ; 0 40 i 0.80*/! I ! | £j\ \ 0.71 ! 40 i U02 d i 78 ! I 0.35 ! i 0.67^! i i ! 0.99 ! ! i. • 0 . 75^ ! : 2.43 : 1 2.40 ! ! i 1 0 40 0 0 1 i 2.54 1 0 27 : 2.20 : ii :i 0 0 i i I i I { 0 ! 2.0 2.0 ! I i ! ! | .. j ! 5.4 [ I i i o Ii uo : o i! ! ! ! ' I i i i J 1.2 : Ii i 1 i ( 0 ! 0 i ! 0 ! : o : ii 0 i 0 33 78 1.0 ! 63 i i j i 80 i 100 ! 4.2 67 i 4.3 13 i 1.0 1.0 o 0 ! i ! \ -87- 2.0 2.4 1 i I j 9 I] 9 : 20 i i 1.0 • 0 0 1.0 38 ! [ 1.3 14 [ 2.0 i i 0 | 50 1 0 1 2.30 ! i i i Sj Data from Courtney and Moore (128). V Investigators thought this data to be close to a maternal toxic dose. £/ Maternal LD-40. i/ p < 0.05. 1.7 4.0 �2,4,5-T containing 0.5 ppm (technical) or 0,05 ppm (analytical) TCDD was administered subcutaneously to iaice at 50 to 150 mg/kg in DMSO and orally to rats at 10 to 80 mg/kg in sucrose on each of days 6 to 15 of gestation. At 100 rog/kg or more, both 2,4,5»»T samples produced significant reductions* which appeared to be dose related, in fetal weight in all strains of mice; rats were not affected. 2,4,5-T was fetocidal at two doses, but the investigators considered this effect to be due to maternal toxicity, Both 2,4,5-T samples produced cleft palate in mice. For CD-I dams treated with 100 mg/kg of either 2,4,5-T samplSj 40$ of the litters and two fetuses per affected litter evidenced cleft palate compared with Q% in the control (Sxpt. 3). rat fetuses. Mo cleft palates were observed, among the- To verify this observation, a second group of rats was given two 150 mg/kg doses of technical 2,4,5-T subcutaneously at the time of palate closure (days 13 to 14}t Again, no cleft palates were observed; however, there was a significant increase in fetal mortality among treated, animals (14$) when compared with the controls (0$). Fetuses of CD-1 mice treated with analytical 2,4,5-T also showed increased incidences of kidney anomalies; the response to technical 2,4,5-T was not as great. At 100 asg/kg, 100J of the litters and 4,2 fetuses per affected litter of dams treated with analytical 2,4,5-T displayed. ,88- �kidney anomalies, compared with B0% and 2.4 for technical 2,4,5-T and 63? and 2.0 for controls (Expt. 3)4 The effect in inbred strains of mice was comparable with control values. In rats, technical 2,4,5-T at all -dose levels produced higher incidences of litters affected and 'numbers of fetuses per litter affected than seen in the control animals. The maximum effects on kidney anomalies in rats were 5Q% of the litters and 4.0 fetuses per litter at 80 Eg/kg, compared with OJ in the control litters. In another study using CD-I mice, Courtney (134) administered 0.45 to 1.0 iaM/kg body weight per day of 2,4,5-T (0.05 ppn dioxin) either orally or subcutaneously during various segments of the gestation period (Table 2 Cleft palate was seen in all groups treated with 2,4,5-T; there were no instances of this anomaly within the control groups. At 0.8 mM/kg, 48J of total fetuses and 37? of the litters evidenced this malformation. cant (p £ 0.05) Statistically signifi- increases in the percentage of fetuses dead and/or resorbed were observed at the highest doses. All dose levels had adverse effects on fetal weight. The author noted that by slightly altering experimental conditions, the cleft palate effect and the effects on fetal mortality and fetal weight could be produced independently. JL3/ Maternal toxicity was also observed, evidenced by reductions in maternal weight gain and increased liverto-body weight ratios (134). -89- �Table 21. 5abrvotoxic Effects of 2.4^-? ir. CD-1 Mies ! ! ! j.VJ.able Norsal Fetuses! IFetal !Cleft Palace (avz. ? ) ! ! ! Dose {Days U/total # % \% Fetal ! Weight (Fetuses i Litters i ! Vehicle ! (iM/ks?) ! Dosed! ! Mortality ' (sraras) i ' \ ! !oil:Ac^! !! — ! S —. t ! 0.45 [ \ 0.80 •E '! ! |lO-15l 75/80 ! 11-13!" 99/112 112-15! 108/126 MO-IS! 86/107 i 11-13! 88/122 ! 0.80 ! 11-14,' 21/59 i d/! ! ! 1 . 0 0 j ' 12-15.' 7<3/82 94 88 86 80 72 ! i ! ! ! 6 11 13 17 14 1 i ! i ! 0.95 I 0.94 ! 1.01 i 0,89 ! 0.87 ! 36 01 ! l 29s7 a f 0.37 ! O.P6 ! ! — • ! — j — 1 7 I 16 i 48 1 — — — 6 14 i ! ! i I 37 1 1 ! ! ! I DMSO2/. I — ! 12-15,1 152/171 I 89 ! 12 i K03 1 — 1 t i i i i «/ i i i i/ ! ! 1.00 !i2-i«5! 11/68 ! 16 J 72 } g,7Q j ug } a/ Data from Courtney (134). Ji/ Com ail j Acetone (9:1)~orsl. S/ Diaethylsulfoxide — subcutaneous. d/ This concentration exceeded the solubility characteristics of the vehicle. Doubling the volune of vehicle resulted in effects more consistent with those found at lower doses. . m 3/ p i 0.05. # p . 0.001. 1 67 Khera and McKinley (130) studied the prenatal and postnatal effects of 2,4,5-T ia Wistar rats, using four samples containing no TCDD (detection limit: 0.5 rag/kg) CTabla 22]. Twenty-five to one hundred fifty Eg/kg body weight per day were administered to the dams, orally in gelatin or corn oil, on days 6 to 15 of gestation* At 2,5 and 50 Eg/kg, the differences between experimental and control values were minimal. However, a't 100 and 150 mg/kg, there were significant (p < 0.05) effects on fetal weight, number of dead fetuses, and percentage of malformed fetuses -90- ! ! i �14/ per litter. : The larger proportion of malformed fetuses in the treated groups resulted from either an increased incidence of skeletal anomalies also seen in the controls or a low incidence of abnormalities not observed in the controls. The former category included wavy ribs, retarded ossification, extra ribs, and a variety of sternal defects; the latter included fused ribs, small-sized distorted scapula, malformed humsrus shaft, and bent radius or ulna. Abnormal kidneys were observed in 7 to 45? of the examined fetuses treated with sample T-1, compared with a control value of 20 to Table 22. Effects of 2.4.5-T on Wiatar Rat Fetuses^ Avg. # per Litter i Fetal iAvg. % Mai- ! ! Weight {formed Fetuses Viable Dead ! Compund Dose # of (mg/kg) Litters ! I Treated ! T-1 14 i Control i 50 7 ! 100 0 Treated i T-2 10 Control i i 25 13 50 12 i j 100 i ! i i i T-3 ! i ! T-^ Treated Control 25 50 100 150 Treated Control 25 50 100 150 50 "etuses 1 V,/ 11.1 0.6 ! 4.65 15 12.9 11.? 9.2 1.3 1.0 0.6 ! 4.84 i 4.60 i 5.34 24 20 10 10.5 11.7 0.8 0.5 2.4 0.7 i 5.06 i 5.15 ! n. 57 i 4.67 i 15 9 0.5 1.4 0.6 2.2 0.7 01 ia 8.6 10 12.6 11 14 10 5 10 12.7 11.5 11.0 14 2 12 1 — -4 <£»£.-- 8 I I ( jf-jjos) 1 9°** L^tt0**^ 11.0 12.6 11.0 ^r-0.3 ' 0.5 0.9 1.0 ! 5.15 ! 4.91 i 4.35 ! ^.08 ! 5.31 i ! 5.00 i 4.75" i 5.00 ! 3.00 11. •? ( ! 4. oil 11.6 11.8 •** 41 A 1.1 26 10 28 36 56 17 11 56 37 Data from Khera and McKinley (130). J&/ One or more skeletal malformation (viable fetuses). £/ No treated control given. 14/ Statistical significance was determined using the average value per dose level. Data from T-4 were not used in th-is analysis. -91- �In the postnatal portion of the study, after normal delivery, survival rats, sex.ratio, and pup weight on days 1 and 21 were compared. Although trea.ted pups surviving from day 2 to 21 were slightly smal-ler at some dose levels» there were no significant differences from controls for any variable. In some experiments, litters were standardised at 8 pups on day 2, and the remaining litterraatss examined for defects. The increased incidences of malformations among treated groups were comparable to those found in the prenatal study. Assuming the same incidence for pups not examined, the investigators concluded that there were no real differences in survival rates among control and treated groups. The butyl ester of 2,4»5-T produced similar toxic effects. Soko.ll/ (13D orally administered 100 and 400 og/kg and 50 and 200 mg/kg of 2,4,5~T and its butyl ester to rats of the Happolovo line on each of days 1 to 14 or 1 to 16 of pregnancy,. At tOO mg/kg, 2,4,5-T produced' embryos with a combination of deformities including absence of lower jaw, abnormal hind limbs, and exophthalaios. At 400 mg/kg, she embryos of treated rats evidenced cleft palate, hydrocephalus, hydronephrosis, and abnormalities of the upper limbs which included tridactyly, webbed toes, and abnormal shortness. .92- �Tha butyl ester of 2,4,5-T was more toxic than the parent compound, causing more than 30J embryonic mortality at 200 mg/kg. The lower dose, 50 mg/kg, also caused high mortality among the embryos. Cleft palate, hydronephro- sis, hydrocephalus, and extensive gastrointestinal hemorrhages were also observed within the treated groups. From these results, the author concluded that 2,4,5-T and its derivatives have a high potential for teratogenic activity. Collins and Williams (124) tested seven samples of 2,4,5-T from different sources for embryotoxie effects in golden Syrian hamsters (H es o crice_tu3 aura t u s) [Table 23]. The dioxin contents ranged from not detectable (detection limit < 0.1 ppm) to 45 ppm. Daily oral doses of 20 to 100 ng/kg body weight were administered in acetone:corn dilicar-. boxymethyl cellulose (1:5-3:10) on days 6 to 10 of gestation. 2,4,5-T with no detectable dioxin significantly (p < 0,05) reduced fetal weight and fetal viability per li.tter at all levels tested* Total fetal mortality was greatly increased at all levels when compared with controls and was dose-dependent, as was the effect on fetal viability. The increased incidence of gastrointestinal hemorrhage also appeared to be dose related. At 100 mg/kg, "pure" 2,4,5-T caused increased incidences of malformations and reductions in the number of live fetuses per litter. One "pure" sample, F, at 100 mg/kg significantly reduced fetal weight from 1.8 • -93- �Table 2?. Sabrvotoxic Effects of 2.U.5-7 4 « Harrs-ang* i i i i 1 i iJE Fetal ViaFetuses i i i i i i ! i Dioxin i % Total! Avg # LivejAvg Weigh t A j bility per i Mortal-! per Litter! (grams) ! i Content Cose i Litter i i (m2/k;0 i i i 1 Conoound ! ( ppn.) i,tv J __.._..i. .. . ' ' i __— ! 1 o£jj ^.4 i i i i ! Control ! 11.0 JjJL ! A 1\ 45 ii ! i i i ! j i 1 i I 3 ! 2.9 i i ; c i i 0.5 i i j '•! I 0.1 I l I ..T MTV" £• u \ 1 ! 1 | ? 40 80 100 40 80 100 20 j 40 80 i | 74.3 1 94.4 i i 100.0 i ! f ! 7.2 ! 9.8 ! i i 8.5 • 4.0 j 43.6 I | 7.3 3.7 j 0.8 0 9.1 10.4 12.8 12.6 13*4 j | i i j M i ~_ 1 1.7 1.7 1.6 1.7 U7 U7 1.7" i i i i ! I ! 1 f I i iii i i i j 1 j i 100 40 80 100 40 80 top 100, i 57.2 i 2.4 malir.ies! per Total per Livej Live Fetuses • Litter ! 33> 5 'f 93.1 90.1" 88.^X 90.8" 95.9 0 12.5 i i i i | i i i i i i 28.4 75.7 42.9 0 2.4 I 0 . n.o i i 8.6 11.1 2.5 1 I ! j ii 33.3 ! ii 4.U 1 10.7 I i 29.9 | i ii "56 . \ ii i 68.1" 25.8" 6.6 1 i ! 5.1 11.4 i " i/ 0 i 7,6 0 68,3" 0 j -2*1 40,2 1 7.8 1.7 j 1 11.2 i 1 8.7 1 I 1tfid/ 1 «5 *& ! j i 1 L£ ! o 88.?^ 0 69.1^ 0 6*2. 1 -ILJ^La | -94- 12.5 97.8 1 1 AS >i/ ! • inn ! wn in n A li *£/ ! Data from Collins and Williams (124). Apparently normal weights for samples A and 3 attributed to edema. Mac detected. p < 0.05. rr I/ \J : / I/ ! ND 20 1 ! E ! i | •ii • i D i t i i 1 i I % Abnor-! % Hemorrhages UO%01/ n i i 5.6 1.5 iii ii i i ! 4,2 6,8 ifi T j �to 1.6 grans, reduced fetal viability from 96.7 to 71.4J, and increased abnormalities from 3.5 to 403. The anomalies associated with 2,4,5-T containing no dioxin.were exencephaly, eye abnormalities, delayed head ossification-, and hind limb deformities. * Increasing the level of dioxin contamination increased fetal mortality and the incidence of abnormalities per litter; fetal viability was reduced. A clear correlation was found between the level of dioxin and abnormalities per litter. Although the incidence of hemorrhages also increased, no relationship between it and dioxin level could be found. Bulging eyes (absence of eyelid) and delayed ossification were the most common anomalies seen among fetuses exposed to dioxin-contaminated 2,4,5-T; exeneephaiy, edema, cleft palate, ectopic heart, and fused ribs were also observed. Smerson et al. (141) found no adverse effects of commercial 2,4,5-T, containing 0..5 ppm TCOD, on fetal development in Sprague-Dawley derived rats and New Zealand white rabbits. Daily oral doses of 2,4,5-T in gelatin were administered to the rats at 1 to 24 mg/kg on days 6 to 15 of gestation; to the rabbits at 10 to 40 mg/kg on days 6 to 18 of gestation. The investigators found no maternal or embryonic toxic effects in either species, nor was 2,4,5-T -95- �eonsidsred teratogenic under the conditions of these experiments* The most frequently observed abnormalities were accessory ri&s, hydronephrosis,, and retardation in the development of the sternebrae* With the exception of partially ossified sternsbrae in both species and bilateral accessory ribs in the rabbit, the incidence of these anomalies was greater in the control animals than in the examined treated groups. Sparschu et al. (140) orally administered 2,4,5-T, containing Q,5 ppm TCDD, to rats in daily doses of 50 and 100 aig/kg on days 6 to 15 and 6 to 10 of gestation, respectively. Results are given in Tabia 24. At 50 mg/kg, there were no significant maternal or eobryonic toxic effects attributable to 2,4,5-T except for an increased incidence of delayed skull ossification, and a single fetus jrlfcij intestinal hemorrhage. At .100 mg/kg, 2,4,5-T was toxic t «s/ to both dams and fetuses.*-1 JJ5L/ The high rate of maternal aortal! ty caused dosing to bs stopped on day 10, instead of day 15. Significant reductions- trr--*sight, gain were also observed. -96- �Table 24. Effects of 2.&.5-T on Fetal Devloosent of Rats* ! Dose (ziz/kx oer dsv) i J— 0 i 50 ! i Parameter ! 100 ! !# Viable fetuses ! i i 1 Total - ! ! Mean oer litter ! 252 11 20-3 ! 11 ! 68 61 i •13* 'I ! 6.7 12.1 i ! Fetal weight (grams) 1 Mai e i ! i ! i 100 i 75^ i i 4.41 4.38 ! 3.57iX! 1 Female !Sex Ratio (M:F) 1 ! 4. 17 5?:H7 4.15 I ? . 5 2-S^ I 23:77 ! i I i ij Resorptions ! Litters i 1 1 i i Total fetuses i Abnormalities t ! (% fetuses examined) I i Poorly ossified sternebraei ! Fifth ! ! Second and fifth ! I Multiple i ! Malaligned sternebrae i ! Delayed ossification ! I Interparietal 1 i Parietals i ! Frontals I i 15.2 3.0 8,3 0.8 3.8 3.0 0.8 44:56! i i i 22.1 ! 4.2 ! 12.6 i 2.1 i I I16.8-S./I l6,8iX! 7 . 4-s-/ 1 --- 5Yp1i/ j 14,3 ! 14.3 ! 28. e-^'i i 28.6-S/l 57. -I.SL/J j Data from Sparschu et al. (140), All viable fetuses from one litter. p < 0.05 Resprptions were observed in all litters; 75J were totally resorbed. Fetal weight was significantly (p < 0.001) reduced in both sexes and the sex ratio was shifted in favor of femalesT"" Abnormalities observed which had significantly (p < 0.05) higher incidences than in the -97- �controls were poorly ossified and malaligned sternebrae and delayed skull ossification. The investigators concluded that the delayed ossification observed in this study was a reversible manifestation, ratbsr than a true teratogenic effect. - . ._ . . ( b ) A d v e r 3 q R a p r o <i u c t i Y er E f_f^.e_t s in 0 the r M a a malian Test S Adverse reproductive effects of 2,4,5-T exposure have been observed in other mammalian test systems. Lloyd et al. (173) reported on in vj^q enzymatic studies showing reduced uptake and metabolism of testosterone by the prostate gland in male mice fcraated orally with doses of 2,4,5-T ( 5 , 5 . J. 2^5 , o^ 25 mg7kg, ten fcijses ^2, daily). lefimenko ( 1 5"> ) reported ors chs affects of acute and chronic exposure to ths butyl estsr of 2»4j5-=T on gonadal and somatic tissue in an jji vj»v_p, cytogsnetic study in male albino rats. Chronic effects on the go- nads were observed after exposure to 0*1 ug/kg for two and one half months. Adverse effects (seen at seven months, when the experiment was terminated ) , which were considered persistent effects-, "Included tssticuiar atrophy, decreased sperm count, desquamated tubules, and aberrant cells in the gerninal epithelium. Chromosomal aberrations were also observed during the chronic phase of the experiment, SPA evaluation of this study found inadequacies in the aethodology which would prevent the drawing of firm conclusions from this data (106). -98- �Recent studies in rats by SJoden and Soderberg [cited in (25)] appear to show that prenatal exposure to 2,4,5-T leads to behavioral abnormalities and changes in thyroid activity and brain seritonin levels in the progeny. Single oral doses of 100 mg/kg were administered to the dams on days 7, 8, or 9 of pregnancy. (c) Adverse Effects in Avian Species Eabryotoxic effects in avian species due to 2,4,5-T exposure have been reported. Verrett (136) studied the effects of 2,4,5-T, containing either 27 or 0.5 ppm TCDD, on chicken eggs. The 2,4,5-T was injected through the air cell of the eggs, either preincubation or on the fourth day of incubation. The sample containing 27 ppm TCDD was found to be more lethal (LD-50 = 25 ug/egg) than the less contaminated sample (LD-50 = 100 ug/egg). Both samples produced teratogenic effects, including chick edema, eye defects, beak defects (primarily cleft palate), and short, twisted feet resulting from tendon slippage. Teratogenic effects were observed at doses as low as 1 ppm (50 ug/egg) with the sample containing 0.5 ppm TCDD and as low as 0.125 ppm (6.25 containing ug/egg) with the sample 27 ppm TCDD. Lutz and Lutz-Ostertag (138) studied the action of 2,4,5-T, in aqueous solution at a concentration of 2 to 10 g/liter, on the embryonic development of quail ( Cotturr.ix coturnix iaoonica ) , chicken ( Gallus gallus ) , -99- �pheasant ( ?_h a si $. ? u 3, g o 1_c h_ic u s)f and two" partridge species (A19etor13 pufa and Perdrix p^rdrix) . The 2,4,5-T was adiairtistarsci by dipping, spraying, and organo-typic cultures. Hbnoraal genital tracts were observed in all 3peci.es, indicating abnormal sexual differentiation. Further, morphological changes in the testes often gave the appearance of true tasticular atrophy. In another study, 2,4,5-T affected fertility in birds of both sexea (139). -100- �( d) Studies in Avj.ar, Sseciqs in Which Adverse cts Were Not Observed Using 2,4,5-T contaminated with less than 0 » 1 ppm dioxin, Strange and Kerr (142) found no abnormal development in chicken embryos. Doses of 12, 5, 25, 50, 75, 100, and 125 mg/kg were injected into eggs on days 0 and 5 of incubation; observations were made 48 hours later. At this developmental stage, kidneys were not sufficiently developed to detect the tubule lesions reported by Bjorklund and Erne (143). (e) Summary Studies have e'sia'b fished that 2,4,5-T is fetotoxic and teratogenic at doses as low as 35 mg/kg (0.05 ± 0,02 ppm TCDD) in mice (125); 4.6 mg/kg (approximately 30 ppm TCDD) in rats (123); and 20 mg/kg (0,5 ppm TCDD) in hamsters (124). Cleft palate and kidney anomalies have been observed in mice, rats, and hamsters. No fetotoxic or teratogenic effects (no-effect levels) have been observed at doses of 20 mg/kg (0.05 *, 0.02 ppm TCDD) in mice (125) and 25 to 150 mg/kg (0.05 ± 0.02 ppm TCDD) in rats (125). ( 3) Exposure Analysis In order to determine whether a rebuttable presumption should be issued based on reproductive and fetotoxic effects, pursuant to Section 1 62. 1 1 (a) (3) (ii) (3) , the Working Group must determine whether or not an ample margin of safety -101- �exists between the levels of 2,4,5-T and/or TCDD which produce reproductive and fetotoxic effects, and the level(s) to which humans can reasonably be anticipated to be exposed. The cancellation of uses of 2,4,5-T on food crops intended for human consumption and for use around the home, recreation sites, aquatic areas, and ditch banks in 1970 was thought to have eliminated the potential exposure to that portion of the population at risk (women of childbearing age). . . -lOla- • . �Social changes over tha last few years, however, have given women the opportunity for employment in areas that once were considered open only to men* Since women of child-bearing age are now employed in occupations such as pesticide applicators, operators of highway construction and maintenance equipment, foresters, and chemical formulatora, they have become part of the population at risk, with potential exposure to 2,4,5-T and/or TCDB* In order to determine whether an ample margin of i, safety exists, the Working Group must first determine how much 2»4,5-T a woman could be exposed to through oral, dermal, or inhalation exposure. For each of these analyses, the Working Group assumes a woman to weigh 60 kg. The following calculations are based on an exposure analysis for 2,4,5-T and TCDD performed by EPA's Criteria and Evaluation Division [CED] (a 1 (164). Oral Exscaurs For purposes of this analysis, the Working Group considered currently registered uses where the possibility of oral exposure to 2,4,5-T and/or TCDD.existed. Treat- ment of range and pasture land could result in oral exposure through ingestion of meat and milk from animals grazing on the treated area. Since actual data on residues of 2,4,5-T in animals grazing on treated rangeland is -102- �unavailable, for purposes of the 2,4,5-T oral exposure .- analysis, the Working Group used residue indorsation obtained -in a feeding study (37) in which cattle were fed considerably higher amounts of 2,4,5-T than.they would normally be exposed to in grazing on treated land. The following calculations are bassd on the average quantities of food eaten par day (1.5 leg), as reported by Lehman (1*4, 165). _ Table 25. __ 2, ^.?-T Oral gysojs'jre Analysis i Whole Milk Meat fgsef*. i iNo-adverse-effeet 20 mg/kg 20 mg/kg ! jlevsl for teratoj igsnicity in mice i ! Average level of {2,4,5-T identified % of food item in ! total human diet i i {Average amount of ! food eaten par day .0.103 pprn"3" 0.2 ppm^ 19.6* 4.6J 1.5 kg ! | 1.5 kg i {Exposure to 2,4,5-T 0.0002 0.0005 sz/kz az / k z a / Animals were fed at 300 ppm 2,4,5-T in the diet for 2 to . 3 .weeks. This is a worst case assumption for cows grazing on freshly-treated pasture without a withdrawal period; all milk and meat was obtained from such cows. Meat (beef) includes muscle, fat, and liver tissues which constitute the major portion of edible meat. ! o9 r dav To find the average daily intake of a single food item, multiply the average daily food intake by the percent of that item in the total diet: for milk, .1.5 kg X 19.55 a 0.294 kg; and for meat (beef), 1.5 kg X 4.6? = 0.069 kg. -103- �The quantity of 2,4,5-T in the average daily diet equals the average daily intake of each food item multiplied by the level of 2,4,5-T in the food item-: for milk, 0.294 leg X 0.103 Ppn * Q « G 3 ngj and for-meat; (-beef), 0,069 leg X 0.2 ppm = 0,014 asg. The theoretical exposure of an. average woman equals the amount of 2,4,5-T in the daily diot divided by the weight of the average woman; for milk, Q.G3 rag / 60 kg a 0.0005 mg/kg; and for meat (beef), 0,014 mg / 60 kg a 0*0002 tag/kg; total exposure from milk and beef products could be 0.0007 mg/kg per day. Existing data on TCftD residues in animals grazing on treated rangeland are too msager to use for an analysis of TCDD exposure to humans through ingastion of meat or milk fram- a-niaals so exposed. The Working Group ccm.sidars that the difference between the no-adverse-effect level of 2,4,5-T for teratogenic effects (20 rag/kg) and the calculated oral, exposure level for 2., 4,5-T' (0.0007 ag/kg per day) does constitute an ample margin of safety. Since this risk criterion for other chronic adverse effects has not been met or exceeded, a rebuttable presumption does not arise. -104- �( b ) Deraal In order to conduct these analyses, the Working Group must determine the amount of 2,4,5-T and/or TCDD which would cone in contact with the skin and— the amount that would be absorbed. (i) Sprav Applicator; Back-pack Sprayer For purposes of this analysis, the Working Group assumes the applicator to be a 60-kg woman of childbearing age, and the site of application either a rightof-way or spot treatment of pasture or rangeland. equipment is a back-pack sprayer (166). The The following -calculations of exposure are based on dilution for spraying of three pints of formulated product per 32 pints of water. Typical 2,4,5-T formulations, based on inspection of a large number of registered labels (164), range from 4 to 6 pounds active ingredient (acid equivalent) per gallon. The product used in this exposure analysis has an assumed concentration of 4 pounds 2,4,5-T per gallon. Label recommen- dations vary from a recommended dilution of 0.094 to 4 pounds acid equivalent per 32 pints of water. A dilution rate of 1.6 pounds per 32 pints has been selected as representative of a typically-used spray mixture. Wolfe et al. (166) studied dermal exposure to fenthion during hand back-pack spraying for mosquitoes -105- �for ten situations. Exposure ranged from 0.1 to 6*3 mg/hr, with a mean value of 3,6 mg/hr (6 nl/hr). Method of applica- tion was a hand pressure sprayer, using a 0.06J spray. Workers wore short-sleeved, open-necked shirtjs with no gloves or hat, 3ased on Wolfe's data, CED (161) calculated a dermal exposure of approximately 0.177 pints per day. CED (164) also determined that approximately 105 of the 2,4,5-T and TCDD coming in contact with the skin of the' applicators would be absorbed even after washing, based on absorption . studies with other pesticides (145, 146, 163). Sack-pack Soraver Deraal E 2.4.S-T itlse Dilution -rate 3 pints j (1.6 pounds 2,4,5-T) per i f 32 pints water I 1 _Tablq 26. ii i Amount of diluted ! material gotten lo-n -skin daily i -t— — \% Diluted material ! absorbed j. _... » 0,18 pint Data I££Q 3 pints (0,00000016 pounds TCDD) per 32 pints water 0,18 pint 10$ 10$ 409 xg 0.0409 ug iDosa Ssvsl 6,8' asg/kg 0.0007 us/kg ! Mo-Adverse«Ef fact i level for teratoLsenic effects 20 mg/kg Q«,Q3 ug/kg ! Exposure level ! 1 The following calculations (see Table 27 for mathewill give the daily dermal exposure for both 2 S 4,5~T -106- �and TCDD: 1) convert the dilution rate to graaa; 2) multi- ply this figure by 1,000 (for 2,4,5-T) to convert to milligrams and by 1,000,000 (for TCDD) to convert to micrograms; 3) multiply this figure by the daily dermal chose of diluted material; 4) multiply this figure by the percent absorbed; and 5) divide this figure by the weight of the applicator for the daily exposure to 2,4,5-T or TCDD per 8-hour working day. ! 2.4.5-T Table 27 i TCDD ! ID 1.6 pounds/32 pt X 454 g/- ID 0.00000016 pounds/i pound s 22.70 g/pt; i 32 pt X 454 g/pound = ! ! 0,00000227 g/pt; ! i ! 12) 22.70 g/pt X 1,00.0 mg/g -s.- J2) 0,00000227 g/pt X i 22,700 mg/pt; j 1,000,000 ug/g = '1 ! 2.27 ug/pt; 13) ! !4) i 15) I 22,700 mg/pt X 0,18 pt s 4,086 mg; 4,086 mg X 10J s 408,6 mg 408.6 mg / 60 kg s 6.8 eg/kg per dav |3) i i4) i i5) j 2.27 ug/pt X 0.18 pt 0,41 ug; 0,41 ug X 10$ = 0,041 ug; 0,041 ug / 60 kg = O.OOQ7 ug/kg per dav ! i ! s ! ! i i !• i The Working Group considers that the difference between the no-adverse-effect level of 2,4,5-T for teratogenic effects (20 mg/kg) and this calculated dermal exposure level "Tor 2,4,5-T (6.8 mg/kg), as well as the difference between the no-adverse-effect level of TCDD for teratogenic effects (0.03 ug/kg) and this calculated exposure level for TCDD (0.0007 ug/kg), do not constitute an ample margin of safety. The Working Group therefore recom- mends issuance of a rebuttable presumption against pesticide -107- �products containing 2,4,5-T and/or TCDD pursuant to '40 CFR Section 1 62. 1 1 (a) (3) (ii) (3) . ( i i ) Spray Applicator; ^Tractpr^pjauntqd f Low-boom S D r a v 5 o_u i p c a n " for the purpose of this analysis, the Working Group assumes the applicator to be a 60»><,g female of childbearing age clearing brush on either rangeland or rightsof-way. The same product cited above (2,4,5-T at 4 pounds/gal) is being used, and the dilation rate is 1.6 pounds of formulation to 32 pints of water (equal to 4 pounds of 2,4,5-T per 10 gallons of water}. Based on exposure studies using similar equipment but a different herbicide (147), the Working Group determined that, during an eight-hour working day, the applicator would get material on her skin. 0.048 pints of diluted The Working Group determined that 10$ of the pesticide on the skin would be absorbed (145, 146, 163).. Table 28 ._ Deraal Exposure Data (Tractor Mounted _ E JLCJiB, iJLiirl iUse Dilution rate 3 pints 3 pints \ ( 1 «6 pounds (0,00000016 pounds TCDD) 2,4,5-T) per i ! 32. pints per 32 pints water water i 1 i Amount of diluted [material gotten — J o n skin daily i \% Diluted material [absorbed 0*048 pint -••" 0,048 pint -—7 — " 10% 10% i Exposure level 109 ng 0.0109 ug iDose level 1,8 mg/kg 0.00018 ug/kg ! No-Adverse-Ef f ect 20 mg/kg 0.03 ug/kg ii i level for cerato- I iflfenii effects -108- �The following calculations (see Table 29. for mathematics) will give the daily dermal exposure for both 2,4,5-T and TCDD: 1) convert the dilution rate to grams; 2) multi- ply this figure by 1,000 (for 2,4,5-T) to convert to milligrams and by 1,000,000 (for TCDD) to convert to micrograms; 3) multiply this figure by the daily dermal dose of diluted material; 4) multiply this figure by the percent absorbed; and 5) divide this figure -by the weight of the applicator for the daily exposure to 2,4,5-T or TCDD per 8-hour working day. _ i 2.U.5-T ID I . Table 2Q - j 1.6 pounds/32 pt X 454 g/- ID pound s 22.70 g/pt; ! TCDD _ i 0,00000016 pounds/i 32 pt X 454 g/pound s I 0.00000227 g/pt; !2) 22.70 g/pt X 1,000 ng/g = I 22,700 mg/pt; I !2) 0.00000227 g/pt X I 1,000,000 ug/g = ! 2.27 ug/pt; !3) I i4) i !5) !3) I 14) i |5) ! 2 2 , 7 0 0 m g / p t X 0 . 0 4 8 pt = 1 , 0 8 9 . 6 nig; 1,039.6 mg X 1035 = 108.96 mg; 108.96 mg / 60 kg = _ 1 . 8 mg/kg_ per dav i 2.27 u g / p t X 0 . 0 4 8 pt a 0 . 1 0 9 ug; 0.109 ug X 10$ = 0.011 ug; 0.011 ug / 60 kg s ! 0. OOP 18 ug/kg per dav The Working Group considers that the difference between the no-adverse-effect level of 2,4,5-T for teratogenic effects (20 ing/kg) and this calculated dermal exposure level for 2,4,5-T (1.8 mg/kg), as well as the difference between the no-adverse-effect level of TCDD for teratogenic effects (0.03 ug/kg) and this calculated exposure level for TCDD (0.00018 ug/kg), do not constitute an -109- ! �ample margin of safety. The Working Group therefore recom- mends issuance of a rebuttable presumption against pesticide products containing 2,4,5-T and/or TCDD"pursuant to 40 CFR Section 1 62.11(a)(3)(ii)(3), ( i i i) Aerial Application: Exposed Population Directly,Beneath Spray Plane Caplan at al. (167), working with aerially applied' taalathion in oil sprays applied at 0.46 pounds per 0.76 gallons water/acre, determined a dermal exposure to persona directly beneath the spray plane for bare skin (head, neck, shoulders, forearms, hands, and thighs) of 3»556 mg/day« With these data, an equivalent dermal exposure for 2 f 4,3~T and TCDD, aerially applied at 4 pounds acid equivalent • 2,4,5-T per 10 gallons water/acre, can be determined. Table 3.0 >.._..D3.r.3al_-Sx30-9.ur.e Data ( Aerial .Aoolicatio.!LL ! Dermal exposure to 3.556 mg/0.46 pounds malathion • i aerially applied per acre imalathion r t ti 2. tt.«5-T JEJ*Hfi 4 pounds 2,4,5-T per 10 gallons of water/acre 0.0000004 pounds TCDD per 10 gallons of water per acre \% Diluted material i absorbed 10? 10* [Exposure level 3.1 mg iUse Dilution rate i ! j j ii i 1 I loose level -6 0.051 rag/kg 5 X 10 ug/kg 20 mg/kg 0.03 ug/kg j |No- Adverse- Effect i level for terato} zenie effect s 0,0003 ug -110- �The following calculations (see Table 31 for mathematics) will give the daily dermal exposure for both 2,4,5-T and TCDD: 1) divide the dermal exposure to malathion by the malathion application rate and multiply by the application rate of 2,4,5-T and TCDD to obtain the dermal exposure; for TCDD, multiply this figure by 1,000 to convert to micrograms; 2) multiply this figure by the percent absorbed; and 3) divide this figure by the weight of the applicator for the daily exposure to 2,4,5-T or TCDD per 8-hour working day. Table 31 2.4.5-T I I* I ah TCDO 1) 3.556 mg/0,46 pounds X ! u . w w w u u u t puuuua s 0.0000004 pounds s 0.000003 mg X 1,000 = 0.003 ug; 2) 0,003 ug X 10$ = 0.0003 ug; 3) 0.0003 ug / 60 kg s .\ ^ 10-6 ug/kg OQr day , J j j * ! l V ^ ^ ! D 3.556 ng/0.46 pounds X •t p u u i i u s = 3 i uibr 4 pounds = 31 .* I !2) 31 mg X 10? = 3*1 mg; 3) 3.1 _w. 60 .„ = mg/ , kg . . 0.051 mg/kg per day I The Working Group considers that the difference between the no-adverse-effect level of TCDD for teratogenic effects (0.03 ug/kg) and this calculated dermal exposure level for TCDD (5 X 10~ margin of safety. ug/kg) does constitute an ample The Working Group also considers, however, that the difference between the no-adverse-effect level of 2,4,5-T for teratogenic effects (20 ing/kg) and this calculated dermal exposure level for 2,4,5-T (0.051 mg/kg) -111 & 112- �does not constitute an ample margin of safety. The Working Group therefore recommends issuance of a" rebuttable presumption against pesticide products containing 2,4,5-T pursuant to 40 CFR Section 162.11(a)(3)(ii>(B). (c) Injialatior. Exposure: Aerial _Ap_pJLjL_ca_t_i,p_i\ • There are no studies available on inhalation exposure of 2,4,5-T. There are, however, several studies on inhala- tion exposure to malathion (167, 168) which CED used as a. model for this 2,4,5-T exposure analysis (164). Caplan et al. (167) determined an air concentration, for unprotected persons directly beneath the spray plane during application and for two hours afterward, of 0.067 mg malathion/nr from aerial application of 0.46 pounds Al/gallon per acre. The collection period spanned the course of the actual application time plus two hours thereafter. The authors considered the sam- pling technique to be equivalent to average inspiration through the nostrils. This inhalation exposure (amount available for inhalation) was 12$ of the applied malathion. Caplan et al. further reported that the average median diameter ( = volume median diameter, or vmd—M was 109 microns. Based on work by Akesson and Yates (168), CED (164) estimated that the size of the malathion droplets which could be inhaled was 16/ The vmd is chat droplet size which divides the total volume of drops in half, i.e., 50% of the volume is in drops above the vmd size and 50* below it. -us- Preceding page blank �under 60 microns. Since 2,4,5-T is typically applied 33 a medium or coarse spray, while malathion is applied as a fine spray, the percent of 2,^t5-^ droplets small enough to be inhaled (under 60 microns) would be less than the percent of malathion droplets snail enough to be inhaled. According to Akesson and Yates (168), 2% of 2,4,5-T spray droplets wou.ld be available for inhalation (or 1/6 the amount of malathion droplets available for inhalation), on a "worst case" basis. Table _In_h,ala.tion_ &.oaur.9- Data 3 I Air concentration of with application 0.067 mg/m {aerially applied rafca of 0. 46 pounds malathion 1 malathion per gallon per acre i 1 ! Use Dilution rate 1 . 1 i ! Lung Absorption {Rate t iSreatbing Rate 4 pounds 2,4,5-T pe r 10 gallons of water/acre ' i 0.0000004 pounds TCDD per 10 gallons of water per acre 100? 100$ 1 .8 m 3 /hr 1.8 mVnr i i per 2 hr 0.000032 ug per 2 hr iDose level 0.023 mg/k g per 8 hr 2 X 1o"°ug/kg per 8 hr 20 mg/kg 0.03 ug/kg {Exposure level j i ! No-Adverse-5f f ect 1 level for teratoiaenic effects .„„„.„ .„,,.„ -114- _ „ „ „ _ _ . „ . . . -.... _ „ „ . _ . , . . . . .»n. '- �The following calculations (see Table 33 for matheaatics) will give the daily inhalation exposure for both 2,4,5-T and TCDD: 1) multiply the air concentration of aalathion by the amount of 2,4,5-T and TCDD applied, then multiply this figure by 1/6 for the inhalation exposure to 2,4,5-T and TCDD; for TCDD, multiply this figure by 1,000 to convert to micrograms; 2) multiply this figure by the breathing rate; 3) multiply this figure by eight [8] to get the 8-hour exposure total; and 4) divide this figure by the weight of the applicator for the inhalation exposure to 2,4,5-T or TCDD per S-hours exposure. - • -• -Table 3"3. j 2 f U.5-T TCDD 1) 0.067 mg/cu a per 0.46 pounds X 4 pounds s 0.58 ng/cu a X 1/6 s 0,097 ag/cu a; ID 0.06? mg/cu in per 0.46 pounds X 0*0000004 pounds s 0.000000058 ag/cu a X 1/6 = 0.000000009 ag/cu a X 1,000 s 0.000009 ug/cu a; 2) 0.097 ag/cu a X 1.8 cu a/- 2) 0.000009 ug/cu a X 1.8 cu a/hr a hr s 0.17 ag/hr; 0.000016 ug/hr; 3) 0,000016 ug/hr X 3) 0.17 ag/hr X 8 s 1.36 ag; 8 = 0,000128 ug; 14) 1.36 ag / 60 kg = !4) 0,00012.8 / 60 kg = I 0.026 mg/kg exposure j -6 * per dav ' ! 2 X 10 ug/ke per dav The Working G'roup "considers that the difference between the no-adverse-effect level of TCDD for teratogenic effects (0«03 ug/kg) and this calculated deraal exposure level for TCDD (2 X 10" margin of safety. ug/kg) does constitute an aaple The Working Group also considers, -115- �however, that the difference between the no-adverse-effect level of 2,4,5-T for teratogenic effects (20 trig/kg) and this calculated dermal" exposure level for 2,4,5-T (0.026 mg/kg-^j does not constitute an ample margin of safety. The Working Group therefore recommends issuance of a rebuttable presumption against pesticide products containing 2,4,5-T pursuant to 40 CFH Section 162.11(a)(3)(ii)(B). (d) Qunu ^a t iy_g_r_v5x_ii p a u r *•! The Working Group has also considered the possibility of a single individual being exposed, through two or more of the above routes. The results (derived from Tables 27, 29, and 3D are shown in Tabls 31» The Working Group also notes that possible cumulative exposure to several dioxin-containing pesticides could increase the total body burden and increase •total risk from dioxin exposure. The Working Group considers that the differences between the no-adverse-effect level of TCDD for tsratogenic effects (0.03 ug/kg) and the calculated cumulative exposure levels for TCDD in Situations 2 and 3 (see Tab-Is do constitute an ample margin of safety. The Working Johnson (63) [see Section I.G.(3)], in a review article, calculated a daily inhalation exposure to phenoxy herbicides of 0.025 ug/kg for a 70-kg adult. The calculations were based on actual air monitoring data of air samples collected in two wheat-growing areas in the state of Washington during spring and summer and analyzed for phsnoxy herbicides. The author did not specify how soon after application the samples were taken* -116- �Table 3*1. Cumulative Exposure to 2.4.5-T and TCDD i Situation » 1 : 2.U.5-T i Situation #1 ; TCDD iOraliDermalilnhal.iCum. = 0.0007 ag/kg 6.8 ng/kg 0.2 mg/kg^7 7.0 mg/kg iOral; [Dermal- 0.'0007 ug/kg ilnhal.- negligible-3-7 iCum. s 0.0007 ug/kg i Situation *2 t 2. *».5-T iOral- -0.0007 mg/kg iDermal- 1.8 mg/kg ilnhal.- 0.05A/ iCum. s 1.85 mg/kg ', Situation *2; TCDD i Oral— -iDermal- 0.00018 ug/kg ilnhal.- negligible3-7 iCum. = 0.00018 ug/kg i :! 'iDermal- 0.051 mg/kg ilnhal.- 0.026 mg/kg iDermal- 5 X 10 ug/kg 6 ilnhal.- 2 X 10~ ug/kg I Cum . s JCum._= i Situation i»3; 2. a. 5-? iOral0.0007 mg/kg 0 .0777 mg/kg Situation H; TCDD iOral. 7 X 10" ug/kg £./ Calculations were made on a worst-case basis as 3% of dermal exposure based on Wolfe (179) who states, "over 97? of the pesticide to which the body is subjected during most exposure situations, and especially to applicators of liquid sprays, is deposited .on the skin." TCDD inhalation exposure values were negligible: Situation #1, 21 X 10~ ug/kg; Situation #2, 54 X 10~7 ug/kg. Group also considers, however, that the differences between the no-adve-rse-effect levels of 2,4,5-T and TCDD for teratogenie effects (20 mg/kg and 0.03 ug/kg, respectively) and the calculated cumulative exposure levels for 2,4,5-T in Situations 1, 2, and 3 and TCDD in Situation 1 (see Table 34) do not constitute an ample margin of safety. The Working Group therefore recommends issuance of a rebuttable presumption against pesticide products containing 2,4,5-T pursuant to 40 CFR Section 162 .1 1 (a)(3)(ii)(B). -117- �IV . STUDIES RELATING TO POSSIBLE ADVE3SE EFFECTS This section addresses other. types of adverse effects of 2,4,5-T for which the Working Group, has deter mined that .insufficient evidence exists fco initiate -a rebuttabie presumption. The Agency solicits comments • from registrants and other interested parties on the evidence listed below, and requests submission of any additional studies or relevant information on 2,4,3-T and/or TCDD relative to these potential adverse effects. Section 162.1 1(a) (3) (i±) (A) provides that a rebuttable presumption shall arise if a pesticide's ingredisnt(s) , metabolite(s) , or degradation product(s) indues oufcagsnic affects, as determined by multitest evidence. ( 1 ) -sLJUSnl C*) Majumdar and Golia (178) fed mala JlTJl5.aJ2,iL!JiJi jULi either 250 or 1,000 ppm dioxin free 2,4,5-T (obtained from Eastman Kodak) for 15 days. They were then mated to sets of virgin females to generate three 4-day broods of offspring. F flies were allowed to mate, and F scored for X-liniced recessive Isthals. -118- flies were No differences among �broods were noted, and data from all broods ware pooled. •The percent lethals in controls, 250 and 1,000 ppm groups were dose-related and were 0.05, 0.25, and 0.66$, respectively.' The control vs« 1,000 ppia lethal rates were significantly different from one another (p < 0.01), Ethyl methane sulfonate (250 ppn) was included as a positive control; it yielded 13.70? lethals. The total number of flies in each experimental group was no larger than 2,000, (b) Negative Studies The mutagenicity of 2,4,5-T was evaluated by Ercegovich st al. (148), employing the procedure of Ames, using five strains of Salmonella tvphiaurium without activation,- They concluded that 2,4,5-T is not mutagenic, Fujita et al. (149) reported chromosomal abnormalities in in vitro cytogenetic studies of human lymphocytes exposed to 10-7 to 10-4 M of 2,4,5-T, which contained ppm TCDD. 0.09 Breaks, deletions, and rings were observed. Chromatid breaks increased with increasing concentrations of 2,4,5-T, It was not possible to distinguish whether this was a toxic effect or a potential genetic effect (150). -119- �Majumdar and Hall (169) reported on the cytogenetic effects of 2,4, 5-r*^ cells of Mongolian gerbils, on in 2JLSL2 bone-marrow The animals ware injected with total amounts of 2,4,5-T at the rate of 50, 150, 250, 350, or 500 mg/kg body weight over the 5-day period of the study. Increasing numbers of chromatic gaps, breaks, and fragments were observed at 250, 350, and 500 mg/kg doses. Mo exchange figures or isochromosome gaps or Breaks were observed* This is not a definitive experiment for indicating the potential of 2,4,5-T for causing heritable chromosome damage (170), Toxicity effects of the chemical could give similar results (170). Davring and Hultgren (171) reported on an j i j ,yjL£S, study on the cytogenetic effects on bone-marrow calls of j j j ,BJLa£.uJLjJL2. (male mice) induced By a Swedish &j. i q/ commercial 2,4,5-T ester formulation-**-* and its components, The study showed that 2,1,5-T commercial pro- ducts can affect chromosomal and reproductive mechanisms. Two different strains of mice were used with similar results for both. seen in Drosophila. These results correlated with affects The authors stated that chrooatid The 2,4,5-T used in this study was purchased from Eastman Kodak Company, Rochester, M.X., and contained no measurable amount of TCDD. The authors do not. indi cate the liaic of sensitivity. JJi/ The concentration of TCDD was guaranteed to be less than 0.1 ppo in the product, -120- �inter- or intraexchanges were never observed. This study wag not carried out sufficiently for the demonstration of chromosomal effects such as rearrangements in future generations of somatic cells (170). Davring and Sunner (172) demonstrated cytogenetic effects of a Swedish commercial 2,4,5-T formulation^ on oogenesis and early embryogenesis in Drosojhila qeer . A 50$ decrease in fertility for the flies was determined to be 250 ppm. This level is 40 to 60 tines less than field use concentration levels. Repro- ductive and chromosomal effects were observed, (2) (a) TCDD Positive Studies Hussain et al. (24) evaluated the mutagenic activity of TCDD (99? pure) on three different microbial test systems. In the first study, TCDD significantly increased the incidence of reverse mutations in Esoherehia coli Sd-4 administered 2 ug/ml TCDD from streptomycin dependence to streptomycin independence. This was the only dose at which mutations were clearly observed. No details of the experimental 2Q/ TCDD concentration was less than 0.1 ppm in this formulation which was tested at practical field use concentrations or lower. -121- �protocol were given, and statistical methods were apparently not employed in assessing the data. The second test by Hussain et al« (24) 'studied reverse mutation from histidins dependence lo~" histidina independence in SaljnonelJ.a tvphiiauriuB (Strains TA 1532 and TA .1530). 1530. TCDD was positive in TA 1532 but negative in TA This indicated that TCDD acts as a frameshift mutagen, ICR-170 was used as a positive control in the test with TA 1332. No positive or negative controls were tested In TA 1530. In the third test Hussain et al, (24) observed slight prophage induction in Ji, coli K-39. However, data from this test were difficult to evaluate because the solvent used, diaethyl sulfoxi.de> causes cellular effects. A preliminary report on the chromosomal analysis of hospital, patients exposed to TCDD in the accident at the Se.veso, Italy, factory was presented at the Department of Health, Education, and Welfare meeting on October 12, 1.976 (152). An increased number of chromosomal lesions (gaps, chromatidic and chromosomal breaks, and rearrangements) were observed in somatic cells of the 2- to 23-year-old males and females tested. Cytogenetic studies of tissues from therapeutic abortions performed on women who were exposed to TCDD during the accident indicated that there was chromosomal �damage to cells in maternal peripheral blood, and placental and fetal tissues. These preliminary results were based on a small nuaber of 'samples, and no specific data are available at this tima (150). (b) Negative Studies Khara and Ruddick (6) conducted dominant lethal tests in which male Wistar rats received TCDD at dosages of 4 and 8 ug/kg per day. The studies indicated that no dominant lethal mutations arose during the 35 days after treatment. The period examined corresponded to postmeiotic stages of spermatogenesis. A cytogenetic screening study of the effects of TCDD on bone marrow cells of male Osborne-Mendel rats was performed by the Food and Drug Administration (119). Two separate experiments were performed. The first was a multiple dose test in which 10 ug TCDD/kg per day was administered by intubation for 5 consecutive days* In the second test, single doses of 5, 10, and 15 ug TCDD/kg were administered intraperitoneally and 20 ug/kg (the highest dose) was administered orally. There was no evidence from these studies to indicate that TCDD produced cytogenetic damage in the bone marrow of these male rats, Toxicity, which was indicated by a slight weight loss, was noted in rats that received a single dose of 15 or 20 ug/kg (the highest dose levels). -123- �Green (119) conducted a short-tern investigation of several dioxins, using male Osborns-Mendel rats, to determine what potential these substances had to produce, cytogenetic damage in rat bone-marrow „ In one study all... of the dioxins were tested by being incubated in the rats for five consecutive days at 10 ug/kg per day, A second study involved TCDD alone administered orally at 20 ug/kg and intraperitoneally at 5, 10, and 15 ug/kg. The author found no evidence that any of the substances tested produced oytogenetic damage in the bone marrow of male rats, In conclusion, although Hussain et ai» (24) have demonstrated that TCDD does appear to act as a point (gene) asutagen, the evidence is weak for heritable genetic effects since the level of mutagenic testing is meager and there were some major deficiences in some tests. However, the study by Hussain ei; al. does not fulfill the criterion of aultitest evidence as prescribed in 40 CFR 162.11. Although TCDD does appear co have the potential to act as a chromosomal rautagen from the j i vj^vs, eytogenetic studies (152), specific j data are not yet available from the Seveso accident. ( 3 ) Chromosoma The Working Group also wishes to call attention to thrse studies [previously discussed in Sections III. B. (2Mb), 17, (1), and 17. (2Mb)], which indicate that 2,4,5-T and/or �TCDD nay cause chromosomal damage. Fujita et al. (149) reported chromosomal abnormalities in j j vitro- tests on j. human lymphocytes exposed to 2,4,5-T; abnormalities included breaks, deletions, and rings. Yefimenko (167) reported damage to - bone-marrow cell chromosomes (including breaks, true aberrations, or rearrangements) in in vivo tests on rat gonadal and somatic tissue exposed to butyl ester 2,4,5-T. The preliminary HEW report (152) on the Seveso incident indicated an increased number of chromosomal lesions (gaps, chromatic breaks, and rearrangements) in somatic cells of 2to 28-year-old humans exposed to TCDD. The Working Group concludes that there is a data gap on mutagenic effects and that further evidence and testing is needed on the mutagenicity of 2,4,5-T and TCDD. The Working Group would like to evaluate more detailed and specific information as it becomes available from the Seveso accident. Relevant information or studies on the mutagenetic effects of 2,4,5-T and/or TCDD should be submitted to the Agency, and the option for re-evaluating.their mutagenic properties must be left open should more conclusive evidence become available. 3. (1) Toxieitv to Hunan3! TCDD Chloracne A number of researchers have reported illness ascribed to TCDD (90, 93, 95, 153). Most of these toxic effects have -125- �occurred in chainical plant workers after accidental exposure to the dioxin. While a number of ill effects have been reported, the most widely known is chloracne. Chlo'racne is a severe skin disease respiting "from exposure to highly chlorinated dibenzo dioxins. It is a disease of the follicular and sebaceous glands,. Its symptoms and signs include skin lesions, follicular hyperkeratosis, and the formation of large sebaceous cysts, inflamnsd tubercles, and pustules. In addition to these symptoms, chloracne is often accompanied by a brownish karatinization of the skin, cystitis, pyelonephritis, depression, hirsutism, fatigue, neurological disturbances, raised cholesterol levels, liver damage, and psychological manifestations (10, 15, 16, 154, 155, 156," 157). Several researchers have observed that chloracne is not only irritating and persistent but also very difficult to cure. It is one of the most frequently contracted forms of occupational dermatitis, occurring primarily in chemical plant eraployees engaged in the production of 2,4,5-T and 2,4,5-TCP (16, 95, 155, 156, 158). i Tha first report on a toxic material being the causative agent for an occupational skin disease appears to have been by Dr. Sari Herxheimer in 1899. Dr. Herxheiaer diagnosed the cause of dermatological problems in a German -126- �factory worker as exposure to chlorine ions in the production of caustic potash (159). It is from this early diagnosis that we get the name chloracne. During the early 1950's there were a series of industrial accidents in Germany resulting in an outbreak of chloracne in the employees of chemical plants manufacturing 2,4,5-T and 2,4,5-TCP. The symptoms of the employees of one of these factories in Hamburg, Germany, were extensively investigated by Kimning and Schulz (16)* These researchers, using the rabbit ear test, proved that the cause of the chloracne was a contaminant found in crude 2,4,5-TCP and not the formulated 2,4,5-TCP. Later on, Bauer et al. (15) conclusively identified TCDD as the causative agent of chloracne. (2) Porphyria eutanqa tarda and o—Aminolevulinic Acid S vnt h eta 3 e i Porphyria cutanea tarda (PCT), a form of hepatic porphyria, is another disease caused by exposure to TCDD and often accompanies chloracne. PCT occurs primarily in industrial workers associated with the manufacture of 2,4,5-T (93, 94, 160).. _.__M.. _ . . .. The symptoms of porphyria cutanea tarda, a defect in hepatic metabolism of porphyrins, are fragility of the skin, photosensitivity of the skin, hyperpigmentation, over-production of porphyrins, hirsutism, and neurological • -127- �and intestinal disorders (94, 160). It is also characterized biochemically by an increase in the activity of the csitochondrial enzyme & -aminolevulinic acid (ALA) synthetase, which is the first and rate-limiting enzyme in heae biosynthesis (160). TCDD was thought to be a potent inducsr of ALA activity in chick embryo liver (115), Goldstein et al. (161) reported that TCDD was found to indues ALA synthetase and hepatic praphyria in mica. These researchers stated that at that time ['19733 TCDD was the most potent porphyrogenic chemical known. Poland and K,ende 1976 (U) found that the duration of ALA induction from TCDD exposure is prolonged, most likely due to the long biological half-life of TCDD, These researchers also found that ALA synthetase inducers have halogen atoms occupying at least three of the four lateral ring positions (positions 2, 3» 7» and 8), and that there is at least one free, nonhalogenated ring position. TCDD fulfills all uf these requirements. -128- �2,4,5-T: Position Document 1 References *1. Raw, G.R., ed. 1970. CIPAC handbook, Vol. I, analysis of technical and formulated pesticides. Collab. Intntl. Pest. Anal. Council Ltd_, , Hertfordshire, England. *2. Meister, R.T., ed. 1977. Farm chemicals handbook, foeister Publishing Co., Willoughby, Ohio. 3» Report on 2,4,5-T: a report of the Panel on Herbicides of the President's Science Advisory Committee. 1971. Executive Office of the President, Office of Science and Technology, Washington, D.C, «4. Poland, A., and A. Kende. 1976. 2,3,7,8-tetrachlorodibenzo-i-dioxin: environmental contaminant and molecular probe. Fed, Proc, 35:2404-2411, •5. Crossland, J., and X.P. Shea. 1973- "he hazards of impurities. Environment 15(5):35-38. *6. Khera, K.S., and J.A, Ruddick. 1973. Polychlorodibenzo-jj.-dioxins: perinatal effects and the dominant lethal test in Wistar rats. Pages 70-84 in S.A. Blair, ed*, Chlorodioxins - origin and fate. Advances in Chemistry Series, No. 120. Am. Chem. Soc., Washington, D.C. 7. Harvey, R.G, 1973. Dioxin, a contaminant in 2,4,5-T. Presented at Wisconsin Pest Control Conference with Industry: January 17, 1973.' (unpublished.) *8. Fishbein, L. 1973» Mutagens and potential mutagens in the biosphere: I. DDT and its metabolites, polychlorinated biphenyls, Chlorodioxins, polycyclic aromatic hydrocarbons, haloethers. Sci. Tot. Environ. 4:305-340, «9. Milnes, M.H. 1971. Formation of 2,4,7,8-tetrachlorodibenzodioxin by thermal decomposition of sodium 2,4,5trichlorophenate. 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Goldmann, P.J. 1972, Extremely severe acute chloracne due to trichlorophenol decomposition products* (Transl, from German.) Indust, Med. Soc. Msd. Indust, Hyg. 7(1)12-18, *92, Schulz-Hamburg, K.H. 1957. Clinical and experimental investigations in the etiology of chloracne. (Transl. from German.) Arch, Klin. Exp, Daraatol. f206:589-596". fi Poland, A,P., D. Smith, G. Metter, and P. Possick. 1971. A health survey of workers in a 2,4-D and 2,4,5-T plant with special attention to chloracne, porphyria -c-u4anea tarda, and psychologic parameters. Arch. Environ. Health 22:316-327. B 94. Bleiberg., J., M. Wallen, H. Brodkin, and I.L. Applebaum. 1964* Industrially acquired porphyria. Arch. Dermatol. 89:793-797* *95. May, G. 1973. Chloracne from the accidental production of tetrachlorodibenzodioxin. 3r. J. Indust. Med. 30:276-283. 93» -137- �•96, 97. Carter, C.D., R.D, Kiabrough, J.A. Liddle, R.E. Cline, M.M, Zack, Jr., and W,F. Barthel, R.E. Koehler, and P.E, Phillips. 1975. Tetrachlorodibenzodioxin: an accidental poisoning episode in horse arenas. Science 188:738-740. U.S. Environmental Protection Agency,'Office of Solid Waste Management Programs, 1975. Hazardous waste disposal damage reports, document no, "2: a current report on solid waste management [EPA/530/SVI-151.2]. Washington, D.C. *98. Beale, M.G., W.T. Shearer, M.M. Karl.,and A.M. Robson. 1977. Long-cerm effects of dioxin exposure. Lancet 1(8014):748. •99. Dewse, C.D* 1975. (7981):363. •100. Hay, A. 1976, 538-540, Dangers of T.CiD.D. Seveso: the aftermath. Lancet 11 Nature 263: 101. Young, A.L., C.E. Thalken, S.L, Arnold, J.M. Cupello, and L*G» Cockerhaa. 1976. Fate of 2,3»7,3-tetrachlorodibenzo-p-dioxin (TCDD) in the environment: summary and decontamination recoraasendatiorss. Department of Chemistry and Biological Sciences, USA? Academy, Colorado, 102. Memo: Rationale for 0.1 ppm limit for tetrachlorodibenzo-p-dioxin in hexachlorophene, dated April 19, 1977. From Orville £„ Paynter, Chisf, Toxicology Branch, to Mary R e e c e v OS?R. 103. U.S. Environmental Protection Agency > Human. Effects Monitoring Branch. 1977. Episode summary for reports involving 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Washington, D.C, (unpublished.) 10^. U.S. Department of Agriculture. 68-1. Looseleaf pub. 5 p?. 1968. PR Notice U«S. Department of Agriculture, 68-2. Looseleaf pub. 5 pp. 1968. PR Notice U.S. Department of Agriculture. 68-9. Looseleaf p u b , 5 PP. 1963, PR Notice U.S. Department of Agriculture. 69-1. Looseleaf pub. 6 pp. 1969. PR Notice -138- �U.S. Department of Agriculture, 69-2* Looseleaf pub. 4 pp. 1969. PR Notice U.S. Department of Agriculture. 69-3» Looseleaf pub. 3 pp. 1969. PR Notice U.S.. Department of Agriculture. 70-8. Looseleaf pub. 1 p. 1970... PR No.tice . .U.S. Department of Agriculture. 70-10. Looseleaf pub. 2 pp* 1970, PR Notice U.S. Department of Agriculture, 70-11* Looseleaf pub. 2 pp« 1970. PR Notice U.S. Department of Agriculture, 70-13* Looseleaf pub, 2 pp. 1970. PR Notice U.S. Department of Agriculture. 70-22. Looseleaf pub« 1 p. 1970. PR Notice fi l05. Muranyi-Kovacs, I,, G, Rudali, and J. Imbert, 1976. Bioassay of 2,4,5-trichlorophenoxyacetic acid for carcinogenicity in mice, Br. J* Cancer 33:626-633. 106. U.S. Environmental Protection Agency, Carcinogen Assessment Group. 1977. Preliminary report on 2,4,5-trichlorophenoxy-acetic acid (2,4,5-T), 2,4,5-trichlorphenol (2,4,5-TCP), 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). (unpublished.) •107. Innes, J.R.M., B,M. Ulland, M.G. Valerio, L. Petrucelli, L. Fishbein, S.R. Hart, A.J. Pallotta, R.R. Bates, H.L. Falk, J.J. Gart, M, Klein, I. Mitchell, and J. Peters. 1969. Bioassay of pesticides and industrial chemicals for tumorigenicity in mic-e: a preliminary note. J. Natl. Cancer Inst, 42:1101-1114, *108. Hardell, L. 1977. Malignant mesenchymal tumours and exposure to phenoxy acids--a clinical observation. (Transl. from Swedish--abstract.) Lakartidningen 74:2753-2754, «109. Van Miller, J.P., J.J. Lalich, and J,R« Allen* Undated. Increased incidence of neoplasms in rats exposed to low levels of 2,3»7,8-tetrachlorodibenzo-^dioxin, (In Press, Chemosphere.) fl 110. Dow Chemical USA. 1977« Preliminary assessment of chronic toxicity study and three-generation reproduction study of 2,3,7,8-tetrachlorodibenzo-p-dioxin. The Dow Chemical Company, Midland, Michigan (unpublished - CONFIDENTIAL.) -139- �•111. 8uu-Hoi» N.P., D. Hien, G. St-Ruf, and J. ServoinSidoine. L971. Biochemistry: carcinomimetic properties of tetrachloro-2,3>7,8 dibenzo-p-dioxine. (Transl, from French.) C.R, Acad» Sci, Paris 272: 1447-1450. *112c Marquardt, H « s J.E. Sodergren, P. Sims, and P.L. Graver. 1974. Malignant transformacloTi in v £ . 2 of jr., mouse fibrobiasts by 7 ,12-dimethylbenz(a)anthracen<i and 7-hydroxymethylbenz(a)anthracene and by chair 'k-region derivatives. Int. J. Cancer 1.3:304-310. •113- Kellermann, G., M, Luyten-Kelierman, and C»R. Shaw, 1973. Genetic variation of aryl hydrocarbon hydroxyla.se in human lymphocytes. Amer. J. Hum. Genet, 25:327-331- •114, Kouri, B.E,, R.A. Salerno, and C.B. Whitmire. 1973* Relafcionshipa between aryl hydrocarbon hydroxylase inducibility and sensitivity to chemically induced subcutaneous sarcomas in various strains of m d c e t J » .Hatl. Cancer Inst. 50(2):363-368. •115* Poland, A t > and E« Glover. 1973* Studies on the mechanians of toxioity of the chlorinated dibenzo-idloxins. Environ. Health Psrspec. 5:245-251. •116« Poland, A,, and E, Glover. 1974. Comparison of 2t3»7,8-t9trachlorodibenzo-jj.-dioxin, a potent inducer of aryl hydrocarbon hydroxylase, with 3™ nacbylcholanthrens. Molec. Pharmacol. 10:349-359. •117. Poland, A., E.t Glover, and A.3. Kende, 1976. Stereospecific, high affinity binding of 2,3,7,3-tetrachlorodibenzo-i-dioxin by hepatic cytosoi, J. Bio c Cham. 251(15):4936-4946. •118, Allen, J.R., D.A. Barsotti, J.P. Van Miller, L.J. Abrahamson, and J.J. Lalich. Undated. Morphological changes in aonkeyes consuming a diet containing low-levels of 2,3,7,8-cetrachlorodibenzo-^-dioxin. (In Press, Fd. Cosmet. Toxicol.) •119* Green, 3. 1975. Cytogenetic evaluation of several dioxins in the rat. (DRAFT - unpublished.) *120. Tung, T,T. 1973, Primary cancer of the liver in Vietnaas. (Transl. from French,) Cnirurgie 99: 427-436. -140- �121«. 0.3. Department of Health, Education, and Welfare, 1969. Report of the Secretary's Commission on pesticides and their relationship to environmental health. Washington, D.C, *122. Clegg, D.J. 1971. Embryotoxicity of chemicals contaminants of foods* Fd. Cosmet, Toxicol. 9:195-205. *123. Courtney, K.D., D*W« Gaylor, M.D, Hogan, H»L, Falk, R»R. Bates, and I* Mitchell. 1970. Teratogenic evaluation of 2,4,5-T. Science 108:864-866, •124. Collins, T.F.X., and C.H. Williams. 1971. Teratogenic studies with 2,4,5-T and 2,4,5-D in the hamster. Bull. Environ. Contam. Toxicol. 6(6):559-567» *1.25« Roll, R» 1971. Studies of the teratogenic effect of 2,4,5-T in mice* (Transl. form German.) Fd. Cosmet, Toxicol. 9:671-676, *126» Roll, R. 1973. Toxicological evaluation of special organochlorinated compounds. Environ. Qual. Safety 2:117-124. •127. Neubert, D,, and I. Dillmann. 1972. Eabryotoxic effects in mice treated with 2,4,5-trichlorophenoxyacetic acid and 2,3,7,8-tetrachlorodibenzo-p-dioxin. Naunyn-Schmiedeberg's Arch. Pharmacol. 272:243-264. - °128. Courtney, K.D., and J.A, Moore* 1971. Teratology studies with 2,4,5-trichlorophenoxyacetic acid and 2,3,7,8-tetrachlorodibenzo-i.-dioxin« Toxicol. Appl. Pharmacol. 20:396-403. 15 Sparschu, G.L., F.L* Dunn, and 7.K. Rowe. 1971. Study of the teratogenicity of 2,3,7,8-tetacholrodibenzojl-dioxin in the rat. Fd. Cosmet. Toxicol. 9:405-412. •130. Khera, K.S., and W,P. McKinley. 1972. Pre- and postnatal studies on 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid and their derivatives in rat's," -TtncTcoi. Appl. Pharmacol. 22:14-28. 0131, Sokolilc, I.Yu. 1973. Effect of 2,4,5-srichlorophenoxyacetic acid and its butyl ester on embryogenesis of rats. Bull. Exp. Biol. Med, 76(7):831-833. *132. Bage, G., E. Cekanova, and K.S. Larsson. 1973. Teratogenic and embryotoxic effects of the herbicides di- and trichlorophenoxyacetic acids (2,4-D and 2,4,5-T). Acta Pharmacol. Toxicol. 32(6):408-416. 129. -141- �*133- Courtney, K.D, 1976. Mouse teratology studies with chlorodibenzo-p-dioxins. Bull* Environ. Contain* Toxicol. 16:(5)674-681. S Courtney, K.D. Undated, Prenatal, effects of herbicides: evaluation by the prenatal development index. (In Press, Arch. Environ* Contan. Toxicol.) •135. Smith, F.A., B.Z, Schwetz, and i.D. Nitschke, 1976* Teratogenicity of 2,3 ,7,8-tetrs-,eblor'Gdibenzy-.2,-di.oxin in CF«1 nice. Toxicol. Appl. Pharnacol. 38:517-523* 136» Verrett, J. 1970. Statement of Dr« Jacqueline Verrett, Food and Drug Administration, Department of HEW. Pages 190-203 in Effects of 2,4, 3-T on man and the environment: hearings before the Subcommittee on Energy,. Natural Resources, and the Environment of the Committee on Commerce „ United States Senate, Hinecy First Congress, Second Session on Effects of 2,4,5-T on Man and the Environment:1 April 7 and 15, 1970. U.S. Government Printing Office, Washington, D»C, 134, •137« Bowes, G.W., 3.R, Simoneit, A. L. Burlingame, 3,W, de Lapps, and H, W'» "H'isebrough* 1973. The search for chlorinated dibenzofurans and chlorinated dibensodioxins in wildlife population showing elevated levels of embryonic death. Environ,, Health Perspec. 5:191-198. •138. Lutz, H», and I, Lutz-Qstertag. 1972* The action of different pesticides on the development of bird embryos. Adv. Sxp« Med. 3iol, 27:127-150. 139* Sal, H.S. 1977. Validation report. U.S. Environmental Protection Agency, Washington, D.C, (unpublished.) *140, Sparschu, G.L., ?«L* Dunn, B « W « Lisowe, and V t K . Howe. 1971. Study of the affects of high levels of 2, 4,5-trichlorophenoxyacetic acid on foetal development in the rat, ?d. Cosmet, Toxicol. 9:527-530. *141, Emerson, X»I~., IL^JU..-. Thompson, R.J. Strebing, C.G. Gerbig, and V.3, Robinson. 1971. Teratogenic studies on 2, 4,5-trichio"ropherjox p yacetic acid in the rat and rabbit. Fd, Cosmet, Toxicol. 9:395-404. & Strange, J*H., and W « E , Kerr, 1976, Teratog-snic and toxlcological examination of 2 , 4 , 5-trichlorophenoxyacetie acid in developing chick embryos. Toxicol. 6?35-40. 142. -142- �n •143. BJorklund, N., and K. Erne. 1971, Phenoxy-acidinduced renal changes in the chicken. I. ultrastructure. Acta Vet. Scand. 12:243-256. *144. Lehman, A,J. 1962. The annual per capita consumption of selected items of food in the United States. Qtly. Bull. Assoc. Food & Drug Offic. _26( 3) : 1 49-151. •145. Wolfe, H.R., K,C, Walker, J.W. Elliott, and W.F, Durham, 1959. Evaluation of the health hazards involved in house-spraying with DDT. Bull. World Health Org. 20:1-14, 146. Federal Working Group on Pest Management. 1974, Occupational exposure to pesticides: report to the Federal Working Group on Pest Management from the Task Group on Occupational Exposure to PesticidesWashington, D»C, *147. Staiff, D » C « , S.W, Comer, J » F « Armstrong, and H,R. Wolfe. 1975. Exposure to the herbicide, paraquat. Bull. Environ. Contain. Toxicol. 1 4(3) :334-340. B Ercegovich, C,D',, and K.A, Rashid. 1977. Mutagensis in mutant strains of Salmonella tvphimurluq by pesticides. Presented at 174th Amer, Chem. Soc. Ntl, Meeting, August 30, 1977. (Unpublished.) *149. Fujita, K., H. Fujita, and 2. Funazaki. 1975Chromospheric abnormalities brought about by the use of 2,4,5-T. (Transl. from Japanese.) J. Jap, Assoc,"Rural Med. 24(2):77-79. 148. 150. Memo: TCDD-dioxin: mutagenicity, dated August 26, 1977. From Ruth Pertel, OSPR, to Mary Reece and - •--Harvey Warnick [Project Managers, OSPR]. *151» XefiiaenkOs L.P. 1974, Data for assessing the gonadotropic and mutagenic effect of the herbicide butyl ether 2,4,5-T. (Transl. from Russian.) Gig. TV, Prof. 2abol. l8(4):24-27. 152. e Communication presented at the HEW Seminar on Environmental Mutagenicity, October 12, 1976. 153* Jensen, M.S., I.B. Sneddon, and A.E, Walker. 1972, Tetrachlorobenzodioxin and chloracne. Trans, St. John's Hosp, Derm. Soc. 58(2):172-177. -143- �•15*. Sleu, G., and R. Goltz, 1971. Late and long-tern injuries following the chronic occupational action of chlorophenol compounds: catasmnetic neurologicpsychiatric and psychological studies. (Transl. from German.) Med. Klin. (Munich) 66(2):53-58, *155. ter Beek, F... R, Bokhorst, M. v,d. Plas, K. Olsthoorn, P.. Vergragt, and G. v.d. Zwan. 1973. ""Dioxine, a dangerous pollutant in a widely used herbicide, .(Transl. from Dutch.) Chemisch Weekblad 69(23):5-6. *156» Zelikov, A.Kh,, and L.N. Danilov. 197*. Occupational dermatitis (acne) in workers engaged in the production of 2,4,5-trichlorophenol. (Transl. from Russian,) Sovfttskaya Meditsina 7:1*5-1*6. •157. Oliver, R.M. 1975. Toxic effects of 2,3,7,8 tetrachlorodibenzo 1,4 dioxin in laboratory workers* Br* J» Indust. Med, 32:49-53. •158. DugoiSj P., and L* Colomb. 1957* Remarks on halogen acne (as regards an outbreak of cases resulting from the preparation of 2,4,5-trichlorophenol)« [Transl. from French*] J. Med. Lyon 33:899-903- •159. Herxheiaer, £. 1899. Concerning chlorine acne* (Transl. from German). Munch,- Med. Woohr. 9:278-279. *160. Woods, J.S, 1973. Studies of the effects of 2,3,7,8tetrachlorodibenzo-i-dioxin on mammalian hepatic ^-aminolevilinic acid synthetase. Environ. Health Perspec. 5:221-225. *161. Goldstein, J.A., P. Kickman, H« Bergman, and J.G. 7os« 1973. Hepatic porphyria induced by 2,3.7,8tetrachlorodibenzo-£-dioxin. Res* Comm. Chem. Path. Pharmacol. 6(3) :919-928. B Commoner, 3., and S,.E. Scott. 1976. Accidental contamination of soil with dioxin in Missouri: effects and countermeasures. C3NSt Washington Univ., St« Louis, Missouri, 162. *163. Durham, W.?., and H.3. Wolfe. 1962. Measurement; of the exposure of workers to pesticides, 3ull. World Healuh Org. 26:75-91. 16*. Memo: Exposure analysis, 2,4,5-T, dated February 1978. From Chief, Chemistry Branch, Criteria and Evaluation Division, co Project Manager, Office o Special Pesticide Reviews. -1*4- �165. Association of Food & Drug Officials of the United States, 1965. Appraisal of the safety of chemicals in foods, drugs and cosmetics. Topeka, Kansas, *166, Wolfe, H.R., J.F, Armstrong, and W.F, Durham. 1974, Exposure of mosquito control workers to fenthion. Mosquito News 34(3):263-257. *167. Caplan, P.E., D. Culver, and W,C» Thielen. 1956. Human exposures in populated areas during airplane application of malathion. AMA Arch. Indust, Health 14:326-332, 168, *169, 170. Akeson, N,3,, and W,E» Yates, Undated, in the air environment, (Unpublished.) Pesticides Majumdar, S,K., and R,C. Hall, 1973. Cytogenetie effects of 2,4,5-T on in yivo bone marrow cells of Mongolian gerbils, J. Hered. 64:213-216. Memo: 2,4,5-T studies: further review, Undated. From Ruth Pertel, Office of Special Pesticide Reviews, to Harvey Warnick, Project Manager, Mary Resce, Project Manager,. Office of Special Pesticide Reviews* *171» Davring, L*, and K, Hultgren, 1977. Cytogenetic effects on in vivo bone-marrow cell.s of M^s au soul us induced by a commercial 2,4,5-T ester'product, Hereditas 85:123-134. *172« Da'Tr-tng, L., and M. Sunner, 1971, Cytogenetic effects of 2,4,5-trichlorophenoxy-acetic acid on oogenesis and early embryogenesis in Drosgohila melanogaatsr. Hereditas 68(1):115-122, *173, Lloyd, J.W,, J.A. Thomas, and M,G, -Mawhinney, 1973. 2,4,5-T and the metabolism of testosterone-1,2-3n by mouse prostate glands. Arch, Environ. Health 26:217-220. B Moore, J.A., B.N, Gupta, J,G, Zinkle, and J.G. Vos, 1973. Postnatal effects of maternal exposure to 2,3 ,7 ,8-tetrachlorodibenzo-ji-dioxin (TCDD), Environ, Health Perspec. 5:81-85, 174. *175, Neubert, D,, ?. Zens, A. Rothenwallner, H,J. Merker. 1973. A survey of the embryotoxic effects of TCDD in mammalian species. Environ. Health Perspec. 5:67-79, -145- �*176« Morris, L«A., M«L. Montgomery, ano S»R. Johnson. 1977. Tha persistence of 2,4,5-T in a Pacific . Northwest forest. Weed Sci. 25 : 417-422. •177. Dougherty, R,C», and K» Piotrowska. 1976, Screening by negative ohesical ionization mass spectrometry for environaental contaaination with toxic residues: application to human urines* Prac,. Hati-. AcacK Sci* USA 73(6) :1777-1731. •178. Majumdar, 3,S., and J r K. Golia. 197^. Mutation teat of 2, 4,5-trichloroph.er.oxyacetic acid on fl**_o a o o h i 1 a a elan _o gas tar . Can* J« G«nst* Cytol,e *179. Wolfe, H.B. ^972. Protection, of individuals who mix or apply pesticides in the field. Pages 35-39 in Federal Working Group on Pest Management, Proc*. Ha tl< Conf, an protective clothing and safety equipment far pesticide warksrs-. Washington, D«C* � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 033 Folder The folder containing the original item. 0626 Series The series number of the original item. Series III Subseries I Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Description An account of the resource 2,4,5-T Working Group, U.S. Environmental Protection Agency (EPA), Special Pesticide Review Division, Arlington, VA Date A point or period of time associated with an event in the lifecycle of the resource March 15 1979 Title A name given to the resource 2,4,5-T Position Document 1 Subject The topic of the resource herbicide properties biodegradation health effects ao_seriesIII Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 030 Folder The folder containing the original item. 0529 Series The series number of the original item. Series III Subseries I Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Source A related resource from which the described resource is derived Dioxin: Toxicological and Chemical Aspects Date A point or period of time associated with an event in the lifecycle of the resource 1978 Title A name given to the resource Chapters 1, 17, and 21 Subject The topic of the resource Italy decontamination biodegradation ao_seriesIII https://www.nal.usda.gov/exhibits/speccoll/files/original/0545f78d07574ee445e99187e3af4175.pdf 37e5b47ce5f485a21c7f95a3702be197 PDF Text Text Item IDNumber.- 00094 Author Corporate Author Department of the Air Force ROpOPt/ArtlClO TitlO Final Environmental Statement on Dispostion of Orange Herbicide by lncinera:ion Journal/Book Title Year 1974 Month/Day November Color Number of Imaoes 798 Descrlpton Notos Friday, Docombcr 08, 2000 Pago 94 of 106 �L. YOUNG, Major, USAF Consultant, Environmental Sciences fc i. DEPARTMENT OF THE AIR FORCE a, 1 DISPOSITION OF, ORANGE HERBICIDE BY INCINERATION •• -•- NOVEMBER 1974 J �THIS PUBLICATION IS PRINTED ON RECYCLED PAPER �FINAL ENVIRONMENTAL STATEMENT ON DISPOSITION OF ORANGE HERBICIDE BY INCINERATION Summary Sheet This final environmental statement was prepared by the Department of the Air Force. For additional information about this proposed action, contact Dr. Billy E. Welch, Special Assistant for Environmental Quality, SAF/ILE, Washington, D.C. 20330, 202-697-9297. 1. The proposal described is an administrative action. 2. Description: The Air Force plans to incinerate Orange herbicide in a remote area of the Pacific Ocean. Incineration will be of only that quantity of the approximately 2.3 million gallons of Orange herbicide which is not registered by the Environmental Protection Agency. The 2.3 million gallons include approximately 1.4 million gallons stored on Johnston Island, and 0.86 million gallons stored at the Naval Construction Battalion Center, Gulfport, Mississippi. Empty drums which once contained the herbicide will be recycled into the manufacture of steel. The proposed action of incineration on a specially designed vessel in the open tropical sea near Johnston Island would take place during three 7 to 9 day periods. Since publication of the revised draft environmental statement, the EPA has reversed their previous position that the Marine Protection, Research and Sanctuaries Act does not apply to incineration at sea aboard an "incineration vessel". The EPA positior is now that ocean incineration requires an ocean dumping permit. The Air Force plans to seek a permit for ocean incineration of Orange herbicide. If, however, the EPA Administrator decides not to issue a permit, the Air Force will pursue the principal alternative of incineration in an incineration facility that would be constructed on Johnston Island. 3. Environmental impact and adverse environmental effects of the proposed action: The proposed incineration will convert the Orange herbicide to its combustion products of carbon dioxide, hydrogen chloride, and water which will be released without scrubbing into the atmosphere. Also, a relatively small amount of elemental carbon and carbon monoxide will be generated in the incineration process and discharged into the atmosphere. Evidence is presented to demonstrate the incineration process can reduce the levels of Orange herbicide to below the detectable limits in the combustion gases. Based on achievable efficiencies ranging from 99.9 to 99.999 percent, environmentally insignificant amounts of unburned and pyrolyzates of herbicide and its impurity 2,3,7,8-tetrachlorodibenzop-dioxin (TCDD) may be released into the atmosphere. �There will be no adverse effect on the envjronment caused by the incineration of Orange herbicide in a remote area of the Pacific. 4. Alternative methods of disposition: a. b. c. d. e. f. g. h. i. j. k. 1. Principal alternative of incineration on Johnston Island. Incineration in one of the 50 States. Use of herbicide. Return to manufacturer. Deep well disposal. Burial in underground nuclear test cavities. Sludge burial. Microbial reduction, Fractionation. Chlorinolysis. Soil biodegradation. No disposal action. 5. Federal and State Agencies and other sources from which written comments have been received: Atomic Energy Commission Department of Agriculture Department of Commerce Department of Defense (Health and Environment) Department of Health, Education and Welfare Department of Interior Department of Transportation Environmental Protection Agency State of Hawaii State of Mississippi American Eagle Foundation Center for Law and Social Policy (representing Friends of the Earth and the National Audubon Society) The Marquardt Company 6. The draft Environmental environmental in April 1974 environmental statement was made available to the Council on Quality and the public in January 1972. The revised draft statement and final environmental statement were made available and November 1974, respectively. ii �TABLE OF CONTENTS PAGE Summary Sheet i TABLE OF CONTENTS - - LIST OF TABLES ii • LIST OF FIGURES vii --- - ABBREVIATIONS -- -- ix EXECUTIVE SUMMARY PART I 1 INTRODUCTION— — 3 A. THE PROBLEM AND PROPOSED ACTION 4 1. DESCRIPTION OF ORANGE 2. LOCATION OF ORANGE-- • 4 4 B. HISTORICAL DOCUMENTATION CF EVENTS C. USES OF PHENOXY HERBICIDES1. REASONS FOR USE2. EXTENT OF USE 3. REGISTRATION PART II - 4 6 — —- — --- - - PROJECT DESCRIPTION A. B. PHYSICAL FACTORS BIOLOGICAL FACTORS MANAGEMENT FACTORS SOCIO-POLITICAL FACTOSS - ----- 15 1. INTRODUCTION 2. INCINERATION AT SEA 3. PRINCIPAL ALTERNATIVE - INCINERATION ON JOHNSTON ISLAND D. FAILSAFE- - 1. INCINERATION AT SEA 2. PRINCIPAL ALTERNATIVE. - INCINERATION ON JOHNSTON ISLAND ni 13 13 13 14 14 14 — C. METHOD OF INCINERATION-ft/'•'' ' • ., • 6 7 7 9 INTRODUCTION INCINERATION SITE CRITERIA 1. 2. 3. 4. viii 15 16 18 — 22 22 23 �E. 24 1. INTRODUCTION — 2. HERBICIDE RESIDUAL IN DRAINED DRUMS 3. HERBICIDE DEDRUM AND TRANSFER TO INCINERATOR VESSEL -4. ULTIMATE DRUM DISPOSAL 5. POTENTIAL FOR ENVIRONMENTAL IMPACT 6. ENVIRONMENTAL IMPACT™ F. HERBICIDE DEDRUM/TRANSFER AND DRUM DISPOSAL 24 26 CHARACTERISTICS OF HERBICIDE 31 1. PROCUREMENT SPECIFICATIONS— 2. CHEMICAL AND PHYSICAL PROPERTIES 3. STATISTICAL ANALYSES OF TCDD CONCENTRATIONS IN ORANGE HERBICIDE STOCKS 4. TOXICOLOGICAL AND ECOLOGICAL CHARACTERISTICS OF CHLOROPHENOXY HERBICIDES PERTINENT TO POTENTIAL BIOLOGICAL EFFECT OF N-BUTYL ESTERS OF 2,4-D AND 2,4,5-T 5. TOXICOLOGICAL CHARACTERISTICS OF TCDD.— 6. EVALUATION OF ENVIRONMENTAL CONTAMINATION POSSIBILITYPART III 27 28 29 29 31 ' 36 36 43 58 61 PROBABLE ENVIRONMENTAL IMPACT OF PROPOSED ACTION- 63 A. SUMMARY STATEMENT OF TOTAL IMPACT B. AIR QUALITY— - 67 68 1. DISPERSION MODEL STUDIES 2. ENVIRONMENTAL IMPACT- • • - C. WATER QUALITY 1. 2. 3. 4. 5. 76 PRESENT WATER QUALITY MOVEMENT PERSISTENCE • MONITORING METHODOLOGY ENVIRONMENTAL IMPACT 76 86 90 92 93 — D. MARINE FLORA AND FAUNA ON JOHNSTON ISLAND 1. SCOPE OF CONSIDERATIONS 2. POTENTIALS FOR IMPACT ON AQUATIC PLANTS AND ANIMALS • — 3. PROBABLE ENVIRONMENTAL IMPACT ON AQUATIC PLANTS AND ANIMALS E. TERRESTRIAL FLORA AND FAUNA 1. FLORA OF ISLANDS 2. FAUNA OF ISLANDS- 68 68 - 103 103 103 103 106 106 107 �F. SOIL (CORAL AND SAND) \ 1. MOVEMENT 2. PERSISTENCE 108 - -- 108 108 G. THE ECOLOGICAL SIGNIFICANCE OF JOHNSTON ISLAND: AUTHORITATIVE OPINIONS 109 H. HUMAN WELFARE- 112 - -- I. BENEFICIAL ASPECTS OF T4E PROPOSED ACTION-PART IV PART V 113 ADVERSE ENVIRONMENTAL IMPACT WHICH CANNOT BE AVOIDED--- 115 ALTERNATIVES TO THE PROPOSED ACTION-- 117 A. PRINCIPAL ALTERNATIVE - INCINERATION ON JOHNSON ISLAND— B. CONVENTIONAL INCINERATION IN THE CONUS — 1. LIQUID WASTE INCINERATORS 2. INCINERATION AT ROCKY MOUNTAIN ARSENAL 3. APPLICATION TO ORANGEC. USE— 119 121 122 - 123 1. DESCRIPTION OF ACTION2. ENVIRONMENTAL IMPACT— D. E. F. G. 119 119 — 123 124 RETURN TO MANUFACTURERS DEEP (INJECTION) WELL DISPOSAL —BURIAL IN UNDERGROUND NUCLEAR TEST CAVITIES— SLUDGE BURIAL 125 125 125 126 1. GENERAL 2. ENVIRONMENTAL IMPACT — 126 126 - 128 • H. MICROBIAL REDUCTION 1. DESCRIPTION OF ACTION— 2. ENVIRONMENTAL IMPACT — — I. FRACTIONATION J. CHLORINOLYSISK. SOIL BIODEGRADATION — 1. INTRODUCTION 2. ENVIRONMENTAL IMPACT — -— - 129 130 132 — 1. DESCRIPTION OF ACTION 2. ENVIRONMENTAL IMPACT L. NO DISPOSAL ACTION 128 128 — 132 135 136 136 136 �PART VI RELATIONSHIP BETWEEN LOCAL SHORT-TERM USE OF MAN'S ENVIRONMENT AND THE MAINTENANCE AND ENHANCEMENT OF LONG-TERM PRODUCTIVITY PART VII 137 IRREVERSIBLE AND IRRETRIEVABLE COMMITMENTS OF RESOURCES WHICH WOULD BE INVOLVED IN THE PROPOSED ACTION IF IMPLEMENTED 137 APPENDICES A. ECOLOGICAL BASELINE SURVEY OF JOHNSTON ATOLL CENTRAL PACIFIC OCEAN B. EXECUTIVE ORDER (NOS. 4467, 6935 AND 8682) ESTABLISHING JURISDICTION OVER JOHNSTON ISLAND C. SAILING DIRECTIONS FOR THE PACIFIC ISLANDS VOL. Ill, THE SOUTH CENTRAL GROUPS, 6TH ED. 1952, PP. 354-367 D. INCINERATION OF ORANGE HERBICIDE E. REPORT ON THE DESTRUCTION OF "ORANGE" HERBICIDE BY INCINERATION F. THE ECOLOGICAL CONSEQUENCES OF MASSIVE QUANTITIES OF 2,4-D AND 2,4,5-T HERBICIDES, SUMMARY OF A FIVE YEAR FIELD STUDY G. FIELD STUDIES ON THE SOIL PERSISTENCE AND MOVEMENT OF 2,4-D, 2,4,5-T AND TCDD H. JOHNSTON ISLAND DATA I. TRANSPORTATION REQUIREMENT J. ANALYTICAL METHODS K. DISPERSION MODEL STUDY L. COMMENTS TO DRAFT ENVIRONMENTAL STATEMENT DISPOSITION OF ORANGE HERBICIDE BY INCINERATION JANUARY 1972 -- AF-ES-72-2D M. BIOLOGICAL MONITORING AND TOXICITY STUDIES IN SUPPORT OF "ORANGE" HERBICIDE INCINERATION TESTS AT THE MARQUARDT COMPANY, VAN NUYS CALIFORNIA N. INFORMATION ON INCINERATOR SHIPS 0. COMMENTS TO REVISED DRAFT ENVIRONMENTAL STATEMENT-DISPOSITION OF ORANGE HERBICIDE BY INCINERATION - APRIL 1974--AF-ES-72-2D(l) LITERATURE CITED vi �LIST OF TABLES TABLE PAGE II-l General Chemical/Physical Properties of Orange ~Q J0 Herbicide.......-.....----------............................ 11-2 General Chemical/Physical Properties of Ingredient Esters of Orange Herbicide--------------..... II-3 General Chemical/Physical Properties of TCDD II-4 TCDD Analyses of Major Manufacturer StocksGulf port - 42 1 1 -5 Acute Toxicity of 2,4-D Derivaties to Terrestrial Animals ------------------------------------------ .,- I I -6 Acute Toxicity of 2,4,5-T Derivatives to Terrestrial Animals------......-...............------------ II-7 Chronic Toxicity of 2,4-D and 2,4,5-T Derivatives to Terrestrial Animals -------------------------- .„ I I -8 Acute Effects of 2,4-D Derivatives upon Aquatic Animals-----.....-.........------------------------- ,-. II-9 Non-Lethal effects of 2,4-D Derivatives upon ................ 40 46 55 Aquatic Animals ---------- ......... -• ....... -------- ......... 11-10 Sensitivity of Selected Plants to 2,4-D Dichlorophenoxyacetic Acid ---------------------------------- III-l Water Sediment Samples, EHL(K) Field Trip, Johnston Island, Oct 73..........- ......................... III-2 Marine Biological Specimens, EHL(K) Field Trip, Johnston Island, Oct 73- „ /0 80 II I -3 TCDD Results, EPA Laboratory, Bay St Louis, MO and Perrine, FL III-4 Water Sample Analyses Results (EHL(M)) II I -5 TCDD Results, EPA Laboratory, Bay St Louis, MO and Perrine, FL -------------------------------------------- «. III-6 Results of Biological and Sediment Sample Analyses by EHL(K).................• ....................... pt. ab vii ...................... 83 �LIST OF FIGURES FIGURE I 1-1 PAGE Histogram Representation of TCDD Concentrations Measured in 200 Orange Herbicide Samples From Johnston Island -------------------------------------- 77 III-l Johnston Island Water Samples October 1973 I I 1-2 Marine Sampling Locations EHL(K) Field Trip, Johnston Atoll, October 1973-—• .................... 7Q /y III-3 Johnston Island - Inferred Circulation, JanuaryFebruary 1965..............................• ........... Q7 b/ III-4 Johnston Island - Easterly Flow, Inferred Circulanfl tion and Turbid Outflow, July-August 196.5 ----- ...... OB III-5 Johnston Island - Westerly Flow, Inferred Circulation and Turbid Outflow, July-August 1965 ---------- V-l Schematic of Commercial Incineratcr Facility --------- viii ........... ., 8g 120 �ABBREVIATIONS AAAS American Association for the Advancement of Science ACGIH American Conference of Governmental Industrial Hygienists BOD biochemical oxygen demand BTU British Thermal Unit 14c radioactive carbon cbm cubic meters CJTF Commander, Joint Task Force cm centimeter CONUS Continental United States 2,4-D 2,4-dichlorophenoxyacetic acid DASA Defense Atomic Support Agency DMA-2,4-0 dimethyl amine salt of 2,4-D DNA Defense Nuclear Agency OoD Department of Defense EHL(K) USAF Environmental Health Laboratory, Kelly AFB TX EHL(M) USAF Environmental Health Laboratory, McClellan AFB CA EPA Environmental Protection Agency ESSA Environmental Sciences Service Agency GB nerve agent MAC Herbicide Assessment Commission of the AAAS HATV High Altitude Test Vehicle HEN Department of Health, Education and Welfare H &N Holmes and Narver, Inc. IMCO Inter-Governmental Maritime Consultative Organization JCS Joint Chiefs of Staff IX �JP-4 jet engine fuel kg kilogram km kilometer KW kilowatt 1 liter Ib/A pounds per acre Ib ai/A pounds of active ingredient per acre Dose which will kill 50% of a species of test animals in a stated period. LORAN Long Range Air to Navigation m meter MG million gallons nig milligram mg/kg milligrams per kilogram ing/1 milligrams per liter mm millimeters MUSTARD a blister agent NBE (nbe) normal butyl ester NCBC Naval Construction Battalion Center NNTRP National Nuclear Test Readiness Program PCB Polychlorinated biphenyl PERT Program Evaluation and Review Technique PGBE propylene glycol butyl ester ppb parts per billion (weight to weight ratio) PPbv/v (PPbv) parts per billion (volume to volume ratio) ppm parts per million (weight to weight ratio) PP^v/v (PPmv) parts per million (volume to volume ratio) pps Pounds per second �pKa Acid dissociation constant ppt parts per trillion (weight to weight ratio) pptv/v (pptv) parts per trillion (volume to voljme ratio) RDES revised draft environmental statement RMA Rocky Mountain Arsenal SMAMA Sacramento Air Material Area (Sacramento Air Logistics Center) SUE;55 "Sudden Expansion" Burner, Registered Trade Mark, The Marquardt Company 2,4,5-T 2,4,5-trichlorophenoxyacet.ic acid TACAN Tactical Air Navigation TCDD 2,3,7,8-tetrachlorodibenzc-1u-dioxin THOR a medium-range ballistic missile USDA U.S. Department of Agriculture VX a nerve agent Mg rnicrograms pg/1 micrograms per liter approximately > greater than XI �(This page intentionally left blank) �EXECUTIVE SUMMARY In April 1970 the Secretaries of Agriculture, HEW, and Interior jointly announced the suspension of certain uses of 2,4,5-T. As a result of this announcement the Department of Defense suspended the use of Orange herbicide since this herbicide consists of approximately 50 percent 2,4,5-T and 50 percent 2,4-D. This suspension left the Air Force with 1.5 million gallons of Orange herbicide in Vietnam and 0.8 milVon gallons in Gulfport, Mississippi. In September 1971, the Department of Defense directed that the Orange herbicide in Vietnam be returned to the United States and that the entire 2.3 million gallons be disposed in an ecologically safe and efficient manner. The 1.5 million gallons were moved from Vietnam to Johnston Island for storage in April 1972. The initial method proposed for disposal was incineration at a commercial facility in the United States. The details of this proposed course of action were documented in a draft environmental statement which was filed with the Council on Environmental Quality and the public in January 1972. The draft statement discussed the studies that were being accomplished but not completed when the statement was filed. Based on the fact that studies were still in progress and the interest evidenced in coirments received on the draft statement, the Air Force decided to conduct additional studies on incineration as well as additional investigation of alternative disposal methods. (See Appendix L for comments.) As a result, numerous studies were conducted to determine the feasibility of soil biodegradation, fractionation, chlorinolysis, and incineration. Also, the Air Force submitted an application to the Environmental Protection Agency (EPA) for registration of that portion of the herbicide which was expected to meet EPA criteria. Return of the herbicide to the original manufacturers was investigated. In addition, the possibility of deep well disposal, burial in underground nuclear cavities, and sludge burial were investigated. It was concluded that the best disposal technique J s incineration in a remote area. The revised draft environmental statement was published to update the work accomplished between January 1972 and April 1974. Thermal decomposition research using differential thermal analysis was conducted to determine the temperatures required for complete combustion of Orange herbicide and its impurity 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Dynamic laboratory studies were next completed to further substantiate the feasibility of incineration and to refine monitoring techniques for subsequent tests. A test program was conducted in a commercial incinerator to document the feasibility of destroying undiluted Orange herbicide by means of combustion. Particular emphasis was placed on the ability to destroy the low quantity of TCDD (low milligram per kilogram concentration, mg/kg) present in the herbicide. Extensive sampling, utilizing time-weighted and concentration techniques, was conducted to evaluate the unscrubbed combustion gases, the scrubbing liquid used to cool and scrub the combustion gases, scrubbed effluent gases, and any solid residues deposited in the system. Program objectives were outlined to determine, among other things, engineering data relative to controlling and monitoring the incineration process, the composition of the combustion products, the toxicity of discharged scrubber water to several aquatic organisms, and the �toxicity of scrubbed effluent gases to tomato plants. These series of tests demonstrated that incineration of Orange herbicide car be accomplished in an environmentally acceptable manner. In addition to the above tests, information on combustion of chlorinated hydrocarbons aboard incirerator ships indicates destruction efficiencies of at least 99.9 percent. The average concentration of TCDD in the herbicide is about 2 mg/kg and the total amount of TCDD in the entire Orange stock is approximately 50 pounds. The commercial incinerator test program indicates that, if any TCDD were present in the exhaust stream, it was analytically nondetectable. Orange destruction efficiencies of 99,,9 percent or better appear feasible for a large scale incineration project. This will result in a total discharge of 0.05 pounds or less of TCDD via the exhaust streams over the duration of the project. The data accumulated, together with theoretical ccnsiderations and applied thermochemistry, clearly indicate that the production of incomplete combustion products can be minimized to insignificant levels. Incineration will convert the Orange herbicide to its combustion products of carbon dioxide, hydrogen chloride, and water which will be released to the atmcsphere. In addition, a relatively small amount of elemental carbon end carbon monoxide will be generated in the incineration process and discharged to the atmosphere. With proper concern for the environment in which such incineration will take place, incineration is an environmentally safe method of disDosal of Orange herbicide. The Air Force proposes incineration upon t.ne open tropical sea west of Johnston Island on a specially designed .vessel of that quantity of Orange herbicide riot registered by the EPA. Since publication of the revised draft environmental statement, the EPA has reversed their previous position that the Marine Protection, Research and Sanctuaries Act of 1972 does not apply to incineration at sea aboard an "incineration vessel".. The EPA position is now that incineration at sea requires an ocean dumping oermit. Therefore, the Air Force plans to apply for a permit for disposal of Orange herbicide via incineration at sea. The incineration would occur during tiree 7 to 9 day periods. The effects of combustion gas discharges upon the environment was accomplished by utilizing "worst case" analyses techniques. A dispersion zone model was used to estimate mass concentrations of unburned Orange and hydrogen chloride in the air and water environment In the vicinity of the discharge, and a meteorological model was applied to predict the atmospheric concentration of unburned Orange and hydrogen chloride at sea level downwind of the discharge location. Predicted results from these models revealed that there will be no significant environmental impact upon either the air or ocean environment. If, however, the EPA Administrator decides not to issue a permit for incineration at sea, the Air Force will pursue the principal alternative of incineration in facility that would be constructed on Johnston Island. Incineration on Johnston Island would require a higher efficiency owing to the ecology of the Atoll and would, for the analysis presented in the text, require approximately 200 days. A complete ecological survey was conducted of Johnston Island by the Smithsonian Institution in order to document the areas of concern. Incineration on-board a specially designed ocean vessel and incineration in a facility of Johnston Island both meet the criteria of remoteness. Incineration can be successfully conducted using either method; however, the predicted environmental effects are minimized by incineration in a remote area of the Pacific on the open tropical ocean. �PART I INTRODUCTION PAGE A. THE PROBLEM AND PROPOSED ACTION 1. DESCRIPTION OF ORANGE 2. LOCATION OF ORANGE 4 4 4 B. HISTORICAL DOCUMENTATION OF EVENTS 4 C. USES OF PHENOXY HERBICIDES 6 1. REASONS FOR USE 2. EXTENT OF USE 3. REGISTRATION 6 7 7 �A. THE PROBLEM AND PROPOSED ACTION: The Air Force is charged with the responsibility for the ecologically safe, efficient and, if possible, low cost disposal of approximately 2.3 million gallons of Orange herbicide. Proposed action is to incinerate the herbicide in a renote area of the Pacific Ocean either on a specially designed vessel or on Johnston Island. Combustion gases from both options are discharged into the atmosphere in an environmentally safe manner and without any significant effect upon the beneficial uses of the area. 1. DESCRIPTION OF ORANGE: This herbicide consists of approximately 50% by volume of the normal butyl ester of 2,4-cichlorophenoxyacetic (2,4-D) acid and 50% by volume normal butyl ester of 2,4,5-trichlorophenoxyacetic (2,4,5-T) acid. A small quantity, known as Orange II, contained the isooctyl ester of 2,4,5-T in place of the normal butyl ester. Unfortunately, as a result of a malfunction in the production process, certain lots of the herbicide contain a contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). In experimental animals this compound was shown to be teratogenic, i.e., it caused the production of malformed fetuses and living offspring in arimals. For this reason the military and certain other uses of 2,4,5-T ceased in 1970. 2. LOCATION OF ORANGE: The herbicide is stored in 55 gallon steel drums at two locations. At the Naval Construction Battalion Center (NCBC), Gulfport, Mississippi, there are approximately 860,000 gallons and on Johnston Island, Central Pacific Ocean, there are approximately 1,400,000 gallons. • B. HISTORICAL DOCUMENTATION OF EVENTS 1. In 1962, the herbicide formulation, Orange, was developed for military use as a defoliant. This herbicide formulation is a mixture of n-butyl esters of 2,4-D and 2,4,5-T. 2. South Vietnamese newspapers reported an increased occurrence of birth defects during June and July 1969. This action elicited far-reaching reactions from governmental agencies, segments of the scientific community, lay groups concerned with environmental problems, and from the communications media. Government-sponsored panels of experts, special commissions established by scientific organizations, hearings before subcommittees of the U.S. Congress, and conferences attended by representatives from industry, government, and universities examined available data and heard expert opinions. These groups were not able to provide a generally acceptable answer to the central question of whether 2,4,5-T as currently produced and used, constituted a risk for human pregnancy (HAC, 1972). 3. On October 29, 1969, it was announced that a series of coordinated actions were being taken by several governmental agencies to restrict the use of the herbicide 2,4,5-T. This was precipitated by release a few days earlier of the findings of a study by Bionetics Research Laboratories, Litton Industries, Inc., in which it was found that mice and rats treated during early pregnancy with large doses of 2,4,5-T gave birth to defective offspring. �4. Additional animal experiments performed early in 1970 confirmed that pregnant mice did deliver some malformed offspring. The question then was one of whether, or to what extent, such animal data could be extrapolated to man. On April 14, 1970, the Secretary of Health, Education and Welfare (HEW), advised the Secretary of Agriculture that: "In spite of these uncertainties, the Surgeon General feels that a prudent course of action must be based on the decision that exposure to this herbicide may present an imminent hazard to women of childbearing age." Accordingly, on the following day, the Secretaries of Agriculture, HEW and Interior jointly announced the suspension of the registration of 2,4,5-T for: "I. All uses in lakes, ponds or on ditch banks. II. Liquid formulations for use around the home, recreation areas ard similar sites" (USDA-PR 70-1, 1970). A notice for cancellation of registration was issued on May 1, 1970 for: "I. All granular 2,4,5-T formulations for use arounc the home, recreation areas and similar sites. II. All 2,4,5-T uses on crops intended for human consumption" (USDAPR 70-3, 1970). 5. All registrants of 2,4,5-T were advised of these actions. Two of the registrants, Dow Chemical Co. and Hercules Inc., exercised their right under Section 4.c. of the Federal Insecticide, Fungicide and Rodenticide Act (7 USC 135 et seq) to petition for referral of the matter to an Advisory Committee. The National Academy of Sciences supplied a list from which was selected a ninemember Advisory Committee of scientists with appropriate qualifications from universities and research institutes over the country. It was the concensus of the committee that the central issue was whether use of the herbicide does in fact constitute an imminent health hazard, especially with respect to human reproduction. 6. During the intervening months since restrictions were placed on the use of 2,4,5-T, a number of additional studies have been carried out on several animal species and a few reports of human exposure during pregnancy have been further evaluated. Although the new data have not answered all of the questions that have been or could be raised, they undoubtedly provided a more substantial basis for making a scientific judgment about possible effects of this herbicide on prenatal development than previously existed. In undertaking such judgment, the committee took into account certain considerations that seemed appropriate to the issue, as follows: 1) As is frequently the case, available data are insufficient for a definitive statement of conditions under which a specified risk might occur, assuming that freedom from risk is ever attained; 2) Since most chemicals under suitable laboratory conditions could probably be demonstrated to have teratogenic effects, and certainly all could be shown to produce some toxic effects if dosages were high enough, it would not be reasonable to consider the demonstration of toxic effects under conditions of greatly elevated dosage to be sufficient grounds for prohibiting further use of a particular chemical; and 3) Benefits are to be expected from the continued use of 2,4,5-T. The necessity of making a value judgment o1" benefit versus risk, therefore, must be accepted, not only for this herbicide, but for numerous valuable drugs, some natural nutrients, and many other chemicals, some of which are known to be teratogenic in laboratory animals. The risk versus benefit judgment for a particular herbicide or drug can be evaded only if it can be shown that another compound is equally as efficient and involves less risk. This presupposes that the risk potential of a substitute herbicide is at least as well known as that of the original (in this case 2,4,5-T) -- a fact that may be difficult or impossible to ascertain. The substitution of a relatively unknown pesticide for an older one with known adverse effects is not a step to be taken lightly.. �7. The task of making a judgment about the central question of hazard to human pregnancy is complicated by still other considerations. Although herbicides are of economic benefit to man, their use is not without possible hazard to the environment and to other aspects of human welfare. In various connections, questions have been raised about: a) damage to nontarget plants caused by spray drift or by movement in water, b) damage to subsequently planted sensitive crops owing to herbicide persistence in the soils, and c) acute or chronic toxicity to man or other animals aside from that related to pregnancy. 8. It is scientifically impossible to prove that a chemical is without hazard. Pesticide regulations now require that new agents be tested for acute and chronic toxicity, mutagenicity and carcinogenicity. These tests may involve the use of two or more species of animals taken through several generations and the examination of thousands of individuals. Since it is necessary to extrapolate from effects in test animals to man arid since species are known to differ in sensitivity to chemicals, the permissible residue levels in food must always be manifold below the minimal effect level for the species tested. 9. A major producer of 2,4,5-T submitted evidence that the 2,4,5-T used in the Bionetics test contained 2 7 + 8 ppm of an impurity identified as TCDD. This impurity was tested and found to produce teratogenic effects in several species of animals at widely varying dose/body weight ratios and by different routes of administration. 10. Human exposure to an environmental chemical such as 2,4,5-T depends on: a) pattern of usage, i.e., how widely and frequently it is applied and in what amounts and b) its fate in the environment, i.e., how it accumulates and degrades in relation to its application rate. The chlorophenoxy herbicides 2,4-D and 2,4,5-T have been widely used to control broad-leaved weeds for over 20 years. Because 2,4,5-T is more expensive than 2,^-D, it has been primarily used to control woody plants and a few herbaceous species against which it is more effective than 2,4-D. Also because of the cost difference, commercial formulations containing 2,4,5-T are usually mixtures of the two herbicides. 11. Most of the 2,4,5-T is applied as a spray to foliage. Lesser amounts are sprayed on the trunks and branches of dormant trees, injected into the bases of trees, poured or sprayed into frills around the trunks of trees, sprayed or painted on newly cut stumps of trees. Ami no salts of 2,4,5-T dissolved in water are most often used when the herbicide is applied to foliage and esters dissolved in oil are most often used when it is applied to bark. The spray concentrations usually vary between 0.1 and 2.5% and the rates of application are usually between 0.5 and 8 pounds per acre, depending on the size and sensitivity of the plants being treated. Higher rates and concentrations were used in Vietnam for military purposes (U.S. Army, 1969). 12. In September 1971, the Secretary o~ Defense directed the Joint Chiefs of Staff (JCS) to dispose both Continental United States (CONUS) and Vietnam stocks of herbicide Orange. The Air Force was assigned this responsibility. C. USES OF PHENOXY HERBICIDES 1. REASONS FOR USE: The phenoxy herbicides 2,4-D and 2,4,5-T, their salts, esters and other compounds, are well established pesticides for the control of �weeds and shrubs in agriculture. In particjlar, as noted by Kingman and Shaw (1967), the phenoxy herbicides are especially useful because; a) they are selective, they kill most broad leaf plants but do not k i l l grasses or grain crops; b) they are potent, many species of weeds are controlled by less than one pound of active ingredient per acre; c) they are easy to use; d) they are only mildly to moderately toxic to man, domestic animals, or wildlife when applied as recommended; and e) they do not accumulate in the soil and they have minimal if any harmful effects on soil .organisms. Klingman and Shaw noted that ester formulations are generally more potent, pound -or pound, than salt formulations. The esters are more effective than salts for killing weeds that are growing slowly; and because esters are oily, they are less likely to be washed off the foliage if rain falls soon after application. 2. EXTENT OF USE: The herbicides 2,4-D and 2,4,5-T were first employed by farmers and ranchers in the mid-1940's and remain the most common synthetic organic herbicides. The largest use of 2,4-C1 is for broadleaf weed control in corn and other grains; the major use of 2,4,5-T is to kill brush (Fox et al., 1970). The combined production of 2,4-D and 2,4,5-T has increased steadily from 34,6 million pounds in 1958 to 96.8 million pounds in 1968. At present, the phenoxy herbicides are the only group of herbicides used to any extent on pasture and rangeland. In 1964, the uses of 2,4,5-T were: rights-of-way - 49%; nonfarm forests - 10%; hay, pasture, and rangelands - 7%; all other farm uses 12%; lawns and turfs - 7%; federal agencies - 6%; and other miscellaneous uses 9% (Advisory Committee). Incomplete information indicates that about nine million pounds of 2,4,5-T esters, acids, and salts were domestically used during 1970. Weeds and brush infesting pasture and rangeland are most widely controlled by 2,4-D and 2,4,5-T, respectively. In 1966, nearly 8 million acres (more than 1 percent) of pasture and rangeland were treated with ohenoxy herbicides (Fox e_t^ al_., 1970). The herbicide 2,4,5-T is a particularly effective tool for vegetation management on forest lands (Montgomery and Morris, 1970). It is used on power-line, railroad rights-of-way; but its most important use is in connection with the establishment and release of conifers on forest lands. For these purposes, 0.5 to 4 pounds of 2,4,5-T per acre were applied as low volatile esters dissolved or emulsified in diesel oil or water. 3. REGISTRATION a. The 15 April 1970 government ed'ct on 2,4,5-T suspended the registration of liquid formulations for use around the home and recreational areas, and for uses on lakes, ponds, and ditch banks. This restriction did not include its use on range and pasture lands, nonagricultural lands, or in weed and brush control programs on communications and highway rights-of-way. Several formulations of 2,4-D and 2,4,5-T are currently registered for domestic use. Orange herbicide is not a registered herbicide and cannot be domestically used or sold. b. The Orange herbicide stock to be destroyed by the action proposed in this environmental statement, incineration at sea, or by the principal alternative of incineration on Johnston Island represents a resource of considerable monetary value. The safe and appropriate utilization of all or part of this resource would be a beneficial action, see Part V.C. The Air Force has been and is continuing to pursue the possibility of EPA registration of portions of the Orange herbicide stock. The Air Force is seeking registration of the maximum possible quantity found acceptable by the EPA. Depending upon the level of TCDD allowed, approximately 1.5 million gallons could conceivably be registered. �(This page intentionally left blank) 8 �PART II PROJECT DESCRIPTION PAGE A. INTRODUCTION .............. ---- ........ ------------------- .......... 13 B. INCINERATION SITE CRITERIA ---- ...... ----------------------------- 13 1. 2. 3. 4. PHYSICAL FACTORS-- ......... ----------- ........ --------- ..... 13 BIOLOGICAL FACTORS ----------------------- ..... --------------- 14 MANAGEMENT FACTORS—......------------------.....----.......-- 14 SOCIO-POLITICAL FACTORS --------------------------------------- 14 C. METHOD OF INCINERATION ------- ...... ------------------------------ 15 1 . INTRODUCTION -------------------------- ..... ----- ........ ----- 15 2. INCINERATION AT SEA ----------------------------------------- 16 a. Introduction --------------- ..... ------------------------ 16 b. The Vessel -------- ....... ------------------------------- 16 c. Incineration System ---------------------------------- ..... 16 (1) (2) (3) (4) Physical Features ---------------------------------- 16 Operation ---------------------- ...... -------------- 16 Effluent Discharges -------- ........ ---- ...... ------ 17 Monitoring ---------------------- ......... ----------- 17 (a) Operational Monitoring ---------------- ....... 17 (b) Ecological Monitoring ------------------------ 18 (5) Additional Environmental Considerations ----------- 18 3. PRINCIPAL ALTERNATIVE - INCINERATION ON JOHNSTON ISLAND ---- 18 a. Introduction----------.....—.....---------------.....- 18 b. Proposed Incinerator on Johnston Island ---------------- 18 (1) Incineration System ..... •-• ...... ------------------- 18 (2) Discussion of Scrubbers Considered ---------------- 19 (a) Alkaline Scrubber ----------- ........... -------- 19 1_. 2_. 3_. 4_. Hydroxide as a Neutral izer --------------- 19 Coral Carbonate? as a Neutral izer --------- 20 Spent Alkali Scrubber Water Character ---- - 20 Spent Alkali Scrjbber Water Treatment and 20 Discharge.....- ....... --*• ---------------- 20 5^ Scrubbed Effluent Gas Character/ Discharge ---------- ..... ----------------- 20 �(b) Sea Water Scrubber 1_. 2_. 3. 4j. Treatment Scrubber Water Character Scrubber U'ater Discharge Scrubbed Effluent Gas Character/ Discharge c. Summary 21 21 21 21 21 21 D. FAILSAFE -- 1. INCINERATION AT SEA-2. PRINCIPAL ALTERNATIVE - INCINERATION ON JOHNSTON ISLAND 22 22 23 E. HERBICIDE DEDRUM/TRANSFER AND DRIF DISPOSAL 24 1. INTRODUCTION 2. HERBICIDE RESIDUAL IN DRAINED DRUMS 24 26 a. General b. The Marquardt Company - Drum Draining c. NCBC Gulfport Drum Draining 3. HERBICIDE DEDRUM AND TRANSFER TO INCINERATOR VESSEL 26 26 26 27 a. Gulfport, MS b. Johnston Island 27 28 4. ULTIMATE DRUM DISPOSAL 28 5. POTENTIAL FOR ENVIRONMENTAL IMPACT 29 6. ENVIRONMENTAL IMPACT 29 F. CHARACTERISTICS OF THE HERBICIDE 31 1. PROCUREMENT SPECIFICATION 2. CHEMICAL AND PHYSICAL PROPERTIES 3. STATISTICAL ANALYSES OF TCDD CONCENTRATIONS IN ORANGE HERBICIDE STOCKSa. b. c. d. Sampling from Johnston Island and Gjlfport Results of Johnston Island Analyses Results of Gulfport Analyses TCDD Content of Total Orange Herbicide Stocks 4. TOXICOLOGICAL AND ECOLOGICAL CHARACTERISTICS OF CHLQROPHENOXY HERBICIDES PERTINENT TO POTENTIAL BIOLOGICAL EFFECTS OF N-BUTYL ESTERS OF 2,4-D AND 2,4,5-T 10 31 36 36 36 36 36 37 43 �a. Behavior in Terrestrial Animals 43 (1) Metabolism and Excretion Kinetics (2) Absorption and Distribution - - (3) Acute Toxicity (4) Chronic Toxicity 43 -- 44 44 44 b. Behavior in Humans - 47 c. Behavior in Aquatic Systems and Aquatic Animals 47 (1) Metabolism and Distribution-- 47 (a) General Comparisons (b) Metabolism in Fish 47 47 -- (2) Behavior in Aquatic Systems - (a) Solubility Limits and Rates Vs Hydrolysis Rates —(b) Circulation of Water in Relation to Availability of Herbicide for Absorption (c) Importance of Hydrolysis (d) Other Factors Affecting Actual Concentration (3) Toxicity d. Behavior in Plants 51 52 52 52 52 53 53 Distribution and Metabolism Toxicity Herbicides as Air PcTutants Relative Species Sensitivity -- 5. TOXICOLOGICAL CHARACTERISTICS OF "CDD 53 56 56 56 58 a. Toxicity to Animals 58 (1) Acute Toxicity- - 58 (2) Toxic Effects on the Fetus (a) Hamsters (b) Rats b. 51 52 (a) Factors Affecting Toxicity(b) Toxicity Comparisons by 'EHL(K) (c) Other Animals and Other Effects (1) (2) (3) (4) -- 51 58 - Industrial Exposure-- 58 -- 58 59 c. Evaluation of Toxicological Testing 11 60 �(1) Requirement for Estaolishing Dose-Related Response-— (2) Bionetics Study -(3) Evaluating Data from Animal Models-(4) Design of Recent 2,4,5-T Toxicity Studies--6. EVALUATION OF ENVIRONMENTAL CONTAMINATION POSSIBILITY-— •--• - a. Knowledge Available From Use b. Application of Testing c. Possibility of Pyrolytically Produced Contamination d. Evaluation by EPA Advisory Committee 12 60 60 60 61 61 61 -- 61 61 62 �A. INTRODUCTION: This part of the Environmental Statement is primarily to describe the proposed incineration of Orange herbicide from the standpoint of facility and operational requirements and effluent stream characteristics. The proposed action of incineration at sea and the principal alternative of incineration on Johnston Island are described. Since publication of the revised draft environmental 'statement, the EPA has taken the position that the Marine Protection, Research and Sanctuaries Act of 1972 does not apply to incineration at sea. Therefore, the Air Force plans to apply for a permit for disposal of Orange herbicide via incineration at sea. The factors applicable to the selection of a disposal site and the situation regarding disposal of empty herbicide drums is also discussed. In view of the importance and interest in the properties of the herbicide, a section titled "Characteristics of the Herbicide" has been included as the final section of this part. B. INCINERATION SITE CRITERIA: This Environmental Statement is for the disposal of Orange herbicide via incineration in a remote area. The proposed action will take place aboard a specially designed incinerator vessel in an isolated location of the Pacific Ocean. The principal alternative would be incineration on the west side of Johnston Island. Either location meets the remoteness requirement. Either location will involve an industrial operation of considerable magnitude in which the undiluted herbicide will be handled and will be the fuel feed into the incinerator(s). Since Johnston Island and the surrounding area will be involved in the proposed action or the principal alternative, considerable information on this locale is presented in Appendix H. General considerations that were used for site selection are summarized and presented below. 1. PHYSICAL FACTORS a. The site should be as remote as possible from both residential and Industrial population centers and from land currently in agronomic production. Vegetation should be sparse, of little agronomic value, and of species resistant to the phenoxyacetic acid herbicides contained in Orange or to the pyrolytic products of these herbicides. The site should be selected so that women of childbearing age have the lowest poss'ible probability of contact with the Orange. b. The topography or surface featjres of the surrounding area should be relatively flat and with a symmetrical, jniform surface. c. A prevailing wind of as nearly constant direction and velocity as possible would be highly desirable. Insofar as possible, the incinerator(s) should be sited downwind of any inhabited areas such as housing, work shop and storage areas, recreational areas, etc. d. The site should be located to provide accessibility of water, rail, or truck transportation but cause negligible interference with any existing patterns of transportation. Further discussion of transportation is contained in Appendix I. 13 �2. BIOLOGICAL FACTORS a. The site should be so located to minimize any unacceptable adverse impact or municipal water supplies, shellfish beds, wildlife, fisheries (including spawning and breeding areas), or recreational areas. b. The site should be located such that the disposal operations will cause no unacceptable adverse effects to kncwn nursery or productive fishing areas. The currents should be such that any suspended or dissolved matter would not be carried to known nursery or productive fishing areas or populated or protected shoreline areas. 3. MANAGEMENT FACTORS: The site should be so located and configured such that it will be conducive to single manager control of the entire disposal operation and peripheral activities, and that adequate control can be exercised over the general population in the area to allow immediate response in the event of an accident, incident, or act of God. Adequate communications must be available that will further enhance management at all levels. 4. SOCIO-POLITICAL FACTORS: The site selected or the transport of the Orange should not require the exercise of the right of eminent domain or result in a trespass or encroachment to private citizens within the U.S. or its possessions or to any other nation's interests. If possible, the site should be completely under the control of the Federal Government to minimize the local political controversial effects on state or other government units. The site location should not result in international controversy, be in conflict with international law, or impair the economic activity of any commercial enterprise. 14 �C, METHOD OF INCINERATION 1. INTRODUCTION: Incineration of Orange has been investigated and it has been concluded that high temperature incineration is capable of destroying the Orange herbicide and its TCDD content in an environmentally safe manner. Appendix D, "Incineration of Orange Herbicide," describes the theoretical aspects of Orange incineration, reviews five separate studies directed toward the evaluation of Orange incineration, and concludes that incineration is an acceptable disposal method. These studies were performed by: I) the USAF Environmental Health Laboratory, Kelly AFB, TX; 2) the U.S. Department of Agriculture and Mississippi State University, State College, MS; 3) the Combustion Power Company, Menlo Park, CA; 4) the Marquardt Co., Van Nuys, CA; and 5) a joint effort between The MarquardL Co. and the USAF Environmental Health Laboratories (EHLs) at Kelly arid McClellan AFB. As shown in Appendix D the first four studies conducted on Orange (1 through 4 above) were of small scale as regards quantity of Orange incinerated and sampling and analyses condjcted. To further evaluate the high temperature combustion of Orange and to obtain incinerator operation parameters which may be appropriate to a commercial incinerator system, it was apparent that a large scale completely monitored Orange test burn using an incinerator with an acid gas scrubbing system was required. As an initial choice, a large scale test burn of Orange incineration was programmed at the Rollins Environmental Services facility in New Jersey. This project never passed the planning state and was concluded because cf technical, environmental and regulatory problems. With this setback and after careful consideration of alternative incineration options, the Marquardt Company SUE^ incinerator was selected tor a test burn. Factors in this decision included: 1) The SUE^is a flame incinerator which could utilize Orange herbicide as the fuel and air to supply the required oxygen; and 2) The modular corcept of the SUE^ is very advantageous because it eliminates scale-up considerations (capacity is increased by increasing the number of modules), and permits ease of shipment, installation, maintenance and dismantling. The purpose of the test burn was to obtain data on Orange incineration and not to determine specifically if the Subsystem was acceptable for the disposal of the entire Orange stock. It is the Air Force opinion that selection of the SUt^was a sound choice for a test burn and that while pure data extrapolations are not possible, the requirements for an overall incineration system for the destruction of Orange can now be specified with a high degree of certainty. The report on the study with a SUlfMncinerator, prepared by the Marquardt Co. and both the USAF EHLs, is titled "Report on the Destruction of Orange Herbicide by Incineration," and is presented as Appendix E. In view of these studies and the disposal site criteria, this environmental statement proposes the action of destruction of Orange herbicide via incineration on a ship at sea. In addition, this Environmental Statement proposes the principal alternative of incineration on Johnston Is'and. It is noted that this proposal is for "incineration as a method of destruction of Grange" and in no way is it intended to imply or state that the product; of any given contractor, firm, company, etc., must be used. 15 �2. INCINERATION AT SEA a. Introduction: As stated, the Ai*1 Force proposes the destruction of Orange herbicide via incineration on a ship at sea; however, its implementation is dependent on the EPA issuing a permit in accordance with the Marine Protection, Research and Sanctuaries Act of 1972. The above mentioned studies and other information from Ocean Combustion Service B.V., Rotterdam, The Netherlands, indicate that shipboard incineration would be capable of destroying Orange herbicide and its TCDD content in an environmentally safe manner. Since September 1972, a ship, the "Vulcanus" has been equipped to carry certain hazardous liquid chemcial cargoes from northern European ports and approved by participating countries to incinerate the waste cargo in prescribed areas of the North Sea. Additionally, U.S. companies have suggested shipboard incineration and have indicated a willingness to investigate it. The following information describes the "Vulcanus" from material supplied ay the Ocean Combustion Service B.V. b. The Vessel (1) The ship is a double hulled and double bottom tanker with an overall length of 331.4 feet, a beam of 47.2 feet and a draft of 22.9 feet. Her construction complies with the latest Inter-Governmental Maritime Consultative Organization (IMCO) regulations of bulk carriage of dangerous chemicals at sea. Because of her size, the vessel is able to operate world-wide, and she is able to operate in very rough weather. The ship has a crew of ten to operate the ship and a crew of six solely to operate and continuously man the incineration process. Two diesel engines drive the single propeller to give service cruising speeds of 10-13 knots. (2) The vessel's cargo tank capacity of 3,503 cubic meters (cbm) (925,493 gallons) is divided into 15 cargo -:;anks ranging in volume from 115 cbm to 574 cbm. None of these tanks are in contact with the vessel's hull and/or bottom. The engine room is separated from the cargo tanks by double bulkheads, the pump room and generator room being situated in between. c. Incineration System (1) Physical Features: The two combustion chambers are installed right aft of the upper de~ck. Each of the bricklined incinerators has a maximum outer diameter of 5.50 meters (m), and inside diameter of 4.80 m, and a total height, including the stack, of 10.45 m. The volume of each combustion chamber is calculated to be 87.9 cbm. Each chamber has three burners with rotating cup fuel injection systems which provide vortex turbulence and distribution of fuel feed throughout the whole chamber. This incinerator is considered a conventional incinerator as discussed in Part V.B. (2) Operation: Incineration will be conducted in a designated area 50-60 miles clear of normal shipping lanes and on the open tropical sea down wind of Johnston Island. Gas or diesel oil will be used to bring the chambers to the required combustion temperature, normally 1400°C (2552°F); the maximum operating temperature is reported as 1650°C. Only when the required temperature is reached will the feed pumps .allow waste to enter the combustion chambers. Waste feed flow and air will be carefully controlled to insure complete combustion. Once the required temperature is obtained, the chambers will be fed solely by the undiluted Orange. The Orange can be pumped to each of two chambers at a rate of 10-12 tons per hour for a total daily pump rate of 16 �about 576 tons. Therefore, about 22-26 days of continuous incineration would be required to burn the entire Orange stock (2.3 million gallons). The vessel's capacity of about 925,OOC gallons.of Orange will require three voyages; 925,000 gallons of Orange would be burned during each of the first two voyages, and the remaining 380,000 gallons of Orange plus ar.y solvents used in drum cleaning would be burned during the third voyage. (3) Effluent Discharges: Data presented in Appendices D and E indicate that incineration of herbicide Orange can be accomplished in an environmentally acceptable manner. A comparison of the incineration characteristics of the "Vulcanus" versus those known to be acceptable based on the data presented in Appendices D and E indicated that Orange herbicide can be successfully incinerated on board the "Vulcanus." (Acceptable parameters: measured combustion temperatures 2400 - 28CO°F; dwell time equal to or greater than 0.14 seconds; a fuel to air mass ratio of approximately 0.1; and excess air greater than 30%. Vulcanus data: 2550°-; 0.6 seconds; 0.1 to 0.12; and 35% respectively.) Information from Ocean Combustion Services has been used to predict the inorganic constituents of the exhaust stack discharges. A total throughput of 576 tons per day (24 tons/hour) of Orange with an average of 30 percent (by weight) chlorine content will giye a discharge of approximately 178 tons/day of hydrogen chloride, some 1,000 tons/day of carbon dioxide, about 50 tons/day of carbon monoxide, and about 3.0 tons/day of carbon particles. Although very low quantities of unchlorinated hydrocarbon pyrolyzates (vg/l range) were detected in -:;he combustion areas of Orange in a commercial incinerator (Appendix E), information from Ocean Combustion Service indicated 99.9 percent of a chlorinated hydrocarbon feed is destroyed. At this high efficiency, approximately 0.576 ton/day (48 pounds/hour) of Orange feed constituents and their pyrolyzates are not completely incinerated and are thus discharged hourly into the atmosphere. Ocean Combustion Services reported that negligible amounts of combustion chamber coke deposits have ever accumulated in the ship's incinerators. Tnis has been attributed to their waste injection system, very high vortex turbulence in the chambers, and 1400°C temperatures on the chamber's firewalls. From such experience, no consequent combustor chamber coke deposit is expected. (4) Monitoring (a) Operational Monitoring: A special monitoring panel continuously displays the following:temperature near the center of each incinerator chamber, temperature in the centerline and about two meters from each incinerator stack exit, date and time, on/off mode of each feed pump and each burner, and grid location of the vessel. This panel is photographed at preset desired intervals by an automatic camera. This panel and camera can be sealed by regulatory authorities to prevent tampering and provide accurate documentation of the incinerator operation and location. Additionally, a navigation plotter automatically charts the vessel's course on a map and is made available to authorities along with certified copies of the ship's log. These operational and navigational documentations have been used to establish the ship's successful incineration of waste cargoes in a designated area. For this project, automatic photographs of the panel and manual observation records 17 �of the incineration parameters will be accomplished. However, the navigational log book rather than the automatic plotter will be acceptable due to the vast expanse affordable in the Pacific Ocean as compared to the North Sea. Based upon the successful past history of incinerating some 60,000 tons of chlorinated hydrocarbons and upon the basis of documentation of operational parameters as outlined above, success of this option is predicted. Additional documentation can be provided by a regulatory representative who can accompany the vessel. As no significant impact is envisioned 1 (See Part III), combustion gas analyses is not necessary as an operational requirement. (b) l£PJ.o.9JcjJ_l^onitpnng: Ecological monitoring is neither required nor feasible for" the following~reasons: 1) the ship will complete the project within a month and always be moving and operating over a large area of the open tropical sea; and 2) as describee in Part III, the predicted impact will be very minimal and transient for this incineration option. (5) Additional] . Enyj\ronm^ntal_Cpr.sid_erati_on^: The ship does not have on board facilities for handling, ~ emptying"," or'cleaning the drums nor does it have pumping capability for on-loading the Orange herbicide. This means that facilities for transferring of the herbicide, enptying and cleaning of drums, and pumping the herbicide aboard the ship will be necessary. Additionally, ultimate disposal of the empty drums will also be required. Duplication of these required facilities at Johnston Island and Gulfport MS depends on either of two methods to be selected for transporting the Gulfport herbicide to Johnston Island: 1) provide facilities at Gulfport for transferring Orange to the ship's cargo tanks, or 2) transport the Gulfport herbicide in existing drums to Johnston Island for loading onto the incinerator ship. The selection of either of these alternatives will depend on considerations of economic, environmental, and operational aspects of the drum disposal method selected. 3. PRINCIPAL ALTERNATIVE - INCINERATION ON JOHNSTON ISLAND a - L^rodyp.tipn.: The system described below is conceptual and based upon prior studies" whichi developed the operational parameters required for successful incineration of undiluted Orange herbicide (see Appendices D and E). on Jphns_tp'.i_ Jsl_and_ (1) Incineration System (a) The proposed incineration system on Johnston Island would incinerate the Orange herbicide at a rate of 1.4 pounds per second (pps) for 24 hours per day and discharge the combustion gases directly into the atmosphere on the west end of the island. At this rate, 11,300 gallons or 206 drums of herbicide could be incinerated per day for -200 burn days to incinerate the entire stock of 2.3 million gallons. The details and design of the hardware for the entire system have not been addressed. However, incinerator systems both with and without combustion gas scrubbers have been considered in order to demonstrate the potential impact of spent scrubber water versus unscrubbed combustion gas dispersions into the atmosphere. For a system operating within the acceptable parameters described ~ln Appendix E (measured combustion chamber 18 �temperatures of 2400-2800°F; dwell time equal to or greater than 0.14 seconds; fuel to air mass ratio of about 0.1; arid excess air greater than 30"), it can be stated that: 1) combustion 3 gas and scrubbed effluent gases are free to undetectable levels (~0.20xlO~ ug/1 for each compound) of herbicide esters, acids, and TCDD; 2) about 103 of the carbon dioxide and greater than 99.93 of both the hydrogen chloride and carbon participates a:"e removed from the combustion gases via an alkaline scrubber; 3) combustion pyrolyzates are unchlorinated hydrocarbons whose total concentrations average less than 0.50 pg/l; 4) alkali scrubbing removes a small fraction of the pyrolyzates from the combustion gases, and with gaseous condensation in presence of chlorine, converts some of the pyrolyzates into chlorinated hydrolyzates; 5) total unchlorinated pyrolyzates average less than 13.0 ig/1 and total chlorinated hydrolyzates average less than 3.0 i.g/1 in the spent scrubber water; 6) carbon particulates contain no detectable levels of any type of hydrocarbon and the mass of these particulates was less than 0.53 of the carbon in the herbicide; 7) carbon dioxide, carbon monoxide, and heat of combustion gases are not environmentally significant; and 8) dispersions of scrubbed effluent gases into the atmosphere have no effect on tomato plant bioassays and attest to the lack of phytotoxicity of the gases. (b) Considering the quality of the combustion gases and absence of herbicide feed constituents and TCDD content, treatment of the combustion gases is not required. Discharged combustior gases from the west end of the island will have minor environmental significance but spent scrubber water discharges, if used, could have an impact on tne island's aquatic environment. For completeness both here and in Part III, both alkali and sea water scrubbers are discussed, but it is emphasized that the most environmentally acceptable incineration system on Johnston Island is one which does not scrub the combustion gases. (c) Combustion gases woulc be discharged without scrubbing via a high stack on the west end of the island. These gases would be free to undetectable levels of herbicide feed constituents ard TCDD but would discharge some 18.5 tons of hydrogen chloride during each burn day. Additionally, the stack gas would also discharge about 0.3 tons of particulate carbon per day and contain microgram per liter concentrations of unchlorinated hydrocarbon pyrolyzates. This option is attractive because it eliminates environmental problems associated with the discharge of spent scrubber water and the economic and logistic problems associated with the orocurement and handling of neutralization chemicals and/or acidic scrubber water. (2) Discussjon_ of_§crubbers Consjidere_d (a) Aj_ka_l_ine_S crubbe_r !_. llydroxide_jis__a__Neitralizer: An average volume of 250,000 gallons of fresh scrubber wate~r containincf about 81,000 pounds of sodium hydroxide (NaOII) would be required to scrub/neutralize the 37,000 pounds of hydrogen chloride produced per burn day in the combustion gas. The excess amount of sodium hydroxide required in the scrubber water is attributed to combustion gas carbon dioxide reactions with the alkali and scrubber system efficiency. If the NaOII were supplied in 55 gallon drums of 50 percent by weight NaOH, then 1-1/4 drums of this NaOH stock solution would be required per drum 19 �of herbicide incinerated For a total of 50,000 drums of NaOH. This NaOH requirement may be reduced by 25',£ if the alkali were recycled and the scrubber design optimized to discharge spent scrubber water at pH 8.E. Daily discharge of spent scrubber water would be about 200,000 gallons because about 50,000 gallons of fresh scrubber water feed are volatilized and discharged with the stack gas as water vapor, see Appendix E. 2_. Coral__C^rbonate_as_a_ Neutral jzj^r: Coral is the primary constituent of the geological mass of Johnsto'n I Viand. As primarily calcium carbonate (CaC03) it represents a source of alkalinity which may be suitable as a neutral izer for scrubber water which contains acid ge.s, hydrogen chloride. On the basis of hydrogen chloride neutralization only, c.bout 43 pounds of CaCOo would be required for each 100 pounds of Orange burned. The daily incineration of 206 drums of Orange would require approximately 26 tons of CaCOg. For consideration of the incineration of 2.3 million gallons (200 days), the neutralization of HC1 would require approximately 5,000 tons of CaCX^. This figure would undoubtedly be higher when system efficiencies and absorption of carbon dioxide are considered. Since CaCO^ does not dissolve in sea water, the scrubber neutralizing system would require two units consisting of a sea water scrubber and a crushed coral contact unit for exposure of the scrubbing water to the coral. The availability of coral and a small scale test of coral usage would be required prior to selection of this method of combuscion gas treatment. 3_. Spent A1J<a1j Scrjbber Mater Character: For an incineration system operating at the acceptable parameters," the spent scrubber waters are free to undetectable levels (-45 nanograms/1 for each compound) of herbicide esters, acids, and TCDD and contain less than 16.0 ug/1 of total hydrocarbon pyrolyzates and hydrolyzates. However, the spent scrubber water is 160-170°F and contains significant concentrations of suspended solids, 80-100 rng/1 ; free available chlorine, 250 mg/1; and chlorides, 20,000 nig/1 (see Appendix E). The free available chlorine, 417 pounds in 200,000 gallons of spent scrubber water per day, and the heat content are primary. problems in disposing of the scrubber water. Bioassays on the spent scrubber water required conditioning of the water for heat and chlorine removal, after which, the toxicity of the spent scrubber water was essentially the same as that of the fresh scrubber water and synthetically prepared spent scrubber water. 4_. Spent Alkflli. Scrubber Hater Treatment and Discharge: Spent scrubber water would need processing through cooling towers or spray ponds to reduce heat and free available chlorine content. The scrubber water would then have to be transferred via force main to the existing sewage outfall pumping station on the southside of the island fcr discharge with the sanitary sewage. Mixing sanitary sewage with spent scrubber water would further reduce the heat and free available chlorine content to levels acceptable for discharge. The outfall discharge point would be near the north-south axis of the island and approximately 500 feet from the shore. 5_. Scrubbed_E_ff_l_uent Gas ..Character/ PJ_schar(je_: Scrubbed effluent gases would be free to undetectable levels of herbicide feed ester, acids, and TCDD. Expected hydrocarbons would be unchlorinated pyrolyzates whose total concentration is less than 0.30 i.g/1 . Inorganic quality of scrubbed ef20 �fluent gases would be excellent: particuletes, <0.1 grains per standard cubic foot, consisting of scrubber water salts and negligible amounts of carbon particles; carbon dioxide, 12-13% by volume; carbon monoxide, '1.0% by volume; water vapor, <50% by volume; nitrogen oxides, <100 ppm; and essentially free of hydrogen chloride. The scrubbed effluent gases would be discharged via stack on the incinerator site on the west end of the island. (b) Sea Hater Scrubber 1_. Treatment: A scrubber system, utilizing sea water as the scrubbing liquid without an alkali agert, could be used for removal of carbon particulates and hydrogen chloride from the combustion gas. Water absorption devices are used to collect hydrogen chlorides gas in the manufacture of hydrochloric acid. Such devices are also used as gas emission control systems. 2_. S£r^^er^Wa_ter_ _Ch_ara_cter: The heat, hydrogen chloride, suspended carbon particles, and hydrocarbon "pyroTyzates and hydrolyzate mass loadings in the spent sea water scrubber wou":d be sinilar to those obtained with alkali scrubbers. In this system, however, the absorption and reactions of hydrogen chloride would make the scrubber water very acidic. For example, if 500,000 gallons of sea water were 100 percent efficient in absorbing 18.5 tons of hydrogen chloride during each day's burn, the resulting spent scrubber water would be about a 1.0 percent HC1 solution and have a pH of <1 . Incineration of the 2.3 million gallon herbicide stock would result in the release via a sea water scrubber outfall of about 3,700 tons of hydrogen chloride into the receiving water environment. 3_. Scj^bber_Water__pi_schar_ge: The acidic nature of the scrubber water would preclude its discharge with sanitary sewage due to material incompatibility with existing sewage pipeline. A seoarate discharge line and outfall would be required to insure that the reef is not affected by this acidic discharge. The outfall would be located either on the southside of the island beyond the location of the present sewage discharge or to the southwest of the island. 1- .s_?D!!k^.d_..EI/JiliIl.t_J'ai Cha^jtejVDisjrJiarge: The scrubbed effluent gas quality will be Yssent i ally the" s'afiie as~"that described for the alkaline scrubber except that the hyc'rogen chloride concentration may be greater. Assuming a 90 percent efficiency of scrubbing, some 370 tons of hydrogen chloride would be discharged in the exhaust gases. The discharge would be from a stack located at the incineration site on the west end of the island. c. Summary: Incineration systems can be used on Johnston Island to provide 99.999 percent efficient incineration of undiluted Orange herbicide. Discharge effluent streams will be free of herbicide feed constituents and TCDD to undetectable levels, see Appendices D and E. An incinerator system has been described which would incinerate the 2.3 nrllion gallons of herbicide in about 200 burn days and discharge the combustion gases from an exhaust stack on the west end of the island. Scrubbing of the combustion gases was discussed for completeness only and to demonstrate the quality and quantity of expected spent scrubber waters. 21 �D. FAILSAFE: operations are to protect the safeguards for 1. As with any process involving mechanical equipment, incineration subject to malfunction and therefore require adequate safequards environment and provide safety of personnel. The necessary each of the incineration options are discussed below. INCINERATION AT SEA a. Procedures and construction of facilities to transfer the Orange to the ship will be accomplished in a manner to preclude and contain any spillage/ leakage into the soil or waters. Procedures will include action to be taken during any unforeseen event resulting in the spillage of Orange. b. The ship has been constructed according to IMCO regulations and will meet current U.S. Coast Guard requirements regarding loading and carriage of hazardous liquid cargoes. Her double hull and double bottom provide added containment protection from collision or other marine hazards. Crew quarters are not located above cargo space, and the incinerator is located on the stern at a safe distance from the crew quarters. Fuel oil for the ship's engines is isolated by double bulkhead from the waste cargo tanks. c. The vessel is designed so that liquid waste cargoes can only be on-loaded via pumps on shore. Once loaded, shipboard pumps are only capable of discharging the "liquid wastes directly into the combustion chambers. However, international regulations require that in the event the safety of the vessel and crew may be threatened, there must be some means of discharging the cargo directly into the sea. This could be effected through gravity release valves which remain officially sealed in normal circumstances. d. Incinerator system monitoring and control of operational parameters have the following failsafe items: (1) Electric waste pumps will not operate to feed herbicide to an incinerator's burners if that incinerator's combusticn chamber temperature falls below 1400°C. If such a situation occurs, the incinerator malfunction is corrected and the combustion chamber temperature is returned to above 1400°C with fuel oil before any herbicide is reintrocuced. (2) An incinerator's burner is automatically shut down if any of the following conditions fall below preset levels: the air feed pressure to a burner, the herbicide feed rate to a burner, and the flame .intensity of the burner. (3) Operational controls and monitoring panels are manned at all times by an engineer whose sole ship responsibility is operating and maintaining the incinerator system at the desired combustion parameters. 22 �2. PRINCIPAL ALTERNATIVE - INCINERATION ON JOHNSTON ISLAND a. The incinerator complex will be constructed so that all transfer operations, such as transfer of Orange from the drums to storage or feed tanks, will be accomplished in a curbed or diked area to insure containment of spills. Procedures will be instituted so that spillage will be minimized during maintenance operations and so that operations will cease if any leaks develop in transfer systems. b. The incinerator will be instruirented so that the combustion zone temperature will be constantly read-out and recorded. An automatic system will be included to notify the incinerator operator if the prescribed temperature condition is violated; upon notification, procedures will provide for immediate cut-off of fuel (Orange). The incinerator w:ll be operated by qualified personnel continuously during an incineration of Orange herbicide. The fuel feed rate, air flow rate, and certain operating pressures will be read-out and recorded at prescribed intervals. Any deviation fron acceptable values will require immediate cut-off of the fuel feed. Possible accidental modes will be investigated and procedures will be written for action to counter the situation. These procedures will provide for the inrnediate cut-off of fuel. c. Real-time stack gas monitoring will be incorporated into the final design. Monitoring of combustion gas temperature and inorganic parameters (carbon monoxide, hydrocarbons, etc.) to determine concentrations and efficiency will be accomplished because of concern for -he environment of Johnston Island. A system of operator notification in the event of unacceptable levels will be included. d. The incinerator system will be run by electric power. Probable power failure modes will be identified and investigated, and procedures will be developed for system shut down and corrective action. 23 �E. HERBICIDE DEDRUM/TRANSFER AND DRUM DISPOSAL 1. INTRODUCTION a. The proposed action, incineration at sea, will result in the accumulation of about 15,700 empty fifty-five gallon drums at NCBC and about 25,000 empty drums at Johnston Island. These drums will accumulate because the herbicide will be bulk loaded aboard the incinerator ship; the ship will be loaded once at the port of Gulfport and twice at Johnston Island. For the principal alternative, incineration at Johnston Island, the Orange stored at Gulfport will be shipped in drums to Johnston Island; therefore., about 40,000 empty drums will result from an incineration operation at Johnston island. These empty drums will require disposal, and, in either case the ultimate drum disposal will consist of recycling the drums as "scrap steel" into steel manufacturing. Recycling as scrap steel is in accordance with the EPA preference for smelting as expressed in their comments to the revised draft environmental statement (Appendix 0), and recycling is also deemed to be within the intent of the recommended EPA guidelines on disposal of pesticides and pesticide containers (39 FR85). b. For the proposed action, Incineration at sea, it is planned that the incinerator ship be bulk loaded at a rate equivalent to 1000 drums per day. Facilities are being designed at NCBC Gulfport and at Johnston Island by the Naval Ordinance Station MD to accommodate this transfer operation. To obtain data relative to this operation, the EHL(K) has conducted ecological surveys at NCBC Gulfport and Johnston Island, and conducted an Orange herbicide drum draining experiment at Gulfport. During the drum draining experiment, personnel from the EHL(M) conducted air sampling for the herbicide in the immediate work area occupied by the personnel performing the drum draining experiment. The ecological survey at NCBC revealed that the normal flora in proximity to NCBC are not generally susceptible to damage from Orange herbicide vapors. The transfer operation is presently planned for the winter months when the plant life would be least susceptible to damage from herbicide exposure. Therefore, the transfer operation oan be accomplished with little or no concern for herbicide vapor control as regards phytoxicity at NCBC and the surrounding area. The air sampling conducted during the drum draining experiment revealed that the atmospheric concentrations of Orange vapors (0.6 ppbv for 2,4-D and 0.4 ppbv of 2,4,5-T) were well below the ACGIH Threshold Limit Values (TLV) of 10 mg/cbm for 2,4-D acid (1100 ppb v ) and 2,4,5-T acid (960 opbv). These very low results were anticipated because the vapor pressure of Orange is only 3.6 x 10"1* mm mercury at 30°C, and therefore the atmospheric saturation concentration is calculated to be 470 ppbv. This is the maximum concentration attainable by vaporization, and it is well below the above mentioned TLV. While it is realized that the surface area available for vaporization will be greater during the actual transfer operation than during the drum drainage experiment (16 drums), the concentration of Orange is expected to remain at least an order of magnitude below the TLV during the transfer operation. Therefore, the atmospheric concentration to which some unprotected project personnel will be exposured during the 16 day project will be below the acceptable value for an occupational life time exposure. The low concentration of Orange in the atmosphere exisiting in the drum draining area will bo rapidly decreased by diffusion and dispersion as this air moves downwind, thus the transfer project could be accomplished with little or no concern for herbicide vapor control 24 �as regards exposure to either project or non-project personnel. Despite the predicted ecological and personnel safety of the operation, it is the Air Force's intention to insure that all appropriate action is taken to minimize the emission of herbicide vapors and, therefore, minimize any possible impact upon personnel or the environment. Also, the controversie.1 situation which has surrounded the use of Orange herbicide ("The Effects of Herbicides in South Vietnam, Part A," National Academy of Sciences, 1974) dictates that any herbicide exposure to personnel or herbicide loss to the environment should be minimized. The action to accomplish this at NCBC Gulfport will consists of protective clothing, mechanical ventilation, and where required the use of cartridge type respirator protective devices. Concerning the latter, Orange herbicide has a very strong, persistent phenol-like odor that is present below the TLV and which can be very disagreeable to personnel. At Johnston Island the precautions will be similar; however, ventilation will not be required because the natural ventilation will be adequate and the environmental impact of vapors from the transfer operation will not be significant. At both locations, a monitoring program will be conducted to document herbicide exposures and environmental affects should they occur. It is anticipated that this program will generate sufficient data to demonstrate the personnel and environmental safety of this operation. For the principal alternative, the NCBC Gulfport bulk transfer operation will not be required and the Johnston Island operation will be expanded,. However, under the principal alternative, the dedrum rate would probably be "owered to about 200 drums per day (Part II.C.3.) as opposed to the 1,000 drums per day required under the proposed action. c. The drum experiment at NCBC Gulfport revealed that about 1.5 pounds of herbicide remains in a well drained drum. Tnis quantity when carried as a film on "scrap drum metal" into the furnaces associated with steel manufacturing is of negligible environmental significance. However, to eliminate any potential for adverse environmental impact during the shipment and storage period between drum drainage and placement of the scrap metal into a furnace, action will be taken to reduce the quantity of residual Orange in the drums. At NCBC, the drums will be drained and rinsed with solvent; the solvent, will be allowed to drain, and the drums will be crushed for storage and subsequent disposal. At Johnston Island, the drums will be drained and then allowed to weather, i.e. be exposed to the environment, after which they will be crushec for storage and subsequent disposal. This action, solvent rinse and weathering, while of questionable necessity as regards environmental impact is being accomplished in keeping with the overall intent of minimizing the potential for adverse environmental impact from the disposal project. Details of the drum draining/cleaning procedures, transfer operation, and recycling of the drums are presented in the following paragraphs of this section. 25 �2. HERBICIDE RESIDUAL IN DRAINED DRUMS a. General^ Data obtained during the incineration project at the Marquardt Co.~TAppendix E) and the Orange herbicide drum draining experiment conducted at IOC have indicated that about 1.0 and 1.5 pounds of herbicide, respectively, remains in a well-drained drum. Most of this residual was removed effectively from the drum by rinsing with a solvent - about 83 per cent removal after 3 rinses of JP-4 (Marquardt Study) and greater than 97 per cent removal after 4 rinses with diesel fuel (Gulfport Study). The diesel fuel appeared to be a more effective solvent for the Orange than did the JP-4. Rinse schemes involving various volumes of fresh rinse solvent and different numbers of rinses were investigated and it was found that the initial solvent rinse was responsible for practically all of the Orange which was removed by the rinsing process. It was also found during the Gulfport test that weathering, i.e. allowing the drained drums to remain exposed to the environment, could reduce the Orange residual in the drums markedly. The drums which were deheaded, drained, and weathered for 14 days prior to the rinse protocol had about 0.32 pounds of herbicide remaining and similiarly drained and weathered notched drums averaged about G.66 pounds of herbicide remaining. It was concluded that the Orange residual ir the notched drum was removed more slowly by weathering than such residual in deheaded drums. A comparison of draining efficiency between drums which were opened by being "deheaded" or "notched" revealed no significant differences and it was concluded that either method was acceptable. The notched drums actually contained slightly less herbicide than the deheaded drums as revealed by the rinse analyses. The deheaded drums were drained in an essentially vertical position and the notched drums were drained at about a 300 angle. The drum draining experiments are described below. b. The MarquardtJ^ompany - Drum Draining: During the test burn conducted at the Marquardt Co., the 28 drums involved were drained and triple rinsed with various quantities of JP-4. Samples of each rinse were collected and analyzed for 2,4,D and 2,4,5-T esters. Tie quantity of Orange in each rinse was back calculated and extrapolated to determine the quantity of Orange remaining in a drained drum. The data analysis and discussion of these experiments are contained in the Marquardt Co. Final Report, in (Appendix E). Less than two quarts of Orange remained in the dru-ns after initial emptying and some of the emptied drums had been sitting in a vertical position for 20 - 25 days when the draining was started. Each drum was upended and allowed to free board drain through the bung; the draining was continued until the steady dripping stopped. The drain time ranged from 6 to 9 minutes and the air temperature during the drum draining was 60°F. The data analyses revealed that approximately one pound of herbicide remains in a drum after drainage under the above conditions. In addition, a single rinse with five gallons of JP-£ removed about 75% of the herbicide from the drum. The second and third rinse (5 gal) increased the removal efficiency to approximately 79% and 33% respectively. The rinses were accomplished by adding the required JP-4, replacing the cap, and rotating the drum on a drum rolling device for five minutes. c. NCBC, were conducted of these tests after draining Gulfport. Drum Draining: On 1C and 11 September 1974, tests on 16 Orange herbicide drums at NCBC Gulfport MS. The purpose was to determine the quantity of Orange remaining immediately for a specified time. In preparation for the tests all but 26 �3 to 9 gallons of herbicide was removed from the drums. These drums remained in a vertical position until the draining test; however, just prior to starting the drain experiment on a given drum, that drum was rotated on a drum spinning device to coat the interior of the drum with herbicide to simulate realistic drum draining conditions. The drums were opened by a manual "notcher" device or deheaded with an electric device. The notcher device leaves a hole in the head of a drum which is similar to the hole left by an opener/spout for one quart cans of motor oil. Unlike a typical can opener which removes only the lid, the deheading device cuts off both the head and the associated "lip". Upon opening, the deheaded drums were drained in a vertical position and the notched drums at a 30° angle for from 10 - 18 minutes. The volume of herbicide dripping from the drum after 5 minutes of draining was caught and measured volumetrically until the diesel fuel rinse w&s accomplished. A representative portion of the diesel fuel rinse was collected and subsequently analyzed and the quantity of Orange in the drum back calculated. In addition to the immediate rinse test, some drums were stored for two weeks after drainage and then rinsed so that the effect of evaporation could be evaluated. This action was taken because inspections of the empty drum storage area (drums which contained Orange but were drained because they were leaking) at Johnston Island have revealed that this area does not have a strong odor of Orange and that the individual drums appeared relatively clean and dry. It is felt that evaporation of Orange from the drums is responsible for significally reducing the Orange content of an empty drun. At Johnston Island, the drums could be allowed to weather after a complete draining, thus providing for additional reduction of the Orange remaining in a drum. The Gulfport data although somewhat variable was sufficient so that va"id conclusions could be reached on the Orange remaining in an unrinsed drum and on the efficacy of solvent rinsing. The Gulfport data is most important to actual plans for 'drum handling and the appropriate findings were stated in paragraph 2(a) above. 3. HERBICIDE DEDRUM AND TRANSFER TO INCINERATOR VESSEL a. Gulfport MS: Under the proposed action, incineration at sea, the 863,000 gallons 057700 drums) of Orange presently stored at NCBC Gulfport will be bulk loaded aboard the incinerator ship at the Port of Gulfport. A dedrum facility will be established at the NCBC and the bulk Orange will be transported via railroad tank car to the pier for loading aboard the ship. The dedrum facility will include a drum deheading and pumping station drainage racks, a solvent spray rinse station and a collection sump. Aircraft refuelers will be used to transfer the Orange from the collection sumps to railroad tank cars. The tank cars will be conveyed once per day during daylight hours to the pier where the Orange will be pumped aboard the incinerator ship. The facility will be designed and operated to dedrum and load 1,000 drums of Orange per day for a total of 16 days. The deheaded drums will be drained in a vertical position for at least 5 minutes, rinsec with high pressure solvent spray (~2 gal.), drained for 2 minutes and then crushed. The spray rinse solvent wil.l be collected with the herbicide and loaded onto the incinerator vessel. All transfer areas including the pier area will be protected to insure that any spillage of material is contained. Strict industrial hygiene measures will be adhered to throughout the operation. As stated in the introduction, the public and scientific controversy associated with Orange necessitates the maximum possible precautions and the documentation of environmental factors during the transfer operation. Approriate safety clothiig/equipment will be used in all operations. Local exhaust ventilation for the drum draining area will discharge 27 �through activated carbon which will absorb odors and further minimize the chance of damage to nearby flora. Ambient air samplers will be utilized to document conditions throughout the operation. The normal flora of the area will be continuously observed and its condition documented, and biomonitoring with selected plans will also be accomplished. All equipment and the railroad tank cars will be flushed with solvent at the completion of the transfer operation, and the flushings will be loaded aboard the incinerator ship for incineration along with the Orange. The Naval Ordinance Station, Indian Head, MD is responsible for the engineering design and installation of the transfer system and will oversee the actual transfer operation. b. Johnston Island: The 1.4 million gallons (25,000 drums) of orange presently stored at Johnston Island will be bulk loaded aboard the incinerator ship at Johnston Island. Two loadings to the ship will be required. The dedruming and ship loading rate will be 1,000 drums per day; approximately 13 days will be required for each load. A dedrwn facility will be established at the storage area on Johnston Island. The dedrum facility will include a drum drainage rack where the drums will be opened with a notching device for herbicide drainage into a collection sump. The Orange will be pumped from the sump to the aircraft refuelers which wil"! then transport the Orange to the pier where the Orange will be pumped onto the incinerator ship. To prevent Orange from entering the ocean, the pier transfer area will be configured to contain any spillage. The drums will be drained for at least 30 minutes. They will then be left to weather (at least 1 month) after which they will be crushed and stored for disposal, All equipment and refuelers will be flushed with solvent at the completion of the transfer operation, and the solvent will be loaded onto the ship for incineration with the Orange. Industrial hygiene measures and monitoring will be accomplished similarly to that described above for NCBC Gulfport. The Naval Ordinance Station, Indian Head MD is designing/co-ordination on the design and installation of the transfer and will oversee the transfer operation. 4. ULTIMATE DRUM DISPOSAL: a. The drums generated by accomplishment of either the proposed action, incineration at sea, or the principal alternative of incineration at Johnston Island will be disposed of by recycle as "scrap" metal into steel manufacturing. Disposal as scrap is considered more favorable from the long term environmental standpoint than disposal of unrinsed drums in a landfill because the Orange and its components would be rapidly destroyed in the steel making process. As the scrap drum metal is reprocessed into new steel, it would be subjected to high temperatures (~2900°F) for an extended period of time (~6 hours). This exposure is much more severe than,that which would be received if the non-combustible drums were subjected to incineration In a pesticide incinerator (2000QF, 2 sec) as defined by EPA in 39FR85. Recycle into steel not only conserves the drum metal but also raw materials for si;eel making are conserved. The utilization of one ton of scrap steel in the steel making process conserves about 4 tons of iron ore, coal, and limestone. Therefore the recycle of 45,000 - 50 pound drums as scrap will conserve approximately 4,500 tons of raw material. This method of ultimate disposal will also preclude the return of any Orange herbicide drums to manufacturers, formulators, or drum reconditioners for reuse. b. It has never been the Air Force's intention that the Orange herbicide 28 �drums be reconditioned for reuse. Beside the negative public relations aspect of reuse, the solvent requirements to affect a triple rinse as recommended by the EPA prior the reuse of containers (39FR85), concomitant complication and the expansion of the disposal project associated with such rinsing operations is not desirable. The solvent volume of 660,000 gallons for rinsing represents greater than one fourth the volume of the total Orange herbicide stock. Since this solvent would require incineration along with the herbicide the incineration phase of the project would be greatly expanded. The logistics of supply and handling of the solvent, including the drum rinse operation, would complicate the industrial management of the project. The freqjency of handling and the tremendous quantity solvent involved would increase the possibilities of a fire hazard and spillage or Orange contaminated solvent. In addition, the use of a large quantity of a petroleum solvent during a period of energy conservation is not a prudent action if it can be safely avoided. In this regard, the rinsing operation at Gulfport may be altered to minimize solvent use i.e. recycle, if appropriate. 5. POTENTIAL FOR ENVIRONMENTAL IMPACT a. Although the procedures described above wi"l be accomplished to minimize the potential for any environmental impact as a result of the herbicide transfer and drum disposal aspects of this project, it is necessary to consider the following situations: (1) The Orange residual remaining on the crushed drums which are put into the steel manufacturing process; (2) The Orange residual which remains on the drums while the drums are in storage and or being transported to the steel manufacturing site; (3) The operations at Gulfport and Johnston Island to reduce the Orange residual in drained drums. b. For the drums at Gulfport, it is anticipated that the pressure solvent rinse will remove greater than 90 percent of the Orange which remains after draining, thus a crushed drum may contain a residual of about 0.15 pound of herbicide. The first rinse of deheaded drums at Gulfport removed greater than 92 percent of the herbicide which was removed by the subsequent rinses. The third and fourth rinses removed almost negligible amounts of herbicide; therefore, the quantity removed in four rinses can be considered as being just slightly less than the actual Orange residual in a drum. Since the Orange residual after draining is a film on the interior drum surface it is anticipated that a pressure spray will be even more effective than simple addition of solvent with gentle mixing. c. At Johnston Island, the drums will be weathered for 30 days to allow for evaporation of a portion of the residual which remains after draining. It is anticipated that 30 days weathering at Johnston Island can reduce the residual in the drums to about 0.3 pound of herbicide. As indicated in paragraph 3.b. above the drums will be crushed after weathering for subsequent disposal as "scrap" for recycle in steel manufacturing. 6. ENVIRONMENTAL IMPACT a. The environmental impact associated with the placement of crushed drums containing a film of Orange of 0.15 to 0.3 pounds into a steel making furnace is not significant. During the pro:ess the Orange would be converted to essentially hydrogen chloride, carbon dioxide, and water. The air pollution 29 �control equipment normally associated with steel making operations would be sufficient to minimize any environmental impact of the combustion porducts. b. The environmental impact associated with the storage and transport of crushed drums which contain a residual of 0.15 to 0.3 pounds of herbicide is not significant. Since the herbicide is a film on the inner surface of the crushed drums, any evaporation would be retarded. The herbicide is not water soluble nor is it easily translocated by water, thus it would also tend to remain in the drums even if subjected to rainfall. c. The environmental impact associated with the solvent cleaning crushing, and storage of drums at NCBC Gulfport will net be significant. The solvent spray will rapidly reduce the Orange residual in the drum and the Orange removed will be contained within the solvent. The drums will be crushed after drainage of the solvent spray. The crushing of the druns will reduce the opportunity of any residual herbicide from entering the environment while the crushed drums await shipment to a steel manufacturing plant. It should be emphasized that the solvent spray cleaning process at Gulfport is being accomplished to minimize any environmental impact associated with the storage of drums at Gulfport and is not to be confused with the triple rinse recommended before reuse of pesticide containers. The use of "weathering" of the drums at Gulfport was considered as a means of reducing the Orange residual to an acceptable level for subsequent storage and transportation of the drums. A subjective evaluation of this method revealed that while a portion of the drums may be safely weathered, it was not environmentally prudent to weather the entire stock (15,700 drums) at NCBC; therefore the use of the solvent spray to minimize the potential for environmental impact is justified. d. The environmental impact associated with weathering of drums on Johnston Island is not significant. The storage area is located such that the prevailing winds would carry any Orange vapor immediately off shore and away from the island. About 5,000 drums which were emptied and drained as part of the regular maintenance of the Orange storage area have in fact weathered at Johnston Island with no noticeable environmental impact. 30 �F. CHARACTERISTICS OF THE HERBICIDE 1. PROCUREMENT SPECIFICATIONS: a. The USAF procured Orange under Purchase Description AFPID 6840-1, dated 23 February 1968, and Amendment 1, dated 11 April 1968. The Orange Purchase Description containing the changes and additions of Amendment 1 is quoted below: 1. SCOPE This purchase description prescribes requirements for an herbicide identified as Orange. The material is used as a systemic growth regulator to kill and defoliate vegetation. 2. APPLICABLE DOCUMENTS PPP-D-729, Drums: Metal 55-gallon, for shipment of noncorrostve material. MIL-H-51148, Herbi.cide N-Eutyl 2, 4, 5 Trichlorophenoxyacetate. MIL-H-51147, Herbicide N-Eutyl 2,4 Dichlorophenoxyacetate. MIL-STD-105, Sampling Procedures and Tables for Inspection of Attributes. MIL-I-45208, Inspection System Requirements. 3. REQUIREMENTS 3.1 Materials. The herbicide shall be composed of the following two ingredient materials. a. N-Butyl 2,A,5 Trichlorophenoxyacetate. b. N-Butyl 2,4 Dichlorophenoxyacetate. 3.1.1 The ingredient materials shall meet the following requirements: a. Specification MIL-H-51148, N-Butyl 2,4,5 Trichlorophenoxyacetate, except free acid will be .5% maximum by weight.* *Changed per Amendment 1 31 �b. Specification MIL-H-51147, N-Butyl 2,4 Dichlorophenoxyacetate except composition (purity) shall be 98.0% minimum by weight, acid equivalent shall not be less than 79.0% nor more than 8.0% and free acid shall be .5% maximum by weight.** 3.2 Finished Mixture (Orange). 3.2.1 Composition. 50% by volume N-Butyl 2,4,5 Trichlorophenoxyacetate 50% by volume N-Butyl 2,4 Dichlorophenoxyacetate 3.2.1.1 Tolerance. Tolerance range for amount of each composition ingredient contained in the final mix will be ±1.5% including the precision allowance for the analytical method used. a. Range for N-Butyl 2,4,5 Trichlorophenoxyacetate is 48.5 to 51.5% by volume b. Range for N-Butyl 2,4 Dichlorophenoxyacetate is 48.5 to 51.5% by volume. 3.2.2 Free Acid. A maximum of D.57 by weight. 3.2.3 Total Acid Equivalent (as 2,4-D Acid). 90.0% minimum by weight. 94.07! maximum by weight. 3.2.4 Specific Gravity. 1.275 to 1.295 at 20°/20°C. 3.2.5 Color. A Clear reddish brown color. 3.2.6 Weight per Gallon - 10.70 ± 0.08 Ibs at 20°C (55 gallons will weigh 584.10 to 592.90 Ibs on a 20°C basis).* 4. QUALITY ASSURANCE PROVISIONS 4.1 Test Methods. *Changed per Amendment 1 **Added per Amendment 1 32 �4.1.1 Composition. Determined by infrared spectrophotometer - Beckman IR-4 or equivalent. An official standard will be used to calibrate the spectrophotometer made up a known 50/50% by volume mixture of the 2,4-D and 2,4,5-T normal butyl esters. This standard for calibration and quality analysis work may be obtained from the government. Request for standards should be forwarded to: Defense Supply Agency Defense General Supply Center Directorate of Procurement and Production Richmond, Virginia 23219 The infrared analysis method is attached to this purchase description. 4.1.2 Free Acid. A sample is dissolved in 91% isopropyl alcohol and titrated potentiometrically with standard alkali solution to a pll of 4.5. a. Apparatus. (1) pH meter equipped with glass calomel electrodes. (2) Stirrer. b. Reagents. (1) Alcohol, isopropyl, 91% neutral. Use commercial 91% isorpopyl alcohol or mix 920 ml of 99% isopropyl alcohol and 80 ml of distilled water. (2) Sodium hydroxide solution, 0.1 N accurately standardized against potassium acid phthalate. (3) Buffer solutions for checking pH meter, pH 7. c. Procedure. (1) With a graduate or automatic pipet measure 100 ml of 91% isopropyl alcohol into a 250 ml beaker. Weigh 10 grams of sample into the alcohol. Turn on the stirrer and mix the solution. (2) Insert the electrodes of the pH meter and measure the pH of the solution. Titrate with 0.1 N NaOH solution to pH 4.5 and record the volume of titrant. If the initial pH is about pH 4..5, conclude that the herbicide is free of acid. 33 �d. Calculation. Calculate the percent free acid using the formula A = FxV _x_N "w" " A = percent free acid F = molecular weight of acid x 100 1000 V = milUliters of 0.1 N sodium hydroxide N = normality of sodium hydroxide used W = weight of sample in grams 4.1.3 Total Acid Equivalent. a. Ingredient Specifications MIL-H-51148 and MT.L-H-51147. The saponification back titration method or the biphenyl reagent with chloride titration meLhod will be used to determine total acid equivalent, b. The final Orange mix. Determine total acid equivalent using the biphenyl reagent - chloride titration methods. 4.1.4 Specific Gravity. Determine by hydrometer or other method accurate to three significant figures. 4.1.5 Color. Visual observation of a 10 ml sample in a 16 mm x 125 mm glass tes. tube. 4.1.6 Weight per Gallon. Specific gravity calculation or other appropriate weight: measurement. 4.2 Responsibility for Inspection. Unless otherwise specified In the contract or purchase order, the supplier is responsible for the performance of all inspection requirements as specified herein. Except as otherwise specified, the supplier may utilize his own facilities or any commercial laboratory acceptable to the government. The government reserves the right to perform any of the inspections set forth In the purchase description where such inspections are deemed necessary to assure supplies and services conform to prescribed requirements. 34 �4.3 Contractor Inspection System Requirements. Specification MIL-I-45208 applies. 4.4 Sampling for Test. Sampling shall be conducted in accordance with MIL-STD-105. 4.5 Acceptance.* Acceptance of the final Orange mixture will be based on test, results for conformance to requirements of paragraph 3.2. Test results for conformance to requirements of paragraph 3.1 will be reported. 5. PREPARATION FOR DELIVERY Packing and marking requirements shall be specified by the procuring agency. 6. NOTES * 6.1 This AFPID replaces AFPID 6840-1 dated 7 Nov 1967. 6.2 The ingredient material requirements contained herein (para 3.1.1) are based on Specification MIL-H-51147A (MU) and MIL-H-51148A (MU) dated 7 Nov 1966. b. The USAF procured Orange II under a separate Purchase Description which was unnumbered, undated and is quoted below: 1. Orange II shall be composed! of: a. 50 percent by volume N-Butyl 2,4 Dichlorophenoxyacetate conforming to MIL-H-51147A (MU) dated 7 Nov 1966 except acid purity shall be 99.0 percent minimum by weight and acid equivalent shall not be less than 79.9 percent nor more than 80.0 percent by weight, and free acid maximum 0.5 percent. b. 50 percent by volume of Isooctyl. 2,4,5 Trichlorophenoxyacetate confonring to MTL-H-60724 (MU) dated 1 M'ay 1967, except Eree acid maximum 0.5 percent. 2. The final herbicide mixture shall neet the following requirements: a. Specific gravity - 1,220 to 1.242 at 20°C. *Added per Amendment 1 35 �b. Free acid maximum - 0.5 percent by weight. c. Weight per gallon - 10.6 to 10.34 per gallon at 20°C. 2. CHEMICAL AND PHYSICAL PROPERTIES: All available reference data on the general properties of Orange herbicide are summarized and presented in Table II-l and 2. General properties of TCDD are presented in Table II-3; the statistical analyses for the TCDD content in the Orange herbicide stocks is discussed in paragraph 3. below. The following references were used in preparation of these tables: USAF EHL(K) a, 1973; U.S. Army, 1969; USAF RPL, 1972 (Dept. Agr.); USDA, 1972; USAF EHL(K) b, 1973. 3. STATISTICAL ANALYSES OF TCDD CONCENTRATIONS IN ORANGE HERBICIDE STOCKS a. Sampling from Johnston Island arid Gulfport: Two different types of sampling procedures were us~ed to supply samp'Tes to the Analytical Laboratory (Dow Chemical Co.). The Orange herbicide at Johnston Island could not be separated into identifiable processing lots. Therefore, two hundred separate samples were collected to represent the entire population of Orange at Johnston Island. It is assumed that these 200 samples were a random, representative sample of the population at Johnston Island. In contrast, the samples taken at Gulfport could be grouped to represent concentrations of TCDD in stocks supplied by certain manufacturers. Generally, six samples were taken to represent each manufacturer's stocks. There were seven major stocks at Gulfport. Specific gravity was assumed to be 1.285. b. Results of Johnston Island Analyses: At the time that the 200 samples were collected the inventory of Orange stock at Johnston Island was 26,689 fifty-five gallon drums. The arithmetic mean TCDD concentration was found to be 1.909 mg/kg; therefore, the total TCDD in the Orange stock at Johnston Island is estimated to be 13.63 kg. Figure II-l below demonstrates that the TCDD concentrations in the 200 samples from Johnston Island did not follow a normal distribution. Of the 200 samples, 153 or 76.5% contained TCDD concentrations of 1.0 mg/kg or less. Of the 200 samples, '95 or 97.5% had TCDD concentrations of 10.0 mg/kg or less. Only 5 samples (2.5%) had TCDD concentrations larger than 10.0 mg/kg. These larger values were 13, 17, 22, 33 and 47 mg/kg. None of these values were discarded as "outliers" in computing the arithmetic mean TCDD concentration of 1.909 mg/kg. c. Results of Gulfport Analyses: Table II-4is a compilation of the results of the TCDD analyses of the seven major manufacturer's Orange stock at Gulfport. The number of drums was obtained from the inventory at the time of the sampling. The calculations for weighted values were based on the following formula: average statistic = sum of each statistic times its weight sum of weighting values At Gulfport, the total milligrams of TCDD were 7,265,975.8. The total kilograms of Orange were 4,100,225.7 kg. The average concentration of TCDD was therefore 1.772 mg/kg of Orange. 36 �d - TCDD Content of Total Orange Herbicide Stocks: At the time of sample collection, the~total Air Force inventory "of Orange herbicide at Gulfport and Johnston Island was 42,015 fifty-five gallon drums or 2.3 million gallons. The weighted average concentration of TCDC ~'s 1.859 rng/kg. Therefore, the total amount of TCDD in the entire Air Force inventory is estimated to be 20.1 kg. 37 �TABLE II -1. GENERAL CHEMICAL/PHYSICAL PROPERTIES OF ORANGE HERBICIDE Pjrp£erty_ Orange_ . j .H 1 J L P"a9... BTU Content per Pound '1' 10,017 (^=00) Liquids at room temperature. Physical State Clear, reddish brown to straw color. Color Dark, rust-colored liquid of oily consistency. Appearance Soluble in diesel vuel and § organic solvents. Solubility Insoluble in water. 9 Freezing Point ( C) n 7 t0 § Unknown Flash Point 146°C (295°F) 1 .220 - 1.242 25°C 1.275 to 1.295 Specific Gravit Weight (Ib/gal 10.2 (+0.09) (@20°C) 10.7 (+0.08) Total ester 7.6" 8.6 Acid equivalent -3.6 x lO'^nim llq ft Vapor Pressure (30°C) Vi iscosity, centipoises 0 unknown ,000 unknown 940 unknown 390 o.o°c unknown 134 10.0°C 43 67 23.8°C 27 24 37.7°C Viscosity, centipoises 0:13) 46 20°C 24 30°C 18 35°C 14 40°C 11 45°C Theoretical % Weight' 49.11* Carbon 52.12t 29,87* Chlorine 27.27t 16,37* Oxygen 15.20t 5.41** 4.55** Hydrogen 0.5% maximum Free Acid (by weight) 0.5% maximum 79.9% minimum Total Acid Equivalent 90.0% minimum 80.0% maximum (% by weight as 2,4-D) 94.0% maximum Moncorrosive on most metals. Deleterious Corrosiveness to some paints, natural rubber, and neoprene. Teflon, viton, polyethylene and * :'£:& *Samp"le contaTnecl 14 pp'm" kyJ-yJL ™!?..k§L j*i£_ j^iisJ^jiL tSample contained 3.7 ppm TCDD. ttCalculdted arid confirmed by E!IL(M). **Calculated by EHL(K), Kelly AFB TX as (100-i:C,Cl ,3 weight parents). 1. 2. 3. 4. USAF EIIL(K) a, 1973. U.S. Army, 1969. USAF RPL, 1972 (Dept. Agr.). USDA, 1972. 38 �Table II- 2. GENERAL CHEMICAL/PHYSICAL PROPERTIES OF INGREDIENT ESTERS OF ORANGE HERBICIDE Normal Butyl Tso-octyl RbrmalBlTtyl" Property 2,4-dichloro- 2,4,5-trichloro- 2,4,5-trichloropherioxyacetate phcnoxyacetate phenoxyacctate NB 2,4-D NB 2,4,5-T 10 2,4,5-T Purity (ester by weight) 98.0% minimum 95% minimum 95% minimum Appearance Clear, reddish brown liquids Acid Equivalent 79.0% minimum (by weight) :o80.0% maximum 78-82% 66-69.5% Free Acid (by weight) 0.5% maximum 0.5% maximum 0.5% maximum Specific Gravity(2QO/20o) 1.316 to 1.340 1.200 to 1.220 29(1,2,3)* Freezing Point (°C) -21 to -23 Molecular Weight 277.15 367.71 311.60 Ci2Hl4Cl203 Molecular Elements C16H21C1303 C12H13C1303 Structural Formula ci Cl Cl foj C10H HO 1 II O-C-C-O-C^lIg H H 0 1 II O-C-C-O-C^Hg 11 (o) H 0 1 II 0-C-C-O I H Theoretical % Weight Carbon Chlorine Oxygen Carbon Chlorine Oxygen Hydrogen Heat of Formation(3) (cal/mole) 57.99(4)* 25.60(4) 17.33(4) 52.01** 25.58** 17.32** 5.09** -152,000*** 46. 23(4)t 34.14W/-I15.4l(4)-|46.26** 34.13** 15.40** 4.21** -159,000*** 52.24.W 28.94J4J 13.'06(4) 52.26** 28.93** 13.05** 5.76** Considered by EHL(K) to have been an error in the reference. tSame value for ester containing 0.1 ppm of 2,3,7,8-tetrachlorodibenzo-pdioxin ("Dioxin" or TCDD). **Calculated by EHL(K), Kelly AFB TX 78241. * * ! .estimated by taking the heats of formation of similar compounds and *'. adding/subtracting the heats of formation of similar/dissimilar groups." 3. 4. USAF RPL, 1972. U.S. Dept. Agr., 1972. 39 �TABLE II-3. GENERAL CHEMICAL/PHYSICAL PROPERTIES OF TCDD Property Content in Orange or Orange II i Data Range 0-47 mg/kg. Estimated mean of 1.9 mg/kg with a 95% upper and lower confidence 5 limit of 2.6 and 1.2 mg/kg, respectively. ( ) i Molecular Weight Structural Formula 321.97 1 jk - ° VNci -o-Vcl Theoretical % Weight Carbon Chlorine Oxygen Hydrogen 44.77* 44.04* 9.94* 1.25* Calculated by EHLfKJ, Kelly AFB TX 4. b. U.S. Dept Agr, 1972. USAF EHL(K) b, 1973. 40 45.41(4> 44.61)4? 9.95(4) �49.,1 thru 50.0 > 39.1 thru 40,0 > -M "O •t— 29.1 thru 20.0 > 2 O) O (O O) 19.1 thru 20.0 > ^ 9.1 thruv 8 10.0 > 0 thru 1.0 •4- 100 50 150 Number of Samples in Concentration Cell FIGURE II-l HISTOGRAM REPRESENTATION OF TCDD CONCENTRATIONS MEASURED IN 200 ORANGE HERBICIDE SAMPLES FROM JOHNSTON ISLAND. 41 �TABLE 11-4 TCDD ANALYSES OF MAJOR MANUFACTURER STOCKS - GULFPORT Mg/Kg Coric. of TCDD Cumulative Total Mg ' of TCDD Number of Drums Number of Gallons 2,652 145,860 709,500.1 <0.05 35,475.0 35,475 6,981 383,955 1,867, 554 ..7 0.12 224,118.6 259,593.6 934 51,370 249,876.7 0.17 42,479.0 302,072.6 1,560 85,800 417.353..0 C.32 133,556.9 435.62b.5 2,185 U.'O.l 75 584,561.7 7.62 4,454,360.2 4,889,985.7 984 54,120 263,253.4 8.62 2,269,244.3 7,159,230.0 30 1 ,650 8,026.0 106,745.8 7,265,975.8 15,326 Kg Orange 842,930.0* 4,100,225.7 13.3 Mg of TCDD 7,265,975.8 * Represents 98% of the 860,000 gallons of total Gulfport Stock. �4. TOXICOLOGICAL AND ECOLOGICAL CHARACTERISTICS OF CHLOROPHENOXY HERBICIDES PERTINENT TO POTENTIAL BIOLOGICAL EFFECTS OF N-BUTYL ESTERS OF 2,4-D AND 2,4,5-T: There have been many scientific studies to determine the behavior of chlorophenoxy herbicides in plant and animal systems under varied environmental conditions. The following paragraphs are not meant to list all those studies. Rather, the purpose is to logically describe the known and probable behavior of Orange herbicide components in biological systems by utilizing the most current and relative information obtainable from the literature and from studies at EHL(K). It is important to note at the outset that in biological systems and aquatic systems the N-butyl esters (NBE) of 2,4-D and 2,4,5-T can hydrolyze. Thus, the behavior of the pure acids and their salts are also pertinent and will be discussed in the following paragraphs along with characteristics of ester forms. The differences in toxic effects produced by the various salts, amines and esters of 2,4-D and 2,4,5-T can often be explained on a pharmacokinetic basis in which the concentrations at the receptor sites in the organism depends on the absorption and distribution rates in relation to the rates of metabolism and excretion. The rate of absorption into plants or animals will be dependent upon various interrelated factors such as route of entry and rate of membrane transport. Specific membrane transport rate will depend upon the characteristics of the membrane in relation to the size, shape, polarity anc lipid solubility of the particular herbicide molecule being considered in each cited study. a. Behavior in Terrestrial Animals (1) Metabolism and Excretion Kinetics: Most of the data derived from acute toxicity studies indicate that neither 2,4-D nor 2,4,5-T are particularly toxic. (Gleason e_t aJL, 1969; Bjorklund and Erne, 1966). In the rat, the single dose, LD5Q ranges from about 250-270 mg/kg depending on the forms of the chemical administered (Christensen, 1971). Several workers have suggested that part of the reason for this lack of toxicity is that the excretion of the herbicices is very rapid in most mammals (Clark et^ a\_., 1964; Khanna and Fang, 1966). Most studies indicate that animals possessing highly developed renal function will rapidly eliminate 2,4-D and 2,4,5-T by active tubular secretion. Cattle and rabbits, which normally actively metabolize compounds mostly by acetylation, excrete 2,4-D and 2,4,5-T in the urine mostly unchanged. Erne, (1966) found that in the rat, rabbit, calf and chicken, 2,4-D and 2,4,5-T had a biological half-life varying from three to twelve hours and that urinary excretion Wc.s the most common route of elimination. Data exist to indicate that only very small amounts of 2,4-D are metabolized by the rabbit (Clark £rt aJL, 1964; Khanna and Fang, 1966). Berndt and Koschier (1973) studied the in_ vvtro uptake of 2,4-D and 2,^-,5-T by the renal cortical tissue of rabbits and rats." Renal cortical slices from both species accumulate 2,4-D and 2,4,5-T with greater uptake occuring in rabbit tissue. Nitrogen and various metabolic inhibitors reduced the uptake thus indicating that both of these organic acid herbicides are transported by the renal organic anion mechanism. Berndt and Koschier (1973) concluded that renal tubular transport by the organic anion mechanism may account for the relatively rapid disappearance of these compounds and this may account for their low toxicity. 43 �(2) Absorption and Distribution: The most common route of accidental absorption of cHlorophenoxy"Herbicide in terrestrial animals is via ingestion. This is especially true in herbivores. However, absorption of toxic doses via inhalation and cutaneous routes is possible, if uncommon. The literature indicates that gastric absorption of 2,4-D and 2,4,5-T and their amines and alkali salts occur readily as would be predicted from classical Henderson-Hasselbalch relationships.However, the gastro-intestinal absorption of 2,4-D in the form of an ester may be incomplete. Erne (1966) administered 2,4-D ester orally and found no detectable esters in the plasma. However, detection of low levels of 2,4-D in the plasma indicated that some hydrolysis of the ester had occurred. Erne (1966) in studies with rats, calves, chickens, and pigs found that the highest tissue levels of 2,4-D and 2,4,5-T were found in liver, kidney, lung and spleen, the levels sometimes exceeding the plasma level. In blood cells, 10-20% of the plasma level was found.. Penetration of 2,4-D into adipose tissue and into the central nervous system was restricted, whereas a ready placental transfer was demonstrated in swine.. The distribution pattern did not show any significant species or--in rats—sex differences. Klingman ejt al_.(1966) measured ppb amounts of 2,4-D in the milk from cows grazing on pasture prooably sprayed with esters of 2,4-D. However, these levels dropped to undetectable amounts (< 1 ppb) on the third day after the pasture had been sprayed. (3) Acute Toxicity: One of the essential prerequisites in the selection of a herbicide forDefoliation programs is selective toxicity. Orange herbicide is characterized by a low order of toxicity to man and terrestrial animals. When properly applied, chlorophenoxy herbicides have presented very minimal hazards to animal life in target areas. The acute oral toxicity of Orange herbicide is summarized below. The data are expressed as LD5Qs in units of mg of chemical per kg of body weight. This is the single oraT dose which was lethal for 50% of the test species. Orange herbicide LD™: rat 566, sheep 250 and cattle 250. The oral toxicities of 2,4-D and 2,4,5-T are quite similar to those of Orange herbicide (e.g., the acute oral LD5Q of 2,4-D and 2,4,5-T in the rat are 620 and 480 mg/kg, respectively). Tables II-5 and II-6 summarize the results of several acute toxicity studies with various salt, ester and amine forms of 2,4-D and 2,4..5-T. (4) Chronic Toxicity: Because of the active secretion of chlorophenoxy herbicides, rather large amounts must be administered over a long period of time to produce symptoms of toxicity. Enormous amounts of Orange herbicide were applied to test plots at Eglin AFB without visible toxic effects or development of herbicide residues in the native animals in the test plots (Young, 1973). In one sttdy, (Palmer and Raceleff, 1964) sheep were given 2 gm of the acid daily and sacrificed on the day following the final dose. Residues in the tissues were less than 1 ppm in all tissues and usually less than 0.05 ppm, which was the sensitivity of the analytical method. Mitchell and co-workers (1946) pastured sheep and cattle on treated foliage without harmful effects to the animals. They also fed a lactating cow 5.5 gm of 2,4-D daily for 106 days without producing poisoning. Palmer (1963) found that cattle were not harmed by 112 daily doses (administered 5 days each week) of 5 mg/kg of alkanolamine salt and that 44 daily doses of 200 mg/kg or 20 doses of 250 mg/kg were 44 �TABLE II-5 ACUTE TOXICITY OF 2,4-D DERIVATIVES TO TERRESTRIAL ANIMALS DERIVATIVE ANIMAL DOSE Alkanolanine Chick 380-765 mg/kg L Isopropy" ester Rat 700 mg/kg LD Rowe, .et _al. (1954) Isopropyl ester Chicks 1420 mg/kg LD Rowe, .et.il. (1954) Isopropyl ester Guinea pig 550 mg/kg LD Rowe, £t _a_K (1954) duty! ester Rat 620 rng/kg LD Rowe, £t _al_. (1954) Butyl ester Guinea pig 848 mg/kg LD Rowe, et _aj_. (1954) Butyl ester Chicks 2000 mg/kg LD Rowe, et _aj_. (1954) PGBE Rat 570 mg/kc LD Rowe, et _al_. (1954) Acid Dog 100 mg/kc LD 50 Rowe, _et _al_. (1954) Acid Chick 541 mg/kg L°50 Rowe, et aj_. (1954) Triethane!amine Swine 50 mg/kg No effect Bjorklund & Erne (1966) Triethanelamine Swine 500 rrig/kg Lethal Bjorklund & Erne (1966) Butyl ester Swine 100 mg/kg No effect Bjorklund & Erne (1966) Triethane 1 amine Cnicken 300 rng/kg No effect Bjorklund & Erne (1966) Butyl ester Rat 620 mg/kg L°50 Edson est_al. (1964) Isopropyl ester Rat 700 mg/kg LD Hayes, (1963) Unspecified ainine Mallard duck 2000 mg/kg LD 50 Tucker & Crabtree (1970) Aciu Pheasant 472 mg/kg LD 50 Tucker & Crabtree (1970) Acid Mule deer 400-800 rrg/kg LD5Q Tucker & Crabtree (1970) 45 EFFECT »5U 50 50 50 50 50 50 50 50 REFERENCE Rowe, et _aj.. (1954) �TABLE I I -6 ACUTE TOXICITY OF 2,4,5-T DERIVATIVES TO TERRESTRIAL ANIMALS ANIMAL, Acid UOS Rat 500 mg/kg EFFECT LD50 REFERENCE Rowe & Hymas (1954) Isopropyl est r Mice 551 nig/kg LDcn Rowe & Hymas (1954) Butyl ester Mice 940 mo/ kg LDcn Rowe & Hymas (1954) Aruyl ester Rat 7bO me-/ kg LDun Rowe & Hvmas (1954) �required to produce fatal poisoning. Palmer and Radeleff (1964) reported that sheep were given 481 daily doses of 100 nig/kg doses of 2,4-D without producing poisoning. 2,4,5-T has not been investigated as thoroughly as 2,4-D, but the reaction of cattle and sheep to massive doses would indicate that absorption and excretion must follow a similar pattern. A study by Palmer and Radeleff (1964) showed that sheop required 369 doses of 100 mg/kg each to induce intoxication. The above resu'ts are summarized in Table II-7. b. Behavior in Humans: Gehring _et a]., (1973) studied the effects of 2,4,5-T at a dose level of 5 mg/kg ingested directly or in a slurry of rnilk. Analytical grade 2,4,5-T having a purity of greater than 99/o and containing less than the detectable level O.OE ppm, of TCDD was used. Complete medical histories, physical and laboratory studies were accomplished before and repeated after the study. It was found that the clearances of 2,4,5-T and the excretion from the body were by first-order rate processes with halflives of 23.10 and 23.06 hours, respectively. Essentially all of the ingested 2,4,5-T was absorbed into the body and war, excreted unchanged in the urine. Following ingestion, 65% of the 2,4,5-T remained in the plasma where 98% was reversibly bound to the plasma proteins. "No untoward effects associated with the ingestion of 5 mg/kg 2,4,5-T were detected in any of the subjects." (Gehring et a_l_. , 1973) A metallic taste lasting 1-2 hours following ingestion was reported by most of the subjects. It was also conduced that essentially all of the ingested 2,4,5-T was absorbed and then eliminated unchanged in the urine. c. Deh_avio_r in Aquatijc_Systejiis_an^d _A_qujtic Anjinals_ (1 ) Me t a_b o 1 i s in and _D i s t r i butjp n (a) GeneraJ Comparisons,_: The behavior of the chlorophenoxy herbicides in non-mammaTi ah" aquatic animals is quite different than the behavior described for terrestrial mammals and birds. The herbicides have a greater toxic potential for aquatic anima's. First, the route of entry is different in most instances. The aquatic animal absorbs the herbicide which is dis:ributed throughout his total environment (absorption is mainly via gills in fish). Then, the differences in renal function must be considered. Generally, non -mamma 1 i an aquatic animals do not have highly developed kidneys. Thus, once the herbicide is in the aquatic animal's body, some metabolic changes must occur ; n the molecule to make it more polar if it is to be excreted. Toxicity testing is also necessarily different with aquatic animals. Usually, aquatic animals are placed in a concentration of the toxicant to gradually absorb the material at a rate depending on the animal's Dhysiology and the behavior of the toxicant in the particular water conditions Therefore, the actual dose to each an'nial is not known in most studies with aquatic animals. In contrast, toxicity studies with terrestrial animals usually allow calculation of a known dose per unit weight of each animal. Thus, toxicities are often reported as "LDXX" (Lethal Dose) for terrestrial animals and "LCXX" (Lethal Concentration) for aquatic animals. (b) Metabol_i_sm_ in_Fish: Donald P. Schultz (Fish-Pesticide Research Laboratory, Bureau of Sport" Fisheries and Wildlife, 1973) studied the uptake, distribution, and dissipation of 14 C-label dimethyl amine salt of 2,4-D (DMA-2.4-D). Three species of fish were exposed to 0.5, 1.0 or 2.0 nig/1 concentrations of herbicide for up to 84 days exposure period. No mortalities 47 �TABLE II-7* CHRONIC TOXICITY OF 2,4-D AND 2,4,5-T DERIVATIVES TO TERRESTRIAL ANIMALS Chronic Toxicity of 2.4-D ANIMAL. DOSE 21MCIM EFFECT REFERENCE None Bjorklund & Erne (1966) Triethanolamine Swine 50/mg/kg/da.y 3 doses Triethanolamine Swine 50/mg/kg/day 8-10 doses Minor trans- Bjorklund & ient effects Erne (1966) Butyl ester Swine 50/rng/kg/day <5 dcses Triethanolamine Swine 500 ppm in feed. 1 month Bjorklund & Some locomotory dis- Erne (1966) turbance, depressed growth rate, no gross pathology Triethanolamine Rats 1000 ppm in water 10 mos. Depressed Bjorklund & growth rate, Erne (1966) no gross pathology Triethanolamine Chicken 1000 ppm in water Daily from Egg size nor- Bjorklund & hatching mal, produc- Erne (1966) tion reduced through first 2 mos, 30% of egg production Alkanolamine Sheep 100/mg/kg/day 481 days No effect Palmer & Radeleff (1964) Alkanolamine Cattle 50/mg/kg/day 112 days No effect Palmer & Radeleff (1964) PGBE ester Sheep 100/mg/kg/day 481 days No effect Palmer & Radeleff (1964) Ethylhexyl ester Cattle 250/mg/kg/day 14 days 111 in 3 Hunt, et al. days, survive (1970~T & recover from 9 doses. 14 doses lethal. Ethylhcxyl ester Sheep 250/mg/kg/day 17 days Ill in 3 Hunt, et aj. days, 17 doses (1970) lethal 48 None Bjorklund & Erne (1966) �TABLE 11-7 (Continued). DERIVATIVE "Chronic Toxicity" ANIMAL DOSE DURATION EFFECT Ethylhexyl ester Sheep & Cattle 100/mg/kg/day 10 days None to minor effects Not specified Dog 500 ppm in feed 2 years Not specified Rat 1250 ppm in feed 2 years No effects House, et al on growth, (1967F survival hermatology or tumor incidence Not specified Rat 500 ppm in feed 2 years No effects in House, et al. reproduction (1967F studies Alkanolamine Chicken 100 mg/kg/day 10 days No effect on Palmer & Radeweight gain leff (1969) PGBE ester Chicken 50 mg/kg/day 10 days None Cattle Acid Mule deer 80 and 240 mg/kg/day 100 mg/kg/day Hunt, et al (19707" House et al ( 19677" No effect on Palmer & Rade- weight gain PGBE ester REFfRENCE leff (1969) ID days No effect Palmer & Radeleff (1969) 30 days Minor symptoms no weight loss Tucker and Crabtree (1970) Chronic Toxicity of 2,4,.5-T DOSE DURATION EFFECT REFERENCE FORMULATION ORGANISM Not specified Dog "0 mg/kg/day 5 days per Minor weight Drill & wk. for 90 loss, no other Hiratzka de.ys effects (1953) Not specified Dog 20 mg/kg/day 5 days per Lethal between Drill & ivk. for 90 11 and 75 days Hiratzka (1953) days PGBE ester Cattle 100 rng/kg/day 10 days None Palmer & Radeleff (1969) PGBE ester Sheep 50 mg/kg/day 10 days None Palmer & Radeleff (1969) 49 �TABLE II-7 (Continued). "Chronic Toxicity of 2,4,5-T" ' DOSE DURATION Sheep 100 mg/kg/day 359 days (dosed by cap- Palmer & Radesule) 111 at leff (1969) 367 doses, lethal at 369 PGBE ester Chicken 100 mg/kg/day 10 days No effect on weight gain Palmer & Radeleff (1969) Tr i e thy 1 cirri ne Sheep 100 mg/kg/day 431 days No effect Palmer & Radeleff (1964) Not specified Mice 21 mg/kg/day 600 ppm in diet. 4 weeks 18 months No mortality Innes, et al. FORMULATION ORGANISM PGBE ester * From Oregon E.I.S. (EIS-OR, 1973) 50 EFFECT REFERENCE �occurred, nor were adverse biological effects observed at these exposure levels. The highest radioactive residue found in muscle tissue occurred in Bluegills exposed to 2.0 rng/1 for 84 days (1.065 mg/kg). However, gasliquid chromatography indicated that over 90£ of the radioactive residues consisted of metabolites of 2,4-D. The major metabolite in the fish was found to be 2,4-D glucuronic acid conjugate. Current investigations have found at least six metabolites of 2,4-D in fish. Thus, in contrast to many of the organochlorine pesticides which undergo biomagnification through the food chain, DMA-2.4-D is iretabolized in fish without accumulation of the parent compound. (2) Behavior in Aquatic Systems (a) Solubility Limits and Rates Vs. Hydrolysis Rates: The esters of 2,4-D or 2,4,5-T found in Orange h~srb'icide" have" a very limited solubility in water. Because of this very low solubility, the actual concentrations of esters produced in a body of watisr by accidental contamination would likely be much less than the "expected value" calculated from the volumes involved. The USAF EHL(K) is in the process of studying the behavior of Orange herbicide in aquatic systems especially sea water. In one study using artificial sea water*, Orange herbicide was mixed into the water in an amount equal to 150 mg/1. Had all components gone right into solution, by computation, ester concentrations would have been 64 mg/1 (2,4-D NBE) and 61 mg/1 (2,4,5-T NBE). The actual, measured concentrations were 2 mg/1 (2,4-D NBE) and 1.8 mg/1 (2,4,5-T NBE) immediately after mixing. These increased to 18 and 22 mg/1 of 2,4-D NBE and 2,4,5-T NBE, respectively, at 24 hours and then started a rapid decline to 7.5 and 9.5 mg/1 at 48 hours after mixing. The rate of disappearance of the ester of 2,4-D was fairly rapid and was assumed to be mainly a result of hydrolysis. The half-life of the ester was 15 hours. The addition of natural biota such as bacteria, algae and fish would be expected to produce ar even faster disappearance of 2,4-D NBE. Evidence that this occurs was observed in studies EHL(K) is conducting with marine animals at the National Marine Fisheries Laboratory in Port Aransas, Texas. In one of these studies, shrimp were exposed in five different concentrations of 2,4-D NBE and natural sea water. The average half-life of the ester in the five concentrations was 5 hours. This was 1/3 of the half-life observed in the situation where no biological systems existed. (b) Circulation ofj|ater_in Relation to Availability of Herbicide for Absorption: Tome oTtTie toxicvFy'stuches completeTTo far " indicate the complexity of trying to predict the ecological results of a planned or accidental contamination of a body of water with phenoxy herbicides. At EHL(K), Orange herbicide was mixed in a fish tank at a concentration that would theoretically produce a 200 ppm v / v concentration if such a high concentration were possible. Most of the herbicide rapidly sank to the bottom of the tank after mixing. Fathead minnows placed in the tank showed no ill effects during two weeks of exposure. Yet in a toxicity study under the same conditions but with continuous agitation of the water by aeration, all of the fish died in a "20 ppm concentration" of Orange herbicide water in 24 hours. Subsequent studies revealed that some circulation of the *Instant Ocean Aquarium Systems, Inc., East Lake, Ohio 51 �water was essential if a dose-related response was to be established in toxicity studies with the N-butyl esters of 2,4-D and 2,4,5-T. Thus, the actual effect seen in nature might well depend on a factor such as the degree of mixing in the affected body of water. (c) Importance of Hydrolysis: It is important that when the esters of 2,4-D and 2,4,5-T Tiydrolyze, their"toxicity to aquatic animals is decreased by almost a factor of 10 (paragraph (3)(b) below). In the static situation described in the paragraph above (no aeration), the rate of hydrolysis was probably faster than the rate that the ester went into solution so that lethal concentrations were never attained. Toxicity studies with freshwater and saltwater animals at EHL(K) have been the, so-called "Static Bioassay" . in which no attempt is made to maintain a constant concentration of the herbicide ester in each test chamber. "Concentrations" are theoretical and based on volumes of herbicide and water mixed together rather than from analysis of water'to quantitate the herbicide. Most studies reported from literature are of the same type. The toxicity tests a"; EHL(K) revealed that in both freshwater and saltwater, nost of the test organisms had responded at twelve hours of exposure. There ^as rarely any increase in mortality past 24 hours. (d) Other Factors Affecting Actual_Cpncentratioj^: Many other factors can influence tHi~concentration oO-'butyl esters of'T^HD and 2,4,5-T in a body of water. In studies where large amounts of Orange herbicide were placed in water, the globules of the herbicide appeared to become coated with an opaque material that may have inhibited the ester from going into solution. Cope (":970) treated ponds with 0.5 ppm to 10 ppm propylene glycol butyl ether ester (PGBE) of 2,4-D. He was able to treasure residues of herbicide absorbed or adsorbed in vegetation and bottom sediment for 6 weeks after treatment in the 10 ppm treated pond. Crosby (1966) reported that 2,4-D decomposes rapidly in the presence of water and ultraviolet light. (3) Toxicity (a) Factors Affecting Toxicity: The toxicity of the chlorophenoxy herbicides to aquatic"animals varies considerably with many factors such as water chemistry variables, temperature, and the particular salt, ester or amine form of the herbicide considered. Soecies susceptibility varies greatly. For example, the 96-hour TI_5Q* for fathead minnows exposed to DMA2,4-D was found to be 335 mg/1. Yet, for bluegills and channel catfish the TLrQ values were 177 and 193 respectively. A temperature increase from 17°C to 20°C increased the relative toxicity to the catfish from a TLrn of 193 mg/1 ou to 125 mg/1 (Schultz, 1973). (b) Toxicity Comparisons, ty EHL(Kj.: The USAF EHL(K) (1974), performed static toxicity studies ~witTf Orange "herbicide. Also, toxicity studies were performed using each individual N-butyl ester of 2,4-D and 2,4,5-T. Freshwater bioassays using the fathead minnow (Pimephales promelas) resulted in a 48 hr LC™ of 3.4 ppm for Orange herbicide containing 14 ppm TCDD. The 48 hr LC^s for esters of 2,4-D and 2,4,5-T were 2.8 ppm and 5 ppm respectively. The 48 h^LC™ for 2,4-D in the minnows was 270 ppm. The 2,4,5-T 48 hr LC5Q concentration was 333 ppm. Note that the toxicity of ester formulations were considerably more toxic than the respective acid. Also, EHL(K) found the N-butyl ester of 2,4-D to be more toxic that the N-butyl ester of 2,4,5-T. *See page 47 for explanation of TD and LC 52 �In salt water studies by EHL(K), the 48 hr LCrn values in the shrimp (Penaeus sp.) were 5.6 ppm for 2,4-D NBE and 33 ppm for 2,4,5-T NBE. Oysters (Crasso'strea vTnjinicaJ were exposed to -'potential concentrations'1 of 2,4-D NBE ranging from" 0..5 "pp:n"to 85 ppm. The only acute effect observed was the death of one of the oyster (10%) in the highest concentration at 48 hours. (c) . t £ . A . ! .! ? aM P..tiL(-r. M.t§T:ts: Many otner aquatic 9^r.OlPa.. animals besides fish can ~be affected by phencxy herbicides. Saunders (1971) studied the effects of the propylene glycol butyl ether ester (PGuL) of 2,4-D on six freshwater crustaceans. He found the following 48 hr TLgQ values: Daphnia magna = C.10 ppm, seed shrimp = 0.32 ppm, scud = 2.6 ppm, sowbug = . 2.2 ppm, glass shrimp = 2.7 ppm, and crayfish had an unknown value larger than 100 ppm. Cope (1970) studied the chronic effects of PGBE ester of 2,4-D on the bluegills. Survivors of ponds treated with high concentrations (10 and 5 ppm) had a 2 week delay in spawning. For pathologic lesions, hightreatmer.t fish had earlier and more severe effects than did low-treatment lish. The pathology involved the liver, vascular system and brain. Remarkably, growth of the fish was faster in the ponds receiving the high-treatment than in the lower-treatment ponds. Tablet II-8 and II-9 were extracted from a U.S. Forest Service Fnvironmental Impact Statement (t'JS-OR. 1973). "The taoles indicate the effects of heroicides on other aquatic species ana point out some toxir: p-Tfects that can be measured other than death of the organisms. d. Behayior i ri Plants (1; Distribution and Metabolism: Orange herbicide is a systematic herbicide that"Vffecfs 'plants' by a'Tibrmonal type of action usually described as "auxin-like" or "auxin-type". Auxins are any of a group of substances which promote plant growth by cell elongation, bring about root formation, or cause bud inhibition or other effects. 2,4-D and 2,4,5-T are compounds of this type. When applied to leaves of a plant, chlorophenoxy herbicides are absorbed through the cuticle into the plant system. The N-butyl ester forms of 2.4--D and 2^,4,5-T found in Orange herbicids are usually more effective than more polar forms becajse of better absorption into the plant. This is also demonstrated in Yamaguchi's work (1965) in which he found that 2,4-D moves into plant leaves better from acidic solutions than from alkaline solutions. Approximately ten times as much 2,4-D was abosorbed from a medium having pH 3 than one with pH 11. 2,4-D has a pK of 2.8 and would be highly disassociated at pH 11. Once the herbicide is in the plant it is translocated to areas where food is being stored as in rapidly growing new roots and shoots. The chlorophenoxy herbicides can be stored in certain cells of the plant. Also, metabolism occurs through degradation of the acetic acid side chain, hydroxylation of the aromatic ring, or conjugation. *TL50 and LC5Q (Tolerance Limit and Lethal Concentration) are concentration values statistically derived from the establishment of a dose-related response of experimental organisms to a toxicant. The LC is based on a measured response of death only. The TL is based on a count of unaffected organisms. The subscript number for both indicates the percent response expected for the calculated concentration. Therefore, in most cases, the TL™ = LC,-Q or the concentration in which 50% death is expecteo. Note that a more toxic chemical has a smaller LC5Q. 53 �TABLE H-8 ACUTL EFFECTS OF 2,4-D DERIVATIVES UPON AQUATIC ANIMALS DERIVATIVE ANIiMAL Isooctyl esters Bluegill (From 3 manufacturers) PGBE ester CONCENTRATION EFFECT "10-31 ppm 48 TLm REFERENCE Hughes & Davis (1963) Bluegill 17 pprn 48 TLm Hughes & Davis (1963) butoxyethanol ester Bluegill "1 .4 ppm 48 TLm Hughes & Davis (1963) PGBE ester Snrirnp 1 ppm (48 hrs) 20% mortality Butler (1965) or paralysis PGBE ester Fish (salt water) 0.32 ppm 48 hr TLm Butler (1965) Alkanolamine Salt Bluegill 435-8^-0 ppm 48 hr LC5Q Lawrence (1966) uimetnylamine Salt Bluegill 166-458 ppm 48 hr LC50 Lawrence (1966) Isooctyl ester Bluegill 8.8-59.7 ppm 48 hr LC50 Lawrence (1966) Dimethyl amine Salt Fathead Minnow 10 ppm 96 hr LC5Q Lawrence (1966) Acetarnide Fathead Minnow 5 ppm 96 hr LC50 Lawrence (1966) Oil soluble amine sal t Bluegill, 2 ppm Fathead Minnow 4 mo. LC10 Lawrence (1966) PGBE Ester* Bluegill, 2 ppm Fathead Minnow 4 mo. LC10 Lawrence (1966) Butoxyetnyl ester Bluegill & Fathead Lawrence (1966) Butyl and isopropyl esters, mixed Bluegill 1.5 - 1.7 ppm 72 hr LC 50 48 hr LC 50 N,N-Dimetnyl cocoami ne salt Bluegill 1,5 ppm 48 hr LC 50 Lawrence (1966) Etnyl ester Bluegill 1 .4 ppm Lawrence (1966) Butyl Ester Bluegill 1 .3 ppm 48 hr LC 50 48 hr LC 50 Isopropyl ester Bluegill 1 .1 pprn 48 hr LC 50 Lawrence (1966) *Propylene Glycol Butyl Ether 54 2 ppm Lawrence (1966) Lawrence (1966) �TABLE: n-9 NON-LETHAL EFFECTS OF 2,4-D DERIVATIVES UPON AQUATIC ANIMALS DERIVATIVE ANIMAL DOSE EFFECT REFERENCE tiutoxyethanol ester Oyster 3.75 ppm (96 hrs) 5Q% decrease in shell growth Butler (1965) Butoxyetnanol ester Snrimp 1 ppm (48 hrs) No effect Butler (1965) i Butoxyetnanol ester Fisn (salt water) 5 ppm 48 hr. TLm Butler (1965) riutoxyethanol ester Phytoplaikton 1 ppm 16% decrease in C02 fixation Butler (1965) Dimetfiylamine Oyster 2 pprn (96 hrs) No effect on shell growth Butler (1965) Dimetnylamine Snrimp 2 ppii (48 hrs) 10% mortality or paralysis Butler (1965) Dimetnylamine Fish (salt water) 15 pprn (48 nrs) No effect Butler (1965) Dimetnylamine Phytoplarikton 1 ppm (4 hrs) No effect on C0£ fixation Butler (1965) Ethylnexyl ester Oyster 5 ppm (96 hrs) 38% decrease in shell growth Butler (1965) Etnylhexyl ester Shrimp 2 pprn (48 hrs) 10% mortality or paralysis Butler (1965) 10 ppm (48 hrs) No effect Butler (1965) Etnylhexyl ester Fish (salt water) Ethylnexyl ester Pnytoplankton 1 ppm (4 hrs) 49% decrease in COo fixation Butler (1965) PdLit. ]/ ester Oyster 1 pprr. (96 hrs) 39% decrease in shell growtn Butler (1965) PGbE ]_/ ester Shrimp 1 ppm (48 hrs) No Effect Butler (1965) 4.5 ppm 48 hr TLm Butler (1965) PubL I/ ester I/ Fish (salt PGBE is propylene glycol butyl etner. 55 �(2) Toxicity: Once in the plant., herbicides act by interfering with the photosynthetic, respiratory, and other plant processes causing the plant to lose its leaves and ultimately die. Plant susceptibility to sublethal exposures of 2,4-D is markedly influenced by the growth condition of the plant and by environmental factors. Sine? most of the injury is expressed by growth response, the plant must be growing in order to show injury. In addition, plants in shaded areas respond more slowly than those exposed to direct sunlight. Because of these various factors which affect plant response to the 2,4-D type herbicide! differences in lists showing plant susceptibility should be expected. Orange herbicide is effective on a wide variety of woody and broadleaf plant species. Other lower p'lait forms can also be affected by auxin-type herbicides. Even unicellular algae exhibit toxic effects or die when exposed to 2,4-D or 2,4,5-T (Walsh, 1972). However, much higher doses of the herbicides are required than for plants with a more complex structure. (3) Merbj£ides_as Ajrr_PpJJut^nt_s: Although herbicides have long been accepted as environmental" pol'lut'ants which affect sensitive vegetation, the air pollution aspects of volatile herbicides have not been widely explored. However, there is growing evidence that some 2,4-D compounds may be present in the ambient atmosphere in some parts of the United States at levels sufficient to cause adverse growth effects on sensitive vegetation. During 1962 through 1964, Vernetti and Freed measured 2,4-D concentrations in air samples taken in an agricultural area of eastern Oregon. Concurrently, they surveyed for auxin-like plant darnags in the areas where the air samples were taken. In the spring of 1962, measured concentrations of the isopropyl ester of 2,4-D in the air ranged from 0.015 ppm to 0.64 ppn. This was during the time of year when the huge wheat fields of the area were being treated for weeds by aerial application of the isopropyl ester. Plant damage to tomato crops appeared to coincide with periods of highest measured concentrations of the isopropyl ester. Other plants, especially locust trees, also snowed growth regulator symptoms. Legislation in the state curtailed the use of the isopropyl ester and decidedly reduced the contamination and resulting plant damage. Laboratory studies by Vernetti and Freed indicated that 0.015 ppin would be the threshold concentration of isopropyl ester that tonato plants could be exposed to and still survive under -;he conditions of ths experiment. Vo"atility studies by the same workers demonstrated that the isopropyl ester was three times more volatile than the butyl ester. In fact, complex analyses of the air samples ruled out butyl and other esters of 2,4-D as principal contaminants. (4) ReljJ_ti_Ye Species JSensitivjjty: Different researchers vary in their results of relative plant sensitivity tD phenoxy herbicides. From field observations, grapevines and box elder appear to be among the most sensitive since they respond to 2,4-D air pollution when other plants showed no evidence of injury. Injury to grapevines may result from exposure to levels in the ppb range. Other workers report tomato plant damage in the ppt range. Walsh (1972) reports a 50% reduction in growth of unicellular marine algae exposed to phenoxy herbicide concentrations of 50 to 300 ppm. Other relative sensitivities are indicated in Table 11-10. 56 �TABLE 11-10. Scnsilmty of selected plants to 2,4-dichIorophenoxyacetic acid* Sensitive Apple Mulus, sp. Birch Retain, sp. Do\clder Acrr negiinJi', L. J)OJ!WL)Oll Cornus, sp. lilderberry Xmnbiicus, sp. l ? orsythia. rnr.\y:lii<i, sp. Grape , sp. Aster, wilil Xi/fr, sp. Cellar Cheny Primus, sp. Cherry, choke Pnmii'i I'irginitina,}.. Corn Zea mays, I.. Gladiolus Gliulioliu, »p. lloinlock Tsuga, sp. Hickoiy Carya, sp. l.auihs-quarlcis Cln-ni'piieliiim all tins, T.. l.iihlon ri/:<i, sp. Loiulnii plane tree Plmanus accriiolia (Ait.) V/illd. MapU', Norway /Irvr plutanoMrs, L. Oak, Hack QIUTCIIS vclntiiia, IJIHI. Sorivll Riimcr, sp. Suin.ic K/iii.t. sp. Tobacco Kicotiana, sp. Tomato Iycopersicon csculentum. Mill. Trceofliviiven Ailantlins altisu'ma, Mill. Wisteria Wisteria, sp. Yellow wood Cladrnstis liitcu, Koch /innia Zinnia, sp. MulbciTy Morns, s.p. Oak, pin Qiii'mm i>ii!ns!ri.\, T.. Oak, red P«iTrif.v ['tiliistris, L. Peiuh Primus I't-rsira, Sicb. & /lice. Potato Solarium tube.'osuin, T.. Privet Ligustnim, sp. Ragweed, giant Ambrosia trifida, L. Rhododendron Rhododendron, sji. Rose Rosa, sp. Spruce,, Colorado blue Pic ea pungfm, linjjhn. Pici'fi punai'tiv, linijlin. Sweetj'.inn Liquidambar styracifliia, 'L. Yew Tnvits, sp. Resistant Ash Frail'iiii, sp. llciin, lni>li /"/KiM'ti.'/iv viiliyirix, 1, s ISiwsirti flifiiicca, I.. * rj:.".pl:int Soliinitin incli-ngriui, L. Pi-ai Pyin.\ comniiiiiix. I.. I'eony Puconia, sp. Rhubarb Rheum iliapemticum, L. Sorghum Sorghum vulgare, Pers. FROM AIR POLLUTION CONTROL ASSOCIATION REPORT NO. 1 �t>. TOXICOLOGICAL CHARACTERISTICS OF TCDD: The word teratology has rather recently become quite familiar to biologists, chemists and certain other persons working in various scientific disciplines. It was applied to 2,4,5-T when studies by Bionetics Research Laboratory, Division of Litton Industries, Bethseda MD in 1969-70 implied that 2,4,5-T was teratogenic in mice and rats (Courtney e_t al_., 1970). Subsequently, studies revealed that a toxic contaminant was responsible for the findings originally attributed to 2,4,5-T. The sample of 2,4,5-T employed in the Bionetics study contained 27 ±8 ppm TCDD. Some studies have shown that oral administration of 2,4,5-T containing < 1 ppm TCDD produces no teratogenic effects on rats, rabbits, mice and other species. a. Toxicity to Animals: TCDD was found to be the most toxic chlorodibenzo-p-dipx1n studied. " It was found to have LDsgs in the vg/kg range for several species of animals and was acnegenic, highly embryotoxic and positive for the chick edema factor. "The no-effect dose levels for embryotoxicity and chick edema were 0.03 to O.lyg/kg/day respectively" (Schwetz et al_., 1973). (1) Acute Toxicity: Studies performed on TCDD by the Biochemical Research Laboratory, Dow" Chemical Co., can be summarized as follows with the data presented as the LDtjc inyg/kg of body weight for several species: rats 20-40; mice, males >64, females 130; guinea pig 0.6-2.0; rabbits -30; dogs >30 (RDWB et aj_., n.d.). The signs of intoxication are characterized by a chronic illness" and liver damage. Half of the deaths occur more than two weeks after treatment while some animals died after 48 hours. Excretion is primarily by way of feces and is very slow. The highest concentrations are found in the liver and fat with a smaller amount being found in the testes. The LD5Q for the rabbit is about the same whether administered intraperitoneally or applied to the skin. In the eye it does 'not cause corneal injury but does produce thickening of the lids. It does cause severe chloracne when applied to the ears of rabbits in yg qjantities. (2) Toxi_c_ Effects on the Fetus (a) Harrsters: Commercial samples of 2,4,5-T were shown by Collins and Williams (l97TTto"be feticidal and teratogenic in the golden Syrian hamster. Dose levels of 2,4,5-T ranged from 20 to 100 mg/kg/day while TCDD content varied from 0.1 to 45 ppm. Doses of 100 mg/kg/day of 2,4,5-T approach levels causing maternal mortality. (b) Rats: TCDD is highly embryotoxic in the rat. No effect was seen at a dose level of 0.03 yg/kg/day but at the 0.125 yg/kg/day dose level there was a significant incidence of fetuses with intestinal hemorrhage; fetal deaths and resorptions increased. Delayed skeletal maturation was seen. At 2 yg/kg/day there were few viable fetuses and the survivors had a high incidence of anomalies. At 8 yg/kg/day there was severe maternal toxicity and there were no viable fetuses. King ejt a] . (1971) studied the effect of 2,4,5-T and 2,4-D administered by gavage and an intrauterine technique using Sprague-Dawley rats as the test species. "Purified" and "technical" grade 2,4,5-T were applied to Millipore^ filters that were then placed on the amniotic sac of the embryo. ' "Purified" 2,4,5-T intrauterinely applied to 93 embryos on any one day of gestation from day 12 to 16 at a dose range of 50 to 120 ug per embryo resulted in no cleft palates. Substituting the 58 �technical for purified grade and using the same technique on resulted in two cleft palates. Oral administration of 2,4-D at a total dose range of 60 to 120 nig/kg to 245 rats yielded nine of which had cleft palates. Again, these are high dose 118 embryos and 2,4,5-T 2,231 fetuses, levels. a b. Industrial Exposure: Dow Chemical Co. prepared an extensive health inventory of 126 manufacturing personnel in an effort to identify harmful effects of inhaled 2,4,5-T. The inhalation rate of the agent was estimated to be from 1.6 to 8.1 mg/day/worker, depending on work assignment, for periods of up to three years. The survey indicates that no illness was associated with 2,4,5-T intake. In plants where 2,4,5-T contained a high proportion of TCDD, Bleiberg et a_l_. (1964) found 18% of the exposed employees suffered from moderate to severe chloracne, the intensity of which correlated significantly with the presence of hyperpigmentation, hirsutism and eye irritation. In the late 1940's a pressure overload resulted in the accidental rupture of a vessel containing the sodium salt of 2,4,5-trichloropheno'i, a precursor of 2,4,5-T. During the following months, 228 persons developed ch'loracne, not only plant employees, but members of their families including wives and children. In workers more intensively exposed as a result of the accident, chloracne appeared about two weeks followed by moderate to severe pain in the skeletal muscles of the legs, arms, back and breath, decreased libido and intolerance to cold. Comedones appeared in areas of adult hair which is not typical of juvenile acne. There were pustules on the face, neck, abdomen, back and scrotum. Serum lipids, prothrombin time and glucuronates were all elevated. Biopsy of peripheral nerves revealed destruction of myelin sheaths and in some instances nerve fibers. Hyperpigmentation, fatigue and marked nervous irritability appeared. Over a period of several months, all of the symptoms and findings, except the scars of acne, returned to normal after removal from exposure. Cases in the families of the workers probably resulted from contaminated clothing and poor personal hygiene. The causative agent was not identified at the time. However, in the light of current knowledge, it was almost certainly a polychlorinated dibenzodioxln and possibly TCDD (Suskind, 1973). 59 �c. * Evaluation of•—•-Toxicological •• •-——.-——•• Testing -——•-" "—• • • " — — —— (1) Requirement for Es tab!ishing posejjtelated_ Response: Insi stence on administenng'T^rnaximunf toTera'ted dose""'may" be™ terribly misleading if this is the only dose tested, as in the Eionetics study (Innes, et a1., 1969). There is no justification for abrogating the need to establish a dose-response relationship, which is fundamental to all toxicological experimentation. The route of administration is al" important in tests for teratogenesis. We are told that "Parenteral admiristrati on is an appropriate test route for pesticides to which humans are exposed by inhalation, or for pesticides which are syslenrically absorbed, following ingestion" (USDHEW, 1969) It is safe to predict that., by appropriate choice of dose, concentration of solution and frequency of administration by subcutaneous route, any chemical agent can be shown to be a carcinogen or a teratogen in the rat and probably in other laboratory rodents (Goldberg, 1971). (2) Ii°Q^J\c..s_Study_: Tne Bionetics study began with the observation that 2,4,5-T was" tTeVa tog erne" and feticidal in two strains of mice when administered either subcutaneously or orally and in one strain of rats when administered orally (Courtney et^ aj_., 1970). Analyses of the sample of 2.4,b-T that had been tested against the animals revealed the presence of 27 t8 ppm TCDD. Subsequent study of standard 2,4,5-T containing less than 1 ppm TCDD given to rats by gavage in doses up to 24 mg/kg daily, failed to reveal evidence of teratogenic or embryotoxic effects (Emerson et^al_., 1970). Under similar conditions, TCDD produced no effect at a dose of 0.03 i-g/kg/day while doses of 0.125 .jg/kg/day or greater manifested toxicity to the fetus and at 8,0 pg/kg/day to the mother also (Sparschu et al_., 1970). (3) Eyaluatirg Data from Animal Models: The metabolism of a test compound is a highly relevant"consTderat'iori in""teratogenesis. If the metabolic pathway in the test animal differs radically from that in man, then the results of a study are unlikely to be useful for the assessment of hazards arising from trace contaminants. The findings of teratogenesis or embryotoxicity has meaning only in the appropriate animal species (Goldberg, 1971). Theodor D. Sterling (1971) of the Department of Applied Mathematics and Computer Science, Washington University, St Louis, examined the difficulty of evaluating the toxicity and teratogenicity of 2,4,5-T from existing animal data. He notes that the question has been raised as to whether the herbicide 2,4,5-T is toxic and teratogenic to an extent to preclude its use, in this country at. least. Sterling states, "Although we can learn a great deal from animal experiments, toxicological and teratological information from animal experiments turns out to be much less useful, especially for making broad policy decisions, than is commonly thought." 60 �(4) Uesign of Recent 2,4,5j^T_Tq_xicity_ Studies: To quote Sterling (1971) agafh,""" 17. there"aVe'Tess tlian'' a"dozen "key" reports.. .of study on toxicity of 2,4,5-T, dating back to the early 1950's for the most part, and on its teratogenicity, mostly done in the iast two years. Whereas the toxicity studies were done at some leisure and the teratogenicity studies had some aspect of emergency about them, they are indistinguishable in their lack of adequate statistical experimental design and analysis of data." 6. EVALUATION OF ENVIRONMENTAL CONTAMINATION POSSIBILITY: The possibility that an extraordinarily toxic contaminant of a widely used herbicide may be sufficiently stable in the environment and soluble in fat or other tissues to enter food chains and ultimately the human diet is worthy of consideration. It was known, of course, that 2,4,5-T does not accumulate to any significant degree in animal tissues, but data on tissue storage of dioxin were not available. Chlorinated dibenzo-jj-dioxins long have been recognized as byproducts from the manufacture of certain chlorinated phenols. For example, 2,4,5-trichlorophenol is prepared industrially by the hydrolysis of 1,2,4,5tetrachlorobenzene at elevated temperatures and pressures, a process which can also result in the formation of traces of heterocyclic impurities including 2,3,7,8-tetrachlorodibenzo-p-dioxin if temperatures are permitted to exceed 160QC and if the reaction becomes alkaline. This dioxin is toxic, teratogenic and acnegenic and its presence appears to account satisfactorily for the alleged teratogenic effects of trichlorophenol derivatives such as the herbicide 2,4,5-T. a. Knowledge Available From Use: No proven instance of toxicity associated with 2,4,5-T intake" in'Tnan'Tias been found in agricultural or industrial workers known to nave had repeated, relatively high levels of exposure to 2,4,5-T of low dioxin content. The safety factor for the general population is estimated to be several orders of magnitude greater than tnat for 2,4,5-T factory workers. Data are too limited for a firm conclusion, but there is no evidence to suggest that TCUD as a contaminant in 2,4,5-T is likely to be encountered by animal or man in sufficient dosage to cause toxic reactions (Advisory •Committee, 1971). b. Application of Testing: "Since most chemicals under suitable laboratory conditions cou"ld"probably be demonstrated to have teratogenic effects, and certainly all could be shown to produce some toxic effects if dosage were raised high enough, it would not be reasonable to consider the demonstration of toxic effects under conditions of greatly elevated dosage sufficient grounds for prohibiting further use of a particular chemical" (Goldberg, 1971). c. Possibility of Pyrolytically Produced Contamination: The question of the formation of'TCDD "as a res'uTt" of "tfie pyrblysis or "Burning of wood, including brush treated with 2,4,5-T, has been a matter of some concern. Langer (1973) states, "The derivatives of 2,4-D, 2 S 4,5-T and Silvex as well as their sodium salts and esters have not produced dioxins in pyrolytic reactions whether carried out in the solid state, in the melt, or in solution. Even dfter conditions of extreme hydrolysis, followed by pyrolysis we could observe only trace amounts of dioxins." Langer (1973) further stated,"Even extreme conditions such as burning of treated wood or vegetation after the use of 2,4-LJ, 2,4,5-T, Silvex or their derivatives is not expected to produce detectable amounts of dioxins or dibenzofuran." However, in a memorandum dated 61 �July 30, 1973, Baughman arid Meselson (1973) reported that the pyrolysis of the sodium salt of 2,4,5-T at temperatures from 300 to 450°C for 30 minutes to 12 hours caused the formation TCDD ranging in concentrations from 0.1 to 0.3% (1,000 to 3,000 ppin). d. Evaluation by EPA Advisory Committee: The data are indeed very limited. NevertTieTess, certain cbncTus:ibns can~Ee made and these as made by the Advisory Committee on 2,4,5-T to the Administrator of the Environmental Protection Agency are, in part, as follows: (1) The herbicide 2,4,5-T does not accumulate in any compartments of the biosphere, nor does it accumulate in any animal tissues or products used for human consumption. 1C (2) The risk of human exposure to 2,4,5-T in food, air and water is negligible. (3) There is no indication that. TCDD accumulates in air, water or plants, although it might accumulate and remain active for some time in soils after heavy application of a highly contaminated sample of 2,4,5-T. (4) Less thc.n 0.2% of TCDD in soil is known to be absorbed into plants. (5) 2,4,5-T is rapidly excretec in animals studied using doses in the range of those likely to be encountered in the environment. (6) Limited data indicate that TCDD is also eliminated, at least some by metabolic breakdown, with a half-life of 20 days. (7) The solubility of TCDD in fat is limited which would preclude appreciable accumulation in body fat. 62 �PART III PROBABLE ENVIRONMENTAL IMPACT OF PROPOSED ACTION A. SUMMARY STATEMENT OF TOTAL IMPACT B. AIR QUALITY - b7 bb 1. DISPERSION MODEL STUDIES 2. ENVIRONMENTAL IMPACT 68 08 a. General • 68 b. Incineration at Sea 68 (1) Potentials for Impact (2) Probable Impact 68 68 (a) Hydrocarbons 69 1_. Dispersion Zone 2. Meteorological Model < (b) Hydrogen Chloride 1. Dispersion Zone ?. Meteorological Model (c) Carbon Monoxide (d) Participates (3) Monitoring 70 71 71 71 72 72 c. Principal Alternative - Incineration on Johnston Island (1) Potentials for Impact (2) Probable Impact a) Hydrocarbons ,b) Hydrogen Chloride (c) Pcrticulates I (3) Monitoring 73 73 /3 73 73 74 74 C. WATER QUALITY 76 1. PRESENT WATER QUALITY a. b. c. d. 70 70 76 Survey at Jchnston Atoll Water Sample Collection Biological/Sediment Sample Collection Sample Disposition -- 76 76 76 ^ (1) Water (2) Biological (3) Sediment 76 76 81 63 �e. Results of Analysis — - (1) Water — (2) Marine Biological and Sediment — f. Conclusionsg. Analytical Procedures 2. MOVEMENT 3. PERSISTENCE a. b. c. 81 81 81 — 81 81 • General Hydrolysis Photodecotiposition •• ••• 4. MONITORING METHODOLOGY5. ENVIRONMENTAL IMPACT - • -- d. Sorption e. Biological Degradation f. Summary-- --- • •- - • a. General -b. Incineration at Sea 8fc 90 91 91 91 - -- 92 93 - (1) Potentials for Impact-(2) Probable Impact (3) Environmental Monitoring at Sea 93 94 — - -- c. Principal Alternative -Incineration on Johnston Island — (1) No Combustion Gas Treatment 97 97 98 -- -- a_. Case 1: Entire Discharge-Reef Area b^. Case 2: Predicted Discharge-Reef Area(c) Monitoring - - (a) Alkaline Scrubber 1_. Potential for Impact 2. Probable Impact _3. Monitoring— -- 98 98 98 99 99 (2) Combustion Gas Scrubbers 64 94 95 97 97 (a) Potentials for Impact— (b) Probable Impact ]_. Open Ocean— 2^ Reef Area— 90 90 90 99 - 99 - 99 100 100 �(b) Sec. Water Scrubber-.....--- ..................... 101 1_. Potential for Impact ---------- ..... - ...... 101 2. Probable Impact-------—.......------------101 3_. Monitoring --------------- ....... - ........... 102 D. MARINE FLORA AND FAUNA ON JOHNSTON ISAL.ND ............. ----- ..... Iu3 1. SCOPE OF CONSIDERATIONS -------- ...... - ................. ------- 1U3 2. POTENTIALS FOR IMPACT ON AQUATIC PLANTS AND ANIMALS ......... U3 3. PROBABLE ENVIRONMENTAL IMPACT ON AQUATIC PLANTS AND ANIMALS-----.......-.....-......• .......... ------ ........ 103 a. Toxic Chemical and Acid-Base Effects (1) Incomplete Combustion Products ----- ...... - ......... lu4 (2) Complete Combustion Products-----...........-- ..... b. Thermal Pollution--- ......................... --- ....... c. Carbon Particle Effects ----------------------- ..... -----104 E. TERRESTRIAL FLORA AND FAUNA- ........ -.....................- ..... U6 106 1. FLORA OF ISLANDS............-----......----------............ lc/ a. Scope of Considerations -------- .................... ------ 1Qb 6 b. Potentials for Impact ....... --------------- ........ -----1Ub (1) Complete Combustion----------......- ...... ---- ......105 (2) Incomplete Combustion----------------.........-----106 (3) Accidental Spills-----------------------........- ..... c. Probable Impact-- ...... ------------------- ..... ---- ...... d. Monitoring Methodology for Air Contamination — ......... 2. FAUNA OF ISLANDS-..........-----------..........--- ..... ------107 a. Scope of Considerationsb. Potentials for Impact c. Probable Impact ........ F. SOIL (CORAL AND SAND)-----.....---------------------------......- 10ci 1 . MOVEMENT-.....---.........---------...........— ..... ------ ]jj° IUo 2. PERSISTENCE-.....................--------------......-.....— 65 �G. THE ECOLOGICAL SIGNIFICANCE OF JOHNSTON ISLAND: AUTHORATIVE OPINIONS - llW H. HUMAN WELFARE 112 I. BENEFICIAL ASPECTS OF THE PROPOSED ACTION 113 bfa �A. SUMMARY STATEMENT OF TOTAL IMPACT: The environmental impact is discussed in the following paragraphs for the proposed action of incineration at sea and the principal alternative of incineration on Johnston Island. In either case the incineration operation will destroy 99.9 to 99.999 percent of the herbicide. These efficiencies will insure that any unbirned or pyrolyzates of herbicide and its TCDD content will not have any significant impact upon the environment. Since the herbicide will be essentially destroyed, the environmental impact of the following major combustion products have been considered: water, heat, carbon dioxide, carbon monoxide, carbon particulates, and hydrogen chloride. These combustion products will be discharged directly into the atmosphere toward the west of Johnston Island over the open tropical ocean. Incineration in either case can be accomplished with mi'iimal environmental impact which will be transient and not significant. Incineration at sea has an advantage in that the beneficial uses of the environment in which the incineration takes place, i.e., tropical ocean, are limited. Under the principal alternative, incin2ration on Johnston Island, the beneficial usagesof the atoll are more numerous and must receive considerations of potential impact - particularly the drinking water source, reef and aquatic community, and bird refuge. 67 �B. AIR QUALITY 1. DISPERSION MODEL STUDIES: A dispersion study utilizing a meteorological model was accomplished by the USAF Environmental Health Lab, McClellan AFB. This study was for the emissions of hydrogen chloride and Orange herbicide for the proposed action of incineration at sea and the principal alternative of incineration on Johnston Inland. The study is presented as Appendix K. 2. ENVIRONMENTAL IMPACT a. General: The environmental impact on the air environment will be discussed for the~~proposed action and the principal alternative described in Part II. In either case, untreated combustion gases will be discharged directly into the atmosphere. The '-emote location of the incineration process combined with the high efficiency of*incineration indicates that the discharge of the combustion gases directly into the atmosphere will not result in any irreversible detrimental environmental impact. The absence of any inhabited land masses or agricultural based economies in the locale of the proposed combustion gas discharges is also favorable. Although the impact upon t.he atmosphere of unscrubbed combustion gases is minimal and transient, even this impact could be reduced for the principal alternative by using combustion gas scrubbers on Johnston Island. However, the impact of the spent scrubber wastewater discharge would be significant. In the analyses that follows, there is no consideration required for TCDD. If any TCDD were present in the combustion gases, its calculated concentration would be an order of magnitude below the analytical detectable limit (typically 0.20 nanograms/1). The additional dispersion of the combustion gas into the atmosphere will further decrease such concentrations. k- In£iJLer.atipn_at Sea_ (1) Potentials for Impact: The evaluation of the impact of the combustion gas will require consideration of the following combustion gas constituents: unburned or pyrolyzates of herbicide, hydrogen chloride, carbon monoxide, carbon particles, carbon dioxide, arid heat. The latter three constituents are discharged daily in considerable quantities (-3.0 tons, 1,000 tons, and ~1650°F, respectively) are not significant as regards impact on the environment. That is, the open tropical sea and atmosphere west of Johnston Island will readily absorb these quantities of carbon particulates, carbon dioxide, and heat during three - 7 to 9 day incineration periods. However, hydrogen chloride discharged at about 178 tons per day and carbon monoxide discharged at about 50 tons per day are toxic and were environmentally assessed. As presented below, the impact: of carbon monoxide discharge was minimal and negligible in comparison to the hydrogen chloride discharge. (2) ProbabLe^Jmpact: Atmospheric impacts of hydrocarbons, hydrogen chloride, carbon monoxide, and carbon particulates in combustion gas discharges have been assessed by using two approaches: 1) determining the average mass concentration which would be present in the atmosphere in the immediate zone of the incineration operation by estimating a "worst case" dispersion zone, and 2) determining the maxinum sea level concentrations at specified distances downwind from the incineration operation by utilizing a "worst case" meteorological model. Upon determination of such concentrations, judgments regarding the environmental impact are made. 68 �(fl) t!^.r2£arJ22rsj An efficiency of 99.9 percent Orange herbicide destruction has been applied to the shipboard incineration process. Therefore, a daily discharge of 0.576 tons of unburned or pyrolyzates of Orange herbicide must be considered for probable environmental impact. To gain a perspective of the environmental impact, the analyses have also been accomplished for efficiencies of 99.0 and 95.0 percent, i.e. a discharge of 5.76 and 28.8 tons, respectively, of unburned or pyrolyzates of Orange. It is noted that all resulting concentrations described for all the "worst case" analyses in the next paragraph are below the ACGIH threshold limit value of 10 mg/cbm for either 2,4-D acid (1,1 ppm) or 2,4,5-T acid (0.96 ppm) which has been established for occupational exposures. Since the RDES was published the Air Force has received information on incineration from the Antillian Incinerating Company N.V. of Curaco and the Hague Holland. This packet of information is entitled "Information/Data/Analysis Incinerator Ships Mathias I & II" and a portion of it is included in Appendix N. The following quote is taken from page 1 of the "Extract from Dr. Klaus Grasshoff of Kiel University's report on possible effects of burning hydrocarbons at sea" (Appendix N). "By means of extensive controlled measurements, the Bayer Company of LeVenhusen, Germany, has established that if burning of chlorinated hydrocarbons is carried out at a temperature hicher than 1000°C, more than 99.9 percent of the materials are completely burnt." The monitoring program conducted by the Bayer Co. is described below and this report is also included in Appendix N. Three separate mixtures of hydrocarbons cortaining chlorinated hydrocarbons were combusted at temperatures between 1400°C ard 1500°C during a 3 to 6 hour operating time. Combustion gas sampling and analyses revealed that the combustion efficiency in all three cases was greater than 99.9 percent. Bioassays conducted on condensates of exhaust gas collected during each burn were satisfactory. The Air Force has also received information concerning ircineration at sea which was generated by the French government as a result of recuests for authorization by Ocean Combustion Services (Vulcanus) and Incimer (Mathias I & II) to incinerate chlorine wastes (hydrocarbons and chlorinated solvents) produced by the chemical industry. This information (as translated)appears in Appendix N. The information includes data from a test burn of chlorinated hydrocarbons on the Mathias II and Vulcanus. The incinerative efficiency is attested to in the following quote: ..."The pyrolysis is then practically complete in the case of the Vulcanus." For the MathicS II, pyrolysis was also very efficient, but the unburned compounds included light molecular weight compounds and "tars" which are insoluble in water. The presence of the light compounds was attributed to the failure to maintain the required temperature throughout the incinerator. The presence of the tars was not accounted for. The French Environmental Agency proposed that ..."very soon a number of arrangements will be made so that the incinerator ships can operate from french ports, and inside a marine zone which will be specially designated for this use, with all precautions concerning the protection of the sea life." The Environmental Agencies also comment on the importance of knowing physical/ chemical characteristics, having test burn data from an incinerator and attaining the temperature for proper incineration, and the minimal environmental impact of chlorine and hydrogen chloride in the exhaust gases. The above is only a summary of the French document which is presented in its entirety in Appendix N. In addition to the above, information relative to the combustion efficiency of the Vulcanus for chlorinated hydrocarbons was presented at a public hearing in Houston TX on 4 Oct 74. The hearing was conducted by the EPA concerning a Shell Chemical Company application to utilize the Vulcanus for incineration of chlorinated hydrocarbon wastes. Mr. H. Compaan, Nationa" Research Council of the Netherlands, testified that tests aboard the Vulcanus revealed a combustion efficiency of 99.996 percent, the testimony appears in Appendix N. 69 �1_. Dispersion Zone: A "worst case" dispersion zone can be predicted by considering the wind speed, the speed and direction of the incinerator ship during incineration, and the mixing height for the material being dispersed. Forthese analyses the dispersion zone is based on a one knot wind speed, "crosswind" of the ship's course, 10 knot speed for the ship during incineration, and an effective mixing height of 50 meters above sea level. The ship's speed is realistic based on information received from the shipping company; the wind speed and effective mixing height are very conservative. For such a low wind speed, it is anticipated that the combustion gases would actually rise higher than 50 meters above sea level before thermal equilibrium is attained. The calculated daily area of this "worst case" dispersicn zone is 240 by 24 nautical miles with a calculated daily volume of about 1.0 x 101? cubic meters. Assuming uniform mixing, the concentration of unburned pyrolyzates of Orange in the zone described would be approximately 42 part per trillion by volume (pptv/y) at an incinerative efficiency of 99.9 percent (420 pptv/v for 99.0% and 2,100 ppt v - y for 95%). These concentrations represent the average mass loadings in the volume described and are not a function of distance/elevation from the source. As such, their interpretation is limited, however, average mass loadings of these calculated concentrations for a 22-26 day period would be acceptable for the environment affected. A meteorological model, next paragraph, has been utilized to determine sea level concentrations of the material downwind of the ship. The disposition of the unburned herbicide upon the ocean surface via fallout or plume/ocean interface reactions and its impact upon the ocean is discussed under Part 11 I.e., Mater Quality. 2_. Meteorological Model: Those analyses determine the concentration of unburned or pyrolyzates of Orange herbicide at/or near sea level downwind from the ship. Input conditions for the model were selected to insure that maximum sea level corcentrations would be attained. These conditions irclude a wind speed of -18 knots, a stationary ship, and a highly unstable atmosphere. The analyses revealed the maximum sea level concentration to be 0.81 ppby/y (99.9% efficiency) at 0.47 kilometers (km) on a line directly downwind of the ship (8.1 ppb , for 99.0% and 40.5 ppbv/v for 95%). At a distance of 10 km from the discharge, the sea level concentration will be approximately 19 pptv/v at an incinerative efficiency of 99.9 percent (190 pptv/v for 99% and 950 pptv/v for 95.0%). These unburned or pyrolyzate concentrations of Orange herbicide are not significant for the relatively small opan tropical sea atmosphere which would be affected. Additionally, the ship will always be moving, and although the volume of affected atmosphere will be increased, the downwind concentrations of these Hydrocarbons will be greatly reduced. See the vertical and horizontal distributions of these concentrations in Appendix K. (b) Hydrogen Chloride: The hydrogen chloride discharge, 178 tons per day is also analyzed using the "worst case" dispersion zone and the meteorological model as described above. 70 �!_• Dispersion Zone: Assuming the same dispersion zone as above.for hydrocarbons, the average mass concentration of hydrogen chloride in the zone would be 0.11 pprnv/v. The highly reactive nature of hydrogen chloride will result in considerable deposition of hydrogen chloride into the ocean; c. "worst case" analyses, in which all of hydrogen chloride generated, is discharged into the ocean in the ship's wake is presented in Part III, C, Water Quality. The dispersion zone is quite large due primarily to the distance which the ship travels during the ircineration. Limited data are available on hydrogen chloride dispersions over the ocean; however, information is available on hydrogen chloride emissions over broad, populated, land areas. For example in a study of air contaminant emissions in Niagara County, N.Y., it was found that 4,083 tons of hydrogen chloride were emitted into the atmosphere per year. Of this total 2,911 tons originated from processing plants, and 1,172 from the consumption of coal and oil for heating purposes. It is concluded that a discharge of 178 tons per day of hydrogen chloride by, an incinerator ship, for three periods of 7-9 days, will not cause any detrimental environmental impact to the atmosphere above the open tropical sea. 2_. Meteorological Model: This analysis determines the hydrogen chloride concentration at/or near sea level downwind from the ship. This information is jsed to evaluate the impact of the ship's discharge upon other possible uses of the area in which the ship is operating. However, it is emphasized that the ship will be required to incinerate in selected areas which will insure no interference with other uses of the area—particularly those o~ other ships. Using the same "worst case" situation for sea level concentrations as described for the hydrocarbon meteorological model, the maximum sea level concentration will be 2.28 ppm v /y and it will occur 0.47 km directly downwind of the ship. At a distance of 10 km from the discharge the sea level concentration will be about 50 ppb v / v . This analyses indicates that the sea level concentration does not exceed ~ne American Conference of Governmental Hygienst's Threshold Limit Value (ACGIH TLV) of 5 ppmv/v at any point downwind ofn the ship's discharge. Also, the downwind ground level zone in which low PP 'v/v concentrations exist is relatively small. The ship will be moving during the incineration operation and therefore the downwind concentrations will be even less than these presented for a stationary ship. For a wind which is crosswind at practically any angle to the ship's course, the downwind sea level hydrogen chloride concentrations will be reduced essentially to insignificance. The vertical and horizontal concentration distribution for the ship's hydrogen chloride discharge is given in Appendix K. (c) Carbon Monoxide: In analogous fashion to the models used above, the ship's daily discharge of about 50 tons of carbon monoxide were assessed. Average mass concentrations of carbon monoxide would be about 0.04 ppmv/v within the "worst case" dispersion zone. Maximal "worst case" sea level conconcentrations predicted by the meteorological model would be 0.8 ppmv/v at 0.47 km directly downwind cf the ship. This sea level concentration would decrease to about 18 ppbv/v at a distance of 10 km downwind. These predicted concentrations are very conservative because continued oxidation of carbon monoxide to carbon dioxide in the exhaust stack and discharge plume are neglected. The affected concentrations predicted by the meteorological model would actually be much smaller because the ship is not a stationary source. None of these predicted atmospheric carbon monoxide concentrations exceed the ACGIH TLV of 50 ppmv/v 71 �or ambient air quality standards: 9 ppm for eight hours only once a year or 35 ppn for one hour only once a year (National Primary and Secondary Ambient Air Quality Standard 40 CFR 50.8). Taking even the most conservative approach, the expected carbon monoxide discharges from the ship will cause no adverse impact on the environment of the open tropical sea. F9_r_y.cuJ_atJLS: The daily discharge of 3.0 tons of carbon particles is based on an" assumption of 0.5 percent .conversion of Orange to elemental carbon. With tie same "worst case" dispersion zone as assumed above, the concentration of suspended particulates would be several orders of magnitude less than dust concentration of clean country air (0.2 mg per cubic meter). In reality, the majority of the particles would be deposited on the ocean surface in a relatively small impact zone; this aspect has been considered in Part III, C, Water Quality. These discharges of particulates would have no significant effect: on the air environment. (3) Morntor.ijTS.: In view of the negligible impact predicted and the remoteness of the incineration area on the open tropical sea, ambient air monitoring is not considered necessary. 72 �c. Principal Alternative - Incineration On Johnston JLsland (1) Pote_nti_als_fo_r Jmp_ac_t: Consideration is given to the following combustion gas constituents": ""hydrocarbons, i.e., unchlorinated pyrolyzates of Orange herbicide and undetectable concentrations of herbicide feed constituents, hydrogen chloride, carbon particles, carbon monoxide, carbon dioxide, and heat. The latter two, while discharged at considerable quantities, 110 tons per clay of carbon dioxide and a stack gas temperature of - 1700°F, are not environmentally significant; in fact, they can be readily absorbed into the atmosphere. The carbon monoxide, while a toxic gas and estimated to be discharged at a rate of 5.5 tons per day, is not considered environmentally significant. This statement is based on a comparison between the mass discharge rates of the carbon monoxide and hydrogen chloride (18.5 ton/day) and the impact analyses for hydrogen chloride which is described later. If scrubbers were used, the general character of the stack gas would be improved and essentially no hydrogen chloride or carbon particulates would be discharged into the atmosphere. However, the scrubber wastewater discharge would have potential for environmental impact and is discussed under Part III. C, Water Quality. (2) Probable Impact: The potential atmospheric impact of pyrolyzates with undetectable herbicide feed constituents, hydrogen chloride, and carbon particulates are based on: 1) calculated average concentrations of these materials within a "worst case" dispersion zone downwind of the discharge point, and 2) predicted downwind concentration profiles provided by a meteorological model (see Appendix K). For the carbon particulates, only the dispersion zone analyses was accomplished. The dispersion zone is based on a wind speed of one knot (cairn) and a very conservative width and height of 100 meters. On a daily basis, the area of the zone would be 24 nautical miles by 100 meters and its volume would be 4.44 X 10s cubic meters. While seemingly large, this zone represents a "worst case" volume for dispersion and it is felt that the gases will actually disperse through a greater volume on a daily basis. Similarly, "worst case" conditions were chcsen for the meteorological model, i.e., wind speed of 13.6 knots and extremely unstable atmospheric conditions. (a) Hydrocarbons: Considering a 99.999 percent destruction efficiency of herbicide feed"," the daily mass emission of unchlorinated pyrolyzates and undetectable levels of feed constituents would be 1.2 pounds. This value is approximately three times that which was found in a test incineraticn program described in Appendix E. It is also noted that the 1.2 pounds of hycrocarbons is essentially all unchlorinated pyrolyzates since no herbicide feed constituents were ever detected in the combustion gases. The average daily mass concentration in the "worst case" dispersion zone is ~100 ppt v / V- The maximum sea level concentration predicted by the meteorological model'is approximately 7.0 pptv/v and occurs 0.2 km downwind of discharge. When discharged from the west end of the island over the open tropical ocean, no significant, environmental impact can be attributed to these predicted "worst case" atmospheric concentrations of these hydrocarbons. The impact of the deposition of these pyrolyzates or any Orange constituents into the ocean from the stack plume is discussed under Part III. C, Water Quality. (b) H^^ro£e_n_C_hJorid£: The discharge of hydrogen chloride will be approximately 18.5 tons per day. The daily average mass concentration in the atmospheric dispersion zone described above will be -25 ppm v / v The 73 �maximum sea level concentration predicted by the meteorological model, for "worst: case" sea level conditions, is 1.85 ppmy/y which occurs at 0.2 km directly downwind of the stack. At a distance of 10 km from the stack, the predicted sea level concentration decreases w 0.007 pprriy/y. The maximum concentration predicted by the model occurs at a distance of 0.2 km from the stack and ar elevation 38.3 meters; this concentration is 2.26 ppmv/v. These predicted hydrogen chloride concentrations in the atmosphere were accomplished to evaluate probable impacts of the hydrogen chloride discharge as regarcs: 1) interference with ships downwind of the stack, 2) interference with aircraft, particular'y those on approach to landing at the west end of the runway, and 3) possible alterations of reef calcification processes due to downwind deposition of hydrogen chloride and resultant depressions of the pH of reef waters. The analyses indicates there is no significant detrimental environmental impact attributable to the hydrogen chloride discharge and resultant hydrogen chloride concentrations in the atmosphere west of Johnston Island. Interference with ships or aircraft, due to transient exposure to low ppm concentrations of hydrogen chloride, would not be a serious constraint on the operation. The reaction between hydrogen chloride and saturated air was considered in the Department of Air Force Draft ES "United States Air Force Space Launch Vehicles." Hydrogen chloride ir a clear atmosphere of saturated air is not expected to result in the formation of droplets which may fall out. Droplets occur in fog or in natural clouds and due to the great affinity of hydrogen chloride for water an acid may be expected. The hydrogen chloride concentration of such droplets has been estimated at less than 1 percent. Although hydrochloric acic mists and solutions are very corrosive to most metals, a literature review in preparation of "Air Pollution Aspects of Hydrochloric Acid" (Stahl, 1969) did net reveal any information describing corrosion or damage to material from environmental concentrations of hydrochloric acid. However, meteorological constraints will be implemented to insure that the incineration is stopped during weather conditions which are not favorable for dispersion of the stack gas westward from the island. The effect upon the fringing reef is discussed under Part III.C., Water Quality, (c) Particulates: The dally discharge of elemental carbon particjlates (0.3 tons) is based on the conversion of 0.5 percent of Orange participates. Based upon proposed incineration parameters, these particulates would not be expected to contain any detectable hydrocarbons. Dispersion of these particles in the "worst case" dispersion zone described above will result in a concentration slightly greater than that of clean country air (0.2 mg/ cubic meter). Although a smaller zone will be affected at higher concentrations, the majority of particles are actually expected to fall out in the ocean over a relatively small impact area. This fallout effect on the ocean is discussed in Part I[I.e., Water Quality. (3) Monitoring: Ambient air nonitoring including sample collection for analytical chemistry analyses and biomonitoring with selected plants will be required to document the impact of the incineration process. The odor perception of humans to hydrogen chloride is very acute, being reported as low as 0.067 ppmv/v. The low sensitivity to odor can be considered as a back-up 74 �monitoring program to supplement the meteorology constraints on the incineration operation and the chemical/biological sampling program. The odor perception is obviously not to be used for quality control of the incineration operation. It is fortunate, however, that hydrogen chloride is the major quantitative constituent of concern in the stack gas and that it can be readily detected at concentrations below that considered safe for occupational exposure. 75 �C. WATER QUALITY 1. PRESENT WATER QUALITY a. Survey at Johnston Atoll: A visit was made to Johnston Atoll in October 1973 by personnel of the~~DsA~F Environmental Health Laboratory, Kelly AFB (EHL(K)) to collect water samples and marine biological samples for analyses for Orange herbicide components and TCDD. b. Water Sample Collection: A total of 17 duplicate water samples were taken during~tFe survey; see Fig III-l, and Table III-l. The rationale of the water sampling was to obtain a comprehensive set of samples which would include: (1) Ocean samples near the herbicide storage area. (2) Ocean samples from locations around the island. (3) An indisputable ocean control sample. (4) Samples at the intake and outlet of the distillation unit. (5) Samples of the freshwater reservoir and distribution system. (6) Samples of test wells in the herbicide storage area. c. Biological/Sediment Sample Collection: The rationale for this sampling was to obtain "representative samples of high food chain predators, coral feeders, coral sediments, etc. for subsequent analysis for herbicide components and TCDD. Figure 111-2 illustrates the biological sampling locations. Area I, consisting of five locations off the west side of Johnston Island, was the most likely area for contamination due to the location of the Orange storage area and the nature of the ocean currents. Area II was north and east of North (Akau) Islands where four locations were selected as controls that would be free of possible contamination. Area III was a "catch-all area," including any area except I & II which was expected to have minimal herbicide contamination but which could have industrial/chemical products indicating man's influence. Table III-2 lists the biological specimens and the sampling areas from which they were collected. Duplicate sediment samples were collected in Biological Sampling Areas I and II and at the shoreline near the Orange storage area. The latter corresponds to the same location as water sample number 8, see Table III-l. d. Sample Disposition: (1) Water: One set of water samples was delivered to the Environmental Health Laboratory, McClellan AFB (EHL(M)) to be analyzed for 2,4-D and 2,4,5-T esters and acids and for polychlorinated biphenyls (PCB). The other set was delivered to the EPA Laboratory at [Jay St Louis MS. The samples were prepared for analysis at this facility and then sent to the EPA Laboratory at Perrine FL for determination of TCDD. (2) Biological: One set of six frozen biological samples identified in Table 111-2 w'as sent to Dow Chemical Co., Midland MI for TCDD analysis. A full set of frozen samples was sent with the water samples to the EPA 76 �FIGURE m _l JOHNSTON ISLAND WATER SAMPLES OCTOBER 1973 USAF ENVIRONMENTAL HEALTH LABORATORY KELLY AFB TX 78241 INDICATES WATER SAMPLE LOCATIONS CONTROL SAMPLES 1 & 15 ARE SHOWN IN FIGURE II I -2 *4 Ek_A,<.. .. --„ JOHNSTON ISLAND �TABLE III-1 WATER/SEDIMENT SAMPLES EHL(K) General Location 2 3 oo 4 5 6 ( A S 7 8 CJ u o 15 a: 9) 0) 4J 4J eg a (A 10 11 OJ •-4 >» 12 13 • •"• 9 « cu o §* 14 17 Approx Sample Depth - Feet Approx Bottom Depth - Feet 20 12 13 below surface 8 10 15 40 20 20 0900 — below surface — ~~ 2 OcL 1445 below surface ^^ 2 2 3 2 3 Oct Oct Oct Oct Oct 1500 1545 1000 1510 1030 ~ — — — — — — Wei] Hole - Center of Herbicide Area Well Hole - West side of Herbicide 2 Oct 1000 ~8 Area Sample Ident . 1 0) tH FIELD TRIP, JOHNSTON ISLAND,OCT 73 3 Oct 1115 -8 Specific Location East of North Island - Inside Reef (Control Sample) Distillation Plant Intake* North Shore Garbage Chute - 10 yds from shore Sea Turtle Area Northwest of Herbicide Area East End of Runway West of Herbicide Area - Shoreline ~1.2 Miles Northwest of North Island Outside Reef (Control Sample) Salt Water Reservoir Distillation Unit Discharge (Sample Tap) Potable Water Reservoir Dining Hall (sink tap) Distillation Unit Brine JOC Bldg (sink tap) Date Time 1 1 1 1 1 1 1 1 Oct Oct Oct Oct Oct Oct Oct Oct 1530 1510 14l5 1430 1440 1425 1500 1720 3 Oct P* CA 9 09 4J r~i a a) a) S • U H •o c Q) 0) 16 -- — — —15 17 30 — —— I 11 S8 Biological Sampling Area I Biological Sampling Area II Same as Water Sample 8 2 Oct 3 Oct 3 Oct 0830 1000 1100 Diver stated that water had a petroleum product taste 15 25 Shoreline 15 25 ~— �••., _, >'"-. .'-'-;•-.. " •• FIGUSE III-2 MARINE SAMPLING LOCATIONS EHL(K) FIELD TRIP, JOHNSTON ATOLL, OCT 73. I\ Sampling locations offshore from Orange Herbicide storage area. Control sampling locations north and east of North (Akau) Island. Miscellaneous control sampling locations. ^15^ Control locations for marine water samples. Orange Herbicide Storage Area. 79 o �TAliLt 111-2! MARINE BIOLOGICAL SPECIMENS EHL(K) FIELD TRIP, JOHNSTON ISLAND, OCT 1973 SPECIMEN* COLLECTION AREA** I II III A. White-tipped reef shark. Triaenpdqn obesus x (liver) x (muscle) Gray reef shark, Charcharlnus amblyrhyucos x (liver)T x (muscle) x (body)'1 section) B. Moray eel, Gymnothorax j^iyanicus C. Sand eel, (Anguilliformes) D. Green sea turtle, Che Ionia mydas (?) x (liver) x (muscle) E. Surgeon fish, Acanthurus ni&roris^ ( ) ? x F. Surgeon fish, Acanthurus achilles xT G. Squirrel fish, Adioryx spinifer x H. Parrot fish, (Scaridae) X I. Sea Cucumber, Holothurea atra & other species XT J. Mushroom (razor) coral, Fungia jscutaria K. Staghorn coral, Acropojra L. Algae species #1 S c h i zo thr ix ca 1 i_cu la M. mixed wiLh other specLcs Alg.de species #2, HaJLinedu Di_scpJLdc-_a N. Algae species #3, Bryoj.sLs sp. sp *Sample is composed of whole specimen(s) unless otherwise noted **Collection areas are indicated on attached map, Figure 2 TSpecimcns sent to Dow Chemical for dioxin analysis 80 x �Laboratory at Bay St Louis MS for preparation with subsequent TCDD analysis at the EPA Laboratory at Perrine FL. The remaining biological samples were retained at EHL(K) for 2,4-D and 2,4,,5-T analysis. (3) Sediment: One set of sediment samples was delivered to the EPA Laboratory at Bay St Louis MS for subsequent dioxin analysis at Perrine FL. The second set was analyzed at EHL(K) for 2.,4-D and 2,4,5-T. e. Results of Analysis (1) Water: As shown in Table III-3 no TCDD was found in any water samples. Acids of 2,4-D and 2,4,5-T were found at the shoreline adjacent to the storage area and in the test wells in the storage area as seen in Table HI-4. The well openings are at grade and the presence of the acid is probably from water-carried (rain) drainage of leaked herbicide into the wells. The shoreline station was just below the redrumming area so it also could receive leaked herbicide. (2) Marine Biological and Sediment: Table 111-5 shows no TCDD in any of the marine samples analyzed except; for sample I-I, Sea Cucumber which is reported as 2.2 ppt (by weight). The analysis which resulted in this concentration was the second analyses conductad on sample I-I by the EPA. The first analyses resulted in a "non-detectable" report but the recovery was low resulting in a TCDD detection limit of 64 ppt. A portion of sample I-I was one of the six samples which was forwarded to the Dow Chemical Company .for analyses. Dow split the sample into "flesh" and "internal organs" and the analyses of each portion resulted in a non-detectable concentration of TCDD at a detection limit of 1 ppt. The remaining samples forwarded to the Dow Chemical Company were also negative for TCDD with detection limits ranging from 1 to <11 ppt. The latter limit, <11 ppt, was for sample III-A, the grey reef shark liver, and was attributed to an interfering substance present in the sample. Table III-6 shows that all sanples were negative for 2,4-D and 2,4,5-T; the detection limits ranged from 0.07 to 2.0 yg/kg for the biological samples and was 5.0 yg/kg for the sediment samples. f.. Conclusions: From the results of analyses of ocean water, drinking water, marine biological and sediment, samples collected in October 1973 by the survey team from EHL(K), it was concluded that there was no evidence of Orange herbicide pollution or environmental effects. g., Analytical Procedjres: See Append~x J. 81 �TABLE III-3 TCDD RESULTS EPA LABORATORY, BAY ST LOUIS MS AND PERRINE FL Sample Location Code Remarks TCDD Detection Limit (PPT) 1 East of North Island - Inside Reef 0.10 ND 2 Distillation Plant Intake 0.11 ND 3 North Shore 0.14 ND 4 Garbage Chute - 10 yds from shore 0.15 ND 5 Sea Turtle Area 0.23 ND 6 Northwest of Herbicide Area 0.31 ND 7 East End of Runway 0.37 ND 8 West of Herbicide Area - Shoreline 0.60 16% Recovery, ND 15 1.2 Miles Northwest of North Island Outside Reef 0.19 ND 10 Salt Water Reservoir 0.85 14?: Recovery, ND 11 Distillation Unit Discharge 0.27 12 Potable Water Reservoir 0.16 ND 13 Dining Hall (Sink Tap) 0.20 ND 14 Distillation Unit Brine 0.23 ND 17 JOC Bldg (Sink Tap) 0.26 ND Well Hole - Center Herbicide Area 0.37 ND Well Hole West Side Herbicide Area 0.24 ND 9 16 i ND 8 Sediment - Contained contaminant I Sediment 1.7 ND II Sediment 0.88 ND 82 �TABLE 111-4 General Sample £ Location 1 i/o !_U _J Q- i GO —^ § LLJ <J o o£ LiJ i 2 3 4 5 6 7 8 15 1.0 11 <c 2 LiJ __J <: fe Q . 12 •13 14 17 9 CO h— —1 CO _l 1 1 1 I-LJ LJ—1 I I I 1— 3 16 WATER SAMPLE ANALYSES RESULTS (EHL(M)) Specific Location East of North Island - Inside Reef (Control Sample) Distillation Plant Intake North Shore Garbage Chute - 10 yds from shore Sea Turtle Area Northwest of Herbicide Area East End of Runway West of Herbicide Area - Shoreline -1.2 Miles Northwest of North Island Outside Reef (Control Sample) Salt Water Reservoir Distillation Unit Discharge (Sample Tap) Potable Water Reservoir Dining Hall (Sink Tap) Distillation Unit Brine JOC Bldg (Sink Tap) Well Hole - Center of Herbicide Area Well Hole - West Side of Herbicide Area *Detection Limits, ng/1 **Less than the detectable limit ***Analyses not accomplished Analyses Results, ng/1 2,4-D 2,4,5-T Ester Acid Ester Acid Aroclor 200* 100* 50* 20* 700* ND** ND ND ND ND ND ND ND ND ND ND ND ND _*** ND ND ND ND 1170 ND ND ND ND ND ND ND ND _ ND ND ND ND 910 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 900 700 900 ND 44,000 ND 1,200 ND ND 77,000 ND 3,600 ND �TABLE 111-5 TCDD RESULTS EPA LABORATORY, BAY ST LOUIS MS AND PERRINE FL Johnston Island TCDD Detection Lmit Specimen I -A i-c I-F I--G I-ri White-Tipped Reef Shark Liver White-Tipped Reef Shark Muscle Moray Eol Sand Ee! Surgeon Fish Squirre'S Fish Parrot I'ish Sea Cucumber Mushroom Coral I-K Algae #1 Surgeon Fish Squirrel Fish Parrot Fish Sea Cucumber Staghorn Coral 1I-L II-M 11' -A Ill-A III-D lii-D I11 -L III-G IIJ-J Algae #1 Algae #2 Grey Reef Shark Liver Grey Reef Shark Muscle Green Sea Turtle Liver Green Sea Turtle Muscle Surgeon Fish Squirrel Fish Mushroom Coral II1-N Algae #3 9.5 6.0 3. .7 8. .7 20. 1 78. .7 1.9 Staghorn Coral j -L 1I-F 11 -G 11 -h1 I1 -I II-K 56 1100 14.3 20.7 21A 1.3 7.1 13.1 9.3 6.7 4.0 8.7 5.0 2.2 8.3 84 TCDD Concentration ND ND ND ND ND ND ND 2.2 Contaminated ilxtrawt Contain inaiud Extract ND ND ND ND ND Contaminated Extract ND ND ND ND ND ND ND ND Contaminated Extract ND �TABLE II1-6 RESULTS OF BIOLOGICAL AND SEDIMENT SAMPLE ANALYSES BY EHL(K)* Johnston Island QpJ_l?c_tJ?P_.Ar_ea Specjmen fM^p _2_i4L,_5-7 Detection Limit Microgram/Kg I-A I-A I-B A-I-C I-F I-G I-H I-I - Shark Liver Shark Muscle Moray Eel Sand Eel Surgeon Fish Squirrel Fish Parrot Fish Sea Cucumber N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 0.25 0.33 0.15 2.00 2.00 0.67 0.67 0.20 I-J i-K 1-L Mushroom (Razor) Coral Staghorn Coral Algae Species #l(Blue Green) N.D. N.D. N.D. N.D. N.D. N.D. 0.07 0.10 1.00 JI-F II-G Surgeon Fish Squirrel Fish N.D. N.D. N.D. N.D. 2.00 0.67 0.40 II-H Parrot Fish N.D. N.D. II-I Sea Cucumber N.D. N.D. 0.67 II-K II-,_ Staghorn Coral Algae Species #1 (Blue Green) N.D. N.D. N.D. N.D. 0.04 1.00 II-M Algae Species #2 N.D. N.D. 1.00 III-A III-A Grey Reef Shark Liver Grey Reef Shark Muscle N.D. N.D. N.D. N.D. 0.50 1.00 IIJ-D III-U III-E 1II-G Ili-u" 1I1-N #8 I II Green Sea Turtle Green Sea Turtle Surgeon Fish Squirrel Fish Mushroom (Razor) Algae Species #3 Sediment Sediment Sediment N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D, N.D. N.D. N.D. 1.00 0.50 0.67 1.00 0.07 1.00 5.00 5.00 5.00 Liver Muscle Coral (Green) N.D. - None Detected *Samples were analyzed for the components of Orange herbicide by Gas Chromatography with Electron Capture detector. Two columns of different polarity were used. Fifteen of the 29 samples analyzed were founc' to be suspect since they had peaks with the same relative retention time, on both columns, as the methyl esters of 2,4-D and 2,4,5-T. These samples required confirmation of the compounds. The fifteen samples were then analyzed by Gas Chromatography/Mass Spectrometry. The suspected compounds were not confirmed by this technique. Therefore, it was concluded that Orange herbicide was not present in any samples. 85 �2. MOVEMENT: The present Orange storage site is on the northwest corner of Johnston Island, and from a meteorology standpoint, the incineration facility should be sited at the same location (dominant east to west wind). There will be a potential for admittance of Orange into the ocean at this location due to accidents resulting in spillage during handling and transfer of the Orange for incineration. However, stringent precautions to prevent accidental spillage and to contain any such spillage will be accomplished. The determination of a location for the programmed long term discharge of scrubber water in the ocean was evaluated to demonstrate the environmental impact of the scrubber water. Selection of a suitable location is complicated by the difference in ocean water circulation and turbid water outflows from Johnston Island. The most detailed work on water patterns in and around the reef complex at Johnston Island has been accomplished by Kopenski and Wennekens (1965). Most of the information to follow is from this reference; the Smithsonian Report, Appendix A, also includes a summary of Kopensk--Wennekens report. During the study by Kopenski and Wennekens, the investigators were able to utilize turbid water, caused by current and wave action on the island's coral shore, as a tracer. Observation of turbid water, documented by aerial photography, was utilized in both the winter and summer surveys to show t're transport of turbid water from the island's environment to the main ocean. In addition, parachute drogues, current meters, and dye studies were also conducted. Johnston Island is a projection of a shallow platform (80 square nautical miles) which is nearly submerged. This shallow platform is a truncated portion of a submarine mountain. A reef and extensive coral shoals occupy most of the northwestern section of the platform. The island is located in the Northwest Trade Belt and is in the North Equatorial Current. The above stated natural geographical factors disrupt the ocean's flow, and the extensions to Johnston Island and the dredging of ship channels have had an affect on the local (island's) flow patterns. In addition, the flow is dependent upon: tidal currents, wavedriven flow over the reef, and the North Pacific Equatorial Current, which during the Kopenski-Wennekens study was fairly strong and steady from the east in the winter but weak and variable in the summer. The flow patterns about Johnston Island for these conditions are shown in Figures II1-3, 4, and 5, which were taken from the Kopenski-Wennekens Report. Inspection of these figures reveals that the Orange storage site is generally satisfactorily located as regards water transport of any Orange which may be accidentally spilled into the ocean at the site. Transport is to the south from the west ship channel in both the Winter Survey, Figure II1-3 and the Summer Survey - Easterly Flow, Figure III-4. Transport is to the norti with the outlet through the reef cut for the Summer Survey - Westerly Flow, Figure III-5. It is this summer flow condition that is responsible for the sluggish action of sanitary sewage discharge commented on in the referenced report. The summer fluctuation is due to tides which occur twice daily and therefore increase the residence time of water in the lagoon on the north side of the island. Transport from the lagoon to the ocean is therefore greater in the winter than in the summer. Under the three flow conditions shown, the west reef below the reef cut is the primary reef area affected by the turbidity transport, and this turbidity has already had a detrimental effect upon the reef (Brock, et al, 1965). �ce "ISLAND WAKE" EDDY NORTH E Q U A T O R I A L CURRENT 169°30' I FIGURE III-3 JOIiiJSTOiJ ISLAND-INFERRED CIRCULATION, JANUARY-FEBRuARY 1965 (KOPENSKI AND WENKEKENS 1965) �DURING EASTERLY FLOW, TURBID "CLOUD" B R O K E N OFF. TURBID WATER BECOMES " S Q U E E Z E D * ' ALONG THE WESTERN SEAWARD M A R G I N OF THE I S L A N D P L A T F O R M AS INDICATED. 16'45'-| TURSID "CLOUD" BREAKING OFF \ /• CURRENT AND SETS ROTATES EASTWARD 169°30' I FIGLIRF III- 4 . JOHNSTON ISLAM-EASTERLY FLOU, INFERRED CIRCULATION AND TURBID OUTFLOU, JULY-AUGUST 196o (KQPENSKI AND WENNEKENS 1965) �DURING W E S T E R L Y FLOW, T U R B I D W A T E R IS T R A N S P O R T E D TO THE WEST AND SOUTHWEST AS INDICATED TURBULENT HELD CURRENT ROTATES AND SETS W E S T W A R D 169°30' FIGURE III- 5 JOHNSTON ISLAND-WESTERLY FLOW, INFERRtL) CIRCULATION AND TURBID OUTFLOW, JULY-AUGUST 1965 (KOPENSKI AND WENNEKENS 1365) �3. PERSISTENCE a. General: The composition of the? liquid discharge from an incinerator operation may include sodium chloride^calcium chloride, hydrogen chloride, particulates (primarily elemental carbon), chloride residual, hydrocarbons (uncombusted or partially combusted Orange) and heat. Excluding the hydrocarbons, only the particulates represents a material which is persistent or which will not be dissipated by the receiving water. Essentially complete destruction of the herbicide and TCDD is anticipated in the combustion process; however, for the sake of completeness, the interactions of this material with the water environment is discussed. Any herbicide which enters the ocean would be subject to various phenomena including: hydrolysis, photodecomposition, sorption, and biodegradation. b. Hydrolysis: The herbicide esters are hydrolyzed to 2,4-D and 2,4,5-T acid and butyl alcohol when subjected to aqueous alkaline conditions; the acid is obtained as its salt and can be liberated by the addition of mineral acid. The ester and acid are not soluble in water,but the salt is water soluble. Aly and Faust (1964), in a study on the fate of 2,4-D and ester derivatives in natural surface waters, have found the solubility of the calcium and magnesium salts of 2,4-D in distilled water at 25°C to be 4,000 and 1,000 mg/1 respectively. An alkaline scrubber using sodium or calcium hydroxide would readily convert very low concentration of ester in the combustion gases (should they occur) to the scdium or calcium salts. Smith (1972) found the hydrolysis, of 2,4-D ester to be extremely fast in a 0.1N sodium hydroxide solution - greater than 50 percent of the ester being hydrolyzed in less than one minute, and negligible hydrolysis was noted in distilled water over a five-hour period. The Environmental Health Laboratory, Kelly AFB.is presently conducting studies in the hydrolysis of Orange herbicide in aqueous sodium hydroxide solutions and in ocean water. Preliminary data analysis indicates good comparison with Smith's results for the hydroxide solutions, and for the ocean water studies, 90% of the Orange esters were hydrolyzed within 7 days, c. Photodecornposition: The phenomena of photodecomposition of 2,4-D has been studied by several investigators. Crosby and Tutass (1966) conducted an experimental study to compare the effect of sunlight on aqueous 2,4-D solutions and to identify any major decomposition products. They concluded: "2,4-D acid decomposes rapidly in the presence of water and ultraviolet light. This decomposition results in the formation of 2,4-dichlorophenol, 4-chlorocatechol, 2-hydroxy-4-chlorophenoxyacetic acid, 1,2,4-benzenetrol, and, finally, polymeric humic acids. The results with artificial light and with sunlight are essentially identical." In tests under field conditions, Penfound and Minyard (1947) investigated the relationship of light intensity to the effect of the herbicide on water hyacinth and kidney bean ard observed more necrosis and greater epinasty in shaded plants than in those in sunlight • TCDD is known to be photosensitive in alcohol to the extent that analytical stancards are protected from sunlight by storage in amber glass. Crosby, ejt al_. (1971) stated as a result of 90 �experiments "Abstract. The toxic herbicide impurity 2,3,7,8-tetrachlorodibenzo-p-dioxin and its homologs decomposed rapidly in alcohol under artificial light and natural sunlight, the ra^e of decomposition depending upon the degree of chlorination. However, phoi;odecomposition was negligible in aqueous suspensions and on wet or dry soil," (Emphasis added). d. Sorption: Aly and Faust (1973) performed studies on the sorption of 2,4-D ester and sodium salt on three clay minerals, bentonite, illite, and kaolinite; tie amounts sorbed were 0.02 to 0.14 mg per gram which was considered to be small and insignificant. The primary cause of turbidity in the ocean near Johnston Island is the coral which is eroded from the shore. Dry coral is a very good absorber of Orange and handling procedures call for the absorption of spilled Orange with coral or calcium carbonate. No data are available on the release of herbicide from contaminated coral particles which may enter the ocean, nor on the absorption/adsorption of herbicide salts or acids which may be in the ocean water. e. Biological Degradation: Aly and Faust (1964) performed studies on the biological degradation of 2,4-D compounds in lake waters and in bottom muds. 2,4-D ester concentrations of 50 mg/1 were placed in biochemical oxygen demand (BOD) dilution water seeded with 5% settled sewage. Oxygen utilization exceeded that of the control, but each ester concentration was not changed after nine days, suggesting biological hydrolysis into the free 2,4-D acid and corresponding alcohol. The oxygen uptake was attributed to biodegradation of the alcohol moieties. Concentrations of 2,4-D sodium salts at 20, 80 and 150 mg/1 were prepared in 50 and 100 percent solutions of settled domestic sewage and oxygen uptake measured over nine days. The oxygen uptake was not different from the control, and no biodegradation of the 2,4-D was concluded. In lake water studies, solutions of 3 mg/1 of 2,4-D sodium salt prepared at various pH's and aerated over a period of 120 days showed no change in the original 2,4-D concentration. In lake mud studies, initial concentrations of 2,4-D of 20 to 30 mg/1 were decomposed biologically from 81 to 85 percent within 24 hours, but only after extensive microbial adaptation techniques. No data are available on biological degradation ir. sea water but based on the above it is not felt that such action would be significant in very low concentrations in the ocean environment.. f. Summary; The phenomena discussed above would tend to indicate that small amounts of herbicide esters discharged to the ocean would be hydrolyzed and exist as the water soluble sodium salt. This compound would be considered persistent because of the lack of removal mechanisms except for photodecomposition. The persistence of TCDD In the ocean cannot be accurately predicted. Baughman and Meselson (1973) have reported TCDD concentrations in fish and shellfish collected in 1970 in Viet Nam from the Dong Hai and Saigon Rivers and along the Can Guo Coast. The Vietnamese fish contained from 18 to 814 ppt TCDD, and a Cape Cod butterfish used for comparison contained not more than 3 ppt TCDD. The rivers from which the samples were collected drained areas on which 45,000 tons of Orange were sprayed between 1962 and 1970. This information is more appropriate to a discussion of biological sampling and analyses for TCDD; however, it attests indirectly to the persistence of TCDD in an aquatic ecosystem. 91 �4. MONITORING METHODOLOGY: Monitoring of the water environment around Johnston Island can be readily and accurately accomplished. The water sampling program would consist of periodic grab samples. Grab samples collected by authorized personnel in specially prepared glass containers with teflon-lined lids are preferred over a continuous sampler arrangement. Samples can be collected along any of the shoreline of Johnston Island, and throughout the lagoon utilizing a motorized catamaran platform. Scuba divers are available on Johnston Island for sample collection within the water column. In addition to water samples, sediment samples, high food chain predators, reef and shoreline scavengers, bottom feeders (sea cucumbers), algae and coral can be readily sampled. Ocean water samples can also be collected beyond the reef, in a limited range, by a vessel which is located at Johnston Island. The rationale for selection of the location of the sampling points would include consideration of: storage and incinerator location, outfall location and ocean currents, impact on the reef and its community, and the island drinking water supply. The analysis cf these samples would be performed by approved analytical chemistry procedures utilizing extraction techniques and gas chromatography-mass spectrometer instrumentation (Appendix J). 92 �5. ENVIRONMENTAL IMPACT a. General (1) The environmental impact on the water environment will be discussed tor the proposed action and the principal alternative described in Part II. Incineration on Johnston Island will be discussed in terms of no combustion gas scrubber; however, an alkaline scrubber and a sea water scrubber are discussed for completeness and to demonstrate the potential for impact due to any scrubber water discharge. For either incineration at sea or incineration on Johnston Island, the destruction of the herbicide and TCDD will be essentially complete as a result of the incineration process. Quality control and failsafe procedures are incorporated into both cases to insure that the Orange is incinerated only under optimal conditions. Since either action involves activities at Johnston Island, the impact upon the island's water supply (lagoon) and the fringing reef is of paramount importance. In this regard, either the proposed action, or the principal alternative which does not include combustion gas treatment, are favorable since neither includes the discharge of scrubber water to the ocean. Of the two, incineration at sea is most favorable since there is literally no chance of impact upon the Johnston Island environment as a result of the incineration process. Potential impact on the island's drinking water supply from the shipboard method is limited to any accidental spillage while loading Orange on the ship for subsequent incineration at sea. This possibility will be remote because stringent precautions will be taken to preclude any accidental spillage. Incineration on JohnstDn Island has potential for the combustion gas plume to impact on the waters just west of the island. If either alkali or sea water scrubbers were used, the spent scrubber waters would discharge into the water environment. This scrubbing would also include major expenses in treatment unit, chemical procurement, shipment, Handling and the ocean outfall.. In the analyses that follows there is no consideration for TCDD because, even if it were present in the combustion gases, its concentration would be at least an order of magnitude below its typical detectable limits of 0.2 nanograms/1. As for the possibility of bioaccumulation of TCDD, incineration at sea would be the better option in that if bioaccumulation does occur, the possibility of occurrence would be slight in the sparsely populated ecosystem of the open tropical sea. At Johnston Island, no evidence of bioaccumulation was revealed during the ecological survey previously discussed. (2) As noted under Part II.D. Failsafe, it is possible to dump the waste cargo if the safety of the crew/vessel is threatened. Also, the possibility of the vessel's sinking while loaded with waste is an environmental as well as personnel concern. Both of these contingencies were considered early in the planning for incineration at sea, and the low probability of occurrence was acceptable when compared%with other positive aspects of this proposed action. The vessel has been approved'by the U.S. Coast Guard for operations from U.S. ports and will follow all applicable maritime regulations. The vessel has operated for about two years without encountering a situation which required cargo jettison. The loading and conveyance via barge or ship of toxic or ecologically harmful cargo (chlorine, petroleum, fertilizer, etc.) is a normal occurrence. Quantification of the impact of cargo jettison or ship sinkage is not prudent because of the many assumptions required. Such an event in the harbor at Gulfport or at Johnston Island would present a very grave situation as regards environmental 93 �resources. At Johnston Island, the island's water supply (ocean water for distil"ation), portions of the fringing reef and the biological reef commurr'ties would be very .adversely affected. Cargo jettison or vessel sinkage in the open tropical ocean is not anticipated to be environmentally disastrous. Any effects would be generally localized and not persistent. The tremendous dilution afforded by the ocean, the physical chemical properties of Orange, i.e. hydrolysis to the less toxic acid, settling due to specific gravity and insolubility, biodegradation and photodecomposition of residual concentration would all tend to reduce the hazard of a large scale release of Orange into the ocean. It is noted that the Orange herbicide stock on Johnston Island was transported there via vessel and that the Orange in Gulfport would be transported to Johrston Island by vessel if the incineration occurred on Johnston Island. b. Incineration at Sea (1) Potential for Impact (a) Evaluation of the environmental impact of incineration of Orange herbicide at sea requires the consideration of six major emission components: 1) unburned or pyrolyzates of Orange herbicide, 2) hydrogen chloride, 3) particulate carbon, 4) carbon monoxide, 5) carbon dioxide, and 6) heat. (b) In order to calculate the quantities of these materials emitted to the atmosphere and ocean during incineration, a set of "worst case" conditions was established, and emission/dilution values were determined. Based on technical literature concerning the operation of the incinerator ship, an incineration efficiency of 99.9 percent for chlorinated hydrocarbon chemicals was used in these calculations. For perspective, the analyses was also accomplished for incinerator efficiencies of 99.0 and 95.0 percent. The service speed of the ship is 13 knots, but in these calculations a figure of 10 knots was used. The average monthly wind velocity in the vicinity of Johnston Atoll is 15 mph (13 knots), although the calculations used a condition of calm, with the combustion gas plume dispersing directly behind the ship and the plume dispersing to no greater width than the 14.4 meter beam of the ship. Ocean currents were not added to the dispersive forces in the following computations, although mass water movement would certainly play a positive role in the total dilution of the incinerative emissions contacting the water. An effective mixing depth of two meters was assumed for these calculations. This depth was an estimated figure that attempts to include such factors as mixing in the wake of the ship, chemical interaction of emission products with sea water, and the possible effects of toxic products on marine organisms, especially phytoplankton, which are the most prevalent life form. (c) The biological aspects of the open sea require further discuss"on because these waters are generally poor in nutrients, and therefore the marine life (from plankton through the food web to large fish and mammals) is scarce when compared to that found in coastal areas or near localized upwellings due to islands. This lack of nutrients, and therefore, lack of productivity, is compounded in tropical/subtropical seas where vertical mixing of water due to seasonal changes is minimal. The clear waters of the tropical 94 �ocean will thus contain relatively small amounts of phytoplankton per unit volurre, but these populations may occur to c. depth of 100 meters due to light penetration (Kinne, 1970). Similarly, most phytoplankton are not found at the surface of the water, but: are located at variable depths, dependent on their specific limitations and requirements regarding light wave lengths, temperature and other physical/chemical factors. Thus, incinerative emissions from the ship which interface with the water will require some degree of mixing to establish substantial contact with the marine biota. However, the greater the amount of mixing, the greater the dilution and hydrolysis of chemical compounds. Therefore, the compromise figure of a two meter mixing depth is quite conservative for dilution and toxicity calculations. (d) The beneficial uses of the open sea are generally limited to commercial fishing, and this utilization is even more limited in tropical/ subtropical latitudes due in large oart to the low primary productivity discussed above. The only major ecosystems that have lower gross per unit area primary productivity than the open ocean are desert and tundra (Odum, 1971). Therefore, the only commercially important crganisms that might occur in the vicinity of the ship during the incineration process would be scattered unpredictable populations of transient biota. As will be discussed below in paragraph (2)(a), even tre oxygen production of the phytoplankton community should not be impaired by the incinerative emissions. (e) Included in Appendix N is a report prepared by the Center of Biological Studies and Research and of Oceanographic Medicine,Nice, France on "Effect on the Marine Environment of the Combustion at Sea of Some Industrial Waste." The objective of the study was to obtain data on environmental aspects during incinerator ship cperations in the North Sea and then to make judgments on the effects of such operation in the Mediterranean Sea. The data acquisition was environmental in nature and did not include monitoring of the incineration process directly (stack samples). This study was of short duration but quite comprehensive. Areas of study include: smoke plume effects, pH, salinity, plankton, toxicity tests (for combustion gas collected 5 meters from the incinerator stack), food chain test and chemical and biological analyses. A conclusion of the report is: "In the present state of our knowledgs, it seems that the process of incineration does not cause, certainly not short term, any special harm to the oceanic environment". This conclusion is conditional in that it may not hold for the long term and is only for the specific waste being incinerated. While the wastes incinerated were not Orange herbicide, the satisfactory results obtained certainly support the case for incineration of Orange at sea. (2) Probable Impact (a) Application of the above set of "worst case" conditions to an evaluation of the impact of the unburned or pyrolyzates of herbicide on the marine environment yields the following results. An incinerative efficiency of 99.9 percent allows 0.576 ton of herbicide to escape the stacks per day (24 hour incineration day) (5.76 tons at 99.0% and 28.8 tons at 95.0%). The speed of the ship as discussed would be 10 knots or 18.5, km/hour, producing a dispersal distance in one dimension of 444 km (444,000 meters) per day. The minimal 95 �lateral dispersal as discussed would be 14.4 meters, and the mixing depth is calculated as two meters. The volume of the dispersion zone, on a daily basis, is 12.6 x 10s cubic meters. Complete mixing of the 0.576 ton of unburned herbicide produces an average concentration of 0.041 mg/1 in the sea water mixing zone (0.41 mg/1 at 99.0% and 2.05 mg/1 at 95.0%). Walsh (1972) found that oxygen production in four species of marine algae was decreased by 50 percent when the algae were exposed for a period of 90 minutes to 50-60 ppm of the technical acid of 2,4-D (author's terminology), 100-200 ppm of the butoxyethanol ester of 2,4-D, and 50-150 ppm of the technical acid of 2,4,5-T. Walsh found very similar results when measuring the effects of the same herbicides on the growth rates of the four algal species. Algal bioassays at the USAF Environmental Health Laboratory at Kelly AFB similarly showed Orange herbicide to inhibit growth at concentrations of 50-100 mg/1. Comparison of bioassay results with the above emission calculation for 99.9 percent incinerative efficiency illustrates that under "worst case" conditions there will exist a safety factor of three orders of magnitude before moderate toxicity effects would occur in the phytoplankton populations. (Reference Part II.F.4. of this statement for further toxicity data and literature.) In several of the referenced cases, Orange herbicide or its components showed greater toxicity (1-10 ppm) to organisms other than phytoplankton; however, the small floating plants of the euphotic zone were chosen for detailed discussion due to their much greater likelihood of exposure to any unburned herbicide fraction. Regardless of the organisms chosen for sensitivity studies, the safety factor involved continues to be at least 2-3 orders of magnitude with a 99.9 percent efficiency of incineration. It must be emphasized that "worst case" analyses is very extreme in that all of exhaust stack emission is considered to be transferred to the ocean directly behind the vessel and mixed to a depth of only two meters. In reality, it is expected that some of the unburned Orange would remain airborne for a considerable time period and that the ocean mixing zone would be much greater than that selected. Therefore, it is felt that even the concentration of unburned as pyrolyzates of herbicide after a 95.0 percent incinerative efficiency would be acceptable, particularly in vieh of the short duration of the incineration period. (b) Hydrogen chloride production and discharge rate from the ship will be about 178 ton/day. Assuming this total daily amount enters the ocean, an average concentration of 12.8 mg hydrogen chloride would be added to each liter of sea water in the previously defined mixing zone. The pH excursion resulting from the addition of this amcunt of hydrogen chloride to sea water was calculated to be not greater than 0..5 pH units. This calculation was based on buffer capacity equations in- which the carbonate system was the primary buffer. The predicted results were confirmed in the laboratory by the additicn of hydrochloric acid to sea water. Any transitory effects produced by the hydrogen chloride emission should have very little disturbance on planktcnic organisms and certainly no long-term effect on these populations. (c) Calculation of particu'late carbon emissions was based on about 0.5 percent of the incinerated herbicide going to the carbon form. An estimated 3.0 ton/day of carbon would be produced in this process, with an average concentration of 0.22 mg/1 in the ocean mixing zone. The carbon emissions should produce no detrimental effect on the ocean environment. 96 �(d) Carbon monoxide and carbon dioxide mass emissions to the atmosphere were calculated/estimated to be about 50 and 1000 tons per day, respectively. While these compounds are major combustion products, their mass emissions should produce no environmentally detrimental effect. (e) Heat production from the ship incineration process was calculated on the basis of a caloric value of 10,000 BTU per pound of undiluted herbicide. A daily amojnt of heat equal to 1.15 x 1010 BTU will be produced during incineration. The emission of heat can be considered in a similar context with particulate carbon and carbon dioxide (as well as the water produced by hydrocarbon combustion); i.e., these products are major components of the combustion of standard ship fuel oils. Thus, in terms of the environmental impact of these inorganic products, the ship can simply be considered to have two additional engine exhaust plumes for the duration of the incineration period. (3) Environmental Monitoring at Sea:: The above discussion of environmental impact indicates a very minimal "and transient effect resulting fron the shipboard incineration of Orange nerbicide on the open tropical sea. The "worst case" analysis is quite conservative, and realistic incorporation of normal wind and ocean current dispersal factors will further reduce even these minimal environmental effects. In view of these facts, and the short duration and nature of the proposed operation, off-ship environmental monitoring of the ocean and air is considered unnecessary and lacking feasibility to adequately detect any transient environmental changes that may occur. c. Principal Alternative - _I ncjjiejra tion at Johnston Is land (1) No Combustion Gas Treatment:_: The remote location on Johnston Island and its meteorology indicates that the discharge of untreated combustion gases directly into the atmosphere would riot result in any irreversible detrimental environmental impact to the air environment, see Part III. B. The immediate Johnston Island environment is the major concern and meteorological constraints may be required to insure that Johnston Island, the atoll, and the other islands are not affected due to changes in the normal weather pattern. The'"e is a fringing reef to the west of Johnston Island, and this reef has been seriously damaged by turbidity from past dredging operations and continues to be affected by turbidity from erosioruof the island's shoreline. Although the condition of the west reef would appear to be of the least significance to the maintenance of the atoll, it is imperative that the reef not be further degraded by fallout of constituents of the stack gas. (a) Potentials for Impact: The constituents of concern as regards deposition from the stack plume, and reaction at the plume/ocean interface are unburned Orange and pyrolyzates, hydrogen chloride, and particulatss. For the analyses that follows, the daily discharge rates are 1.2 pounds of unburned Orange and pyrolyzates, 18,5 tons of hydrogen chloride and 0.3 tons of particulates. The above discharge rate for the uhburnod Orange and pyrolyzates is approximately 3 times greater than that reported in Appendix E, in which the Orange constituents were undetectable and reported as less than 0.00095 pounds per day, and the pyrolyzates are 0.387 pounds per day. 97 �(b) !?IpbaJ^ljj!_Jnip_act_: This discussion is in two parts, impact upon-the open ocean and impact upon the lagoon (primarily as related to interference with the development of the reef). 1_. Open Ocean: As a "worst case" situation, it is assumed that the entire mass of each of the above combustion gas constituents is deposited onto a very small area of the ocean surface. The area has been selected to be plume shaped with a major axis of 1,000 feet and a minor axis of 100 feet. The mixing depth is conservatively estimated to be six feet, thus providing about 300 thousand cubic feet as a mixing zone. It is further assumed that ocean current in this impact area is 0.5 knots and that this condition would provide for the mixing zone to be replenished about 72 times per day. Therefore, an effective mixing volume of about 21.6 million cubic feet of ocean water can be considered to receive the deposition/reaction of the constituents of the plume. The average daily mass concentration of the unburned Orange and pyrolyzate, the hydrogen chloride, and the particulates in deep ocean water would be 0.0009 mg/1, 28 mg/1, and 0.45 mg/1, respectively. From a comparison of those concentrations with the concentrations and predicted effects on the ocean discussed under the proposed action, it is concluded that the discharge of the combustion gases into the atmosphere with resultant deposition on the open ocean surface would not cause any detrimental environmental impact in the water environment. ?_• M§-f.Ar.?JL: Tne major concern of this analysis is the impact of hydrogen chloride exposition on the pi- of ocean water in the reef area and thus on possible inMbition of the deposition/precipitation of calcium carbonate by the reef community. The discussion will consist of a comparison of two approaches to "worst case" analysis of this discharge with a format as follows: Case 1 - assume a "worst case" deposition (that is, deposition of the entire discharge) in the general area of the reef, calculate the resulting concentration of hydrogen chloride, and comment on the significance of this calculated concentration; Case 2 - predict (utilizing the meteorological model, Appendix K) the mass of hydrogen chloride which is present in the atmosphere above the reef impact area, and comment on the significance of the deposition of the entire predicted mass. a_. Case^Jh _ Entire^ Djscharge_:Keef__Area_: It is assumed that the entire daily hydrogen chloride discharge" is'depbsTted into the ocean over a square area (0.25 sq. mile) with the reef running through the center of the area. For a mixing depth of 1 meter (based on depth at the edge of the reef), the average additional concentration of hydrogen chloride from the stack discharge would be about 26 mg/1 per day. The water in the impact zone is not stagnant, as assumed in the above calculation. The current can be conservatively estimated at 0.1 knot thus providing for replacement of the water in the impact zone about five times per day. This replacement factor would adjust the calculated addition of hydrogen chloride to about 5 mg/1 in the ocean water. This would cause a reduction of less than one-half pH unit which would be acceptable for practically any ecosystem except possibly a living reef. Although not considered in the above calculations, the natural buffer capacity of the water in the zone described is higher than normal ocean water due to the 98 �presence of turbidity in the form of coral (calcium carbonate) which has been eroded from Johnston Island. Therefore, even under "worst case" situation, the extent of damage on an acute basis to the reef in the localized impact zone may be quite minimal. However, the damage to the reef on a chronic basis over the duration of the disposal project cannot, be predicted and continuous discharge with the deposition described under this "worst case" situation would not be recommended. b_. Case 2: Predicted Discharge-Reef Area: In actuality, the deposition of hydrogen chloride in the general area of the reef will be much less than under the above "worst case" situation. The sea level concentration of hydrogen chloride below the centerline of the stack discharge plume, at points 0.25 rrles inshore of the reef, at the reef, and 0.25 miles beyond the reef are predicted under "worst case" sea level conditions to be 0.78 ppmy/v °-^2 PPmv/v ancl 0-05 ppmv/v respectively. The isopleths shown in Appendix K are for these sea level concentrations. The concentrations in the vertical direction can also be calculated. The results of the meteorological model represent a steady state solution showing the distribution of the mass of hydrogen chloride on a daily basis. The model results were applied to determine the quantity of hydrogen chloride which is present on a daily basis in the space above the impact area (0.25 sq. mile) to a height of 100 meters. This mass has been calculated to be 0.082 tons and represents 0.44 percent of the daily discharge. For determination of the average concentration within the zone, the highest level found by ~he meteorological nodel, 0.78 ppm y / v was applied. This value is very conservative. If the entire predicted available mass under this "worst case" approach were deposited into the ocean impact zone (1 meter deep), the average daily concentration of hydrogen chloride would be increased by 0.12 mg/1. Application of the ocean water replacement factor of five would result in a lowering of this concentration. The pH depression in this case would be negligible and, therefore, would not cause any acute or chronic damage to the reef. Comparison of above concentrations of hydrogen chloride calculated under both Case 1 and 2 with those calculated for the "worst case" situation described under the "open ocean" above indicates that the respective values of Orange and pyrolyzates and carbon particles would not cause any signifcant detrimental environmental impact. (c) Monitoring: Monitoring of the ocean area is not necessary fron an environmental standpoint. Monitoring of the Johnston Atoll would be accomplished to insure that the local area was not to be affected by disposal operation. (2) Combustion Gas Scrubbers (a) Alkaline Scrubber ]_. Potentials for Impact: The constituents of the spent scrubber water which may have an environmental effect include: heat, chlorine residue, total dissolved solids, suspended solids, and hydrocarbons. The heat and chlorine residual would constitute major pollutant loads and, therefore theie constituents are to be reduced by an appropriate treatment device, i.e. 99 �cooling tower, spray pond, etc. Such treatment would also reduce the suspended solids concentration in the discharge. The hydrocarbon content is a minor fraction of the scrubber water and the discharge rate would consist of: undetectable Orange constituents <0.00036 pounds per day, pyrolyzates and hydrolyzates at 0.021 and 0.005 pounds per day, respectively (Appendix E). The major substance in the scrubber water will be the total dissolved solids. Although not specifically addressed, the alkaline scrubber will be operated so that the pH of the spent scrubber water will be about 8.5 units. 2_. Probable Impact: The spent scrubber water will be discharged to the marine environment on the south side of the island via the sanitary sewage outfall. The mass transport of the sea water and its suspended matter (turbidity) from the sewage outfall is generally to the southwest and therefore, the remainder of the island's aquatic environment is minimally involved. However, during certain conditions, summer season and easterly regional flow, sluggish circulation has been observed along the southern shore of the island. This has resulted in a long residence time and very limited mixing for the sewage discharge (Kooenski and Wennekens, 1965). The reef area which would be primarily affected :>y this flow situation is located on the west side of the island. The disruption and extensive silt production from the major dredging operation in the early 1960's and the characteristic of the ocean currents (high turbidity from erosion of the south side of the island) have already resulted in a depauperate reef community on the island's west shore (Brock et al., 1965). The high total dissolved solids concentration of the spent scrubber water will cause a relatively small mixing zone in the area of the discharge where the specific gravity will be adjusted. Calculations show that one million gallons of ocean water will be more than enough to adjust the specific gravity of one day's flow of spent scrubber water to a specific gravity which is essentially the same as that of the ocean. For an ocean current of 0.25 knots and a dispersal pattern 10 feet wide and 10 feet deep, approximately one million gallons of ocean water would be available to adjust the specific gravity of one hour's spent scrubber water flow (8,300 gallons). In addition, a major part of the total dissolved solids is sodium chloride -35,800 mg/1 (chloride -22,000 mg/1), with the normal ocean chloride concentration being ~20,OOQ mg/1. Therefore, under the above conditions, the mixing zone should not extend farther than 3,000 feet from the ou't~all line. The suspended solids (80-100 mg/1), some o-c which may be removed in the treatment processes, represents a discharge of solids. The suspenced solids are primarily elemental carbon, see Appendix E, and at a maximum of about 200 pounds per 200,000 gallons are not considered significant. The turbidity present in the Johnston Island aquatic environment, particularly south- and scuthwest of the island, would tend to negate the impact of a wastewater discharge containing suspended solids. The minor fraction of hydrocarbons would be further diluted in the receiving water and not be significant from an environmental standpoint. The environmental impact of this alternative is minimal and would be manifested in a small mixing zone near the wastewater outfall. A- Monitoring: This alternative is excellent from the monitoring aspect in that water, sediment, and marine biological samples in the impact area can be readily collected. The discharge occurs in the lagoon ecosystem and extensive analytical chemistry and biomonitoring of spent scrubber water prior to discharge will be required. 100 �]• E2t§Dtja_T_for__Impact_: The constituents of the spent scrubber water which would have environmental impact include: heat, chlorine residue, hydrogen chloride (hydrochloric acid), suspended solids and a minor hydrocarbon fraction. Of primary concern are the heat, chlorine residue, and the dissolved hydrogen chloride.. A daily discharge of 500,000 gallons of spent scrubber water would contain some 37,000 pounds (-1.0%) of hydrogen chloride, and have a temperature of ~160°F and a chlorine content of -250 ing/1. The hydrocarbon content would be similar in magnitude to that stated above for the alkaline scrubber. I- El£^le Jmpact: Although the environmental impact of this wastewater stream could be significant, the major constituents are not considered as persistent pollutants; the heat and chlorine residual will be dissipated and the hydrochloric acid is readily absorbed in the ocean. The buffer capacity of ocean water and its regenerative natural forces make the ocean an acceptable sink for certain acids, particularly hydrochloric acid. On a mass basis, the discharge of 18.5 tons of hydrogen chloride into the ocean is insignificant; however, the impact of such a discharge on the pH in the discharge zone must be considered. Buffer calculations, using the carbonate species as the only buffer, reveal that if 75 million gallons of ocean water are mixed with one burn day's discharge that the pH excursion would be from 8.3 to 6.5 units. It is noted that the pH change w i l l be temporary and the normal ocean pHVill be rapidly established. On a mass basis, the chloride added to this volume (75 million gallons) is 58 mg/1 which is of minor consequence when compared to the usual concentration of -20,000 mg/1. The ocean water required to dissipate the heat and chlorine residual is less than that required for absorption of the hydrogen chloride. To determine a mixing zone, the rate and method of waste stream discharge and the flow of the receiving water is required. If an ocean flow of 0.25 knots and a dispersal zone of 10 feet wide by 10 feet deep is assumed, then in one hour some one million gallons of water will flow by the outfall. Since approximately three million gallons are required for neutralization of one hour's wastewater discharge, the mixing zone may extend to 6,000 feet from the discharge point. This relatively long mixing zone will require that the outfall be placed so that the acidity of the discharge does not affect the reef during the time duration of the project. The ability of the ocean to accommodate acid waste on a "slug" discharge basis has been documented. The following is from Technical Memorandum No. 39, U.S. Army Corp of Engineers: "The permissible pH range for the coastal waters of New York and New Jersey, according to water quality criteria (EPA, 1972), should be from 6.5 to 8.5. The1 pH range observed in the vicinity of the dumping grounds of the N.Y. Bight, ranges from 7.10 to 8.40, and does not exceed the prescribed limits. The only drop in pH would be observed in the waters of the acid dumping grounds, immediately after an acid dump. The low pH value in this area would occur for brief periods. As discussed earlier, Redfield and Walford (1951) have shown that the pH of the water from the wake of an acid dumping barge was above 6.0 in all samples collected more than 3 minutes after dumping and a pH of 7 was reached about 3.5 minutes after dumping." The daily discharge of 500,000 gallons of spent scrubber water containing 18.5 tons of hydrogen chloride represents a 101 �stream of sufficient acidity to cause certain detrimental environmental effects. In addition, the heat and chlorine residual of this stream are sufficient to cause localized detrimental effects. The suspended solids and the minor hydrocarbon fraction of the wastewater are, as previously described, not considered significant as regards environmental impact. It is imperative that this stream not be discharged into the ocean where there are beneficial uses, i.e., swimming, fishing, reefs, water supply within the mixing zone. 3_. Monitoring: The discharge point would be located within the vicinity of Johnston Island, either in an area further off-shore than the present sanitary sewage discharge or in an area to the southwest of the island. In either case, ecological monitoring, primarily in the form of water samples and other samples which can be collected from a boat, can be readily accomplished within the impact zone. 102 �D. MARINE FLORA AND FAUNA ON JOHNSTON ISLAND 1. S^COPE OF CONSIDERATIONS: The potential for adverse effects on marine ecosystems is greater with incineration on Johnston Island than with incineration on the open ocean. The fertile waters of the atoll yield a biomass many times greater than that of the relatively nutrient deficient open ocean. The potential effects of the incineration of Orange herbicide on both marine flora and fauna of Johnston Atoll are considered together in this section since the potential for harmful effects will originate from the same source and will concern the same areas of the underwater atoll. The distribution of fish on the atoll is divided into three zones: 1) the northern peripheral reef area, 2) the southern shoal reef area and 3) the bank or lagoon shoals. The "northern reef area" is characterized by pelagic species of fish such as the shark on the seaward side of the reef and by inshore types of fish on the lagoon side of the reef. The "southern reef area" has fewer nunbers and varieties of fish. The "bank shoals" or lagoon area is characterized by large numbers of inshore types of fish. In all, 194 species of inshore fish have been identified on the atoll. Gosline (1965) classifies the Johnston Atoll fish fauna into 4 components: 1) endemics, 2) fish that have made Johnstcn a stopping point on their migrations north, 3) fish that have made Johnstcn a stopping point in their southward travels, and 4) the pelagic fish to whom Johnston is of little or no significance. Only two species of Johnston fishes have not been taken elsewhere. These are Centropyge nigriocellus and C_. flammeus, both butterfly fishes; neither are abundant' at Johnston. A total of 175 species of marine arthropods inhabit the lagoon water together with 37 species of Echinodermata and 18 species of Cnidaria (e.g. jellyfish, corals). Dredging operations in 1964 directly destroyed 700 acres of living coral. The silt from the operation seriously affected much larger areas of coral. A parallel reducticn in the number of associated invertebrate species and fish also occurred (Amerson, 1973). A large portion of the southwestern reef was seriously affected and remains so today. The algae were also damaged by the increased silt in the credging operation. Also, the dredging affected the distribution of the 67 benthic marine algae identified on the atoll. At least 58 species of mollusca and 12 species of annelida inhabit the atoll. The ocean currents approaching the atoll have a relatively sparse plankton population. 2. POTENTIALS FOR IMPACT ON AQUATIC PLANTS AND ANIMALS: It is obvious that contamination of the waters of Johnstcn Atoll with large amounts of Orange herbicide would result in disastrous effects upon the biota of the lagoon and reef. Thus, the storage of the herbicide and the proposed incineration site was so situated that any unenvisioned, catastrophic accident would not affect the majority of the barrier reef and lagoon. The use of a scrubber system to treat combustion gas would produce a certain localized and controlled amount of water pollution in the down-current area of the cutfall. The use of no scrubber system would be expected to affect a larger area where the exhaust gases contact the ocean. However, meteorological models, Part III, C., indicate that combustion gas components at the plune/ocean interface would be in such low concentrations that there would be minimal effect on the marine ecosystem. 3. PROBABLE ENVIRONMENTAL IMPACT ON AQUATIC PLANTS AND ANIMALS a. Tjxic Chemica'! _and_ Ac id-Base J. f fects_ (1) JjTcpjnpJete Combustion Products: Possible toxic chemicals from incomplete combustion wou'ld" include Orange herbicide components and their pyro103 �lytic products. However, the test incinerations and bioassays (.see Appendix E) proved that Orange herbicide can be incinerated without the production of highly toxic effluents. Continuous analytical monitoring, biomonitoring and failsafe mechanisms described in this report will safely protect against the release of harmful toxic chemicals. Therefore, environmental effects from incomplete combustion products are not considered probable. Biomonitoring would detect very minute amounts of unoxidized herbicide. (2) Complete Combustion^ Produces: Environmental effects could result from the planned, efficient combustion of Orange herbicide which will produce potentially harmful corrosive gases, carbon particles, heat and a minor fraction of hydrocarbons. Two situations are considered where no treatment (scrubbing) of the gases would be used: 1) incineration on the boat would nave no impact on the waters around Johnston Island, especially because of wind and distance factors, and 2) incineration on Johnston Island using no scrubber would be expected to impact on the waters west of the island in a manner quantitatively similar to that predicted for incineration at sea. The major difference between the two is the increased numbers of plants and animals in the waters on, and closely surrounding the atoll. If the saltwater scrubber were to be used, the scrubber water must be delivered into the ocean far enough beyond the reef to provide sufficient dilution in deep water and to insure that the diluted effluent does not flow back onto the reef. The alkaline scrubber system would neutralize the acidic elements' potential toxicity by conversion to their salt forms. Other treatments described earlier would remove chlorine and produce cooling of spent scrubber water. Therefore, probable environmental impact will be confined to a small, definitive mixing zone. The salinity changes would be expected to be of minimum consequence in the warm surface water which has a normal salinity between 34.6% and 34.8%. b. Thermal Pollution: The size and position of the thermal mixing zone will affect the extent"of the environmental impact of thermal pollution from the incineration of Orange herbicide. Normally, the extent of a mixing zone is directly related to requirements for maintaining free passage of migrating aquatic organisms in the body of water. In contrast, the major concern for Johnston Atoll was to select a mixing area away from the lagoon and reef. The location required that currents would d'rect the effluent away from the atoll in the most efficient manner available. The current sewer outfall on the south side of Johnston Island wojld be the optimum site for the alkaline scrubber water outfall. This already-proven site would place the thermal mixing zone in an area where a mixing zone already exists and ecological alterations have already occurred. Thus, t'ie major expected impact would be the resulting shift to more heat tolerable species of plants and animals inhabiting the mixing zone. The warm-water inshore fishes of the lagoon and migrating fishes can easily avoid the mixing zone without harmful effects from the increased warmth of the water. Since the salt water scrubber effluent would entail a much larger mixing zone, the outfall would be placed southeast of the reef. This will place the effluent mixing zone in deeper, colder water in an area where currents will direct it away from the reef. The effects of the heat should be rapidly dissipated. c. Carbon Particle Effects: Fine carbon particles, suspended solids, in the effluent could produce damage to living coral. Suspended fine particles from earlier dredging operations and sediment-laden water from the shoals have severely affected the coral on the southwest: portion of the reef. Carbon particles from the incineration operation are not: expected to contact the living coral 104 �reef. The observations made during the test burn of Orange herbicide indicate that these particles will rapidly suttle out. However, the situation will have to be monitored to determine any impact on living coral. Again, the alternative salt water scrubber effluent would be placed so that currents would carry the carbon particles away from the reef. The use of no scrubber system would result in such a widespread dispersion of the particles as to be of no ecological significance. 105 �E.. TERRESTRIAL FLORA AND FAUNA 1. FLORA OF ISLANDS a. Scope of Considerations: Terrestrial vegetation is relatively sparse on the 4 islands of Johnston Atoll. Only three species of native, vascular plants existed in 1923. .However, the activities of man upon the islands have been responsible for most of the intentioral or accidental introduction of 124 other species. Many species are ornamental and exist only by benefit of special care. Other introduced species or adventive types have adapted to the coral soil and climatic conditions. Damage to the terrestrial flora on Johnston Atoll, is not expected to occur due to Orange disposal. b. Potentials for Impact (1) Complete Combustion of Orange herbicide resulting in the production of corrosive hydrogen chloride and chlorine in the exhaust gases. (2) Incomplete Combustion resulting in escape of unoxidized herbicide and other pyrolytic products tn"exhaust gases. (3) Accidental Spills of liquid herbicide on land producing localized effects on terrestrial plants. c. Probable Impact: No detrimental effects to terrestrial vegetation would be expected from the incineration of Orange herbicide on Johnston Island. Meteorological constraints would be utilized -co insure that the effluent gases from the unscrubbed stack gases do not impact on the islands in harmful concentrations. The incinerator operation under the principal alternative would contain sufficient safeguards to protect against incomplete combustion or accidental spills. However, should even these safeguards fail and the unlikely event of.an atmospheric contamination occurs, the physical position of the operation on the atoll in relation to prevailing winds would protect the flora on the four islands from atmospheric exposure.. d. Monitoring Methodology for Air Contamination: With incineration aboard ship no products of combustion would ever reach the atoll area so that monitoring will not be necessary. For the principal alternative of incineration on Johns-:on Island both analytical and biological monitoring for air pollution would be used. Biological monitoring using highly sensitive indicator plants would signal trace air contamination with herbicides or corrosive chemicals in time to prevent extensive damage to other plants should man-made safeguards fail. 105 �2. FAUNA OF ISLANDS a. Scope of Considerations: Except for man, seabirds are the most ecologically important species on the four islands of Johnston Atoll. There were originally no mammals on the islands and only one species of reptile. Man introduced the dog and cat, rodents and three species of geckos. Also, sixtyeight species of arthropods are associated with arid distributed in relation to the bird populations on the islands. All the terrestrial animals on the atoll are of relatively little importance in relation to the considerations that must be given to protect the large number of seabirds that use the islands for breeding and nesting rounds. Sand Island is the major island of importance to the birds. Man's activities on the other islands limit the size of their bird populations. b. Potentials for Impact: Exposure of the animals on the atoll's islands to atmospheric contamination from improper functioning of the incinerator could result in harmful effects related to the concentration-dose of such theoretical contamination. 1 The noise and activity of the incineration operation could discourage seabirds nesting activities if placed too close to the nesting areas. Damage to the birds' food supply would also be detrimental if it should occur. c. Probable Impact: No impact on the terrestrial fauna of Johnston atoll is expected from tfie incineration of Orange herbicide. Any atmospheric contamination would be signaled early by indicator plant damage at concentrations low enough to forestall damaging doses to animal life should any incineration safeguard systems fail. Most certainly, incineration of the herbicide on shipboard, downwind from the atoll, poses the least chance of all of exposing the animals of the atoll to combus:ion gases. With the option of incineration on Johnston Island, the proposed location of the incinerator on the southwestern tip of the island is purposely positioned so that any air contaminants will be carried away from the other islands. Winds are from between northeast and east 85% of the time on the yearly average. Also, the site of the incinerator will be Far enough from Sand Island to prevent any disturbance of the birds there. Sand Island is 2-1/2 nautical miles from the proposed incinerator site. The seabirds feed from the ocean in a 100 mile radius around Johnston Atoll rather than from the shallow waters of the atoll. Thus, their food supply could not be affected by the incineration operations. As noted earlier, studies with phenoxy herbicides indicate that they are not highly toxic: to birds. Also, these herbicides do not accumulate in the food chain. 107 �F. SOIL (CORAL AND SAND) 1. MOVEMENT: There are no research data on the movement of the herbicide Orange in compacted coral. However, it is known that CaC03 rapidly "fixes" herbicide Orange and in fact has been suggested as a chemical compound to "clean up" spills of the herbicide. Based on observations made on Johnston Island, spills of the herbicide are readily and rapidly contained. After 2,4-D, 2,4,5-T and TCDD reach the soil each moves through the biosphere and accumulates or degrades according to its own chemical and physical properties (Advisory Committee, 1971). Once the herbicides and TCDD reach the soil they become immediately subjected to physical and chemical actions that continually reduce the amount remaining at the site of application. These actions include degradation by soil microorganisms, leaching and surface movement by water, volatilization, movement by wind and photochemical decomposition (Amerson, 1973). 2. PERSISTENCE: There are no available data on the persistence of 2,4-D and 2,4,5-T in compacted coral. However, the limited diurnal and annual variation of the relatively high temperatures - annual mean of 79.3°F with daily variations of only 7-8°F - and of the high relative humidity (annual mean is 75%) (Amerson et^ aJL, 1973) should favor "he rapid decomposition of the herbicide. The persistence of 2,4,5-T, influenced by its rate of application, climatic conditions and other factors, occurs most rapidly under conditions that are optimal for the growth of soil bacteria (Zelinski and Fishbein, 1967). Loss of all phytotoxicity of 2,4,5-T applied to the soil was reported to occur in 3 - 6 months after application (Kearney arid Negh, 1972). 108 �G. THE ECOLOGICAL SIGNIFICANCE OF JOHNSTON ISLAND: AUTHORITATIVE OPINIONS. Amerson (1973) states in the "Ecological O.aseline Survey of Johnston Atoll, Central Pacific Ocean" that the document was reviewed by four well known Geologists in various fields. The purpose of the reviews was to assess the ecolcgical significance of Johnston Atoll. Their opinions have been summarized as follows: 1. Ray Dasman of the International Union for Conservation of Nature states: "Because of its small size, and extreme isolation Johnston Atoll was originally of considerable ecological interest as an area in which it would have been possible to follow the slow process of colonization and establishment of species on oceanic islands and to study over the years the processes that may have led to the development of new races or species in its limited biota. The opportunity was lost with the exploitation of the island and later with its development as a naval and air base. Hcwever, human occupancy of the island followed by the irtroduction and establishment of many new species of plants and animals has created an equally interesting ecological situation in which the interactions among its still limited biota could profitably be studied. Such situations, however, occur Dn many other isolated oceanic islands, and Johnston cannot be considered as particularly unusual or of outstanding interest from this point of view." "Considering the dry land area of Johnston Atoll, the greatest concentration of ecological interest is to be found on the remaining natural island, the ten acres of the western portion of Sand Island. This is the principal breeding area for seabirds and appears to support the most complex terrestrial biota. Sand Island is of major importance for its breeding population of Sooty Terns and of significant importance for breeding populations of Red-footed Boobies, Brown Noddies, Wedge-tailed Shearwaters and Great Frigatebirds. It is significant also as a wintering area for shorebirds, notably the Golden Plover and Ruddy Turnstone. Every effort should be made to minimize disturbance of this area in the future and to maintain it as a refuge for seabirds. With protection and freedom from disturbance its value as a seabird breeding center can be expected to increase, and it will achieve greater value as a site for ecological studies. By contrast, the ecological interest of the eastern, man-made portion of Sand IsTand, of JohrisTpn'TsTancT oOTcati an3~oTTTiklna'TsT'ari'ds TTTHgfil jfF" tfie present t^eJ"a^TioJ£n_Tf~disturbance' pTTTJese areas we're to~b"e greatly" reduceTTn tfie future','they would no douEt_be coTpHTzejJ in~tTme by breeding po'puTations~of sealairds.""" TEmpRasis Added!" "The marine area of Johnston Atoll can be considered of equal interest to the terrestrial area. Although the marine biota has not been thoroughly studied, the inshore fish population appears to be of considerable biological interest and it is likely that further studies will reveal a higher degree of endemism than is now reported, particularly among the marine invertebrates. Considerable damage to the marine fauna has resulted from past dredging and filling operations. Future activities of this nature, when necessary, should be conducted with greater precautions to minimize damage to reef and lagoon fauna." "Considering that Johnston Atoll may continue to be used for a variety of purposes in the future it is recommendec that particular attention be given to protection of the western portion of Sand Island for the purpose of maintaining the seabird breeding colonies and their associated biota and to maintaining 109 �the reef and lagoon biota in a healthy state, allowing for its recovery from past disturbance. Avoidance of pollution and siltation of the reef-lagoon complex should be given priority." 2. Robert E. Jenkins of The Nature Conservancy state_s: "Of particular importance to Johnston Atoll is the recurring theme of its seabirds. In spite of all of the "reconstruction" which has severely changed the original natural environments in the area, there is still a tremendous seabird population using the near-shore feeding grounds or breeding-primarily on Sand Island. The information collected on these birds forms a truly inpressive body of data. The monumental accomplishment of having banded over 300,000 individual birds in the course of 6 years has already added greatly to our knowledge of .population dynamics, distribution, faunal exchange, site constancy, breeding systems, species composition, etc., and in the years ahead should add even more to our understanding of some important components of the oceanic system." "There have also been fairly extensive studies made on the effect of the dramatic and pervasive human alteration of Johnston Atoll. A continuation of these studies will give us new insight into the effect of dredging on the physical and biological environment of coral reefs, the effects of greatly enlarging the terrestrial mass in the area tnrough the creation of entirely new superaquatic platforms from native materials, and the effects of stocking these (howeve-" haphazardly) with a large number of exotic species of plants and animals. The increase in the vascular plant flora from three species in 1923 to 127 in 1973 provides us with a very interesting case in point. In the last few years, the relatively young discipline of "island biogeography has been yielding new insights on a number of ecological and evolutionary phenomena such as colonization, competition, extinction, community stability, genetic adaptation, ecological exclusion, niche dimensions, etc., and the Johnston Atoll situation represents a unique experiment in this field which could richly reward intense scrutiny. Aside from the population and community phenomena which are favorably isolated for investigation, the effects of the biota in modifying the raw, new substrates over time should be carefully observed and documented. Within the aquatic environment, the same processes of ecological recovery from the effects of dredging and filling provide us similar opportunities." 3. Lee M. Talbot, Senior Scientist, Council on Envirpnmental Quailty states: "Johnston Atoll has high ecological significance for two primary reasons.. The first derives from its isolated location in the central Pacific Ocean. Study of the organisms found there can contribute significantly to the understanding of migration and distribution nechanisms and evolutionary ecology of a variety of types of organisms. The inshore fishes are exemplary of this in connection with the distribution, disperse01, and introduction of warmwater fishes." "Another allied source of ecological significance to this isolated Atoll derives from what studies based there can indicate about the migratory movements of birds, their parasites and pathogens, marine mammals, reptiles, and fishes. The bird studies have been the most extensive to-date, of course, and the detail in this paper reflects that." Ill) �"The other, and in my opinion more important reason for its significance, derives from the history and natjre of the Atoll. In its present form it is very largely man-made. Even tnose parts that have not literally been constructed by man have been very significantly modified. This history is well documented with scientific collections, descriptions, and maps and with extensive photographs. At the same time, it is a relatively simple ecosystem from the standpoint of topography and other physical aspects. A high percentage of the terrestrial organisms have been introduced by man (e.g., 124 out of 127 species of vascular plants, and all of the terrestrial mammals and reptiles). Since most of these introductions are of comparatively recent origin and many can be reasonably well dated, the Atoll provides an almost uniqje laboratory in which the mechanisms of dispersion, introduction, adaptation, and development of an ecosystem and its component species can be studied. The uniformity and simplicity oi7 a substrate further facilitates study and comprehension of the mechanisms and isolation and understanding of the dynamic processes involved." 4. George W.. Watson, Curator of Birds,, National Museum of Natural History states: "The birds frequenting the atoll may be classified according to activity into breeders, offseason or prebreeding migrants, and vagrants. The ecological significance of the last is nil. The island does not play any role in the survival of the species and perhaps very little role in the long-term survival of the errant individual. Far and away the most important breeding bird is the Sooty Tern which produces about 50,000 chicks a year on Johnston Atoll. Lesser numbers of Brown Noddies and Wedge-tailed Shearwaters use the island for breeding as do relatively insignificant numbers of other species. None of these species is restricted to Johnston Atoll nor is the population on Johnston Atoll a significant fraction of the Pacific Ocean population of the species. There are no endemic landbirds or seabirds restricted to the islands." "The same is true of the five species of shorebirds that regularly visit the islands on migration. Most of these are wide-ranging and scatter from their largely arctic breeding grounds over much of the tropical oceans of the world. One species, the Bristle-thighed Curlew is considered rare and endangered on its breeding grounds in Alaska. It disperses so extensively to islands in the tropical Pacific Ocean, however, that even if the Johnston Atoll birds were eliminated, the total species population would not be jeopardized." "What still remains unknown is the importance of seabirds in the overall marine environment. Obviously in the waters near the island concentrations of birds can exert predation pressure on sma"1 fish, crustaceans and squid and thus limi: populations in relatively infertile tropical waters. There is little feeding by seabirds in the lagoon or other waters near the atoll. (Emphasis Added) Sooty Terns are probably feeding at up to a full day's flight away from the atoll. Some of the other species may also have great daily flight ranges. Nor is it known exactly where most of the individuals that breed on the island go during the period when they are not breed'ng. It is known that the island serves as resting or roosting ground for numbers of birds that breed elsewhere, particularly boobies from islands to the north in the tropical Pacific Ocean." Ill �H. HUMAN WELFARE: The discharge of effluent streams resulting from the incineration of Orange at sea or on Johnston Island will not endanger the health of any personnel either aboard ship or on Johnston Island. The data contained in Appendices D and E attest; to the essentially complete destruction of herbicide by the incineration process. For the proposed action of incineration at sea, only those personnel who are directly involved in the disposal project, that is the ship's crew, will be subject to any of the project's risks. The potential for exposure of personnel aboard the ship to herbicide will be very minimal. The Orange storage tanks are enclosed and the exhaust gases from the ship's incinerators will be carried away from the ship. In addition, there is no means possible for contamination of the ship's drinking water supply with Orange. The relatively few personnel involved, the fact that all personnel involved are actually working on the project, and the complete lack of a means of exposure of personnel to the incinerator effluent stream, makes incineration at sea highly favorable from the human welfare standpoint. For incineration on Johnston Island, consideration must be given to all of the personnel employed on Johnston Island both from the standpoint of potential air and drinking water contamination. The exhaust stack will be located on the west side of the island so that the normal and dominant winds will carry the combustion gases away from the atoll. Drinking water is provided for Johnston Island via distillation and the water intake is located on the north side of the island, "he scrubber water discharge, if a scrubber was to be used, would have to be constantly monitored, and the discharge point would have to be selected so as to minimize any potential for contamination of the water supply. If a scrubber was not used, the water supply will still be constantly monitored to insure that any impact by fallout of stack gases will be detected. In addition, the stack height will be such that the majority of the exhaust gas will riot fallout in the atoll. The principal alternative incineration on Johnston Island - while acceptable as regards human welfare is not as favorable as the proposed action - ircineration at sea. This is due to the proximity of personnel not directly related to the project and of the source of the island's water supply. In addition, the proposed action is more favorable since it minimizes exposure time of personnel who will be involved in handling and transfer operations. While proper industrial hygiene procedures will be required, incineration at sea can be completed much faster than incineration on Johnston Island and, therefore, any exposure time will be reduced. The safety and industrial hygiene aspects of each option have not been discussed, but any contractor working on this project will be required to concur with all applicable legislative criteria. 112 �I. BENEFICIAL ASPECTS OF THE PROPOSED ACTION: There are no beneficial aspects, in the absolute sense, for the proposed disposal action. However, there are very important benefits to be obtained by performing the disposal action in a timely manner. These benefits include: 1) ninimizing the cost involved in maintenance of the Orange storage areas, 2) naking the land in the current storage areas available for other use, and 3) eliminating potential contamination/pollution of the Johnston Island lacoon. The present storage of the Orange at Johnston Island is in 55-gallon drums at a site adjacent to the lagoon which is not a desirable situation from these three aspects. Routine maintenance of the storage site is accomplished to identify leaking drums, fix or redrum the leakers, and contain (by absorption in coral) any spillage resulting from the leakers or the redrumming operation. This operation is quite expensive. The land area which comprises the storage site on Johnston Island is high value property and its dedication for long term storage of Orange represents a constraint on future plans and activities on the island. The normal operation of the storage site represents a low level potential for contamination of the lagoon water. However, a catastrophic event affecting the herbicide storage area could cause massive spillage and could result in pollution of the lagoon, possible contamination of the drinking water supply, and possible damage to the reef. Incineration at sea is favorable from these considerations in that the Orange herbicide would be quickly and totally removed from the Johnston Island environment. The removal of Orange at Johnston Island would require two loadings of the ship, which means that all of the Orange could be removed from Johnston Island in less than one month from the start of the project. Incineration on Johnston Island would require that operations involving Orange handling and transfer be continued for the duration of the incineration process. It would also probably require use of even more land, for installation of the incinerator, than is currently used for storage. The time period for incineration on Johnston Island has not been fixed since an incineration scheme has not been decided as yet; however, it is felt that, in a trade off between facilities and manpower cost, about one year would be required. Another somewhat indirect benefit which can be discussed on the basis of the time and place of the incineration project is the costs associated with ecological and technical monitoring associated with the project. Monitoring programs are very expensive as regards equipment, manhours, travel requirements, chemical analyses, and data analyses. Incineration at sea which does not require ecological monitoring would be more favorable than the principal alternative of incineration on Johnston Island, in which an extensive monitoring program will be required during and for a distinct time period after completion of the project. In summary, there are very important beneficial aspects which can be attained by the timely completion of the disposal project and these are best served by incineration at sea. 113 �(This page intentionally left blank) 114 �PART IV ADVERSE ENVIRONMENTAL IMPACT WHICH CANNOT BE AVOIDED: There will be no adverse envrionmental effects from the disposal of Orange herbicide by the proposed incineration. A manufactured product, which cannot be utilized for the purpose for which it was .nanufactured and purchased, is to be disposed of via incineration which converts it into the basic chemical compojnds: carbon dioxide, water, and hydrogen chloride. The incineration process will discharge these compounds in exhaust streams into the environment. Their discharge will result in a minimal impact of a transient nature in a relatively small zone near the point of discharge; however, these compojnds are compatible with the atmosphere and ocean environment of the open tropical sea. It is feasible to destroy at least 99.9 percent of all the herbicide and its TCCD content, see Appendices D and E. Any pyrolytic hydrocarbon products of undetectable herbicide feed constituents in the combustion gases will not be of sufficient rragnitude to be environmentally significant, see Appendix E. Less than one percent of the herbicide will be converted to particulate material, primarily elemental carbon, which will be discharged with the exhaust stream. These particulates will not be of sufficient magnitude to result in other than minimal localized environmental effects. 115 �(This page intentionally left blank) 116 �PART V ALTERNATES TO THE PROPOSED ACTION PAGE 4 A. PRINCIPAL ALTERNATIVE - INCINERATION ON JOHNSTON ISLAND -------------119 B. CONVENTIONAL INCINERATION IN THE CONUS -----------------------------119 119 1. LIQUID WASTE INCINERATORS------------------------------------------ a. General b. Diagram 2. INCINERATION AT ROCKY MOUNTAIN ARSENAL -------------- ..... ------121 a. b. c. d. Introduction -----------------System Description--------..... Proposed Incineration - RMA Exhaust Gas Discharge 122 3. APPLICATION TO CRANGE----------.....------------------------------- c, usr---------------------------------------------------------------------------123 123 1. DESCRIPTION OF ACTION----------------------------------------- a. General b. Purpose ENVIRONMENTAL IMPACT --------------------------------------------124 f.. 125 D. RETURN TO MANUFACTURERS------.....--------.....----------------------125 F. L)FFP (INJECTION) WELL DISPOSAL—-......----------------------------- F. BURIAL IN UNDERGROUND NUCLEAR TEST CAVITIES ----------------------- 125 126 G. SLUDGE BURIAL-------.....--------------------------.....------------------126 1 . GENERAL---------------------------------------------------------- ?... 126 ENVIRONMENTAL IMPACT—......----------------------------------I Of' a. b. c. d. General Impact --------------------------------------------- '£° Impact on Air Quality----------------......------------------' ^ Impact on Water Quality-------------------------------------V? Land Use—.......----------------------.....-----------..... C e. JU I I soil--------------------------......------------------------ f. Vegetation------------------------------......---------------- 117 �128 H. MICROBIAL REDUCTION--------------------------......----------------128 1. DESCRIPTION OF ACTION-----------------......------------------- a. Genewl--------------------------------------------------------]28 8 b. Treatment Methodology-------------------------------------128 2. ENVIRONMENTAL IMPACT------------------------------------------129 I. FRACTIONATION--------------------------------------.....-----------13 J. CHLORINOLYSIS---------------------.....----------------------------- ° 132 K. SOIL BIODEGRADATION--------------------.....------------------------132 1. DESCRIPTION OF ACTION------------------------------------------- a. General------------------------------------------------------- ]32 b. Site Criteria for Soil Biodegradatiori--------------------- 3 33 (1) Physical Factors-------------------------------------(2) Biological Factors -----------------------------------(3) Management Factors-------------.....------------------- c. Method of Incorporation -------------------------------------135 2. ENVIRONMENTAL IMPACT----------------------------------------------- a. b. c. d. 3 General-----------.....------------------------------------Air Quality Impact on Water Quality-----Vegetative and Animal Communities 136 L. NO DISPOSAL ACTION-------------.....---------......------------------- 1 . INTRODUCTION---------------------------------------......— ......136 136 2. ENVIRONMENTAL IMPACT-----.....----------------------------...... 118 �A. PRINCIPAL ALTERNATIVE - INCINERATION ON JOHNSTON ISLAND: The Air Force proposes the destruction of Orange herbicide via incineration on a ship at sea. However, this action is dependent on the !:PA issuing a permit in accordance with the Marine Protection, Research and Sanctuaries Act of 1972. If the EPA administrator decides not to issue a permit, the Air Force will pursue the principal alternative of incineration in .a facility which would be constructed on the west side of Johnston Island. A detailed description of the incineration parameters and the environmental analyses of the operation are presented in Parts II and III. The facility on Johnston Island would probably be designed to inciaerate about 206 drums of herbicide per day. At this rate, approximately 200 Durn days would be required to incinerate all 2.3 million gallons of the Orange stocks. If a portion of the herbicide is registered by EPA, then the project time would be shortened or a smaller facility would be constructed. The incineration facility on Johnston Island would provide essentially complete destruction of undiluted Orange herbicide, and the environmental impact of the facility would be minimal. The potential impact on the delicate ecosystem of Johnston Atoll and lengthy project duration make this alternative less desirable than the proposed action. B. CONVENTIONAL INCINERATION IN THE CONUS 1. LIQUID WASTE INCINERATORS a. General: The term "conventional" is used to describe incineration systems which have a refractory lined combustion chamber and afterburner section and use a "flame" concept of combustion. These systems can handle a wide range of waste volumes from 1,000 T.O 10,000 pounds per hour. The normal design termperature range is 1800 to 2100°F; above 2100°F construction material becomes an operational and economic problem. The temperature attained in a given incinerator "is a function of the physical unit, i.e. size, shape, construction materials, the caloric value of the waste fuel, and the fuel to air ratio. To insure efficient combustion, at least 20 percent excess air is required . The means of conditioning and injecting of the fuel are also important factors in incineration efficiency. A turbulent environment is desired in the combustion zone to insure exposure of tie fuel to the heat sink and to prevent insulation of fusl particles by other fuel particles. Fuel injection systems are designed to insure intimate nrxing in the combustion chamber; the viscosity and atomization of the fuel must be controlled to insure thorough vaporization and combustion before being exhausted from the incinerator. Atomization can be accomplished mechanically (nozzles), by two phase flow (fuel/ air nixture) or by a corrmnation of both methods. For atomization, the liquid waste should have a maximum viscosity of about 160 centipoises. At greater viscosities, atomization may not be fine enough and the resultant droplets of unburned liquid may cause smoke or other unburned particles to leave the unit. Viscosity is usually controlled by heating the liquid with tank coils or inline heaters. Another important factor in system efficiency is the "stay time," i.e. the time duration in which a fuel particle remains in the combustion zone. The longer the "stay time" for a fuel particle the better its chance for combustion. The stay time, around three seconds for conventional incinerators, is limited by system size, air flow, turbulence, and gas dynamics. A conventional incinerator is best operated on a continuous basis as the cooling and heating of refractory material must be done properly to insure that such materials are 119 �Scrubber Combustion Gases Vented To Atmosphere .[Sampling Hplatform Deluge Tank Stack Ignition Afterburner* Section ; Exhaust Draft Fans ^-Filtered Liquid Waste ^-Auxiliary Fuel (as needed) FIGURE V-l: Caustic Scrubber Water -Spent Scrubber Water SCHEMATIC OF COMMERCIAL INCINERATOR FACILITY I �riot damaged. This situation makes the conventional incinerator more appropriate to long term burning projects as opposed to projects which require frequent start/stop procedures. In addition, the size of the units and the type of construction are not generally conducive to transportation and construction on a portable or semi-permanent basis. b. Diagram: A schematic of a commercial incinerator system is shown in Fig V-l. Incineration of chlorinated hydrocarbon fuels such as Orange will resu'it in hydrogen chloride in the combustion gas; the hydrogen chloride is removed by the venturi scrubber which uses a caustic scrubbing liquid. The scrubber water may require neutralization prior to discharge to a natural water system. The incinerator system also includes gas analysis equipment, accessory fuel storage/feed systems, and process control systems. 2. INCINERATION AT ROCKY MOUNTAIN ARSENAL a. Introduction: An incineration system has been constructed, « installed, and operated at the U.S. Army Rocky Mountain Arsenal (RMA) in Colorado which, by technical investigation, appears to be capable of incinerating the Orange in an environmentally sa~e manner. The RMA incinerator is used to destroy mustard agent and many of the problems associated with the incineration of mustard and Orange are similar. The problems arise from the similarity between mustard and Orange as regards certain physical and chemical properties and environmental impact. These problems include: fuel conditioning, high temperature incineration, acceptable effluents, real time monitoring arid drum disposal. The problems are handled at RMA; but, the facility is necessarily of considerable value, and the waste feed rate of ~2 gallons per minute (gpm) requires considerable time to incinerate a given quantity of material. The information below regarding the RMA facility has not been reviewed by U..S. Army., nor has any action been taken to contract the RMA facility for Orange incineration. This proposal is presented to show that incineration in the CONUS is a viable technical and environmental option. For additional information on the RMA facility the reader is directed to "Final Environmental Impact Statement for Project Eagle - Phase I, The Disposal of Chemical Agent Mustard at Rocky Mountain Arsenal, Denver Colorado, Headquarters, Department of the Army, Washington 25, D.C." b. System Description: The system consists essentially of fuel feed tanks, incinerator, packed Tower scrubbers, electrostatic precipitator, a spray drier, and a "thaw house" for temperature control of the fuel. The combustion gases are passed through a packed column liquid scrubber which utilizes sodium hydroxide for acid gases removal, and then through at electrostatic precipitator for particle removal. The gases are then discharged to the atmosphere through a stack; there is a stack gas monitoring system; and RMA has established monitoring stations on the facility's perimeter. The scrubber water is spray evaporated, and a sodium salt is produced as a residue. There is no liquid effluent from the system, but the solids generated in the precipitator and evaporator require final disposal. Fifty-five gallon drums can be treated by being "burned-out" in two special furnaces which are adjacent to the main incinerator. The exhaust from these furnaces is treated in the same manner as 121 �that from the incinerator unit. The heat destroys the integrity of the drums and they are sold as scrap. Paragraphs 4 arid 5 of Tab C to the Final Environmental Impact Statement for Project Eagle - Phase I concern the combustion of mustard in a bench scale unit which does not include effluent gas scrubbing. Mustard agent, as the sole fuel, was destructed to 99.9999994 percent in the laboratory unit under conditions less than the design criteria for the full scale RMA facility: shorter residence time, no atomization of fuel, lower air supply, lower temperature, and less turbulence. Personal communications with a representative of RMA revealed that no combustion gas samples (prescrubber) have been collected, but that scrubbed gas samples are collected and analyzed on a continuous basis. To date, Jul 74, no mustard has been detected in these samples, and the detection limit is 0.03 mg/cbm. In addition, RMA representatives were of the opinion that mustard agent would not be removed in the scrjbber process. Therefore, based on the detection limit and an input of 2 gallons per minute the calculated destruction efficiency is 99.9887 percent,. The chemical/physical similarities between Orange and mustard considered with ths demostrated capability of Orapge combustion and the very efficient combustion of mustard accomplished at RMA indicate that the facility could adequately destruct the Orange. c. Proposed Incineration - RMA: Incineration of 2.3 million gallons would require approximately"27 months. The system can operate at >2,000°F with a stay time of 2-6 seconds. Although no actual Orange incineration data is available, it is felt that the experimental data, Appendix D and E, show that such operating conditions will adequately destroy the herbicide and TCDD. In addition, the caustic scrubber will provide additional treatment of the combustion gas. The elimination of the liquid discharge, the slow rate of incineration, the combustion gas treatment, the monitoring systems installed, and the drum cleaning capability make this option extremely attractive. d. Exhaust Gas Discharge: The exhaust gas is discharged through a 55 feet stack located near the center of the RMA facility. The stack gas will contain essentially no herbicide esters and acids, TCDD, and particulates. The amount of hydrocarbons, based on comparison with data from Orange incineration projects, in the stack gas will be extremely small (fractional microgram per liter concentration). 3. APPLICATION TO ORANGE: Based on technical and environmental considerations, incineration in the CONUS in units such as the RMA facility could be safely accomplished. Unfortunately incineration units of sufficient capacity are located near centers of population and industry, and these areas are already marginally acceptable from a pollution viewpoint because of presently occurring degrees of air pollution. Furthermore, local and state governments are generally opposed to the importation of waste for disposal within their areas of jurisdiction. For the above reasons, incineration yi the CONUS is not a viable alternative. 122 �C. USE 1. DESCRIPTION OF ACTION a. General (1) Orange herbicide is not an EPA registered pesticide and cannot be domestically used or sold. The Orange herbicide stock to be destroyed by the action proposed in this environmental statement represents a resource of considerable monetary value. The safe and appropriate utilization of all or part of this resource would certainly be a beneficial action. The Air Force has been and is continuing to pursue the possibility of EPA registration of portions of the Orange herbicide stock. Affirmative action on registration prior to the contractual initiation of the proposed action, incineration at sea, or the principal alternative, incineration on Johnston Island, would insure that the stock which is registered would not be destroyed. Orange herbicide has a potential use on Federal lands as well as on privately owned lands; however, any use would require registration. The prudent disposition of Orange herbic'de for use on privately owned or governmentally owned lands may have a tremendous impact on increasing the availability of certain natural resources, e.g. rangelands and forests. (2) Undesirable weed and brush species are widespread in every region of the United States. Their combined impact on rangelands and production of commercial timber is enormous,. Approximately half of the total land area of the United States is used for pasture and grazing purposes, and weeds and brush are a problem on nearly all these forage lands. Economic losses from weeds on forage lands are virtually incalculable and include low yield of forage and animal products per jnit area, reduced livestock gains, and livestock poisoning. Although herbaceous weeds are found on all rangelands in the United States and result in forage losses, brush is the primary problem. Various brush species dominate an estimated 320 million acres of rangelands (Palm, 1968). More than 80 percent of 137 million acres of grazing land in Texas alone is infested to some extent with brush. Once established, woody plants such as mesquite (Prosopis spp.), juniper (Juniperus spp.), oak (Quercus spp.), and Sagebrush (Artemisia spp.) cannot be eliminated by good grazing practices alone. Measures must be taken to convert brush-dominated rangeland to more productive types of vegetation. Good brush control and striking improvements in the grazing capacity of rangeland may be obtained most economically by low-rate and low-volume applications of phenoxy herbicides (Kirch, 1967). (3) Commercial forest land in the United States is estimated at 509 million acres. Although much of this land is not under any form of planned management for production of forest products, management for an increased productivity will soon become essential to meet the needs of the United States population (Palm, 1968). Walker (1973) summarized the total area of forest lands supporting important amounts of undesirable vegetation at some 300 million acres, 'or a land area of potentially commercial timberland equal to roughly the combined areas of Texas, California, c.nd Washington. Gratkowski, Hopkins and Lauterback (1973) have estimated that there are some 4.7 million acres of commercial forest land in western Oregon and Washington on which the land is occupied by vegetation whose presence precludes reestablishment of conifers. Much of the area is in the highest productivity class for growth of forest products. 123 �(4) Concepts of selective brush control have been developed for reforestation with the aid of commercial formulations of 2,4-D and 2,4,5-T. There are presently some 100,000 acres being treated each year with various formulations of these materials, all as the low-volatile esters. Success has been good, especially in operations on the slower-growing brush species (Lauterback, 1967) (Theisen, 1967). b. Purpose: J"he purpose for using herbicide Orange on rangelands and reforestation "is" to* reduce the amount of undesirable vegetation that dominates in selected regions of the United States because of past disturbWith' ^e use of"herbicide . ^ Orange, a more diversified and desirable variety of plant species may become established. This in turn i/vill have a substantial impact on increasing productivity of these regions. 2. ENVIRONMENTAL IMPACT: The environmental impact of using herbicide Orange for chemical brush control will vary from region to region and whether it is for range or forest use. However, regardless of the region of use,or for rangeland or reforestation, critical assessments of effects on vegetation, wildlife, domestic livestock, soil microorganism, aquatic life, rangeland or forest waters, and man must be evaluated. Young et^ al_. (1974) have evaluated the ecological consequences of massive quantities of 2,4-D and 2,4,5-T, i.e., Orange. Their five-year study documents the persistence, degradation, and/or disappearance of the herbicides from soils and drainage waters of an approximately one square mile area that had received 345,117 pounds of herbicide. Moreover, ecological assessments were made of the herbicides' subsequent effects (direct and indirect) upon the vegetative, faunal , and rnicrobial communities. The summary of their five year field study is included as Appendix F. 124 �D. RETURN TO MANUFACTURERS: In March 1972, seven manufacturers of herbicide Orange were contacted regarding the possibility of chemically reprocessing Orange herbicide whereby all impurities, including dioxin, would be extracted or destroyed. Results from all manufacturers were essentially the same; i.e., they did not feel that they were capable of reprocessing the product without extensive investment in .equipment and/or development of new processes. Lead time for this type of action would require in excess of 18 months before large scale reprocessing could begin. As a result of EPA's acticn on 24 Jun 74 to cancel hearings on the possible further restriction of 2,4,E-T, the manufacturers have again beer contacted (Aug 74) via letter to determine if their position may have chanced. Manufacturers have indicated that they do not have the capability to reprocess Orange without major research efforts and capital expenditures. E. DEEP (INJECTION) WELL DISPOSAL: This process involves injection of the herbicide into a deep sub-surface formation. This well hole down into the formation is lined with casing which has been cemented into place to prevent fluids from rising to the surface outside of the casing. A packer tube runs from the surface inside the casing to a permeable geologic formation. The herbicide drums are emptied into tanks or vats on the surface where the Orange is diluted and then pumped down the tubing to the permeable formation. The packer tool prevents fluid from returning to the surface inside the casing and impermeable upper and lower formations adjacent to the permeable formation restrict vertical movement. This process has not been approved by state agencies, or the EPA, and deep well injection is not considered environmentally safe or desirable disposal method for waste materials. The policy is to oppose all storage or disposal of wastes in deep wells without strict controls and a clear demonstration that such disposal will not: a) interfere with present or potential use of sub-surface water supplies, b) contaminate interconnected surface waters, or c) otherwise damage the environment. Little concrete information is available on what degradation of the Orange would occur at the depths, temperatures, and pressures encountered in deep wells. This coupled with the possibility of sub-surface disturbance at a later date allow Orange to migrate into formations leading to water supplies or othe1" valuable formations, has prevented any of the firms interested in disposing of Orange in deep wells from obtaining state or Federal permits. F. BURIAL IN UNDERGROUND NUCLEAR TEST CAVITIES: The Atomic Energy Commission was contacted regarding the possibility of disposing of the Orange by burying it in an earth cavity formed during underground nuclear testing. They advised that a major research, development, and experimentation effort would be required to prove the practicality of this alternative. In view of the time required for this effort, it is rot considered a feasible alternative. 125 �G. SLUDGE BURIAL 1. GENERAL: This technique offered definite promise, but there was a lack of interested and qualified industries to undertake the necessary preliminary investigations. This process involves one concept of destroying the Orange through bacterial action. T.ne proposal envisions constructing trenches in geologically suited formations on isolated government land. The type of formations picked for the trenches would preclude vertical and lateral movement of the Orange. The trenches would be filled with drums containing the Orange and would then be surrounded by secondary sewage plant sludge, which would provide a growth medium for the bacteria. The tops of the drums would be holed to allow a controlled release of the Orange. The trenches would then be mounded with dirt fill and aggregate. Depending upon the type of bacteria selected to decompose the Orange, vents might also be required. This process is not considered acceptable because of the time to completely destroy the herbicide is quite lengthy, possibly as long as 10 to 25 years, and because a system of monitoring would be required throughout this time period. The earth covering would require maintenance and additional time would also be required to develop a strain of bacteria suitable for use with Orange. 2. ENVIRONMENTAL IMPACT: a. General Impact: Environmental impact of a sludge burial proposal will be concentrated for the most part in the approximately 30 acres of land utilized for the operation. The most significant impact of this proposal is the denial of land for reclamation or recreational uses for a period ranging from 15 to 25 years. Other effects include alteration of the soil profile and structure, temporary destruction of all vegetatfon, and disturbance and possible destruction of ecosystems in the area. The irrpact on air and water quality of the site is anticipated as nrnimal, providing site selection criteria and proposed burial procedures are followed. b. Impact on Air Quality: The biological degradation of organic matter results in the formulation of various gaseous products including, in this case, phenol, carbon dioxide, methane, and the volatile fraction of the n'formal butyl ester of the herbicide. Dependent upon various parameters, these products may exist in significant quantities. To contain the fractions, five feet of compacted earth cover is proposed with e.n additional two feet of earth placed at the center line of each drum row. Indications are that this cover will be adequate to preclude escape of gases into the atmosphere. It should be noted that two feet of compacted earth is used e.s final cover for a sanitary landfill. Odor problems will be prevalent during the dumping of the sludge into the trenches. Volatilization of the normal butyl ester will occur to some extent prior to covering of the drums. The extent of volatilization will depend upon atmospheric conditions at the time, the number and size of holes punched into the drums, and the time period during which the punched drums are uncovered. To a lesser degree, air pollutants in the form of dust and emissions from the excavating equipment will be emitted during "construction" of the trenches. Significant degradation of air quality during this phase is not anticipated. c. Impact on Water Quality: The site selected for sludge burial will be either a portion of a flat, dry lake bed where the depth to the water table is several hundred feet, or on an alluvial fan bordering a saline playa where the water table beneath the fan is also several hundred feet deep. In either case, several hundred feet of unsaturated earth exists between the bottom of the trenches and the water table. Precipitation in both of these settings 126 �would tend to be insufficient (less than five inches per year) for unchanneled water to penetrate through the unsaturated materials and reach the water table. Prior to the selection of a suitable site, data must be gathered describing the parent material and underlying rock formations with indications of possible discontinuities, including a geological profile and information on the existence of faults or fissures. Having satisfied these requirements, the selected site would have no significant adverse effect on the water quality of the area selected. d. Land Use: A significant impact of a sludge burial disposal alternative is denial of land for a significant length of time. Approximately 30 acres of land will be danied for reclamation or recreational uses for a period ranging from 15-25 years. e. Soil: The sludge burial proposal involves construction of trenches. These trenches will vary in number and dimensions. Trench depths of 10 to 15 feet minimum will be required for the operation. Excavation of these trenches will cause complete destruction of vegetation and the soil profile, disturbance and possible destruction of wildlife habitat, and disturbance of the bioecology of the particular area. The total environmental impact can only be determined if base line data is gathered prior to construction. This data should include an accurate description of (1) permanent inhabitants (2) migratory inhabitants and (3) the identification of any endangered species which may occupy the site. f. Ve^etatjon: Approximately 30 acres of vegetation would be destroyed if the proposal were implemented. Depending upon the geographic location of the site, natural vegetation will begin to reestablish itself within a year with weed species being the first to invade. 127 �H. MICROBIAL REDUCTION 1. DESCRIPTION OF ACTION a. General: This process involves the biological degradation of the herbicice through fermentation. It requires the development of a microorganism to "feec" on the herbicide. From the literature, it seems apparent that microorgarisms have developed unbelievable capabilities for handling organic compounds. However, two factors severely complicate the biological degradation of this refractive material: 1) its insolubility in water and 2) its chemical structure (specifically the number and position of chlorine atoms attached to the aromatic ring). Many investigators have showed that 2,4-D is rapidly decomposec in soils, and that high concentrations of the material have no appreciable effect on the soil population of bacteria, fungi, and actinomycetes (Stojancvic, 1972). The persistence of 2,4,5-"" is usually two to three times longer than 2,4-D (DeRose, 1947) and very few microorganisms have been identified as having the ability to break down the 2,4,5-T molecules (Aly, 1964). Leopold, VanSchaik, and Neal (I960) found that increasing chlorination of phenoxyacetic acid decreased its water solubility while increasing its absorption onto activated carbon and organic matter, thus making less available for microbial degradation. Stojanoyic et al_. (1972) added a mixture of 2,4-D and 2,4,5-T to soil at a concentration of 5 tons/A (5,000 ppm in top 6 inches).. It appeared that mixtures of 2,4,5-T were more rapidly degraded than were the single compounds. Very little work has been done on the microbial degradation of TCDD; however, Matsumura and Benezet (1973)., have studied the problem. Using 100 microbial strains., they found that only 5 strains showed some ability to degrade the compound. Thus far, Matsumura and Benezet have not been able to manipulate cultural conditions to increase the rate of degradation of TCDD in any of the microorganisms. Worne (1972) reported in a paper presented at Ghent, Belgium, that he has developed mutated organisms which have the capability to cause 100 percent disruption of the aromatic ring of several chlorinated phenols. He reported a detention time of 52 hours for concentrations of 200 ppm. b. Treatment Methodology: Detoxification of the herbicide would be accomplished utilizing one of many conventional systems, including lined stabilization ponds, activated sludge, anaerobic digestion, or complete mixing activated sludge. The latter method offers many advantages. A plant in Canada uses complete mixing activated sludge (Besselievre, 1969) to treat phenol bearing wastes containing up to 3,000 ppm phenol, the effluent containing .04 ppm. Utilizing a 20 MGD conventional activated sludge facility with treatment capability of 200 ppm, the herbicide would be treated in a period of 2 years. Plant cost would approach $2 million. The feasibility of and using microbial fermentation as a disposal alternative is largely contingent upon the concentration of waste to be treated. Treatment of concentrations of between 1,000 to 3,000 ppm herbicide would make this alternative attractive. 2. ENVIRONMENTAL IMPACT: The environmental impact of a microbial reduction method is dependent upon the fate of TCDD in a biological treatment facility. It must be established that no TCDD is remaining in the effluent, or a problem of enormous consequences can occur. Thus far no data are available on the fate of TCDD in a biological system. All other aspects of such an alternative can be controlled and minimized to an acceptable level. Monitoring methodology and a failsafe system would be required. Until more data are developed the 128 �particular environmenta" aspects cannot be evaluated. More specific information concerning the process, size of facility, land acreage required, and effluent parameters are needed. I. FRACTIONATION: Fractionation is the process of converting Orange into its acid ingredients by means of distillation. This would separate the normal butyl esters of 2,4-D and 2,4,5-T and its contaminant TCDD. The 2,4-D and 2,4,5-T would be reformulated for commercial use. TCDD would then be destroyed by chemical, biological or incineration techniques. Actual distillation efficiencies theoretically could approach 90-95%. One investigator stated that any TCDD residue could be destroyed by splitting the ether bonds of the molecule. In the process of fractionation, the dioxin would be isolated or destroyed. A small scale study was funded, but the results were inconclusive. Fractionation is not acceptable because: s) the fate of the dioxin has not been demonstrated, b) in the process, 3% of the Orange processed could not be accounted for, c) standards to control and monitor vapor and fluid emissions into the environment have not been identified. Further discussion is contained in paragraph J. 129 �J. CHLORINOLYSIS 1. From the theoretical engineering poin-" of view, chlorinolysis offers an efficient, controlled, and safe method for disposal of the herbicide, as well as other hydrocarbon formulations. Chlorinolysis is a process that breaks down the molecule and adds a chlorine molecule to produce carbon tetrachloride, phosgene, and anhydrous hydrogen chloride, all of which have established commercial value. i 2. Chlorinolysis as a means to dispose of Orange herbicide was evaluated over a period of almost two years. In July of 1972, discussions and correspondence with the Environmental Protection Agency (EPA) committed the Air Force to pursue the testing and research program necessary to determine the feasibility of converting Orange to salable products by chlorinolysis. In September 1972 a Memorandum of Agreement between the EPA and the Air Force was initiated. The objective of the agreement was the development of a laboratory program to evaluate the practicality of the application of chlorinolysis for the disposal of Orange. The investigation was also to determine the extent of destruction of the impurity dioxin. The information and data obtained in this research was to be utilized by the Air Force to determine whether the proposed concept could be applied and used to dispose of Orange and by the Environmental Protection Agency to determine if it could contribute toward solving the disposal problems of the petrochemical industry. It was agreed that the EPA would manage the research and provide a report containing all data collected, together with conclusions and recommendations. The Air Force agreed to fund the effort in the amount of $35,000. An additional $10,000 was provided for analysis of dioxin. Three drums of Orange containing 14 ppm dioxin (analysis by Dow Chemical Company) were provided by the Air Force. 3. Reports received in November 1972 indicated that no dioxin was detected (sensitivity level of 100 ppb) in the carbon tetrachloride extracted during the first run. A later report of analysis indicated no dioxin at a sensitivity of less than 10 ppt of dioxin in carbon tetrachloride subjected to improved distillation. 2,4-D which was fractionally distilled from Orange by the Diamond Shamrock Company contained less than 1 ppb of dioxin. The material remaining after distillation is predominantly 2,4,5-T and dioxin. After fractionation the residual must still be disposed of by an acceptable method. 4. In December 1972 a presentation was mede by EPA to the Air Force regarding total and partial chlorinolysis (fractionation of 2,4-D followed by chlorinolysis of the 2,4,5-T and dioxin residue!). It was explained by EPA that to convert 26.5 million pounds of Orange to carbon tetrachloride, phosgene and hydrogen chloride would require about 170 million pounds of chlorine. For a 10-ton per day chlorinolysis plant, the cost to the Air Force for the worst case commercial sale value of the produced products would be about $9.1 million. For the best case sales, the cost would be about $2.4 million. A cost uncertainty of $6.7 million results. One of the disadvantages pointed out by EPA was that quartz lined reactors of the size needed do not. exist and that development of a large scale reactor would be required. It was estimated that 18 to 24 months 130 �would be needed to design and construct a plant after a 6 month pre-engineering study. It was further estimated that 24 to 30 months would be needed to process the Grange. A total time of 38 to 60 months would thus be required. 5. In January 1973 Air Force officials, accompanied by two consultants, visited the Diamond Shamrock facilities and essentially confirmed the cost estimates and time frames previously presented by the EPA. It was confirmed that some 85,000 tons of chlorine would be needed. The Diamond Shamrock officials discussed a commercial operation by a German firm which had been successfully processing hydrocarbons by chlorinolysis using a higher pressure process than that of Diamond Shamrock. An advantage of the German process was that a quartz reactor was not necessary. 6. The EPA investigated the German plant for the possibility of chlorinating Orange herbicide. Two drums of Orange were provided by the USAF to the EPA for testing purposes in Germany. EPA officials visited the German facilities in July 1973. In September 1973 EPA officials reported that because Orange is approximately 16 percent oxygen (by weight), corrosion of the reaction vessel was feared. Bench scale tests indicated 20-30 percent greater corrosion than observed when hydrocarbons containing no oxygen were tested. This observation may have occurred due to the problem of test size as the full scale plant has not experienced any corrosion processing hydrocarbons which do not contain oxygen. Nevertheless, additional tests were thought to be needed prior to ccnducting a full scale evaluation. The reaction kinetics and thermodynamic differences between the Diamond Shamrock process of high temperature/low pressure and the German process of low temperature/high pressure also needed to be understood according to the EPA before any full scale test. During the bench scale tests C02 was unexpectedly produced. The reason for its formation was rot known and further testing was indicated as being required. Further tests and another visit were planned for December 1973. It was indicated that a firal report containing the Diamond Shamrock, German, and EPA data would be provided shortly. 7. In April 1974, the EPA, in discussing chlorinolysis in a newsletter indicated that "The process...has been proven on a small scale and research is continuing to demonstrate its usefulness on a large industrial scale." 8. The EPA report, "Study of Feasibility of Herbicide Orange Chlorinolysis" (EPA-600/2-74-006, July 1974), covering only the work of Diamond Shamrock Company was delivered on 2 Oct 1974. A limited number are also available for loan from the ISAF Environmental Health Laboratory, Kelly AFB Texas 78241. The report covers the results of bench scale tests and concludes, based on these bench scale tests, that chlorinolysis under the proper conditions effectively converts Orange herbicide and its TCDD contaminant to carbon tetrachloride, carbonyl chloride and hydrogen chloride. Destruction of the TCDD was complete, and preliminary toxicology tests of the recovered carbon tetrachloride on rabbits showed no evidence of TCDD contamination. The report also contains cost estimates which include credit for the sale of chemicals from a 25 ton/day plant. The cost in the worst case is shown to be $11 million arid in the best $4 million. 9. Owing to the uncertainties associated with developing this technique to a full scale plant capable of processing 2.3 million gallons of Orange in a timely and economic manner, partial or total chlorinolysis was not selected as the method of disposal even though it is satisfactory from an environmental point of view. 131 �K. SOIL BIODEGRADATION 1. DESCRIPTION OF ACTION a. General (1) Soil biodegradation is a soil incorporation technique based on the premise that high concentrations of the Orange herbicide and the contaminant TCDD will be degraded to innocuous products by the combined action of soil microorganisms and soil chemical hydrolysis. The rationale for soil incorporation of herbicide as an ecologically-safe disposal method comes from pertinent laboratory and fie'd studies. (2) When soil microorganisms are exposed to high concentrations of a herbicide, there is usually a lag period before utilization of the material begins. This lag period represents the time required for the microorganisms to become adapted. Once breakdown of the herbicide is initiated and completed, the soil microorganisms retain an enhanced capacity for degradation of that herbicide. For example, Audus (1960) treated a soil with 100 ppm 2,4-D and 20 days were required for 80% detoxification, but when the soil was treated again only three days were required for 80% detoxification. Colmer (1953) found that 5,000 pprr 2,4-D were at first inhibitory to a bacterium, but after subculturing three times the organisms grew rapidly in the 5,000 ppm concentration. Stojanovic, Kennedy, and Shuman (1972) added a mixture of 2,4-D and 2,4,5-T (similar to the formulation of herbicide Orange) to soil at a concentration of 5 tons/acre (5,000 ppm in top 6 inches of soil). Seventy-eight percent of the herbicide carbon was given off as carbon dioxide in 56 days. It also appeared that mixtures of the herbicides were more rapidly degraded than were single compounds. (3) In the laboratory, Shennan and Fletcher (1965) subjected 38 species of soil bacteria fungi, actinomycetes to 2,4-D and 2,4,5-T at concentrations of 100 to 10,000 ppm in the soil, respectively. Twenty-six species were not inhibited by 10,000 ppm 2,4-D. Twenty-four organisms required 10,000 ppm 2,4,5-T for growth restriction to occur. In the study by Stojanovic, Kennedy, and Shuman (1972), 5,000 ppm of an eque.l mixture 2,4-D and 2,4,5-T inhibited growth of bacteria and actinomycetes but the total number of fungi increased during the 56-day incubation period. Kearney, Wool son, and Ellington (1972) in the laboratory studied the persistence of TCDD in two soils, Lakeland sand and Hagerstown silty clay loam, at three rates of application (1, 10, and 100 ppm) for 360 days. The soils represented extremes in biological activity and in physical and chemical properties. The soils were maintained at 28 to 30°C with a moisture content equivalent to 70% of field capacity. After 1 year, 56 and 63% of the originally applied TCDD was recovered in the Hagerstown and Lakeland soils, respectively. As Kearney et al. (1972) pointed out, however, a concentration of 1 ppm of TCDD in soils is W times greater than the residues likely to be encountered in a 2 pound/acre (Ib/A) application of 2,4,5-T containing 1 ppm TCDD. However, Young et_al_.(1974) has reported soil persistence of TCDD in Lakeland sand which had received 947 pounds/acre 2,4,5-T nine years earlier (1962-1964). A TCDD concentration of 0.71 parts per billion (ppb) was found in the 0-6 inches of soil profile, see Appendix G. (4) It seems apparent from laboratory studies that microorganisms have developed extensive capabilities for handling organic compounds. Moreover, 132 �most organisms seem to have a latent ability for decomposition of halogenated hydrocarbons. 'However, the amount of active herbicide applied to soil may diminish by means other than biological deccmposition; e.g., chemical degradation, absorption, volatilization, leaching, and photodecomposition. (5) Lutz, Byers, and Sheets (1973) studied the persistence and movement of 294,5-T in soils of a western Ncrth Carolina watershed. They found that at 50 and 10Q days following applications of 2 Ib/A 2,4,5-T less than 10 ppb remained at depth below 7.5 cm (3 inches). O'Connor and Wierenga (1973) studied the persistence of 2,4,5-T in greenhouse lysimeter studies. They found 3 ppm 2,4,5-T at a depth of 24 cm (14 inches) in soil cores following 3 irrigations with 80 ppm 2,4,5-T (10.5 months elapsed time from first to the third irrigation). Total degradation time for 2,4,5-T was calculated to be 85 days for this pretreatment and concentration. Hanks (1946) has shown that 2,4-D was much more resistant to leacning from alkali soil than from a peat soil. ».' (6) Until recently there was very little information concerning the breakdown of 2,4-D or 2,4,5-T in a soil incorporation site. However, Goulding (1973) has conducted field experiments on the use of soil incorporation as a method of disposing of massive quantities (approximately 1-1/4 million gallons) of 2,4-D and waste by-products. Goulding found that when he employed a trenching technique, simulating subsurface injection, he could place 500 Ib/A 2,4-D (plus waste) at a depth of 10 inches into 5-inch bands on two-foot centers. With this placement the actual concentration of herbicide within these bands was approximately 1250 ppm. Samples taken between trenches and in soil profile segments from the surface down through the point of application indicated minimal vertical arid horizontal movement of the herbicide (or phenolic waste) from the site of initial deposition. Results from this experiment indicated little differences in rates of degradation in the trenched plots or a surface application of 500 Ib/A: 95% degradation in 540 days. (7) Young, Arnold and Wachinski (1974) have studied the persistence and movement of herbicide Orange (and TCDD) following soil incorporation at rates of 1,000, 2,000 and 4,000 pounds active ingredient 2,4-D and 2,4,5-T/acre (Ib ai/A). The percent loss of herbicide over a 330 day sampling period was 78,2%, 75.2% and 60.8% for the 1,000, 2,000 and 4,000 Ib ai/A plots, respectively. They calculated that the half-life of herbicide Orange in alkaline (pH = 7.8) desert soils was approximate 150 days at these massive rates. Data on soil penetration indicated that less than 3.7% of the herbicide was found at depths greater than 18 inches 282 days after soil incorporation of 4,000 "ib ai/A. Preliminary data based on levels of TCDD in the formulation (3.7 ppm) and those encountered in the soil profile 265 days following soil incorporation suggested that under these environmental conditions the half-life of TCDD was 88 days. A copy of this report is attached as Appendix G. b. Site Criteria for Soil BiodegrajJatlon: It is important that the criteria for selection of a site for soil biodegradation include certain physical, biological, and managerial factors. (1) Physical Factors: From the standpoint of just physical consideration, the soil incorporation technique provides an array of alternatives as to the selection of site. In general: 133 �(a) A minimum of 2,000 acres must be available. (b) The site must be remote. It cannot be adjacent to land currently in agronomic production. (c) The land must have a lowjo^ potential, i.e., it should be marginal land. Moreover, the lane should not be considered land that will be significantly productive in the foreseeable future. (d) Water resources must be sufficiently far away so as not to be contaminated. (e) The topography of the land must be relatively flat with a uniform surface. (f) The texture of the soil should be sandy-loam or siltyloam with a pH of approximately 8.0. (g) The area should not.be characterized by rock outcrops or areas of marked deflation or dunes. The area should also have minimal surface erosion. (h) Data should be available on subsurface geology and hydrology. (2) Biological Factors: The vegetation that characterizes the particular site must be uniform with a ground cover of at least 10-15%. Such a plant community will provide the organic matter and microclimate that supports the growth and maintenance of the microflora (e.g., fungi and bacteria). Ideally, the vegetation should be low-growing shrubs, forbs and grasses to facilitate the incorporation equipment. (3) Management Factors: The management factors that will influence the selection of the site are: (a) The requirement for established all weather roadbeds to and within the disposal site. (b) The distance to the disposal site from an off-loading station (e.g., rail to truck). (c) The requirement for security of the disposal site. (d) Availebility of personnel facilities. (e) Adequate storage space at. the disposal site. c. Method of Incorporation: A subsurface injection system will be used to incorporate the herbicide into the soil at a depth of 6-10 inches. The injection would be done by using a conventional agricultural subsoiler, drawn by a heavy industrial tractor. The subsoiler would consist of a vertical blade on which a chisel, or foot, is mounted at an angle of approximately 15° from horizontal. A piece of metal tubing will be attached to the blade (and terminating at the base of the chisel) in such a manner that a piece of hose from the injection pump could be inserted to permit deposition of the herbicide immediately behind the chisel. The equipment, with eight injectors (shanks), should be calibrated to apply 4000 Ib/A of Orange. The eight shanks should be en 20-inch centers. During the process of application the overlying vegetative structure will be damaged. To prevent the loss of soil "noisture and to reseal the soil (thus minimizing volatility and damage from wind), a soil compacter (cultipacker) will be required and a drought resistant, salt tolerant grass will be planted. 134 �2. ENVIRONMENTAL IMPACT a. General: The environmental ^mpact of soil biodegradation will be expressed in two major areas; the most significant of which is the denial of a 1,000 - 2,000 acre tract of land for reclamation or recreation use for a 3 - 5 year period during biodegradation.. The proposed site would require continuous monitoring during the lifetime of the project. Also occurring will be damage and/or kill of the overlying vegetative structure in the immediate disposal area, drastic alteration of the soil structure, and disturbance and/or temporary destruction of local ecosystems.. Adherence to the above site criteria and incorporation method will optimize the soil biodegradation procedure and minimize adverse environmental impact. b. Air Quality: Impact on air quality will be confined to the period of incorporation. Some volitalization of the n-butyl esters will occur during loading of the incorporation equipment. To a lesser degree volitalization may occur while actually injectrig the herbicide into the soil. Air pollutants in the form of dust and emissions from the incorporation equipment will be emitted during the treatment of tie site. c. Impact on Water Quality: The impact on water quality will be minimal. Actual field data for soil incorporation at 4,000 Ib ai/A herbicide Orange indicated only minimal leaching (in alkaline soils) below 18 inches of depti. However, the incorporation site should be in an area of sufficiently deep soil to prevent unchanneled water from penetrating through the unsaturated materials. d. Vegetative and Animal Communities: The soil biodegradation method would disrupt and/or kill the vegetation :in a minimum of 1,000 acres of land. This would significantly influence the animal community dependent on this vegetation. However, if a site is selected that fits the criteria, the animal population will be minimal. Immediate-action to establish salt-tolerant grasses will minimize potential long-term damage to the animal community. 135 �L. NO DISPOSAL ACTION 1. INTRODUCTION: If none of the disposal methods listed above can be employed at the present time because: 1) they are not ecologically acceptable, 2) technology not sufficiently far advanced, 3) excessive capital investment required, 4) unacceptable time delay, and 5) socio-political opposition, it is possible to put herbicide Orange into "permanent" storage in an above ground steel storage tank on Johnston Island. The required capacity of the tank would be approximately 1.8 million gallons. This volume is an estimate based on the assumption that about 500,000 gallons having a TCDD content of 0.1 ppm or less and presently in storage at the NCBC, Gulfport MI will be registered. The estimated cost of construction of a storage tank with a capacity of 1.8 - 2.3 million gallons on Johnston Island is $875,000 - $1,000,000. The transportation of the drums presently stored at the NCBC, Gulfport MI to Johnston Island would probably add another $450,000 to the total cost increasing it to about $1.35 to $1.45 million dollars. There are several methods of treatment available which could be used to prevent external corrosion of the tank. Pitting or abrasion of the paint or other coating due to blowing send might constitute a problem. Orange and dioxin are inert to mild steel and, in the absence of water, internal corrosion should not be a problem. This "permanent" storage offers several advantages as follows: 1) it would eliminate the cost of continuing redrumming on Johnston Island where redrumming is a major problem and would also eliminate the same problem at the NCBC, Gulfport MI where the problem is not as acute, 2) during the period of storage advances in technology would occur, 3) the cost of certain closed systems, i.e., chlorinolysis, microbial degradation, etc., would be technologically advanced and probably reduced in cost. If for any reason the construction of a tank or tanks is not considered feasible on Johnston Island, storage in already existing tanks or other Pacific islands might be considered. 2. ENVIRONMENTAL IMPACT: Only during the construction phase would there be any impact on the environment. If it became necessary for any reason to provide additional land area for the construction (placement) of the storage tank, dredging would be necessary. However, it is believed that sufficient land area is available on the southwest corner of the island to permit the construction of a storage tank with a capacity of 2 to 2.3 million gallons. The land area for a storage tank of the above stated capacity and the necessary impoundment area and dikes would be about 2 acres. This area includes a part of the storage site where drums of Orange are currently stored and it would be necessary, probably, to move some and perhaps all of these drums. Extensive construction has been conducted on Johnston Atoll in the past. This work has involved drilling and blasting; the use of heavy earth moving equipment and dredging. Explosive devices have been detonated in the area and nuclear devices have been fired at high altitude. Except for dredging which almost certainly altered the ecosystem of the lagoon and nearby waters, changed the direction and velocity of the currents, altered tidal and wave actions, increased the land area of the island, resulted in the creation of two man-made islets and altered the shoreline of all islands, none of these activities has resulted in the permanent disturbance of the ecosystems of the atoll. While space may be available for -tank construction at this time, the available land on the island is very limited and competing missions must be considered. Storage has been continuous for a number of years since the cessation of use. The alternative simply prolongs storage at great expense but does not dispose of the material. Ultimate disposal of the Orange is only delayed and for no purpose as an acceptable disposal method has been identified. 136 �PART VI. RELATIONSHIP BETWEEN LOCAL SHORT-TERM USE OF MAN'S ENVIRONMENT AND THE MAINTENANCE AND ENHANCEMENT OF LONG-TERM PRODUCTIVITY: Bioaccunulation in the environment has been proposed as an adverse environmental consequence of using 2,4,5-T as a defoliant. This Orange herbicide disposal action is not expected to contribute to the bioaccumulation of TCDD in the biosphere on or near Johnston Island because of the high efficiency of the proposed incinerator and the sparsely populated ecosystem of the open tropical sea. The destruction by incineration would eliminate the shortand long-term risks that may be involved with continued storage of the material. Incineration under the controls and precautions to be included in the final contract would not narrow the range of beneficial uses of the environment or pose long-term risks to health or safety. PART VII. IRREVERSIBLE AND IRRETRIEVABLE COMMITMENTS OF RESOURCES WHICH WOULD BE INVOLVED IN THE PROPOSED ACTION IF IMPLEMENTED: This action would not involve the irrevocable use of resources other than the small amount of fuel required to bring the incinerator to proper operating temperature. The action would not involve changes in land use, destruction of archaeological or historical sites, or unalterable disruptions in ecosystems. It will not curtail the beneficial uses of the environment. 137 �(This page intentionally left blank) �APPENDIX A ECOLOGICAL BASELINE SURVEY OF JOHNSTON ATOLL CENTRAL PACIFIC OCEAN by A. Binion Amerson, Jr. Ecology Program Office of Environmental Sciences The Smithsonian Institution Washington DC 20560 17 December 1973 (The document consists of over 300 pages. For the sake of space conservation, the Table of Contents and Summary only are included here. Copies of the document are available on a loan basis to qualified interested parties and may be obtained by request from ISAF Environmental Health Laboratory, Kelly AFB Texas 78241.) �(This page intentionally left blank) �Johnston Atoll, located between the Hawaiian Islands and the Lino and Phoenix Islands, is one of the most isolated coral atolls in the world. Military activity has greatly altered the atoll: two of the four islands are man-made arid the original two have been greatly changed. Since World War II, the atoll has been a military base. The wildlife on the atoll is protected under a little-known 1926 Executive Order. The flora of Johnston Atoll is we'll known. There are 67 species of benthic marine algae known from the lagoon. Increased silt from dredging activities in 1963 and 1964 cecreased the number of algal soecies in the dredged areas. original two islands;, Three vascular plants occurred on the man has apparently introduced 124 species since 1923. The invertebrate fauna is not we'll known and dredging has further reduced or eliminated seme species. The known groups are: 18 species of Cnidaria (Coelenterata), 58 species of Mollusca, 12 species of Annelida, 75 species of marine Arthropods, 85 species of terrestrial Arthropoda (including 2 tick species, 7 chiggers, 23 biting lice, and 2 louse flies), and 37 species of Echinoderrnata. The vertebrates are well known. Thsre are at least two species of pelagic fishes and 194 species of inshore fishes. Dredging operations have drastically reduced the fish population in certain A-l �lagoon areas. Ciguatera is prevalent among the inshore fishes, with Che moray eel, white-tipped reef sharx and grey sand shark being most toxic.* Five species of reptiles are ^nown; all but one were introduced by man. Likewise, no mammals are native to the atoll; however, man has introduced six species. Fifby-six species of birds, whose total population ranges upward to 600,000, are known from the atoll. Of the 22 seabird species, 12 species are breeders, 3 are forrger breeders, and 7 are visitors. Of the 34 species of waterfowl, marsh, and land birds, 7 species are regular migrants, 6 are irregular visitors, 2 are stragglers, 16 are accidentals, and 3 are introductions. Analysis of 60,932 returns of 303,901 birds comprising 21 species banded at Johnston Atoll reveals that the atoll is the major focal point for interisland movements in the north-central Pacific. A total of 733 individual banded birds have moved to or from Johnston Atoll; most interisland movement involves the northwestern Hawaiian Islands. Johnston Atoll is perhaps the most scientifically studied atoll in the central Pacific. Despite man's disturbance, the atoll is ecologically significant because of its isolation and from the standpoint of its opportunities for island ecological research. Although much ecological research has been accomplished, the potential of additional ecological understanding of the atoll is great. A-2 �TA B L E C F . _ _ _. 1 _ . PAGE Foreword ii List of Figures List of Tables List of Appendix Fables v ii xii xv Introduction 1 Physical tnvironment Description and Maps Marginal Re2f 3 3 4 Shoals 4 Islands 7 Akau Island Hikina Island Johnston Island Sand Island 7 7 8 8 13 Climate Temperature Surface W i r d s Trophosperic Hinds Stratospheric Winds Precipitation R e l a t i v e Humidity Sky Cover Oceanography Lagoon Currents Tidal Waves History Discovery M i l i t a r y Occupation Plants 17 18 18 21 24 24 26 26 26 34 41 43 43 44 48 Algae Vascular Plants Akau Island Hikina Island Johnston Island Sand Island Original Man-nic.de 48 54 55 56 57 58 58 61 Invertebrates C n i d a r i a (Coelenterata) 61 62 Geology Mollusca Annelida 65 66 Arthropoda Marine Terrestrial Medically Important Species 69 69 69 70 A-3 �PAGE Ixjdides Trombiculidae Mallophaga Hiopoboscidae Echinodermata Vertebrates 70 79 8.1 81 82 82 Fishes Pelagic Fishes 84 84 Inshore Fishes 84 Distribution and Abundance Within the Atoll 86 Effects of Dredging 89 Ciguateric Fishes Species Accounts Moray Eel Reptiles Species Accounts Black Sea Turtle Mourning Gecko House Gecko 90 93 94 100 100 101 101 102 Fox Gecko 102 Snake-eyed Skink 102 Mammals 103 Species Accounts Mouse Mouse 103 103 Roof Rat 106 Domestic Dog Domestic Cat Hawaiian Monk Seal 106 107 108 European Rabbit 109 109 Birds Introduction 109 Seabirds 112 Breeders Former Breeders Visitors Waterfowl, Marsh, and Land Birds Regular Migrants 112 112 112 113 114 Irregular Visitors 114 Stragglers Accidentals Introductions 114 114 • . . . . 115 Annual Cycles Breeding Cycles Winter and Spring Spring and Summer Summer 115 115 117 117 118 Suiorner and Fall Extended Population Cycles Breeding Seabirds 118 118 119 119 A-4 �PAGE Former Breeding Seabirds Regular Migrants 122 122 Irregular Visitors, Stragglers, and Accidental Birds Introduced Birds At-Sea Birds Ecological Distribution Within the Atoll' Seabirds Breeding Visitors Waterfowl, Marsh, and Land Birds Regular Migrants Irregular Visitors, Stragglers, and Accidentals. Introductions Island Accounts Akau Island Hikinc Island Johnston Island 124 125 125 133 133 133 135 135 135 135 135 135 135 136 137 Sand I s l a n d 137 Banding and Iriterisland Movement Banding In ten's land Movement Species Accounts Black-foo~ed Albatross Laysan Albatross Phoenix Petrel Bulwer's Petrel Wedge-tailed Shearwater Christmas Shearwater Newell's Shearwater Sooty Storm Petrel Red-billed Tropicbird . Red-tailed Tropicbird '. . 141 141 143 148 149 152 154 154 160 168 172 173 174 ' . ' , ' . ' . ' . ' . ' . ' . ' . ' . ' . ' . ' . ' . . 175 White-tailed Tropicbird Blue-faced Booby Brown Booby Red-footed Booby Great Frigatebird Lesser Frigatebird Cattle Egret Pintail American Wigeon Northern Shoveler Domestic Chicken Peregrine Falcon American Golden Plover Black-bellied Plover Semipalmated Plover Bristle-thighed Curlew Lesser Yellowlegs A-b 181 184 189 194 • 202 209 209 210 211 212 213 213 214 218 218 219 220 �PAGE i Spotted Sandpiper Millet Wandering Tattler Ruddy "urnstone Short-billed Dowitcher Sander! ing Western Sandpiper Pectoral Sandpiper Sharp-tailed Sandpiper Buff-breasted Sandpiper Ruff 221 221 222 226 227 228 229 229 230 231 231 Wilson's Phalarope 232 Glaucous-winged Gull Herring Gull Laughing Gull Franklin's Gull Gull species Gray-btcked Tern 233 233 234 235 236 236 Sooty Tern 241 Eleganl. Tern Blue-gray Noddy Brown Noddy Black Noddy White Tern Rock Dove , • Short-eared Owl Skylark Japanese White-eye Society f-'inch 255 256 257 262 267 273 273 275 275 • . . . . 276 Ecological Significance Consultants Summary Acknowledgments Literature Cited Appendix Tables 277 277 293 295 298 308 A-6 �APPENDIX B EXECUTIVE ORDERS (NOS. 4467, 6935, & 8682) ESTABLISHING JURISDICTION OVER JOHNSTON ISLAND �(This page intentionally l e f t blank) �Executive ©vbe It is hereby ordered t h a t two small islands known :is Johnston island nnd Sand , locntod in (he 1'aoilic Oivun, approximately in l a t i t u d e 16° 44' 45" North and longitude 169° 30' .'JO* \Vosl. from Greenwich, as segregated by the broken line upon the diagram hereto attached and inado a part of this order, be, and the same arc hereby reserved and set a p a r t for (he use of the Department of Agriculture as a refuge find breeding ground for native birds, It is unlawful for any por.->on to hunt, trap, captures, wilfully disturb or kill any bird of any Kind whatever, or take the eggs of suc.h bird within the limits of this reserve, except under such rules and regulations as may be prescribed by the Secretary of Agru'ultuic. Warning is expressly given to till persons not to commit any of the acts herein enumerated, under the penalties prescribed by Section 84 of theU. S. Penal Code, tpproved March 1, 1909 (35 Stat., 1088), as amended by the Act approved April 15, 1924 (43 Stat., 98). This reservation to be known as Johnston. Island Reservation. CALVIN COOLIDGE THE V/JIITE HOUSE, June 29, 1926, [No. 44i)7.| B-l �V /~\ Tf T7"*v> Ty^S PT^ /"~\~T'- "V "*— JOiiNSTCi\« For the Protection of Native Birds Embracing two small islands known asJohnston Island and 5znd Island located in the Pacific Ocean approximately in Latitude I 6°44' 45 "North, Longitude 1S9°30'30" West Lfft.t6°444S'lNorth Rocks above water DEPARTMENT OF THE INTERIOR Hubert Work, Secretary GENERAL LAND OFFICE Willjo.m Spry, Commissioner B-2: �PLACING CERTAIN* ISLANDS IN THE PACIFIC OCEAN UNDER THE CONTROL AND JURISDICTION OF -HIE SECRETARY OF THE NAVY \V'AKE ISLAND, KING MAN KEEP, AND JOHNSTON AND SAND ISLANDS By virtue of nnd pursuant to the authority vested in me by the not of June 25, 1910, ch. 421, 36 Slat. S47, (is amended by iho Jict of August 24, 1912, ch. 369, 37 Stat. 497, nnd as President of the United States, it is ordered that Wake Island located in the Pacific Ocean approximately in latitude 19°17'2S" N. and longitude 1G603-1'42" E. from Greenwich, Kingman Reef located in the Pacific Ocean approximntc.ly in latitude 6°24'37" X. and longitude 162°22' W. from Greenwich, and Johnston and Sand Islands located in the Pacific Ocean approximately in latitude I6t>44'32" X. and longitude Jfi9°30'39" W. from Greenwich, together with the reefs surrounding all the aforesaid islands, us indicated upon the di.igro.Tn attached and_mado, a part of_this_ordcr, be, and they are hereby, reserved, set aside, and placed under the control nnd jurisdiction of the Secretary of the Xavy for administrative purposes, subject,, however, to the use of the said Johnston and Sand Islands by the Department of Agriculture as a refuge aud breeding ground for native birds us provided by Executive Order No. 44G7 of June 29, 1926. This order shall continue in full force and effect unless and until revoked by the President or by act of Congress. FRANKLIN D ROOSEVELT THE WHITE HOUSE, December 29, 103/f. [No. G935J upricii fin B-3 �KINGMAN REE jfy'£&>'*? ^^.,-&£i<r - /»^.t9-J irt ^j £-/ ., -rlC-ii,'. •;=, '• Vc l o •.'!•*, VJ /^".'"r .-•••' --.^ v--1r ! n •-/ *%^ : < r,J t' l ,.5 o>, ^ -,^u 5- i. |- c..-,^-S £>•'.,. ^^M\ -v^^* >i5 ji « afc^Vi-v *"" .^"WW^""^ 'i-^i''"-;, "-^. ; J*v^^ >-KJ Ci 7^-y . "••.•- '••" -is: 41 JOHNSTON ISLAND SAND'fsLAND Kaiitical Miles rtTTV- 165'M' B-4 3S' �Title 3—Tin- 1'n-^i.lent E. O. (1G02 ioe'il \r-\v enforcement officers of tiin United .States and of rht Yeiritory of fl.iwuii; and the Si-creijiiy of tiio Nuv> is hereby anth.H'i/o.! 10 iire-^crihe siii-l: i emulations as may lii 1 ncijcss.iv, to c.ii'ry out such provi.iion 1 ;. Any pjri-'on violating any of the provisions of I hi.i order relating to the abovenamed naval defensive sea areas sha:i bu subjoct ho the ppruiltioi provided by section 44 of the Criminal Codf* as amended (U.H.C., title 18. sec. 96), an-1 any person violating any of the provision--; of this order rclatins to the above-narnet1 naval airspace rcsorvatlons shall be .subject. to the penalties prescribed by the Civil Aeronautics Act of 1938 (52 Stac. 973). This order shall take effect ninety days after date hereof. rr.ANKUM D ROOSEVELT TJSE WHITE HOUSE, February 14, 194 1. E X K C l TIV1-: OlthKK SliS2 EsT\Br.r;!:i:i(i NWAL DKi-Tj.vsivr SEA ARRAS AnocM) A N D NAVAL AIRSPACE ilEStnvATro.'is O1. FK TIIK ISLANDS OF PALMYRA. Jcm^ro.v. MIDWAY, WAKF, ;.ND KIN<;I.HN PACIFIC OfTAN By vi: tuc of the iiuthority vested in me by thu provisions of section 44 of the Criminal Code, as amended (U.SC., title IB, sec. 96) , and section 4 of Hie Air Commerce Ar,t approved \l:iy ?.0. W16 (44 Stnt. 570. U.S.C., title 4!), sec. 174), the territorial waters between the extreme high-water marks in the three-mile marine boundaries surrounding the islands of Palmyra, Johnston, Midway, Wake, and Kinsman Rcsf. in the Pacific Ocean, arc hereby established and rnseivcd as naval defensive soa areas for purposes of national defense, such areas to be known, respectively, as "Palmyra Island Naval Defensive Sea. Area", "Johnston Island Naval Defensive Sea Area", "Midway Island Naval Defensive Kea Area", ''Wake Island Naval Defensive Sea Area", and ''Kinsman Koef Nav;il Defensive Sea Arpa"; and the airspaces over the said territorial waters and island.-; arc hereby set apart and reserved a.; naval .ilrsp-.icc reservations for purposes of national defense, such re.servatior.s to be known, respectively. as ' Palmyra Wand Naval Airsparp Ke.'.ervation". "Johnson Island Naval Airspace IJe.->ervatn>n'', "Midway Island Naial Air.spacp Reservation", "Wak<> IslMid Niual Air.spacn. Reservation", and "Km",man Reel Maval Au.S'aot: Reservation". At no tinif --hall any prison, olhei tl'an ppi:ioi:s on pubV.i: vp.-, ,els oE the Uni'.ed Statps, enter .my of tilt: n.ival d -It'nslvi; sea areas her.-m set apart and r-'ii-ived, nor shall any ve.s-'-l or other c i a f t . other than public ii".spK of Hie Unur-d y'ale;;. be navie.afed m:o any nf said :ir< -n. unlrss auihoi-;.7(.'d by Hie Sec -i-t:i:y ( i t the N-r.y. At no tlinr- .-;ha!l any :i:ix: a f t . T.'IPI than pulilic. ai-.ciaU o! ll'e L'r;:ii il Srah",. 1 I). nsivisa'rd into anv i.; iln- i i u v a l a i r spacp IOM :-'.Til :n:i'- lu-i":n M". L i ; a i l and roiei'.Pii. u : i ! - - - . a u r h - i r ' / . - i ! hv i:u Uecrorary nf the N.r. > . '[T.i- provi .'.n:v; cf the pn u'd:n': i n i . i l.ctphs M-I.I" be i i i l . i s c i ' r i \;. t l - i - H n ' - . ' L a i y Of tile N:n J . - M i l l I lip Cli(.|M" ,i".iri (,| (;-,(; EXr.CUTIVK OKOKR SH8.T NAVAL DEFENSIVE SSA AREAS AROUND -\ND NAVAI. AIRSPACE RESFKVATIONS OVER THE ISLANDS OF Rose, TcTOIL.'., AND GUAM PACIFIC OCFAN By virtue of the authority veiled in me by the piovisions of section 44 of thi Cnrninal Code, as amended (TJS.C., tide in, s.?c. 06 > , and .section -\ of tW Air Cor.imcice Act approved May 20, 1925 '44 Hrat. :170. CISC., t u l o 49, .sec. 174), the trrnto'.ial waters between the extreme h;<?h -water marks in the r.hrci;-mile marine bc-ur.(!aries Mirroundin;; the i "stands (if HO.-.I'. Tiituila. and (.iu.ini, in the Pacilk1 Ocean, a i e hereby established and i t >c" vi'd a.; naval defensive sea a:eas for inu;io'-.\i of n.icionai defcnT 1 , such areas to be k V)-A n. R'specti 1 "lily, as "lie -n I'lar-d Naxal Dilen.iivi Sea Au-:i". "Tut'.iiln 1.;I.IIK N'.ual IJt-fecisp. e Sea Are.i". iintl "Ciii'irr Inland N.i' al DC fen ;;ve ?ja A i e a " ; and the nr..p .i.e., O v t - r i!i» ^,i;.l t t r r i i o n a l w a t e i s :-.:id i&latiili urn hcreuy M t ap'.rl and re.-"i vec: a 1 , n u a l a'.r'p'ire it -(-I vai ions for purpose > (>f nati(;:ul ii.:[( n;.-e, inch r c M ' r i y r i o n - , 10 lie km-'.vn. ni: pi r t i v p i y , a.-> 'i;o -p [.<!.. nd N.I'. ::1 .Air^nnco Ki/senatxi:;", '-Tuiui'..! I.'.'uir.; N"1.'. i1 B-5 �(This page intentionally left blank) �APPENDIX C SAILING DIRECTIONS FOR THE PACIFIC ISLANDS Vol III, The South-Central Groups, 6th Ed. 1952, pp. 354-357 �(This page intentionally left blank) �o "1 !p ii .-> " v'V'- ^X vi / ^ .$&Q&^s's4$ co O O u Ol 1 : 1 Ciii'.r .'! i-.l'.a shewn jro of the iji'at soii.i' ch.-irts ?sucd '.a nnvu . vessels uy the L'.S. Nm a! Oceuno/raphlc Offiso. l:c-'.".!cn ruinl.-er:'. refer '.o the ••' LCO :r. in.1 tex: vhi're u 'Jc'rfr-rilc:! of -he doti^naToi'. !iv Llity i«'ji r is. CHAPTER 13-GRAPHIC INDEX �CHAPTER 13 JOHNSTON ATOLL 13-1 JOI/NSTON ISLAND (Johnston Atoll) (16'45'N., 169°:»l'VV.)f a possession of the United States, consists of four islets that lie on a reef about 9 miles long in a northeast and southwest direction. The .southwcstornmost of the Islets, known as Johnston Island, Is about 3,500 yards long in a northeast and southwest direction, and about 70Q to 1,200 yards wide. The smaller island, about 3/4 of a mile to tho northeastward is known a.s Sand Island. An airfield is located on Johnston Island. Two small arti:lcal islands, known as Akau and Hlklna Island, are located at about 1 1/2 miles northward and 2 1/3 miles oast-northeastward, respectively, of the east end of Johnston Island. Johnston Island is a Naval Defense Sea Area and Airspace Reservation and is closed to the public. The airspace entry control has been suspended, but is subject to immediate reinstatement without notice. The administration of Johnston Island is under the jurisdiction of the Joint Chiefs of Staff,, Defense Atomic Support Agency and Joint Task Force Eight. Johnston Island Air Force Base is closed to all traffic except emergency landings and flights directed or approved by Commander Joint Task Force Eight, or by the island c o m m a n d e r . Commander, Joint Group 8.6. No vessels, except those authorized by Commander, Joint Task Force Eight or Commander, Joint Task Group 8.6, shall be navigated within tho three-mile limit. For merchant vessel entrance procedure see section 1-22. In addition to these procedures authorities at Johnston Atoll must receive ship visit requests a minimum of 5 days in advance, and include certifications of masters' and ships' crew security clearances in the request. WINDS—WEATHER.—Weather is usually excellent for navigation. Winds average 10 to 15 knots in summer, and ID to 25 knots in winter. They are from east to northeast about 90% of the time. During kona weather, the occasional Hawaiian Island storms are characterized by stormy southerly or southwesterly winds and heavy rains. Brief showers occur frequently, but protracted bad weather is rare. Average rainfall var'es from 30 to 550 inches. Visibility is good, usually over 12 miles. There is no fojT. TIDES.—The hi^h-water interval at full and change is 3h. 15m. The mean range of. the tide is 1.8 foot. DEPTHS—DANGERS.—A barrier reef extentis in an arc from west to northeast of the islands. Depths outside the reef line drop off to 102.9m (100 fm.) in about 700 yards. With heavy breakers on tho reef, a 0.6m (2 ft.) to 0.9rn (3 ft.) surge exists in the lagoon. From northeast, via south, to southwest is a foul area with very Irregular bottom. The 182.9m (100 fm.) curve lies 4 miles due south of the center of Johnston Island, proper, however, there are 10.4m (34 ft.) shoals lying as close as 550 yards inside the curve and to the southeastward of the island. From south of Johnston Island the 182.9m (100 frn.) curve extends to the eastward about 083° about 11 miles, thaneo veering off northwestward. From this same point, 4 miles due south of the conter of Johnston Island, the 182.9m (100 fm.) curve continues on about 240" for a distance of least ?. 1/2 miles. L ANDMARKS. —The control tower and aviation beacon on Johnston Island and the towers on Sand Island are prominent. A tank, with a dlsJi antenna, marked by an obstruction light and located on the northeast side of Johnston Island, is prominent. The 640-foot loran tower on Sand Island was reported visible at 27 miles. The towers and buildings on this island show as separate radar targets. The outline of the island does not show until within 10 miles of the island. HARBOR.—The harbor consists of a turning basin within the lagoon about midway between Sand :"sland and Johnston Island. The turning basin and harbor area are dredged to 10.7tn (35 rt.). The berthing area alongside the main pier has been dredged to 9.1rn (30 it.) 19G8. Vessels may anchor in the turning basin or berth at Johnston Island Navy Pier or Main Wharf. Mooring buoys are moored in the turning basin between 550 yards and 1,000 yarc-s northeastward of tho pier head. H.O. 80—Change 12 C-2 355 �Sec. 356 The main entrance channel is entered southeastward of Johnston Island and is Indicated on the chart by dashed lines. Tho channel, which bears true north and south, VMS dredged (1904) to a depth of 10.7m (35 [t.). Maximum cirafc for vessels entering the harbor under normal conditions is 0.5m (98 ft.) (1960). The navigable width of the channel is 400 feet. Tho largest ship that has entered and docked (19G6) was 523 feet In length with a beam of G8 feet. Th'j channel to Sand Island narrows from about 200 feet to 100 feet as the dock Is approached. Sand Island dock, approximately 60 feet long, is suitable only for small craft. A channel with a least depth of 4.6m (15 ft.) (19G7) has been dredged from the southwestern corner of the turning basin through the roof close westward and close southwestward of Johnston Island. 13-2 NAVIGATIONAL AIOS.-J o h n S t on A:oll Fairway Entrance Buoy, equipped with a radar reflector a.nd pointed In black and vr'alte vertical stripes, is moored in about 36 feet In position 1G°41'54.5"N., 1B9°3X'07.3"W. Johnson Atoll Channel Entrance Lighted Buoy 2 i.s moored in approximately l(i°4.rN., 169°3l'W. arid Is equipped with a radar reflector. Channel Lighted Buoy 3, is moored about 1/2 mile northward of Buoy 2, on the west side of the channel. Channel Buoy 4, moored 150 yards eastward of Buoy 3, Is equipped with a rod reflector. The remainder of the channel to the turning basin Is marked as follows: the west sido by square concrete pile beacons fitted with green reflectors; the er.st side by square concrete pile beacons fitted with red reflectors, the beacons are at the channel limits. .Several beacons have lights. The channel f r o m the turning basin to Johnito:1. Dock is marked by buoys. Knngc lights, marking the entrance channel arc shown from rectangular-shaped dayrruirlrs; the front beacon is located at the northeastern corner of tlw turning basin; the r o a r beacon is 300° f r o m the front beacon, distant about C40 y.irds. A llclii Is shown f r o m tli3 northeast end oi the island. A light is shown on the seaward end of the breakwater on Johnston Island. C-3 13-2 A light is shown near the northeastern corner of the Navy Pier. Obstruction lights arc shown f r o m the loran tower on Sand Island. An aeronautical radioheacon t r a n s m i t s from a tower near the center of Johnston Island. REGULATIONS.—Tho following regulations are in effect: As of April 1068, entrance to the harbor Is not recommended at night. Ships are requested to night steam or anchor 3 miles southward of Johnston Island to v/ait for daylight. Observe carefully rules and regulations prescribed by the Commandant for navigation in harbors and anchorages of Johnston Island, and have on board an officer familiar with these waters while undorway in these areas. All persons on board shall be U.S. citizens. No photographs will be taken from the vessel. All cameras will be kepi/ in the custody of the Master so long as the vessel is within waters contiguous to Johnston Island. While anchored the vessel will maintain stoain up and be prepared to get underway. Dogs, cats, and other animals sha.ll ba confined on board. Plants and fruits will not be Imported without specific authority of the Commander of Johnston Island. No garbage or ashes will be dumped overboard within three miles of Johnston Island. Ships will normally dump garbage before entering the channel. During the stay in port garbage and trash removal will be arranged. ttnt guards will be placed promptly on all lines, chains, hawsers, etc., used to make fast. No oil or oily bilges may be pumped while in the harbor. CAUTION.— An explosives clumping area has been established .souohwdstv/ard of Johnston IsUmd, between the parallels of lfi°?,5' N., and IG^Bo'N., and between the meridians of 1G9°-15'W., nnd 1G9"53'W. 13-3 ANCHOI.eA.GES. —It is suggested that vessels drawing more than 0.5m (28 ft.) anchor in the channel approach area south of the channel entrance. �Sec., 13-4 H.O. 80-Change 12 E m e r g e n c y Anchorage can bo taken In the turning basin. As soon as practicable ships will he moved pier side or to a mooring buoy. The bottom in the turning basin Is sand and coral, poor holding p, round. CAUTIONS. — A submarine cable is laid f r o m Ihu east end of Johnston Island southward down the main channel for about 2 1/4 miles. Submarine cables are laidtactween Johnston Island, Sand Island, and Akau Island. Submarine cables are laid between the latter Island and Hikina Island. (See H.O. Chart 550r..). PILOTS. — No licensed pilots are available. Ships normally may not enter at night or when cross-channel winds exceed 25 knots. The harbormaster will board ships at the fairway entrance buoy with current information as to channel and harbor conditions. A navy tug is available for cocking. DIRtlCTIONS.—Vessels bound for Johnston Island ship channel should approachthe channel f r o m southward passing through position 16e4l'00"N.. 169"3l'00"W., thence proceed northward to the fairway entrance buoy. When abeam the fairway entrance buoy they should heave to and await the boarding officer. While have to, a drift to the westward will usually be experienced. This drift must be checked, because the exact limits of the foul area on the port hand a r c not determined. There is usually a current in the channel, determined by tlrlal conditions. During the rising tide she current flows north and during the falling tide it flows south. It attains a rale of 1 knot to ?, knots. At low tide transition (low plus or minus 1 1/2 hours) the current flows southwest ward at a rate of about 1 knot,, At high tide transition (high plus or minus 1 hour) the current flows northward but is weak. Vessels with low power or with a relatively high wind area should favor the eastern side of the channel. A minimum speed of a knots should be maintained to overcome the effect of wind and current and increased proportionally with unusual conditions. During periods of heavy swell on the barrier reef, a .strong easterly set may be encountered at the junction of the entrance channel and the turning basin, particularly during ebb tide. C-4 357 13-4 FACILITIES.—Johnston Island Naval Pier is 400 feet long by 50 feet wide with pierhead of 106°, and has a timber deck supported by steel piling. Ships tie up starboard fiicle to. The pier will accommodate ships with a maximum d r a f t of 4.6m (15 ft.) Diesel oil pipelines are Installed on the dock. Johnston island Main Pier, 570 feet in length with pierhead of 23G° is constructed of steel piling with concrete cap and has a depth of about 9.1m (30 ft.) alongside. There is a small boat dock with five 50foot slips. It has a depth of 2.4m (8 ft.) alongside, and is located westward of the Navy Pier. At Sand Island there is a 60-foot long lumber quay wall, which is used only by station craft. Cargo handling facilities include one 60-ton capacity crane and two 45-ton c a p a c i t y cranes. fresh Water can be furnished to transient ships. Repair facilities are available for local small craft. COMMUNICATIONS with the island is under military control. When ships are v/ithln 100 miles, they are requested to contact the harbor master by voice radio on 2716 kc. The voice call Johnston Control is used and this frequency has a. 24 hour guard, ttadio contact can also be established on other marine frequencies it prior arrangements are made. The island uses zone •f 10 time. .13-5 Or1 P - LYING B ANKS. — A ba nk with a depth of 12.8m (7 fin.) to 14.6m (0 fm.) over It, lies at a distance of about 7 3/4 miles eastward from the eastern end of Johnston Island. NOVELTY SI[OAL.-Captain P. Herrirnan, mister of the schooner Novelty, reported in '.897 that with the eastern end of Johnston Island bearing 257", distant 12 miles; in approximately 1G°49'N. latitude, lG9°14rVV. longitude, ho obtained soundings of 5 1/2 fathoms, rocky coral bottom. The bottom was visible for halt an hour after taking the soundings while the vessel ran north2miles. Light breakers were seen about 3 miles to the eastward while the vessel was passing over the shoal. �APPENDIX D INCINERATION OF ORANGE HERBICIDE �(This page intentionally left blank) �APPENDIX D INCINERATION OF ORANGE HERBICIDE A. GENERAL INFORMATION: The purpose of tnis appendix is to provide basic information concerning the combustion of Orange herbicide, to review all previous Orange herbicide incineration studies, and to comment on the applicability of incineration as a method of Orange herbicide disposal. It is noted tha-: an incineration method known as "rno'ten salt incineration" is not included in >;he review of previous studies contained in paragraph C. This method has been favorably applied to certain pesticide incineration studies; however, the method has not been applied to Orange herbicide incineration and therefore no Orange incineration data is available. The lirrrted data on this system preclude any judgment as to its application to the large scale disposal of Orange. In addition, the fate of KDD in this system will require investigation in view of concern over possible KDD production at the temperature, pressure, and in the sodium environment in which the reactions occur (Baughman and Meselson b, 1973). 1. COMPLETE COMBUSTION: The theoretical products of combustion of Orange herbicide are carbon dioxide, hydrogen chloride, and water. Fifty pounds of normal butyl 2,4-D and 50 pounds of normal butyl 2,4,5-T would require 74 pounds and 67 pounds of oxygen, respectively, for complete combustion. Therefore, approximately 141 pounds of oxygen is required for the complete combustion of 100 pounds of herbicide. With the oxygen supplied in air, 610 pounds or 8200 cubic feet of air at 25°C, 760 mm is required for the combustion of 100 pounds of herbicide. 2. TEMPERATURE REQUIREMENTS: The Mississippi State, U.S. Department of Agrculture Report on Thermal Decomposition of Orange Herbicide, referenced in paragraph B, 1, reports the temperatures required for the complete combustion of Orange herbicide. The analysis was accomplished by the differential thermal analysis method utilizing a "Deltatherm" Model D2000, Technical Equipment Corporation, differential thermal analyses aparatus. The following is quoted from the referenced report: "The results show that both 2,4-D and 2,4,5-T analytical standard materials (free acids) are readily combusted between 330 and 360°C (Table 2). Esterified materials, i.e., no Trial butyl esters of 2,4-D and 2,4,5-T and the isooctyl ester of 2,4,5-T, on the other hand, require roughly twice as high a temperature for degradation as do their counterpart free acids. All three esters are combusted between 550 and 700°C. Dioxin (TCDD) is completely combusted between 980 and 1000°C. The bulk of the TCDD molecule, however, appears to be disintegrated at 850°C as indicated by an extremely large exothermic peak on the DTA curve (Figure 7). It is estimated (please note estimated) that about 70% of the TCDD molecule is degraded at that temperature alone. Two small exothermic peaks are shown at the completion of burning at 955 and 975°C with complete burning taking place at 980 to 1000°C. Similarly Orange and Orange II herbicides are completely combusted between 960 and 980°C. The normal butyl 2,4,5-trichlorophenoxyacetate containing 0.1 ppm dioxin (TCDD) is thermograded in the same temperature range as the esters without TCDD. Apparently the TCDD concentration was too small to be of any consequence, although it was conspicuous with Orange and Orange II herbicides." The caloric value of the Orange is 10,000 Btu per pound. This data was obtained on the basis of 200 samples collected at random from the Gulfport stock and analyzed at the Aerospace Fuels Laboratory, Wright-Patterson AFB, Ohio. The theoretical adiabatic flame temperature for complete combustion, under the test conditions described in Appen- .D-l �dix E, i.e., 1.55 pounds per second of air at, 520"F and 0.185 pounds of herbicide per second at 77°F, is calculated to be greater than 3,000°F. B. PREVIOUS STUDIES ON ORANGE INCINERATION I. MISSISSIPPI STATE UNIVERSITY AND THE U.S. DEPARTMENT OF AGRICULTURE, STATE COLLE3E, MS. a. Report^ Technical Report on Thermal Decomposition of Orange Herbicide under the Amendment No.2 to the U.S.D.A. Cooperative Agreement No. 12-14100-10, 673(34); submitted by Mississippi Agricultural and Forestry Experiment Station end Plant Science Research Division of the United States Department of Agriculture to the Department of the Air Force, Headquarters San Antonio Air Material Area (AFLC) Directorate of Aerospace Fuels, Kelly Air Force Base, Texas 78241; June 1, 1972 State College, Mississippi 39762. This report was prepared by Mr. B.J. Stojanovic, Mr. M.V. Kennedy and Mr. W.C. Shaw. b. Objectives: The objectives as quoted from the report are: "The objective of this laboratory study was to determine temperatures required for complete thermal degradation, the degradation products, and the volatile gases of Orange herbicides containing dioxin (TCDD) and evaluate suitable scrubbing agents to remove toxicants from the effluent. Another phase of this project was to determine the biological activity (phytotoxicity) of the residues resulting from Orange herbicide incineration." c. Tyj3e_p_f_Jncineratipnj Herbicide samples were placed in ceramic combustion boats "which" we're placed in a Vycor glass combustion tube (length 121 cm, O.D. 2.5 cm). The tube was placed in a resistance-type furnace; the total heated length of the tube was 80 cm. A s:lica combustion tube (30" x 1" I.D.) replaced the Vycor tube after some initial experiments. Commercial oxygen or air was passed through the combustion tube at a prescribed rate. d. Quantity of Oraruie Incinerated: A series of experiments were conducted at various temperatures", 700 to "1000°C to determine chloride recovery, particulate recovery., scrubber efficiency, and carbon monoxide and carbon dioxide recovery. Experiments were conducted for mass spectograph analysis of exhaust gas samples and extracts of particulate filters. Experiments were also conducted for phytotoxicity analysis. Herbicide and TCDD analyses were accomplished throughout these experiments. The ceramic combustion boat was usually loaded with 100 mg of test material for each experiment; in all, approximately 5-6 grams of Orange and Orange II (isooctyl ester) were incinerated. e. Monitoring: All of the carrier/combustion gas for each experiment was passed through collection devices, particulate traps, impingers, which utilized selective collecting medias depending on the analyses to be performed. f. Results: The results were excellent, as regards herbicide and TCDD destruction; the chlorine is released as essentially all hydrogen chloride as opposed to chlorine; particulate levels were significant; and the carbon was released essentially as carbon dioxide. No TCDD was indicated in any of the tests performed for TCDD. The phototoxicity experiments showed that hydrogen chloride is very phytotoxic (as expected) and that alkaline scrubbers are very efficient in entraining hydrogen chloride and any other phytotoxic gaseous compound in the combustion qas from Orange incineration. D-2 �g. I. ncgmpjete Combusti on: Orange contains roughly three times as much carbon and oxygen; incomplete"combustion could result in particulate matter and possibly carbon monoxide. In addition, roughly one-third of Orange herbicide is chlorine; therefore, certain chlorine comoounds could result from the combustion Orange. The technical report lists the following theoretical compounds which could result from the corrplete/incomplete combustion of Orange: chlorine, chlorine monoxide, chlorine dioxide, chlorine hexoxide, chlorine heptoxide, chlorates, hydrogen chloride, hydrochloric acid, chlorinated water, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, chlorine hydrate, and phosgene. All of these compounds a^e highly corrosive and toxic, about onethird are gases at normal temperature. The technical reports that "thermochemically speaking, however, hydrogen chloride and hydrochloric acid may be expected to be the chief, if not the only, chlorinated compounds released upon incineration of Orange herbicide." The experiments, as noted above, revealed the chlorine to be released as hydrogen chloride. In the experi-nients conducted for mass spectrograph analysis, the combustion gas was passed through a particulate trap (pyrex wool) and three irnpingers (benzene) in series. The analyses of the impinger samples for herbicide and TCDD was negative. The particulate matter traps were extracted with hexane and then with sodium hydroxide. The results are quoted from the technical report: "Trace quantities (2.0-200 ppb) of 2,4-D and 2,4,5-T free acids were detected in the NaOH extracts of the particulate matter (Table 12). The 2,4-D n-butyl ester and 2,4,5-T isooctyl ester were, however, present in quantities ranging from 0.70 to 370 ppb in both the hexane and NaOH extracts of each particulate matter trap. The presence of 2,4,5-T isooctyl ester in the traps was unexpected as the 2,4,5-T component of Orange herbicide is the n-butyl ester. The origin 6f this compound cannot, definitely be established on the basis of these investigations. It is, however, suspected to be an artifact, formed during combustion of the herbicide, which has an elution time coinciding with that of 2,4,5-T isooctyl ester and appears as such on the chromatogram. The gas chromatograms of the hexane extracts of the particulate matter traps indicated the presence of approximately 20 additione.1 compounds which were not identified. Dioctylphthalate was identified as a contaminant by infrared spectroscopy. The results of this experiment have shown that at 1000°C traces of herbicides may be volatilized and be carried out of the burning range of the furnace. From a practical point of view, none of these materials would be expected to pass an alkaline scrubber where they would very likely be trapped and destroyed by the alkali." h. Conclusions and Recommejidatjor)^: The conclusions and recommendations are quoted from the technical report: (1) Conclusions: "a. A minimum temperature of 1000°C is necessary to insure complete combustion of pure dioxin (TCDD). b. The bulk of the TCDD molecule (estimated 70%) is disintegrated at 850°C. c. Both Orange arid Orange II herbicides are completely combusted at 980°C, whereas normal butyl 2,4,5-T herbicide containing less than 0.1 ppm TCDD is combusted at 550°C. D-3 �d. More than 95% chlorine is recovered from burning "orange herbicides at 800°C. The chlorine is released chiefly if not entirely as hydrogen chloride gas. e. Dioxin (TCDD) was not detected in the incombustible residue (including the particulate matter) and the effluent scrubbing solutions following incineration of orange herbicides at 750, 800, and 850°C. f. Incineration of herbicides under these experimental conditions does not produce carbon monoxide as none was detected in the effluent gas stream. g. Oxygen supply during the incineration process appears to be less critical for dehalogenation than for cleavage of carbon-to-carbon bonds of herbicides. h. Sodium hydroxide solutions of appropriate strength are for all practical purposes found to be the most efficient and desirable scrubbers for the effluent stream. 1. Unscrubbed effluent gases are found to be extremely toxic to young tomato plants. Hydrogen chloride in itself causes almost instantaneous kill. j. One or more secondary burning chambers appear to be necessary for efficient incineration of orange herbicides." (2) Recommendations: "1. Even though the procedures used to obtain the preliminary data on thermal degradation of orange herbicides yielded important and very useful fundamental information, this information cannot be extrapolated and applied directly to a commercial incinerator. 2. A series of incineration runs with orange herbicides should be conducted within a short-term testing program in a research pilot incineration system. 3. The testing program should have as its chief objective the establishment in the shortest possible time of feasible parameters for the complete and safe incineration of Orange herbicides. 4. It is considered most urgent that the testing program should involve determination of the following: a. Temperature profile *n the system b. Herbicide flow-rate (dwell time) c. Products of combustion Dy monitoring effluent gases, and d. Scrubber efficiency and composition of residues. Other factors may possibly also have to be considered but these could be established during the incineration tests. D-4 �5. Based on the tests currently being conducted by the investigators (with a pesticide pilot incineration system), it is estimated that a minimum of 90 days will be necessary to carry out the testing program and translate the laboratory research to a practical incineration system." 2. USAF ENVIRONMENTAL HEALTH LABORATORY, KELLY AFB TX a. Report: Technical Report, Incineration of Orange Herbicide, July 1972, EHL(K) 72-7, USAF Environmental Health Laboratory, Kelly AFB TX. This report was prepared by Dr. R.A. Callahan. b. Objectives: The scope of the laboratory work described in this report is to!1) determine the feasibility of using Gas Liquid Chromatography (GLC) alone to analyze combustion gases and scrubbing blow-down water for the herbicide esters and TCDD, and 2) development of efficient methods of extracting the normal butyl esters and TCDD from gaseous and water discharges. In addition, the status of i;he Orange disposal via incineration including trip reports, impact statement comments, etc. was documented in this report. c. Type of Incinerator: A small continuous burning flow through incinerator which approximated the fuel/air injection method, dwell time, air/ fuel ratios and temperatures anticipated in commercial facilities was configured for the laboratory experiments. The incinerator chamber consisted of a Vycor-Pyrex tube with a length of 33 cm and a volume of 156 cc. This tube was placed in a Lindberg heavy duty furnace equipped with heating elements capable of operating at 1200°C. The system functioned as follows: "Fuel (Orange Herbicide) was continuously delivered at a metered rate (via Hamilton 2.5 ml gas syringe mounted on a Sage Model 350M pump) to the tip of a blunted stainless steel 22 gauge needle. The tip of this needle was sealed in a stainless steel Luer Lock syringe fitting. Compressed air was metered into this fitting via a 0-1 ml/min rotometer. The Orange was continuous'y aerosoled from the tip of the fuel probe into the furnace tube. The air/fuel mixture was then deflected upwards by a dispersing cup. The combusting gases passed directly up and out of the furnace tube. The aerosol injection probe was a 20 gauge stainless steel pudental needle; the dispersing cup was also stainless steel." d. Quantity of Orange Incinerated: Fourteen test runs are reported with a total of 14.12 ml of Orange incinerated. The run time for the experiments averaged 12 minutes with a minimum of 10 and a maximum of 30 minutes. The temperature of the combustion gases at the exit of the tube ranged from 740 to 950°C. e. Monitoring: The entire combustion gas volume was passed through a sampling train consisting of midget impingers and a freeze trap. The apparatus was all glass and both tapered and fritted impingers were used. The impinger media was either distilled water or benzene. The sampling time was the same as the above mentioned run time; the air flow rate was usually 0.65 liters/min; therefore, the sample size was approximately 8.0 liters. f. Results: Twelve runs were sampled, analyzed, and reported for herbicide; of these two were monitored, analyzed and reported for TCDD. The TCDD concentration in the Orange used for these two runs was 14 ppm while that of the remaining runs was <0.1 ppm. A summary of the results from the report is quoted: D-5 �"The destruction of the NB esters and TCDD in the model incinerator at 920°C, 2-3 second dwell times, and 150-130 percent stoichiometric air exceeded 99.999 percent for the esters and 93 percent for the TCDD. Total discharges of the combined esters ranged from 8.0-50.0 poo (parts per billion)'in the untreated gas discharges. The TCDD discharged when burning Orange containing high concentrations of TCDD were 3.0 and 18.0 ppb. Detailed data is presented in Appendix A, pg. 8." g. Incomplete Combustion: The identification of incomplete combustion products or intermediate pyroTyzates was riot within the scope of this project. Two chromatograms are shown in the technical report to depict the difference between a "clean" chroinatogram - showing only residues of the herbicide esters and TCDD, and, a "less clean" chromatogram in which the peaks of five chlorinated pyrolyzates are present along with the peaks of herbicide esters and TCDD. The difference was .attributed to temperature and excess air with the run having the higher temperature and greater excess air having the clean chromatogram. h. Conclusions and Recommendations: Those conclusions and recommendations pertaining to the 'laboratory Tncineration test runs are quoted from the technical report. (1) Conclusions: "1. Monitoring the NB esters of 2,4-D and 2,3,5-T and TCDD in water and gas effluents resulting from commercial incineration appear feasible. 2. Limits of detection for each of the NB esters in effluent gas and water are 2.0 and 1.0 ppb respectively. The corresponding limits for TCDD are 3.0 and 1.0 ppb respectively. 3. Interference from other phyrolyzates will be negligible at temperatures of 1000°C, dwell times of 3 seconds and stoichiometric air/fuel ratios of 150%. 4. The very high water content of the gas samples taken from the incinerator stacks may interfere with the benzene charged fritted impinger extraction system. This condition is readily detectable. Substituting ethylene glycol for benzene in the first impinger should overcome this potential problem Other alternatives are available. 5. Emissions of the NB esters of 2,4-D and 2,4,5-T and TCDD when burned at 1000°C with 150% air and'a dwell time averaging 3 seconds will be very low and safe to all forms of life. Incineration in tandem with the monitoring program developed above and outlined in detail in Appendix B of this report will offer negligible risks to the environment or human health from emissions of NB herbicide esters or from TCDD." (2) Recommendations: "Identification of other pyrolyzates formed during the incineration of IFrange herbicide should be accomplished as soon as possible. Pyrolysis of herbicide in such experiments should be accomplished in a continuously burning liquid injection incinerator as described herein to provide valid results," 3. THE MARQUARDT COMPANY, VAN NUYS, CA a. Report: Report 5-1224, "Report On The Feasibility of Destroying Herbicide Orange by Incineration Using the Marquardt SUE Burner," Ausust 1972, D-6 �the Marquardt Company, Van Nuys, CA. This report was prepared by Mr. R. Babbitt and Mr. J.L. Clure. b. Objectives: The objective as described in the technical report was: "A test program was conducted to determine the feasibility of destroying herbicide Orange by means of combustion. Particular emphasis was placed on the ability to destroy the trace quantities of dioxin present in the herbic'de. Attention was also places on the ability to destroy the herbicide itself and.to determine the nature and extent of the undesirable components in the exhaust gases and in the scrubbing l-'quid used to cool and scrub the exhaust gases." c. Type of Incinerator: The incinerator system consists of a 12" dianeter SUE Burner witn a 48" air cooled combustion chamber and a 120" uncoo'ed reaction tailpipe. The SUE" stands for "sudden expansion" which describes the injection aid combustion of fuel within the combustion chamber. The fuel injection sytem is at the entrance to the combustion chamber (a poppet value was used in these test runs) and an alkaline scrubber device (a venturi scrubber) is connected to the exit of the reaction tailpipe. The. scrubber is connected to a gas/water separator and stack. The incinerator system is described fully in Appendix E. d. Quantity of Orange Incinerated: A total of 56 test runs were made, 34 were in Phase I - Exploratory Testing, and 22 were in Phase II - Data Gathering Test Program. Of the 22 in Phase II, 11 were with the incineration of Orange only and no auxiliary fuel. The run time of the Phase II burns ranged from <1 to 5 minutes and the fuel flow rate and air flow rate ranged from 0.032 to .200 and 0.979 to 1.525 pounds per second, respectively. The temperature., measured about half way down the reaction tailpipe, ranged from 1730° to 2360°F. In all, approximately 37 gallons of Orange was incinerated in the Phase II testing. e. Monitoring: During Phase II, samples of the combustion gases (near the exit of the reaction tailpipe), stack gas, and spent scrubber water were collected. Collection devices and techniques are described below; impinger trains were not used. The following is quoted from an Appendix of the report; the Appendix was prepared by the West Coast Technical Services Inc., Cerritos, CA, who performed the analytical analysis. "APPENDIX A: The combustion products from the various test runs on the Marquardt Company SUE Burner have been analyzed by gas chromatography and mass spectroscopy. The gas analyses were performed by mass spectroscopy while the condensable materials were analyzed by gas chromatography and combined gas chromatography-mass spectroscopy. I. SAMPLING PROCEDURES A. Combustion Gases An air-cooled probe was inserted into the center of the combustion tube immediately before the venturi scrubber. The entrance to the probe was restricted with an 0.015 in diameter orifice. The sample probe was then attached to a glass trap containing a built-in electrostatic precipitator. The outlet of the glass trap was attached to a ti-7 �vacuum system equipped for flow measurement. The glass trap was cooled to 0°C in an ice bath and the electrostatic precipitator attached to a 3000 VDC. The samples were taken when the combustion system had reached equilibrium by opening the trap to the vacuum system. The flow rate and time were recorded. At the end of the desired sampling time the valves on tne sample trap were closed. The gases contained within the trap were analyzed by mass spectroscopy. The probe anc glass traps were then washed with methyl ethylketone and chloroform. The washings were concentrated and analyzed by gas chrornatography or ccmbined gas chromatography-mass spectroscopy. B. Grab Samples (Combustion Chamber Gases) These samples were taken using the air-cooled sample probe described in "A" above. A standard glass sample bomb was used in place of the glass tray. The sample was taken by evacuating the bulb and Durging the system with combustion gases. The bulb was allowed to fill with gas after which it was removed from the system. The gases were analyzed by mass spectroscopy. C. Scrubber Exhaust Gases The gases leaving the scrubber were purged through a glass sample tube. They were then analyzed by mass spectroscopy. D. Scrubber Liquid A sample liquid from the scrubber tank was removed. The sample was acidified with sulfuric acid and extracted with diethylether and carbontetrachloride. The extracts were dried over anhydrous sodium sulfate and removed by distillation. The concentration was treated with diazomethane in ether to convert the acidic compounds into their methyl esters or ethers. The methylated extracts were then analyzed by either gas chromatography or combined gas chromatography-mass spectroscopy." f. Results: For ten runs analyzed for condensible products in the combustion gas, the results were less than the detectible limit for herbicide components (<20 ng) and TCDD (<15 ng). For one run, a total herbicide concentration of 19 ppm was detected in the combustion gases. During this run, the sample volume was increased 10 fold from the usual 14 liters to 140 liters. The results of analysis of scrubber gas is given for two runs, one of the runs being the same as the above mentipned run in which herbicide was measured in the combustion gases; both analyses revealed no herbicide or chlorinated compounds above the detection limit (.1 yg per liter of gas). Samples of spent scrubber water was analyzed from 6 test runs. All samples were below the detection limit for TCDD (.015 ppb) and the concentration of chlorinated compounds ranged from 0,4 to 17.0 ppb. Analyses of samples of spent scrubber water from two additional runs revealed total herbicide concentration of 172 ppb and 2,199 ppb. In addition, the combustion and scrubber exhaust gases were analyzed for the components: nitrogen, oxygen, argon, carbon dioxide, hydrocarbons as butane, hydrogen chloride, nitric oxide and phosgene. These were all within acceptable limits. D-8 �g. Incomplete Combustion: Eleven samples of combustion gas and 14 samples of scrubber exhaust gas were analyzed for phosgene, all results were reported as 0.0 mole percent. From a thermochemical standpoint, a computer program for the calculation of complex chemical equilibrium compositions was used to obtain theoretical combustion temperatures and products for Orange/ natural gas/air ratios. The computer program is contained in NASA Report SP-273, "Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and ChapmanJouguet Detonations by Sanford Gordon and Bonnie J. McBride," 1971. The computer output is presented in graph form in the technical report as a function of temperature and auxiliary fuel to air ratio. For a temperature of 2000°F and no auxiliary fuel, the predicted combustion products to a volume >99.9" are nitrogen, oxygen, water, carbon dioxide and hydrogen chloride. h. Conclusions and Recommendations: The conclusions and recommendations are quoted from the technical report. (1) Conclusions: "1. Herbicide Orange can be effectively and safely destroyed by combustion. 2. The absence of raw hsrbicide, phosgene, hydrogen chloride and dioxin in the scrubber gases indicates that the impact on the atmospheric environment is not damaging. The impact on the ground and water environment is dependent on the type of scrubber material used and the ultimate disposition of the expended neutralizer. 3. Exotic type materials are not required. The 310 stainless steel material used for the combustion chamber and reaction tailpipe showed no evidence of deterioration due to the interaction of the hot exhaust gases with the metals. The durability of refractories for this application was not evaluated. * 4. The incinerator must be gas tight up through the scrubber, otherwise hydrogen chloride vapors will be emitted and pose a serious problem. 5. A full scale incinerator system should have very large filter capacity with two parallel filter systems. This arrangement will permit cleaning one system while the other system is in use." (2) Recommendations: "Additional design study and testing should be funded to determine the most feasible and economical type scrubbing system and scrubber material. The study should a"so include ways of disposing of the expended neutralizer." 4. THE MARQUARDT COMPANY, VAN NUYS CA AND THE USAF ENVIRONMENTAL HEALTH LABORATORIES, MCCLELLAN AND KELLY AFB. a. Report: Report on the Destruction of Orange Herbicide by Incineration, 1974; this -"eport was prepared by the Marquardt Company with inputs prepared by the USAF Environmental Health Laboratories. The Marquardt Company was primarily responsible for Orange handling and incineration operations; the Air Force conducted the majority of the D-9 �monitoring effort, and the West Coast Technical Services, Inc. performed, under contract to the Marquardt Co, most of the analytical chemistry. A FINAL^ DRAFT copy of this report is included as Appendix E to the Environmental Statement. The report was accomplished by Mr. R.J. Haas, Mr. R.P. Babbitt, and Mr. J.E. Hutson of the Marquardt Co. (TMC), with appendicies preparec by Captains C.W. Bullock and J.W. Je.ckson of the USAF Environmental Health Laboratories. The scope of the project reported on was to incinerate the contents of 28 drums of Orange herbicide, with complete operational and environmental monitoring, in test incineration runs of approximately 3 hours' duration. The objectives and conclusions are quoted below: (1) Objectives "Test Objectives: The objectives of the contract effort, as listed in the Statement of Work, were as follows with agencies of prime responsibility noted: a. Determine the capability of an incinerator system to destruct the "Orange" Herbicide over a range of selected incineration conditions (TMC and EHLs). b. Obtain the necessary engireering data to adequately monitor, control, and document the incinerator operation during the project (TMC). c. Evaluate the test burns' effects and project the long term effects of the combustion gases on the material of the incinerator unit (TMC). d. Determine the combustion gas, scrubbed effluent gas, and "spent" scrubber water discharge mass rates of herbicide constituents and any other organic compounds which may be detected (EHLs). e. Determine the presence of herbicidal pyrolyzates and hydrolozates, if any, in the combustion gases, scrubbed effluent gases, and "spent" scrubber water (EHLs and Analytical Chemistry Laboratory). f. Determine the toxicity of "spent" scrubber water to several aquatic indicator organisms (EHL/K). g. Evaluate the noise produced by an incineration system and assess its occupational hazard to operators (EH-/K). h. Evaluate the effectiveness of a proposed drum cleaning procedure (EHL/K)." (2) Conclusions "14.0 CONCLJSIONS (Prepared by USAF EHL/K, EHL/M and TMC) 14.1 Destruction_o_f '_Orajige^ Herbicide by Incineration "Orange" Herbicide was effectively and safely destroyed by incineration. No "Orange" Herbicide constituent was detected D-10 �in any system effluent when operating with the slot nozzles, and only in one spent scrubber water sample (Burn IT!) when operating with the poppet nozzle. Likewise, very favorable relative pyrolysis efficiencies were obtained, ranging from 99.98% to 99.999%. Also, no chlorinated phenolic compound was detected in any of the scrubbed effluent gas samples, and only in one combustion gas sample. The spent scrubber water from all burns contained monochlorophenol but at a level not exceeding 0.14 x 1CT6 grams /liter in the last five burns or 53 x 10~6 grams/liter in all burns. 14.2 Eng i neeri ric)_Da ta Preheat of "Grange" Herbicide fuel prior to injection in the combustion chamber was an important combustion efficiency parameter. The RPE was improved significantly where the "Orange" Herbicide fuel was preheated to 17E°F. Preheat of "Orange" Herbicide fuel to at least 90°F was required to accomplish acceptable fuel injection characteristics. s The method of fuel injection was an important combustion efficiency parameter. The radial slot nozzles produced a higher RPE (Appendix I) and only about 1/20 the mass of combustion chamber coke deposits produced when central poppet nozzles were used. In the incineration system utilized, the slot, nozzles provided satisfactory results at higher fuel/ air mass ratios and combustion temperatures and therefore permitted a higher destruction rate of the 'Orange" Herbicide. The basic flow control required for this incinerator was quite simple in that only fuel and air mass flow regulation was required once steady state was achieved. Transients were performed without incident due to the ease of ignition of "Orange" Herbicide into an established flame. The manual control systems were quite satisfactory in these regards and the only real flow control monitoring needed was to correct for minor changes in flow caused by changes in facility air storage pressure or changing fuel properties. It can be concluded that "Orange" flow regulation is no problem as long as temperature is maintained within a reasonable band as determined by system sizing and is properly filtered to prevent plugging of fuel nozzles. Basic incinerator control therefore consisted of fuel and air flow regulation with monitoring of the combustion gas temperature to verify the presence of combustion and provide a relative indication of combustion and consistency of operating parameters. Air and fuel mass flow depended on delivery system pressure. The burner system pressure provided an indication of combustion gas flow and downstream conditions. These control parameters were conventional and could be readily automated using existing process industry control components. Such systems quite routinely monitor and control flow and combustion processes and take appropriate corrective action in the event of system anomalies. From purely a combustion point of view, this incineration process was not much different than when using conventional fuels. However, the serious differences were in the structural integrity (safety) of the incinerator and the safety aspects, of storage and delivery of the "Orange" Herbicide. Scrubbing of the combustion gases and neutralization of acids was accomplished satisfactory. Optimization of this system was not within the scope of this effort and it J's recognized that other types of D-ll �scrubbers may be more desirable. adequate analyses sampling analysis scope of The on-line gas analyses equipment used was for CO, NOX, and HC monitoring of scrubbed effluent gas only. Gas equipment incorporating additonal features would be suitable for of combustion gas.. However, the application of on-line sampling to a production process would require additional study beyond the this effort. 14.. 3 Ef£ects_ on _Inc i nera t p r_ Mate rial s Considering the absence of structural or sealing problems in the physical combustion chamber enclosures, the lack of evidence indicating physical deterioration in the materials utilized, the qualities of the materials used, and prior experience in similar systems, it can be concluded that the basic incinerator design would provide a unit of considerable longevity. There are design considerations that would be required, "external" to the basic combustion process, which could further ensure longevity and provide a reliable unit. Such design factors do not appear to be particularly unusual or exotic in nature. It can also be concluded that durability would be enhanced by long term continuous operations where start-stop transients are minimized. 14.4 Mass Discharge Rates of "Orange" Herbicide Constituents. TCDD was detected in the spent scrubber water from Burn III at 0.25 x 10 grams/liter. Otherwise, no "Orange" Herbicide constituent was detected ir any scrubbed effluent gas sample or in any spent scrubber water sample. "Orange" Herbicide constituents were detected in the combustion chamber coke deposit from Burn III but these deposits were contained and the mass of the "Orange" Herbicide constituents in the coke was 64.4 nig. Table 5 presents the maximum potentially undetected "Orange" Herbicide constituents that could have been discharged without being detected. The TCDD in the spent scrubber water from Burn III was included in the discharge. The average mass that could have been discharged in the scrubbed effluent gas during each burn was 9.3 mg (& = 2.7 mg). The average mass that could have been discharged in the spent scrubber water was 3.4 mg (-6 = 1/4 mg). 14.5 Spent Scrubber _Wat er_Q uaj ity Spent scrubber water inorganic quality was directly related to applied caustic. Mineral content of spent scrubber waters would be minimized and acid gases effectively scrubbed if applied caustic were 2.0 (± 0.1} times tnat required to neutralize the theoretically expected amount of HC1. Primary settling, and dechlorination, and adjustment of pH to about 9 may be required before discharging the spent scrubber water to natural waterways. For burns using the slot nozzles, the total average hydrocarbons were less than 20 pg/L and no hydrocarbons were detected in the water's suspended carbon particles. Of the 20 Mg/L total hydrocarbons, less than 1.5 percent of them could have been undetectable compounds of the original herbicide feed. D-12 �14.6 Pyrolyzates and Hydrolyzates All of the detected unchlorinated aliphatics, aromatics, and biphenyls were considered pyrolyzates. The total mass of these pyrolyzates in the scrubber water, corrbustor coke deposit, and scrubbed effluent gas averaged 1.32 gms as carbon per drum of herbicide incinerated in the less efficient burns (I, II, III) and was an order of magnitude less (0.42 gms as carbon per drum) in the high efficient burns (IV through VIII). All of the detected monochlorophenol and dichlorobenzene were considered hydrolyzates. Since they were detected in only one effluent stream from the incinerator scrubber water, their total effluent mass averaged 0.86 grams as carbon per drum of herbicide incinerated in the less efficient burns (I, II, and III). These effluent masses of hydrolyzates decreased three orders of magnitude to an average of 0.006 grams as carbon per drum of herbicide incinerated during the more efficient burns. "14.7 Air Sampling It was concluded that the data from the Beckman 109A hydrocarbon analyzer was not an indicator of RPE (Appendix I). The formation of dichlorobenzene, dichlorophenol, and monochlorophenol by ~he reaction of nonchlorinated aromatic hydrocarbons with HC1, C12 and Cl was indicated in locations of rapid combustion gas cooling. The quantity of these compounds that might: be formed in other systems would not be expected to exceed the mass of aromatic hydrocarbons existing in the gas. 14.8 Bioassays Conclusions about bioassay data will be published under separate cover by USAF EHL/K. 14.9 Noise Hazards Unprotected personnel occupationally working within fifty feet of the incinerator(s) should be provided ear protection and be monitored via a hearing conservation program. The conventional masonry control room walls effectively protected the operators from the incinerator's hazardous noise levels and provided them an area quiet enough for reliable communication. Masonry walls around the incinerator pad would preclude ambient incinerator noises from interfering with any adjacent operations. 14.10 Drum Cleaning Data of this study can be used to determine the volunetric rinses of used or contaminated JP-4 needed to meet any prescribed drum cleaning requiremerts. Under the following constraints, separate rinse procedures should be used to obtain maximal removal of the 450 (± 25) grams of herbicide in the drained drums: a. Some cleaning required but ^5 gallons of clean or contaminated JP-4 available per drum. Use the five gallons in a single rinse D-13 �to obtain 70 percent herbicide removal. b. Maximal cleaning required but =10 gallons of clean or contaminated JP-4 available per drum. Use two rinses of five gallons each to remove 79.1 percent of the herbicide. c. Third rinses of less than five gallons of JP-4 did not improve overall herbicide remova" by more than three percent. Removing drum ends and spraying the rinse downward through the open drum would provide better rinse drainage. Depending on rinse volumes used, such a rinse application technique may improve herbicide removal efficiencies by 10 to 25 percent over the results of this study." 5. COMBUSTION POWER COMPANY INC., MENLO PARK, CA a. Report: Technical Report TR 73-7., Progress Report of Determining the Feasibility of Disposing of Air Force Liquid Wastes in the LSW-500 Industrial Prototype, August 15, 1973, Contract No. F29601-73-C0128 for Air Force Weapons Laboratory (AFSC), Kirtland AFB NM 87117, by Combustion Power Inc, Menlo Park CA. This report is not a final report but is a progress report, the last revision was incorporated as of 18 Jan 74. b. Objectives: To determine the feasibility of disposal of selected Air Force liquid waste including paint stripping waste, petroleum based wastes, wash rack wastes, and Orange herbicide via fluidized bed incineration. c. Type of Incineration: The incinerator unit used is the LSW-500 Industrial Prototype. "TEe combustion zone is 3 feet in diameter and the bed material is normally sand. Air is used to fluidize the bed and the velocities through the unit have been usually 4 to 6 feet: per second. For acid gas control, dolomite or limestone is placed into the unit as part of the bed material. The acid gas produced by the incineration is then absorbed chemically within the fluidized bed. As the limestone is used up, it has to be removed and replaced with fresh limestone. This method eliminates the need for a liquid scrubber for acidic combustion gases. The combustion gases are presently passed through three separators for particulate removal and sand recovery. Prior to incineration of Orange, tests were conducted with dichloro-benzene to determine the efficiency of dolomite in hydrogen chloride absorption. d. Quantity of Orange Incinerated: Five test runs of Orange have been conducted; the total v6lume~bf OTange incTnercted, in a chronological order per run, was 3.10, 2.18, 5.5, 10 and 18.3 gallons respectively. The feed rates for these runs were 0.505, 0.705, 2.36, 2.79 and 3.25 pounds per minute. In the first two runs the bed material was all dolomite, the bed temperature was 1500°F and the superficial velocity was 4 and 6 feet per second respectively. For the third run the bed material was 50 percent dolomite and 50 percent sand, the bed temperature was 1490°F and the freeboard temperature was 1150°F, and the superficial velocity was 4.0 feet per second. The bed material for test 4 and 5 was a combinction of sand and limestone and the average bed temperature was 1530°F and 1510 C F respectively. e. Monitoring: The exhaust gas of each run was sampled for subsequent herbicide and TCDD analyses by Combustion Power Co personnel using an impinger train with benzene as collec~ing media. In acdltion, monitoring was accomplished D-14 �for oxygen, carbon dioxide, carbon monoxide, hydrocarbons, sulfur dioxide, and oxide of nitrogen. The analyses of herbicide components and TCDD is to be accomplished by Stoner Laboratories, Inc, Santa Clara CA. At present, the results have been documented for the first three runs for the herbicide components and no results have been attained for TCDD. The TCDD analyses has been delayed due to problem associated with obtaining a laboratory standard: however, action has been taken to be sure that, the TCDD samples will be analyzed. gases, ppb nb ppb nb Run 3: ranges f. Results: The concentrations of herbicide components in the exhaust corrected to 10% Oj, were as follows: Run 1: 4.068 ppb nb 2,4-D, 10.96 2,4,5-T, 0.2913 ppb 2,4-D acid and 0.5044 ppb 2,4,5-T acid; Run 2: 0.3196 2,4-D, 2.370 ppm rib 2,4,5-T, and none detected (NO) for either acid, and 0.5221 ppb nb 2,4-D, 0.5418 nb 2,4,5-T, and ND for either acid. The of the other constituents were all within acceptable limits. g. Conclusions: This report being reviewed is a progress report whose function is primarily to report data. A discussion of date and conclusion will be contained in the final technical report to be prepared by Combustion Power Co. It is apparent that practically all of the ester components herbicide are being destroyed by the incineration process. C. SUMMARY AND CONCLUSION: The results of two laboratory, two full scale, and one industrial prototype scale Orange incineration projects have been reviewed. The methods of incineration have included heating, flame, and fluidized bed. The data and conclusions of the investigations have revealed incineration an efficient method of large scale destruction of Orange herbicide. The essentially complete destruction of the herbicidal components of Orange as reported in all of the projects, dictates that the herbicidal effect of combustion gases will be mirimal to non-existent. Therefore, such gases could be discharged into a remote, non-vegetative environment. The hydrogen chloride generated by the incineration process is phytotoxic; the rerroval of hydrogen chloride via alkaline scrubbing is extremely efficient and is also positive as regards removal of particulates from the combustion gas. The data shows that the discharge of alkaline scrubbed combustion gases via a stack would be acceptable to practically any environment. The discharge of spent scrubber water will require consideration for its impact on the receiving water. The TCDD situation requires placement into proper perspective. The total anojnt of TCDD in the entire Orange stock is approximately 50 pounds. All the reviewed projects revealed the TCDD concentration in the exhajst streams to be non-detectable or extremely small. Under high temperature incineration, the data indicated that essentially all of the TCDD will be destroyed. Orange destruction efficiencies of 99.9 to 99.999 percent appear feasible fDr the large scale incineration project. This will respectively result in a total discharge o~ 0.05 to 0.0005 pounds of TCDD via the exhaust streams over the duration of the project. The exhaust streams would, in turn, be diluted in the environment into rthich they are discharged. When judged against certain alternatives, for example, storage under conditions where a catastrophic event could result in gross detrimental environmental imoact, the incineration of Orange, with due considerations for the extreme toxicity of TCDD, is an acceptable method of disposal. In addition, USDA (1970) reports that some 9.0 million pounds of 2,4,5-T were being applied annually in the United States when in April 1970, restrictions were placed on its use. If these nine million were assumed to have 2 mg/kg of TCDD, the same as that of the Orange stock, then the TCDD released to environment annually during application was about 18 pounds. The possible incineration effluent discharge noted above, 0.05 to 0.0005, rc- D-15 �presents only 0.27 to 0.0027 percent of the estimated release which had occurred during one year of application of 2,4,5-T. The situation as regards pyrolyzates and hydrolyzates of Orange heroicide incineration has been addressed in this review. Existing data, together with theoretical considerations and applied thermochemistry, show tnat such products are minimized with efficient, high temperature incineration. The data also indicate that if such products were present their concentrations would be extremely small and environmentally insignificant. In view of the above, it is concluded that incineration, with proper concern for the environment in which such incineration will take place, is an environmentally safe method for disposal of Orange herbicide. D-15 �APPENDIX E FINAL REPORT REPORT ON THE DESTRUCTION OF "ORANGE" HERBICIDE BY INCINERATION /f �(This page intentionally left blank) �FINAL REPORT REPORT ON THE DESTRUCTION OF f "ORANGE" HKHniCIDC BY INCINERATION Approved by: Prepared by: R. P". "Babbitt, Manager, Environmental Process Systems RuEsonV" P.~E. i/ Project Engineer R. J^Haas, General Manager CCI Environmental Systems Division April, 1974 THE MARQUARDT COMPANY 16555 Saticoy Street Van Nuys, California Prepared for: UNITED STATES AIR FORCE ENVIRONMENTAL HEALTH LABORATORY Kelly Air Force Base, Texas CONTRACT NO. F41608-74-C-1482 �ACKNOWLEDGEMENTS During this project, personnel from the USAF Environmental Health Laboratories performed the gas sampling, scrubber water sampling, biornonitoring, noise testing, and analyses of data for certain portions of this report. Team members from the USAF Environmental Health Laboratory Kelly AFB TX (EHL/K) were Majors Carl ton R. Williams and Roger C. Inman, Capt Charles W. Bullock, TSgt Jerrold C. Akey, SSgt John J. DiLorenzo, A1C Gregory S. Knerl and Mr. Leopoldo L. Rodriguez; and team members from the McClellan AFB, CA (EHL/M) laboratory were Maj John J. Gokelman, Captains Jerry W. Jackson, Marl in L. Swegart and Kenneth E. Hundley, and Staff Sergeants Fred Ward and Henry F. Pauley. Capt Charles Bullock (EHL/K) prepared Appendices C, Sample Code Designations; E, Scrubber Water Monitoring; F, Drum Cleaning, Disposal, and Analyses of Drum Rinse Samples; and J, Noise Monitoring. Capt Jerry Jackson (EHL/M) prepared Appendix D, Combustion and Scrubbed Effluent Gas Monitoring. Both Captains Bullock and Jackson prepared Appendix I, Evaluation and Discussion of Organic Analyses of Blended Herbicide, Scrubber Water, Combustion Gas, Scrubbed Effluent Gas, and Residues. �FOREWORD The work reported herein is submitted in fulfillment of Contract No. F41608-74-C-1482, let hy USA!-', AFLC, Son Antonio Air Materiel Area (SAAMA), Procurement Directorate, Kelly Air Force Mase, Texas. The project was monitored by USAF Environmental Health Laboratory, Kelly Air Force Hase, Texas, in coordination with SAAMA Procurement, This report was written and concluded jointly by The Marquardt Company, Van Nuys, California; USAF Environmental Health Laboratory, Kelly Air Force Oase, Texas (USAF EFIL/K); and USAF Environmental Health Laboratory, McClellan Air Force Base, California (USAF EHL/M). The work was accomplished between 8 October 1973 and 21 December 1973 at the Air Force-Marquardt Jet Laboratory (AF-MJL) at Van Nuys, California. Activities were conducted and monitored by a team consisting of-The Marquardt Company, the USAF EHL/K, find the USAF EI1L/M. Organic analyses of samples from test burns were performed by West Coast Technical Service, Inc. (WCTS) of Cerritos, California. Inorganic analyses of test burn and drum cloiining samples were performed by the EHL's. The Marquardt Company has no proprietary interests or restrictions on this report. �ABSTRACT A test program was conducted to evaluate the incineration of "Orange" Herbicide in a commercial incinerator over a range of selected incineration conditions. Particular emphasis was placed on the ability to destroy the parts per million quantities (11-16 mg/kg) of 2,3,7,8-tetrachlorodibenzo-p-dioxin present in the herbicide. Extensive sampling was conducted to evaluate the unscrubbed combustion gases, the scrubbing liquid used to cool and scrub the combustion gases, scrubbed effluent gases and any solid residues deposited in the system. Additional objectives were: to obtain engineering data relative to controlling and monitoring the incineration process, to evaluate noise produced by the incineration system, to evaluate long term effects of herbicide combustion on incinerator materials, to evaluate the effectiveness of a proposed drum cleaning procedure, to assess the toxicity of discharged scrubber water to several aquatic organisms, and to assess the effects of scrubbed effluent gas on tomato plants. The program xvas conducted using a Marquardt incinerator system. Samples were analyzed by mass spectroscopy, flame ionization gas chromatography, and atomic absorption. A total of 30.5 hours of burn time on undiluted "Orange" Herbicide fuel was accumulated during eight record burn periods. Test data demonstrated that the incineration system operated very satisfactorily using undiluted "Orange" Herbicide as a fuel and that the herbicide was effectively and safely destroyed in the combustion process; i.e., gaseous and spent scrubber water effluents, within the analytical limits of detection, did not contain any of the compounds identified in the herbicide feed. Criteria were also established regarding effluent biological-impact, incinerator noise generation, drum cleaning procedures, and incinerator process system functions. E-ii �TABLE OF CONTENTS Page FORPWORD i ABSTRACT ii GLOSSARY OF TERMS AND SYMBOLS x 1.0 SUMMARY 1 2.0 INTRODUCTION 3 2.1 3 Program History 2.2 Description of "Orange" Herbicide 3 2.3 Test Objectives 3 2.4 Program Scope 4 2.5 Program Task Organization 5 2.6 Theoretical Combustion Data 5 3.0 TEST FACILITIES 6 3.1 Incinerator and Reaction Tailpipe • 6 3.2 Venturi Scrubber and Scrubber Tank 6 3.3 Air Supply System 6 3.4 Natural Gas System 6 3.5 Primary Fuel System 10 3.6 Caustic Solution and Water Supply Systems 10 3.7 Scrubber Liquid Collection System 10 3.8 Control Room 14 3.9 Test Cell 14 3.10 Herbicide Storage and Drum Rinsing 14 3.11 Bioassay Test Area 14 3.12 Air Sample Preparation Area 14 3.13 Other Facilities 14 E-iii �TABIE OF CONTENTS (Cont'd) Page 4.0 GAS AND LIQUID SAMPLING SYSTEMS 20 4.1 On-Line Equipment 20 4.2 Combustion Gas Sampling 23 4.3 Scrubbed Effluent Gas Sampling 23 4.4 Spent Scrubber Water Sampling 23 4.5 Herbicide Sampling 23 46 . Drum Rinse Sampling 23 4.7 System Residue Sampling 23 5.0 SAFETY AND HANDLING 28 6.0 INCINERATOR TEST BURN PROCEDURES 28 6.1 Systems Preparation 28 6.2 Preliminary Testing 28 6.3 Herbicide Loading and Preheating 6.4 7.0 29 29 Typical Burn Sequence of Events 30 7.1 General 30 7.2 Combustion Temperatures 30 7.3 Summary of Incinerator Functioning; 33 7.4 Test Descriptions and Data 34 7.5 8.0 INCINERATOR TEST PROGRAM Summary of Each Test and Record Burn 36 GAS SAMPLING RESULTS AND COMMENTS 39 8.1 Combustion and Scrubbed Elf fluent Gas Sampling Results 39 8.2 41 On-line Gas Sampling E-iv �TABLE OF CONTENTS (Cont'd) Page 9.0 42 9.1 Inorganic Quality of Spent Scrubber Water (SSW) 42 9.2 10.0 SCRUBBER WATER SAMPLFNG RESUITS Organic Quality of SSW 45 COMBUSTION CHAMBER COKE DEPOSIT RESULTS AND DISCUSSION 45 10.1 Quantity ,md Quality 45 10.2 Fuel Injection Characteristics Relative to Coke Depositing 46 11.0 PYROLY7ATE AND HYDROLY/ATE RESULTS AND DISCUSSION 48 12.0 BCOASSAY, NOISE TESTING, AND DRUM CLEANING/DISPOSAL RESULTS DO , 12.1 50 12.2 Noise Testing 51 12.3 13.0 Bioassays Drum Cleaning Analyses and Comments 51 OTHER TEST PROGRAM COMMENTS 52 13.1 52 13.2 Herbicide Handling 52 13.3 14.0 "Orange" Herbicide Properties Effect on Incinerator Materials 53 CONCLUSIONS 53 14.1 Destruction of "Orongc" Herbicide by Incincration 53 14.2 Engineering Data 54 14.3 Effects on Incinerator Materials 55 14.4 Mass Discharge Ratos of "Orange" Herbicide Constituents 55 14.5 Spent Scrubber Water Quality 55 E-v �TABLE OF CONTENTS (Cont'd) 14. G Pyroly/ates and Hydrolyzatcs 57 14.7 Air Sampling 57 14.8 Bioassays 57 14.9 Noise Ha/ards 57 14.10 Drum Cleaning 58 APPENDICES (See Separate Table of Contents in Appendices D, E, F, G and I) APPENDIX A - THEORETICAL COMBUSTION TEMPERATURES AND PRODUCTS FOR "ORANGE" HERBICIDE AND AIR COMBUSTION APPENDIX B - DETAILED DESCRIPTION OF TEST FACILITY FOR "ORANGE" HERBICIDE INCINERATION APPENDIX C - SAMPLE CODE DESIGNATIONS (EHL/K) APPENDIX D - COMBUSTION AND SCRUBBED F.FFUJENT GAS MONITORING (EHL/M) APPENDIX E - SCRUBBER WATER MONITORING (EHL/K) APPENDIX F - DRUM CLEANING, DISPOSAL, AND ANALYSES OF DRUM RINSE SAMP1ES (EHL/K) APPENDIX G - ORGANIC ANALYSES OF BLENDED HERBICIDE, COMBUSTION AND SCRUBBED EFFLUENT GASES, SPENT SCRUBBER WATER, AND RESIDUES (WCTS) APPENDIX H - SAFETY AND HANDLING APPENDIX I - EVA1AJATION AND DISCUSSION OF ORGANIC ANALYSES OF BLENDED HERBICIDE, SCRUBBER WATER, COMBUSTION GAS, SCRUBBED EFFIAJENT GAS, AND RESIDUES (EHL/K AND EHL/M) APPENDIX J - NOISE MONITORING (EHL/K) APPENDIX K - REFERENCES E-vi �TABLES MAIN REPORT Pace TABIE 1 - GENERAL TEST PROGRAM EVENT SUMMARY 31 TABLE 2 - COMBUSTION SYSTEM PARAMETERS DATA SUMMARY (RECORD BURNS ONLY) 35 TABIE 3 - INORGANIC LOADING AND RANGE OF QUALITY IN SPENT SCRUBBER V/ATER 44 TAB IE 4 - AVERAGE RANGE OF DETECTED HYDROCARBON MASSES CONSIDERED TO HE PYROLYZATES AND HYDROLY/ATES OF "ORANGE" FIERI II • 0.96-O. 13 | ;105.8-7.9 Nunchlorinatcd Aromatics (('(illifC^lg)) | l.Hl-().2r> I ND Hiphcnyl (unchlorinalcd) ND I NU Dichlorononzcnc ND j ND Hunochlorophcnol M) 1.O' Dirliluraphenol * " ' ND 2,1-D Divtilorophunox} Acetic A c i d * " ;i,!,5--T Trichl«rophenox> A c e t i c Ac i il Hhcnoxy Acetic A c i d ( u n c h t n r i i u i l c d ) \l) \l) ND \ D - \ o t detected. ' j V) ND ND ND ND ND \l) ND N'D ND ; ] . HtRIUClUK INCINERATION scrubber! K C f l u e n t da.-. Combust or ^ Coke Uepo.-it Spent scrubber W a t e r Sediment l> ND OKA.NGE ! ND Kor tleleclulile l i m i t s sec I'j:blo» (1-2 tliroiiRli G-9 0.07-0.0') O.Ori-O.Ob O.01-O.OC ND ND MJ MJ M) '^D M) \D \D M) ND ND ND ND M> NU ND ND ND ND ND NU NU NU ND ND ND ND NU 31.0-^-2.0 1O5.0-126.O «. 7.1-4. ae .ND ND 2.--1.3 2.3- NU ND ND MJ ND ND ^. 1* 0.3' Average height Percent Present in H e r b i c i d e Feed ND NT) M> .NU MJ \U NL) ND ND ND NU ND NU .ND i.'lo 0.73 O.J2 ND Rcported as mass of compound * In Combu>tor Cuke i>cposit. Iliirn 1 1 1 o n l y . 1. Jg per liter of ita.-, (STP) •• Iturn 1 only. 2. '-K per liter' of spent scrubber water 1 ••• Thc.->e cu!B|M>uN(!i were in 'Or.iiige" H e r b i c i d e - - m.iy not h,-i\i- been p) rol \/.ites. 3. -g per 1OO i;runi.- 3TP - 70°F, 29.'J21 HK, and Dry Note: 'I'lic Cir-l l i i l n o in em h c o l u m n v»,i.- ;in ,ncr;iq<> of llurns I II i-ind I I I . >o< und i . i l u c i n o«i( b coliimn uji<- ,m ,-iver,'ii;(> of Biirn- I V , X , V I . I l l .mil U l l - L.-iAl- LI11./M and K �scrubber while the biphonyls completely penetrated through the scrubber. The respective penetration of these pyroly/,atcs through the scrubber was probably due to their relative solubilities and vapor pressures in hot NaOll solution. (Sec Appendix I.) The biphenyl pyroly/atc undoubtedly existed in the combustion gases but its detection was considered to have been masked via gas chromatograph peak interference (see Comments section of Appendix G). MonochLorophcnol «uid dichlorobcnxenc were consistently detected in tho spent scrubber water but never in the herbicide feed or in any of. the combustion or scrubbed effluent gas samples except for the monochlorophcriol in Burn I combustion gas. Since the precursor (s) (unchlorinatcd aromatics) of these compounds were present in the combustion gas along with HC1, C12* <™d monatomic chlorine, it was reasoned that condensation and hydrolysos of these combustion gas products occurred in the venturi scrubber to produce monochlorophcnol and dichlorobenzcnc as hydrolyzates. Since the 2,4-D ;md 2,4,5-T ehLorophcnoxy acetic acids and rtiehlorophcnol averaged 2.71% by weight of the blended "Orange" Herbicide feed, these compounds may i)r may not have been pyroly/atcs. These compounds were found only in the combustor coke deposit. The phenoxy acetic'acid was however not detected in the blended herbicide feed samples. Thus this acid was considered a pyroly/atc formed when, combustion chiuiibcr mixing was its poorest' and combustor coke deposit was at its maximum (Burn III). lonol and didccylphthlate were detected in all combustion and scrubbed effluent gas samples and all spent scrubber water samples. However, as discussed in Appendices G and I, these compounds were considered environmental contaminants and not pyrolyzates or hydrolyzates. 12.0 UIOASSAY, NOISE TESTIXG, AND DRUM CLEANING/DISPOSAL RESULTS AND DISCUSSION (Prepared by USAF EI1L/K) 1.2.1 B_i_qassays_ Dynamic bioassays of up to 96 hours were conducted with thrce-spined stickleback fish (Gasterosteus aculeatus) in the spent scrubber water. Static bioassays "were" aTso^condiTcTect with brine shrimp (Artemia jsalina) in spent scrubber water for periods up to 24 hours. "Plant" "bTomoni t or ing was. initiated several days prior to Burn I, during all burns, and five days after Burn VIIT. Monitored flora consisted of the indigenous plants around TMC's perimeter and ten young tomato plants at each of sixteen locations evenly distributed around the incinerator facility. Results and discussion of these bioassays and plant biomonitoring will be published by EHL/K under separate cover. [The EHL/K report on biological monitoring has been included as Appendix M to the Final Environmental Statement] E-50 �12.2 Noiso Testing; Incinerator noises were predominately in the 2 0 - 0 0 0080 Hcrl/ hands and had an overall noise level of 01 (+• 2) dhA at a distance of twelve feet. A fifty-foot radius around the incinerator was a hazardous noise area to unprotected personnel occupationally exposed to the noise. The control room effectively attenuated incinerator noises so that no speech interference levels were observed in the control room. Calculations wore made to determine the noise levels at various distartccs from one or more incinerators. See Appendix J. 12.3 Drum Cleaning Analysers and Comments Appendix F presents and discusses the drum cleaning procedures, drum disposal, .and analyses of rinse samples in detail. An abbreviated summary of these results is presented here. During initial transfer of "Orange" Herbicide to the fuel feed tank, a drum pumping device was used which left usually less than two quarts of herbicide in each drum. Before the cleaning phase each drum was upended and allowed to free drain until steady dripping stopped. Each drum was then rinsed three times with various amounts of JP-4 for five minutes each on a barrel rolling device. Rinse quantities of clean JP-4 in each drum rinse set were 5/5/5, 3/3/3, 2/2/2, and 5/3/2 gallons. Each rinse was drained into a holding tank for subsequent incineration. Samples were taken of each rinse solution midway during the draining. The cleaned drums were safely disposed of in an environmentally approved manner in the Los Angeles County "Class 1" Landfill Number 5 at Calabasas, CA. Evaluation of drum rinse sample analyses provided an estimate of total herbicide mass left in a freshly drained drum: 450 (+_ 25) grams. On a proportional basis, slightly more of the herbicide's 2,4,5-T nb ester was removed during rinsing than the 2,4-D nb ester. Smaller rinse volumes produced significantly more variable results. Nonetheless., a given total volume of rinse removed about the same amount of herbicide whether it was used in subdivided volumes or in a single volume with the restriction that a total volume was S5 gallons, from 6 to 10 gallons, or from 9 to 15 gallons. The percent efficiency of herbicide removed increased with total rinse volume applied: range 45% for 2/2 gallons to 79% for 5/5 gallons. A third drum rinse of S5 gallons did not improve the herbicide removal efficiency any more than 3%. Analyses of TCDD in the rinse solutions was beyond the scope of this study. With TCDD solubilities similar to that of the herbicide esters, it was indicated that as much as 1.25 mg of TCDD may have been left in the best rinsed drums. This amount of TCDD in these drums represented the worst case, however, since these drums contained herbicide with the highest TCDD contamination known to exist in Air Force stocks. E-51 �All rinse samples have been stored at KIIL/K should any further analyses of them be needed to select a drum disposal method,, 13.0 OTHER TEST PROGRAM COMMENTS (Prepared by TMC) 13.1 "Orange" Herbicide Properties Problems were caused by the high viscosity of "Orange" Herbicide with the unexpectedly low ambient temperatures at the start of testing. Figure B-6 shows viscosity vs. temperature and indicates that even at 1 0 F the viscosity of "Orange" Herbicide 0° is very high (16 centistokes) compared to other conventional fuels. At 65°F the viscosity rises to 48 centistokes. The temperature/ viscosity characteristic was also quite evident during transfer operations. The flow problems in the incinerator system were alleviated by heating the herbicide feed to 9 ° or higher. However, 0F the herbicide remained quite difficult to atomize even at these elevated temperatures. No filtration or plugging problems were noted in the fuel feed system during the program. Although a parallel filter system was available, a 5 micron filter pot selected for initial use was utilized without cleaning throughout the entire program. The maximum pressure loss noted during testing was about 20 psid across the filter. This absence of filtration problem was attributed to the complete flushing of the fuel feed tank during system assembly and the filtering of the "Orange" Herbicide during loading. No slot nozzle plugging problems were experienced. All testing using slot nozzles was performed with herbicide temperatures about 90 to 110°F. The nozzle slots were 0 0 9 inch wide. Slot .0 nozzle combustion was very smooth and no indications of plugging were noted. Removal of the manifold after testing revealed the slots had remained clean. The fuel slot nozzles were placed inside the natural gas nozzles as described :Ln. Appendix B. This arrangement kept the fuel slot nozzles cooled and precluded the possibility of "Orange" Herbicide being exposed to a hot metal surface during initial injection and thus prevented the formation of any deposits in the nozzle slot. This feature and the 5 micron filtering system was felt to have prevented any slot nozzle plugging problem. 13.2 Herbicide Handling The safety program established for this effort is described in Appendix H. There were no problems experienced in handling of the "Orange" Herbicide during the program. There was no spillage or other release of the herbicide to the environment, except for minor drips.normally occurring during transfer or fuel system modifications. These drips were promptly absorbed with a E-52 �rag soaked in JP-4. Contaminated rags and other materials were kept in a sealed container and disposed of by the Air Force at test program completion. All contaminated utensils employed during transfer or systems operations (funnels, hoses, drip pans, etc.) were thoroughly rinsed in JP-4 after each use and the rinse solution incinerated. 13.3 Effect on Incinerator Materials A total of 44 hours of operation, including 30.13 hours on undiluted herbicide, was accumulated during the program with 16 complete start/stop transients. During this period no structural problems were noted in the units themselves or at gasketed mating flanges. There were no emergency shutdowns or shortened runs due to physical incinerator problems. Examination of the incinerator during and after the program indicated no evidence of scaling or other physical deterioration indicating impending failure. General experience with Type 310 stainless steel, and our specific experience with Marquardt incinerators made of 310 stainless, indicate long term durability at the temperatures experienced, particularly at the low stresses and creep rates created by near ambient pressure operation. Even at a chamber pressure as high as 16 psig, the creep rate is 1% per 1 0 0 0 0,0 hours at 1500°F. Also, the maximum skin temperature noted on the uncoolcd reaction tailpipe throughout the program was 1 0 ° 70F which was below the temperature ( 0 0 ) at which oxidation scal20° ing becomes appreciable. 14.0 CONCLUSIONS (Prepared by USAF EHL/K, EUL/M and TMC) 14.1 Destruction of "Orange^ jlcrbicidc by Incineration "Orange" Herbicide was effectively and safely destroyed by incineration. No "Orange" Herbicide constituent was detected in any system effluent when operating with the slot nozzles or the poppet nozzles except for the combustor coke deposit and spent scrubber water sample of Burn III. Very favorable relative pyrolysis efficiencies were obtained, ranging from 99.98% to 99.999%. Chlorinated phenolic compounds were undetected in all of the scrubbed effluent gas samples and detected only in one combustion gas sample (monochlorophenol at 1 0 x 10-6 grams/liter in Burn I). .6 The spent scrubber water from all burns 6contained monochlorophenol but at a level not exceeding 0 1 x 10~ grams/liter in the last .4 five burns or 53 x 10-6 grams/liter in any of the burns. E-53 �14.2 Engineering Data Preheat of "Orange" Herbicide fuel prior to injection in the combustion chamber was an important combustion efficiency parameter. The RPE was improved significantly (from 99.99 to 99.99990 when the "Orange Herbicide fuel was preheated to between 900 an,i 175°F. Preheat of "Orange" Herbicide fuel to at least 9 ° was required to accomplish acceptable fuel injection charac0F teristics. The method of fuel injection was an important combustion efficiency parameter. The radial slot nozzles produced a higher RPE (Appendix I) and only about 1/20 the mass of combustion chamber coke deposits produced when central poppet nozzles were used. The slot nozzles provided satisfactory results at higher fuel/air mass ratios and combustion temperatures and therefore permitted a higher destruction rate of the "Orange1 Herbicide. Basic flow control was quite simple in that only fuel and air mass flow regulation was required once steady state was achieved. Transients were performed without incident due to the ease of ignition of "Orange" Herbicide into an established flame. The manual control systems were quite satisfactory in these regards and the only real flow control monitoring needed was to correct for minor changes in flow caused by changes in facility air storage pressure or changing fuel properties. It was concluded that "Orange" flow regulation is no problem as long as temperature is maintained within a reasonable band as determined by system sizing and is properly filtered to prevent plugging of fuel nozzles. Basic incinerator control therefore consisted of fuel and air flow regulation with monitoring of the combustion gas temperature to verify the presence of combustion and provide a relative indication of combustion and consistency of operating parameters. Air and fuel mass flow depended on delivery system pressure. The burner system pressure provided an indication of combustion gas flow and downstream conditions. These control parameters were conventional and could be readily automated using existing proces,s industry control components. Such systems quite routinely monitor and control flow and combustion processes and take appropriate corrective action in the event of system anomalies. From purely a combustion point of view, this incineration process was not much different than when using conventional fuels. However, the serious differences were in the structural integrity (safety) of the incinerator and the safety aspects of storage and delivery of the "Orange" Herbicide. Scrubbing of the combustion gases and neutralization of acids was accomplished satisfactorily. Optimization of this system was not within the scope of this effort and it is recognized that other types of scrubbers may be more desireable. E-54 �The on-line gas analyses equipment used was adequate for CO and NOX monitoring of scrubbed effluent gas only. Gas analyses equipment incorporating additional features would be required for sampling of combustion gas and for representative hydrocarbon sampling of the scrubbed and combustion gases. Application of on-line sampling analyses to a production process would require additional study beyond the scope of this effort. 14.3 F.f f ccts on Incinerator Materials Considering the absence of structural or sealing problems in the physical combustion chamber enclosures, the lack of evidence indicating physical deterioration in the materials utilized, the qualities of the materials used, and prior experience in similar systems, it was concluded that the basic incinerator design would provide a unit of considerable longevity. There are design considerations that would be required, "external" to the basic combustion process, which could further ensure longevity and provide a reliable unit. Such design factors do not appear to be particularly unusual or exotic in nature. It was also concluded that durability would be enhanced by long term continuous operations where start-stop transients are minimized. 14.4 Mass Discharge Rates of "Orange" Herbicide Constituents TCDD was detected in the spent scrubber water from Burn III at 0.25 x lO-6 grams/liter. Otherwise, no "Orange" Herbicide constituent was detected in any scrubbed effluent gas sample or in any spent scrubber water sample. "Orange" Herbicide constituents were detected only in the combustion chamber coke deposit from Burn III but these deposits were contained find the mass of the "Orange" Herbicide constituents in the 12.9 pounds of coke was 64.4 mg. Table 5 presents the maximum potentially undetected "Orange" Herbicide constituents that could have been discharged without being detected. The TCDD in the spent scrubber water from Burn III was included in the discharge. The average mass that could have been discharged in the scrubbed effluent gas during each burn was 9.3 mg (<& = 2.7 mg). The average mass that could have been discharged in the spent scrubber water during each burn was 3.4 mg (^ = 1.4 mg). 14.5 Spent Scrubber Water Quality_ Spent scrubber water inorganic quality was directly related to applied caustic. Mineral content of spent scrubber waters would be minimized and acid gases effectively scrubbed if applied caustic were 2.0 (^f 0.1) times that required to nuetralize the theoretically expected amount of HC1. Primary settl ing, dechlorination, and adjustment of pH to about 9 may be required before discharging the spent scrubber water to natural E-55 �TABLE 5: MAXIMUM POTENTIALLY UNDETECTED "ORANGE" HERBICIDE MASS DISCHARGE RATES FROM INCINERATION OF "ORANGE" HERBICIDE (includes TCDD, nb 2,4-D and nb 2,4,5-T esrers, and 2,4-L) and 2,4,5-T acids) I II III IV V VI Total Volume (STP) Produced During Burn (x 106 liters) 6.35 7.75 8.58 9.47 7.65 5.03 7.55 i'• 8.76 Undetectable Mass Concentration (x 10~3 pg/l)+ 1.05 0.90 1.15 0.80 1.00 3.00 1 . 30 Total Burn Undetectable Mass (x 10~3 grams)- 6.88 6.98 9.87 7.58 7.65 15.09 9.82 10 . 5 1 191 218 235 236 213 213 Burn Number VII i VIII SCRUBBED EFFLUENT GAS Burn Time (minutes) 136 1 . 20 356 i Undetectable Mass Discharge Rate (lag/rain)"1 m en 40 30 40 30 40 110 50 30 7.2 14.3 12.1 SPENT SCRUBBER WATER C*i Total Volume Discharged During Burn (x 1O3 liters) 15.7 15.0 15.1 15.9 13.5 Undetectable Mass Concentration (x 10-3 ng/l)+ 225 225 430* 225 225 225 225 225 Total Burn Undetectable Mass (x 10~3 grams )+ 3.54 3.39 6.46* 3.57 3.05 1.62 3.22 2.74 191 218 236 213 136 213 356 20 20 20 10 10 20 10 Burn Time (minutes) Undetectable Mass Discharge Rate (ug/min)-1 235 30* *Only gas or water sample in which any subject compounds were detected: 0.25 x 10~^ gm/1 +These values expressed as the total of the five herbicide constituents USAF EHL/M and K �waterways. For burns using the slot nozzles, the total average hydrocarbons were less than 20 l-ig/1 and no hydrocarbons were detected in the water's suspended carbon particles. Of the 20 ug/i total hydrocarbons, loss than 1.5 percent of them could have been undctcctablc compounds of the original herbicide feed. 14.6 Pyrolyzatcs and Ilydrolyzates All of the detected unchlorinatcd aliphatics, aromatics, and biphenyls were considered pyrolyzates. The total mass of these pyrolyzates in the scrubber water, combustor coke deposit, and scrubbed effluent gas averaged 1.32 gms as carbon per drum of herbicide incinerated in the less efficient burns (I, II, III) and was an order of magnitude less (0.42 gms as carbon per drum) in the more efficient burns (IV through VIII). All of the detected monochlorophenol and dichlorobenzene were considered hydrolyzatcs. These compounds were detected in only one effluent from the incinerator (spent scrubber water). Their total effluent mass averaged 0.86 grams as carbon per drum of herbicide incinerated in the less efficient burns (I, II, and III) but decreased three orders of magnitude to an average of 0 0 6 grams as carbon per drum of herbicide incinerated during the .0 more efficient burns (IV through VIII). 14.7 Air Sampling Data from the Dcckman 109A hydrocarbon analyzer was not tin indicator of RPE or combustion efficiency (Appendix I). The formation of dichlorobenzene, dichlorophcnol, and monochlorophenol by the reaction of nonchlorinated aromatic hydrocarbons with HC1, Cl2 and (Cl) was indicated in locations of rapid combustion gas cooling. The quantity of these compounds that might be formed in other systems would not be expected to exceed the mass of aromatic hydrocarbons existing in the combustion gas. 14.8 Bioassays Conclusions about bioassay and plant biomonitoring data will be published under separate cover by USAF EHL/K. 14.9 Noise Hazards Unprotected personnel occupationally working within fifty feet of the incinerator(s) should be provided ear protection and be monitored via a hearing conservation program. The conventional masonry control room walls effectively protected the operators from the incinerator's hazardous noise levels (91 + 2 dbA) and provided them an area quiet enough for reliable communication. Masonry walls around the incinerator pad would preclude ambient incinerator noises from interfering with any adjacent operations. E-57 �14.10 Drum Cleaning Data of this study can bo used to determine the volumetric rinses of used or contaminated JP-4 needed to meet any prescribed drum cleaning requirements. Under the following constraints, separate rinse procedures should be used to obtain maximal removal of the 450 (•+ 25) grcims of herbicide remaining in the drums after drainage: a. Some cleaning required but 35 gallons of,clean or contaminated JP-4 available per drum. Use the five gallons in a single rinse to obtain 70 percent herbicide removal. b. Maximal cleaning required but 510 gallons of clean or contaminated JP-4 available per drum. Use two rinses of five gallons each to remove 79.1 percent of the herbicide. c. Third rinses of less than five gallons of JP-4 did not improve overall herbicide removal by more than three percent. Removing drum ends and spraying the rinse downward through the open drum would provide better rinse drainage. Depending on rinse volumes used, such & rinse application technique might improve herbicide removal efficiencies by 10 to 25 percent over the results of this study. E-58 �APPENDIX A (TO APPENDIX E) THEORETICAL COMBUSTION TEMPERATURES AMD PRODUCTS FOR "ORANGE" HERBICIDE AND AIR COMBUSTION A computer program for the calculation of complex chemical equilibrium compositions was used to obtain theoretical combustion temperatures and products for "Orange" Herbicide/air mass ratios. This program is "NASA Report SP-273, Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and Chapman•Jouguet Detonations by Sanford Gordon and Bonnie J. McBride, 1971." The chemical composition of the "Orange" Herbicide was assumed to consist of: 50% by volume of N-Butyl 2,4,5-T and 50% by volume of N-Butyl 2,4-D The heats of formation used for each fuel were as follows: Heat of Formation Cal/Molc Fuel N-Butyl 2,4,5-T -159,000 N-Butyl 2,4-D . -152,000 The heats of formation of these compounds were estimated by taking the heats of formation of similar compounds and adding/ subtracting the heats of formation of similar/dissimilar groups. The results of computer analysis are summarized in Figures A-l through A-4. Figure A-l presents the theoretical temperature of "Orange" Herbicide and air combustion plotted against "Orange" Herbicide/air mass ratios for ambient air temperatures of 537 and 1000°R. The mass ratios were those of interest in the understoichiometric range which would provide combustion temperatures spanning the 2100° to 2900°F range to meet program requirements. Figure A-2 presents equilibrium products of "Orange" Herbicide/ air combustion plotted against theoretical combustion temperature for an ambient air temperature of 537°R. This data was used as a basis for prediction of incinerator combustion gas product composition. E (A-l) �Figures A-3 and A-4 present similar data for the overstoichiometric combustion of 2,4,5-T herbicide in 537°R ambient air. This data was computed to predict the effects of incomplete combustion or pyrolysis at very fuel rich conditions which could be created by incinerator failure, particularly regarding the formation of phosgene. Mass ratios were analyzed to approximately 1.5 times stoichiometric. Figure A-3 presents theoretical combustion temperatures versus 2,4,5-T herbicide/air mass ratios. Figure A-4 presents equilibrium products of combustion. No phosgene or any other potential gaseous products of incomplete pyrolysis were indicated within the limits of the computer program (less than 5 x 10"** mole fraction). E-(A-2 ) �MAC A Dll-2 /sflaiuuardt PREPARED BY ICORPOMtriON CHECKED BY . P ^LiANINI© HACINQ MFIN LA 1241 E(A-3) PAGE. DATE_ '73 FIGURE A-l �"I -I -- • ' - fHtntZKTtCAL- _,. — . . . I .... .j.. -_ .a?...:—a —^-, .+ : °." 9* HI '. en. I' L < , O .'J -I - 0 —y-~ i_ .„_/. ._j.—i-j...—rFIGURE A-2 �MAC A 811-2 THE PREPARED BY JjL tCOKPOMTION CHECKED BY M 5«H»NIM«© "£ TiMimrUK wuaidi LA 1241 _» A— 5} PAGE_ DATE 2-S-74. FIGURE A- 3 �to* •r-::/;'l:^4i • I"--' - • • ; - • ! • I '- - I ' -- .-—+. _.J—.-+_—, —t . _ J. - . • --• T -r— r'- -< \ i- -4-----OLOL. i i ' p— • | . _.T . - _ _ : i _. _ •" J^i ir+H-V"-.il-LlVJd.rc* : I I E(A-6) • • ! • • . .; LLL FIGURE A-4 -, �APPENDIX B. (TO APPENDIX E) PETATIJED DESCRIPTION OF TESTFACI LITY FOR "ORANGE" HERBICIDE INCINERATION A schematic of the complete test facility is shown in Figure B-l. The following discussion will describe the components and systems used during this program. SUE!® Burner Incinerator and Reaction Tailpipe The incinerator consisted of a 12-inch diameter SUE® Burner with a 48-inch long air cooled combustion chamber and 180-inch long uncoolcd reaction tailpipe. The SUE® Burner insert and cooling jacket shown in Figure B-2 was identical to other standard commercial SUE® Burner units used except that the test unit had not boon acoustically treated and longitudinal air vanes had been added to aid combustion chamber cooling. The SUE® consisted of an inlet pipe joined to a larger combustion chamber by a flat expansion plate (see Figure B-3). Fuel was injected through the plate at the "step." Because of this unique injection method, combustible fuel-air ratios were maintained in the recirculation zone, regardless of the overall fuel-air mass ratio. With this method of flame stabilization the burner was capable of operating at average combustion temperatures from 1800°F to the maximum allowable of 2 0 ° by varying the "Orange" Herbi80F cicle/air mass ratio. The maximum allowable temperature was determined by this program's restraint of providing a 30$> minimum of excess air. * This SUE® incinerator was equipped with three separate fuel injection arrangements. One set of fuel injectors or nozzles, located in t-he burner expansion plate, was used to inject the pilot fuel (natural gas). The burner was started with the pilot fuel and a spark type igniter. Two different injection nozzle systems were employed for injecting "Orange" Herbicide. For tests up through Number 9 (RecordBurn IV) a central poppet type nozzle was used to inject the herbicide in a finely atomized spray. This nozzle was attached to the inlet plate as shown in Figure B-4 and extended into the burner inlet pipe.. Water flowing through the poppet nozzle (Figure B-4) shows its atomization characteristics. For subsequent testing (Test Numbers 10 through 13, Record Burns V through VIII) herbicide was injected with slot type nozzles located inside the natural gas nozzles in the step plate. The slot nozzle manifold and nozzles were located entirely within the natural gas manifold and sprayed into the combustion chamber through the much larger slots in the natural gas nozzles. Refer to Figure B-3. This arrangement kept the fuel nozzles cool at all times due to a small flow of air ( . 4 pps) in the outer manifold. 00 E (B-l) �C3 ro B-2 FIGURE B-l �COOLING JACKET AND SUE BURNER INSERT tOUTER COOLING JACKET NtG 72-Z2O-9 SUE BURNER INSERT (COMBUSTION CHAMBER) �/-JOT OUTLET 3D TYP/CAL OI CROSS- S£C T/O/U �C E N T R A L P O P P E T T Y P E FUEL I N J E C T I O N ..i*;' '' tn' 11 BURNER FACE PLATE SPARK IGNITER •'.' ' LEAD^f C= NOZZLE �The combustion clmmbor and reaction tailpipe were fabricated from 310 stainless steel. The combustion chamber was actively cooled by passing the process air over the outside of the chamber prior to its entry into the combustion /one. Thus, the incoming air was preheated 400 to 800°F before entering the combustion /one. The 180-inch long reaction tailpipe was uncooled except by radiation to the surrounding environment. This arrangement simplified construction of the test unit and provided a hot wall for completion of the incineration process in the event combustion was not complete within the 48-inch long combustion chamber. The mating flanges of the reaction tailpipe incorporate internal water cooling which prevented warping and leakage. l-Mangc sealing was accomplished with high temperature asbestos fiber material. Ports were provided in the reaction tailpipe for combustion gas sampling probes and instrumentation. Vcnturi Scrubber Sj£s_tem A ventnri scrubber was located at the end of the reaction tailpipe, connecting the tailpipe to a scrubber tank. The scrubber tank was approximately eight feet in diameter, 15 feet high and was equipped with an internal water deluge system and a metex screen demistor. The spent scrubber water collected in the tank during a burn was transferred by a cyclic pumping system to holding tanks. The venturi scrubber shown in Figure B-5 was made according to conventional design from 1/8-inch thick 310 stainless steel. The inside diameter of the inlet and exit sections were 12 inches and the convergent and divergent angles were 40° and 20°, respectively. The throat was 4.4 inches in diameter and 5 inches long. Fresh caustic scrubbing solution mixed with tap water was introduced through a manifold located at the inlet section of the venturi. The mixture was injected through twenty-four 0.094-inch diameter jets directed toward the venturi throat. See Figure B-5. The pressure in the manifold was maintained at approximately 40 psig. The caustic scrubbing solution cooled and scrubbed the combustion gases as well as neutralized any HC1 and Cl2 that may have been present. Varying amounts of cooling tap water and caustic solution could be applied to the scrubber depending on the requirements for a given burn condition. Caustic Solution Supply System Caustic solution was supplied to the venturi scrubber from a 4500 gallon tank with a 2 HP pump. The flow was regulated by a remotely controlled valve and metered by a turbine flowmoter. Sodium hydroxide was loaded into the tank and diluted to a solution of desired strength. The tanks contents were mixed by shop air bubbling and the concentration of NaOH determined from the specific gravity of the mixed solution. E-(B-6) �VENTURI SCRUBBER \ INJECTION MANIFOLD r G1 NEC 72-Z2O-S ^VENTURI THROAT �Sciiibbor Water Col Lection Sy_s_tem The spent scrubber water collected in the bottom of the scrubber tank was transferred by a 2 IIP pump to one of throe holding tanks. The pu.np was actuated by a float switch in the scrubber tank when the Liquid Level had reached about eight inches. Lights in the control room indicated when the pump was on so that the pumping cycle could be monitored and scrubber water samples collected. All the scrubber solution from a burn was pumped into a holding tank and held until released by the Air Force, at which time it was drained to the main facility I.-I million gallon concrete waste water reservoir. Air Supply System For flexibility in varying arid measuring the air flow rate, the GOO psig facility air supply system was used. The incinerator could also be operated with a blower if required. As shown on the schematic in Figure R-l, the air mass flow was regulated remotely with a 3-inch Annin valve raid was motored by a 0.80-inch throat diameter sonic venturi. Air mass flow could thus bo calculated by knowing only air pressure and temperature upstream of the venturi. The air was introduced at the downstream end of the cooling jacket at four locations through 2-inch diameter hoses (see Figure 3). The air cooled the combustion chamber and was thus preheated to 400 - 8 ) ° before entering the combustion zone. (0F Herbicide Fuel Supply System "Orange" Herbicide or JP-4 was stored and supplied from a r>()() psig, 300 gallon fuel feed tank. The tank was pressurized with nitrogen at a pressure required to force the fuel through the supply system and fuel injection nozzles. Fuel was delivered through either of two parallel o-micron filters and controlled by a "a" Annin valve. Fuel mass flow was measured by a turbine flowmeter. A recirculating heater system was used to preheat the "Orange" Herbicide to 90° - 180°F prior to injection into the combustion chamber. A G.\2 purge system was incorporated to allow purging of the fuel supply line downstream of the controls during shutdowns. Natural Giis Supply System ."Natural gas was supplied from the 30 psig facility system as a pilot fuel to establish temperature equilibrium in the incinerator ( 0 ° ) prior to injection and ignition of the herbicide. Natural 80F gas flow was terminated after ignition of the herbicide and an air flow established through this system to cool the natural gas nozzles, Remotely controlled Grove regulators were used to control the natural gas or cooling air flows and metering was provided by the same 0.27-inch diameter sonic venturi. E-(B-8) �Iristrutncntfition and Controls All the parameters required for determining process mass flow rates, pressures, and temperatures were measured and recorded during each run. The parameters measured and the location of each is shown in Figure B--1 and listed in Table B-l. llcisc gauges were used to indicate total and static pressures. Barton gauges were used to measure pressure differentials. Model CF501R Anadcx counters were used to indicate herbicide fuel and scrubber waters mass flow rates in pounds per second. Fluid and gas temperatures were recorded on both an 8 point 0 to 600°F and a 16 point 0 to 2400°F Honeywell Drown recorder. Iron constantan thermocouples were used to measure process temperatures below 500°F arid chromcl-alumel thermocouples were used to measure temperatures between 500 and 2400°F. All gauges, counters and recorders were certified by the Marquardt Instrumentation Laboratory prior to use for this program. In measuring actual "Orange" Herbicide mass flow rates during a burn, estimated specific gravity and viscosity corrections were applied to the Anadex counters. After the burn, the herbicide mass flow rate was corrected to reflect actual herbicide specific gravity and viscosity as determined by measured herbicide temperature at the flowrncter. Figure B-6 presents "Orange" Herbicide specific gravity as a function of temperature as plotted from measurements taken during the program. Figure B-7 presents "Orange" Herbicide viscosity as a function of temperature.(4 ) E-(B-9) �TABLE B-l INSTRUMENTATION SYSTEM Air FOR "ORANGE" HERBICIDE TESTING SYMBOL FUNCTION d* Air Flow Venturi PTa NOTE SIZE OR RANGE 0.80" Upstream Total Pressure 2 0 - 200 psig TC-1 Inlet Total Temperature 1 0 - 10F 0° d* Gas Flow Venturi PT2 Upstream Total Pressure 2 0 - 5 0 psig P Throat Static Pressure 2 0 - 50 psig TC-2 Inlet Total Temperature 1 0 - 100°F PT5 Manifold Pressure 2 0 - 1 0 psig Turbine Flowmetor 2 .05 - .20 pps Inlet Fuel Temperature 1 0 - 20F 0° PT4 Manifold Pressure 2 0 - 500 psig Pi Supply Tank Pressuree 2 0 - 500 psig P2 Natural Gas or Nozzle N/A Supply Pressure D/S 2 0 - 500 psig S2 Wf Orange Herbicide or JP-4 TC-3 N/A 0.27" Filters LI SUE® Burner Fuel Tank Liquid Level 3 Sight Gauge PT Ap i Burner Inlet Pressure 2 0 - 1 0 psig Burner Pressure Drop 2 0 - 25" 1I20 TC-4 Burner Air Inlet Temperature 1 0 - 10° 00F TC-5,6,7 Exhaust Gas Temperature 1, 2 0 - 20° 40F TC-8,9 10,11 Exhaust Duct Skin Temperature 1, 2 0 - 20° 00F E-(B-IO) �TABLE B-l (Continued) INSTRUMENTATION FOR "ORANGE" HERBICIDE TESTING 1 SYMBOL SYSTEM Scrubber FUNCTION SIZE OR RANGE NOTE 0.5-2 pps Water Flowmeter 2 0.5-3 pps Scrubbed Effluent Gas Temperature 2 0 - 20F 0° TC-14 Scrubber Water Exit Temperature 1 0 - 20F 0° TC-15 Caustic Solution Inlet Temperature 1 0 - 10F 0° I*T6 Bcckman Probe Cooling Air 2 0 - 100 psig PT7 AF Prope Purge Air 2 0 - 100 psig TC-12 NOTES: 2 TC- 13 Sampling Systems Caustic Solution Ww Systems Wc Beckman Sample Gas Temperature 2 0 - 30F 0° 1. Continuously measured and recorded parameter. 2. Continuously measured but manually read/recorded every 30 minutes or whenever deemed necessary by operational changes.. 3. Manually measured/checked and recorded whenever deemed necessary. E-(B-H) �PREPARED BY_ CHECKED BV_ M DATE. 12-i4- 73 FIGURE B-6 �loj2 -r T-— 9-..1. 8_L ..._.I... . L_|__ hi- .. 7^.-'. •a si -r <**)&' -.L. 'ey^tt \ -_l \ \ \ \ \ I- X \ 3 f \ S L' 80 too /4o E( B-13) 180 FIGURE D-7 �(This page intentionally left blank) �USAF ENVIRONMENTAL HEALTH LABORATORY Kelly AFB, TX 78241 APPENDIX C (TO APPENDIX E) SAMPLE CODE DESIGNATIONS A set of sampling codes was developed arid is presented in Table C-l. Each sample collected by either EHL was assigned a code for laboratory control and reporting analytical results. Samples are referenced to these codes throughout this report. E( C-l �TABLE C-l: Type/Source of Sample Code Letters I Blended Herbicide Feed SAMPLING CODES FOR SAMPLES COLLECTED BY EHL'S - Interpretation Test Burn numbers, I through VIII (Roman numeral) -BH- Blended herbicide feed sample. -number/nunber/etc. EHL(K) red drum-head-number for drums placed into feed tank fur the test burn. (Date of Collection) Scrubber Water Fresh scrubber water feed sample. -FSW- FSW sample sent to UCTS for =A. to analyses. FSU sample for EHL(K) analyses. -5SW- Spent scrubber water Into holding tank(s). -A- 20-minute grabs for compositing (1500 ml). -B- 20-minute grabs for reserve samples (1500 ml). -C- Composite hourly sample (-4500 ml). -D- Hourly grabs for EHL(K) analyses (1500 ml). -TBC- Total bum period composite (4500 to 6000 ml for WCTS and EHL(K) analyses). -ARL. (Table C-l cont'd next 2 pages) Total burn period composite, -1200 ml, for ARL analyses. �TABLE C-l: (cont'd) Type/Source of Sample Scrubber water (cont'd) Code Letters -number. Interpretation Sequential number from 1 to 3 for each type of grab or hourly composite sample. SSW collected from holding tank. -HT-1. HT sample collected from port on side of HT after tank contents had settled for >24 hours. -2. HT sample of settled solids collected from bottom of HT after tank contents had settled for >24 hours. (Time and Date of Collection) Gases -CG- Combustion gases collected via sampling train at end of reaction tailpipe. -SG- Scrubbed effluent gases collected via grabs or sampling train in discharge stack. Impinger number (1 through 4) in sampling train from which sample was taken. -ACP. Sample rinsing of air cooled probe. -HCP. Sample rinsing of water cooled probe. -p- Particulate sample collected isokinetically from SS. -CT. Cold trap sample. -number (s). Impinger number (1, 2 and/or 3) in particulate sampling train from which impinger contents were mixed for sample. -ARL. Samples collected for ARL analyses. (Time Period and Date of Collection) �TABLE c-i; Type/Source of Sample Residue from within Incinerator Code Letters Interpretation -R- Chucks/particles of residue collected from within the Incinerator. -A- Residue sample sent to WCTS for analyses. -B- Residue samples kept by EHL(K) for any future analyses. -CC- Location of sample from within the incineratorconbustion chamber. -1. Orange flakes of residue. -2. Carbon/black flakes of residue. (Date of Collection) Holding Pond Holding Pond HP- -number. Sequential number from 1 to 4 for each composited sample collected from holding pond. (Time and Date of Collection) Drum Rinsing Samples Letter- Alphabetical letter (A.B.C or D) to indicate the set of drums receiving a particular rinse procedure. -number- (EHL(K)'s red number on head of drum. -number- Sequential number from 1 to 3 to indicate the rinse number for that drum. -number. Rinse volume in gallons. �USAF ENVIRONMENTAL HEALTH LABORATORY McClellan AFB, CA 956b2 APPENDIX D (TO APPENDIX E) COMBUSTION AFID SCRUBBED EFFLUENT GAS MONITORING �(This page intentionally left blank) �TABl-E OF CONTENTS Page 1. Introduction D- 1 2. Sampling Requirements D- 1 3. Sampling Technique D- 4 4. Validation of Sampling Technique D- 7 5. Sampling Procedures D-18 6. Partial Field Sampling Results and Discussion Hydrocarbon data and discussion is presented in Appendix I. D-20 7. Definitions and Formulas D-26 8. References D-27 FIGURES 'ae 'g D-l. Hypothetical Partial Degradation Products of 2,4,5-T and 2,4-D Butyl Ester D- 2 D-2. Schematic of Sampling Equipment for TCDD, Butyl Esters and Acids of 2,4-D and 2,4,5-T D- 5 D-3. Schematic of Sampling Equipment for Particulate Source Sampling D- 6 D-4 through D-9. Chromatographs D-12 T ABIES Page D-l. Description of Sampling Techniques Tested in the Laboratory D- 8 D-2. Laboratory Testing Results D-15 E-(D-i) �TABLES (Continued) Page D-3. Scrubbed Effluent Gas Particulate Sampling Data D-21 D-4. TCDD, Butyl Ester and Acid (of 2,4-D and 2,4,5-T) Sampling Results D-23 D-5. CO, C02, 02, H20, and NOX Sampling Results D-24 D-6. Carbon Mass Balance on Scrubbed Effluent Gas D-25 E-(D-ii) �' APPENDIX D COMBUSTION AND SCRUBBED EFFLUENT GAS MONITORING 1. Introduction Monitoring the combustion find scrubbed effluent gases from the incineration of "Ortinge" Herbicide presented several unusual sampling situations. The combined sampling and analytical techniques had to be sensitive at the parts per billion level for several compounds. The sampling environment was hostile regarding temperature, moisture and potential interfering compounds. Finally the contaminants to be monitored in the scrubbed effluent gas could exist as a vapor, an aerosol or both. A literature review did not reveal a proven source sampling technique for this work. Consequently, it was necessary to develop one. A technique used in "Orange" Herbicide pyrolysis studies at the Environmental Health Laboratory, Kelly AFB, provided a basis for this development. (D-O Several sampling techniques were tested. The one finally chosen was absorption in benzene using a modified EPA source sampling train. The following sections describe the sampling requirements, the sampling technique and methodology, the laboratory validation of the sampling technique, and the results of field sampling and inorganic analysis of gases. (Sec Appendix I for hydrocarbon results.) 2. Sampling Requirements a. Potential Contaminants. TCDD was considered the potential contaminant of primary importance. It is a trace contaminant in many lots of "Orange" Herbicide, requires greater heat energy for pyrolysis than the basic compounds of "Orange" Herbicide, and is a hypothetical partial degradation product from the incomplete pyrolysis of nb 2,4,5-T and 2,4-D ester. (See Figure D-l.) The nb esters of 2,4-D and 2,4,5-T, the principal compounds in "Orange" Herbicide, were potential contaminants and had to be monitored. The acids of 2,4-D and 2,4,5-T could be formed from the butyl esters through two mechanisms: cleavage of the ester to the acid and butanol in the presence of heat and moisture; and hydrolysis of the ester in the caustic scrubber. Due to the possible formation of these acids they had to be monitored. E-(D-l) �2 , 4 . 5-T Oxygen Sufficient Oxygen Deficient CHgCOOH Cl CL2 CH2COOH Cl Cl CH S =CH-R ,OCH3COj C13 Cla OH 0 / COOH ci3_L \COOH HOCH2COOH HOOCCOOH HC1 C02 HaO C12 FIGURE D-l: HYPOTHETICAL PARTIAL D OF 2, 4, 5-T N-BUTYL E(D-2) TION PRODUCTS 2 ') �Consideration was given to hypothetical partial pyrolysis products. Figure D-l is a list of hypothetical products from the incomplete pyrolysis of 2,4,5-T ester.(D-2) jt would be impossible to design a practical system for each specific hypothetical pyrolysis product. As the final sampling system was developed, it was found that a majority of the hypothetical products would be trapped in the system by condensation or by absorption in the solvent. While the products might not be collected at a 100% efficiency level, they would be detected. If the products were considered significant, later laboratory studies could simulate the field conditions that existed during sampling and the efficiency of collection could be estimated. Total particulatc loading was considered important for two reasons. An environmental statement would require this information and the particulatc matter could be qualitatively and quantitivcly analy/ed for additional information. Finally, to evaluate the overall performance of the incinerator, it was necessary to measure the emissions of the common combustion products, CO, C02, NOX, 02, H20 and total hydrocarbons. b. Sampling Locations. To evaluate the capability of the incinerator to incinerate "Orange" Herbicide, it was necessary to sample at two locations: in the reaction tailpipe just prior to the caustic scrubber and in the scrubbed effluent gas stack. These locations presented different sampling conditions and necessitated the use of slightly different sampling techniques. (1) Reaction Tailpipe; In the reaction tailpipe, combustion gas temperatures averaged 1 ( 0 F TCDD and the butyl esters 9)°. and acids of 2,4-D and 2,4,5-T existed only in the vapor phase. Isokinctic sampling was not necessary to obtain a representative sample. Samples of combustion gases had to be cooled quickly to depress chemical reactions as the gas traversed the sampling probe to the absorbent. However, the gas sample temperature had to be maintained slightly above the boiling point of TCDD and the butyl esters and acids (>3f>0°F) to prevent condensation of these compounds in the sampling train upstream of the impingcrs. Finally, measurements of combustion gas velocity were not attempted in this area because of the high temperature and unavailability of specialized equipment. The gas velocity was obtained from Marquardt theoretical data and the temperature was measured by n thermocouple installed by Marquardt. The sampling train did not need a temperature sensor or a pitot tube. E-(D-3) �(2) Scrubbed Effluent Gas; The scrubbed effluent gas temperatures were expected to average 170°F. Any TCDD or butyl esters and acids would therefore have existed in the vapor and aerosol phases simultaneously. Isokinetic sampling was required to obtain a representative sample. The scrubbed effluent gas, after passing the caustic scrubber, would be saturated with water vapor and contain water droplets. To prevent moisture saturation of the particulate filter it was necessary to heat the sample gas above 212°F in the probe to vaporize the water droplets. 3" Sampling Techniques. To accomplish the sampling requirements of Section 2, it was necessary to operate three sampling systems simultaneously. One system was used at the reaction tailpipe section to monitor the potential vapors of TCDD and butyl esters and acids of 2,4-D and 2,4,5-T. The other two systems were used on the scrubbed effluent gas stack, one to monitor the potential vapors and aerosols of TCDD and the butyl esters and acids and the other to monitor particulate matter, Hydrochloric acid, free chlorine, and total moisture in the stack. a. TCDD, Ester and Acid Sampling Trains. The trains used to sample for TCDD .and the butyl esters and acids are shown in Figure D-2. The first four GreenburgSmith impingers were modified with coarse frits and each contained 250ml pesticide quality benzene. Two modified Greenburg-Smith impingers, one containing silica gel and one containing activated carbon, were placed downstream of the four benzene impingers. The main difference between the two sampling trains was the type of probe used. At the reaction tailpipe section, the train box was connected to a stainless steel sampling probe (air cooled in burns I-V and water cooled in burns VI-VIII) via a ground glass joint. The sampling probe was cooled to prevent damage to it in the high temperature of the reaction tailpipe ( 9 0 F . This 10°) cooling of the probe also provided the required cooling of the combustion gases (to 300-400°F) in order to suppress any continued combustion reaction within the sampling probe. The sampling train on the scrubbed effluent gas stack was attached to a heated 3-foot glass probe wrapped in asbestos and foil. Since it was necessary to sample isokinetically in the event of aerosol formation, the glass probe had a glass sampling tip of 0.25 inch inside diameter. b. Particulate Sampling. The train used for particulate matter, hydrochloric acid, free chlorine, and moisture is shown in Figure D-3. The water E-(D-4) �r^ ~x \J Filter-Cyclone ^Thermocouple * -P. rProbe Tip * rcProbe r^8* I 250 ml Benzene Silica Gel — 4pPitot Tube * ~ 350°F S = .Activated ^Carbon ' 1 \ 1 J~350°F \ r I Vacuum Gauge? Joggle Valve Throttle Dry Gas Meter Thermometers * O Ol Greenburg-Smith Impingers With Coarse Frits Magnahelic Gauge Dual Manometer Not Used For Combustion Gases in Reaction Tailpipe FIGURE D-2: SCHEMATIC OF SAMPLING E3QUIPME2«T FOR TCDD, BUTYL ESTERS AND ACIDS OF 2,4-D AND 2,4,5-T "ORANGE" HERBICIDE PROGRAM NOV 73 Drawn By: Sgt. Frank Lessirig USAF EHL(M) �Temperature Indicator Filter Holder Dry Gas Meter Thermometer s 125 ml water Toggle Valve Dry f Silica Gel Vacuum J? Throttle Valve - m, yj ' Ice BathtX" Magnahelic Guage Dual Manometer—Z-» *— FIGURE D-3: SCHH4ATIC OF EQUIPMENT FOR PARTICULATE SOURCE SAMPLING "ORANGE" HERBICIDE PROGRAM NOV 73 „ Dra\vn By: Sgt. Frank Leasing USAF EHL(M) �collected in the first two impingers was used to determine hydrochloric acid and free chlorine concentrations in the stack gas. c. Other Contaminants. El'A procedures given in 40 CFK GO were used to sample and finalyze the stack gas for CO, COo, 03, and NOX. Hydrocarbons were continuously monitored by The Marquardt Company using a Beckman 109 Hydrocarbon Analyzer. (Sec paragraph 4.1.) 4. Validation of Sampling Tjpc_hn_ic[uc_. Prior to use in the field, the technique of absorption of the butyl esters nnd acids (of 2,4-E> and 2,4,5-T) in benzene was tested in the laboratory. Other sorbents were also evaluated in an effort to avoid using the very toxic and flammable benzene. Sec Table D-l. These included adsorption on Chromosorb 102, absorption in acetone, arid collection in a cold trap. A brief explfmation of events is given below to explain the order of testing and validating the candidate sampling techniques. The original scope of the combustion gas monitoring project was the detection and quantitization of TCDD and the butyl esters (2,4-D and 2,4,5-T) that might escape pyrolysis in the incineration process. The first nine experiments concentrated on the butyl esters and three candidate techniques were evaluated for collecting these esters. Then, it was speculated that acids might be formed by either hydrolysis of the butyl esters in the caustic scrubber or by cleavage of the butyl esters in the presence of heat and moisture in the combustion chamber and reaction tailpipe. The scope was expanded to include the detection and quantitization of the acids (2.,4-1) and 2,4,5-T). Since absorption in benzene and adsorption on Chromosorb appeared equally effective for the butyl esters, both sorbents were tested for collection of the acids. a. Testing Procedure. The validc-vtion procedure was based upon mass balance. A known mass of the butyl esters and/or acids was vaporized and drawn through the sampling system. The collection efficiency was determined by comparing the total mass collected in the collection media with the mass vaporized. The sampling train was operated in the laboratory exactly as it was planned to be used in the field. This procedure insured that the collection efficiency in the field would not be changed clue to different operating conditions., b. Sample Gas Generation. Two small glass containers were used to hold incividual samples of the butyl esters and acids. The containers were E-(D-7) �TABI£ D-l DESCRIPTION OF SAMPLING TECHNIQUES TESTED IN THE LABORATORY Experiment # 1. Series of 4 fritted Grecnburg-Smith impingcrs, each charged with 250ml pesticide quality benzene. Butyl esters collected. 2. Repeat of Experiment 1. 3. Series of 4 Greenburg- Smith impingers, 1 and 2 were standard, 3 and 4 were modified,* each charged with 250ml ben/cne. Butyl esters collected. 4. Series of 4 Greenburg- Smith impingers, 1 was standard,** 2, 3 and 4 were fritted. 1 was charged with 250ml of 10% NaOH solution, 2, 3 and 4 with 250ml benzene. Butyl esters collected.. 5. Same as 4 except all irapingers were fritted and 1 was charged with 250ml of a 2.5% CaOII solution. Butyl esters collected. 6. Repeat of Experiment 1. 7. A fiberglass filter, 6" in diameter, followed by the scries of impingers described in 1. The filter had 31 gms of 40/80 mesh activated carbon spread evenly on it. Butyl esters collected. 8. Repeat of Experiment 1. 9. Chromosorb 102, 12 gms packed in the filter section glassware, followed by the impingcr series described in 1. Butyl esters collected. 10. Same as 1. Acids of 2,4-D and 2,4,5-T collected. 11. Same as 1. Butyl esters and acids collected. 12-16. Same as 9 except butyl esters and acids collected, 17. Cold trap, acetone in an alcohol-dry ice bath followed by the series of impingcrs described in 1. 18. Same as 9 except only 2,4-D acid collected. E-(D-8) �TAB1E D-l (Continued) Experiment jj Description 19. Scries of 4 impingers, 1 was standard charged with 250ml acetone, 2, 3 and 4 were fritted and charged with 250ml benzene. Acids and esters collected. 20. Same as 19 except impinger 1 was charged with benzene. 21. Repeat of Experiment 18. 22. Same as 1 except frits on the impingers were changed from fine to coarse frits. Butyl esters and acids collected. 23. Repeat of Experiment 22. "The modified impingers had a glass insert that was not tapered at the end. **The standard impinger had a glass insert that was tapered at the end and had an impaction plate attached. E-(D-9) �attached to the end of the sampling probe by means of a glass tee and ground glass joints. The containers were designed to have identical flow resistance and to require a small vacuum to obtain a flow rate of 1 liter per minute through each. The vacuum prevented the loss of sample vapor through the container air inlet. The rate of sample vaporization was controlled by placing the containers in a portable gas chromatograph oven. The probe from the sampling train was inserted through an asbestos grommet into the oven and the sample containers were connected to it. The butyl esters were vaporized between 80 and 100°C and the acids at 160 to 180°C. In initial experiments, excess ester was placed in the glass container. The time required to vaporize a given mass was determined and a contaminant concentration calculated from the mass and air flow rates. The results indicated that collection efficiency was independent of contaminant concentration. c. Sampling System Operation. Prior to each test, the sample was placed in the glass container and the entire unit was dessicated for two hours. The entire unit was then weighed to the nearest tenth of a milligram. The probe on the sampling train was maintained at approximately 180 to 190°C. This temperature prevented condensation of the butyl esters or acids on the glassware. When the oven and sampling train components were at the correct temperature, the sampling train was turned on. The sample flow rate was maintained at 2 to 6 liters/minute (STP), and the samples were vaporized to provide contaminant concentrations of 0.1 to 50 ppm in the air being drawn into the sampling probe. At the end of the sampling period, the remaining fraction of the sample was weighed to the nearest tenth of a milligram after dessication for two hours. The net difference in sample weight was used to determine the mass of sample vaporized. d. Analytical Proccdurcs. Electron capture gas chromatography was used for quantitative analysis. Two different units were used at different times. One was equipped with a Mi""-* detector and an 8-foot column packed with 3% OV17. The other unit was equipped with a T3 detector and a 6-foot column packed with 3% SE 30. Both columns were 1/4 inch outside diameter. The column and detector temperatures of the units were maintained isothermally at about 1650 and 195°C, respectively. Peak height comparison was used for quantitative analysis. Area measurement is usually preferred; however, peak height E-(D-IO) �comparison can be more accurate when the peaks arc sharp and narrow. UJ-3) The samples in this work were essentially as pure as standards and the resulting peaks were sharp and mirrow and riot degraded by interfering peaks (sec F'igure D-5). To obtain maximum accuracy each sample peak height was compared with a standard peak that was within 90 to 110% of the sample peak height. Each sample and standard was injected twice and if the injections differed by greater than 5% of their average, new injections were made until each peak height in a series of three was within 5% of the average. Linearity in the working range was verified before and after each series of samples was analyzed. c. Analytical Accuracy. Weighing of samples before and after vaporization, weighing and dilution of standards, dilution of samples for analysis, and peak height variation were all sources of analytical error. However, peak height variation was considered the major source of error. Figures D-4 through D-6 were used to illustrate this potential error. These figures depict'the chromatographs of impingers 1, 2 and 3 from experiment 2. Assume the standard 2,4-D N-butyl ester peak height of 18 divisions in Figure D-4 represented 96 picograms/2 nl, i.e., the true value. The impingcr 2-1-2 sample peak height of 19 divisions in Figure D-5 represented (19/18) times 96/2 or 51 picogramsAil. Let the standard peak height be 5% greater than true and the sample peak height be 5% less than before. Then the impinger 2-1-2 sample peak height of 18 divisions represented (18/19) times 96/2 or 45 picograms/|Jl. The 45 picograms was 11% less than the true value. This potential error applied to the total mass in the sample. The total mass in impingcr 2-1-2 was in the milligram range while the mass in impinger 2-2 was in the microgram range. Since the overall efficiency wfis calculated from milligrams to the nearest tenth, the error in impinger 2-1-2 was significant while the error in impinger 2-2 did not affect the calculation of overall efficiency. The total mass vaporized during a given test was measured to the nearest tenth of a milligram. This mass always exceeded 4 milligrams; therefore, the maximum error in determining the total mass evaporated was 2.5%. The mass used in standards was weighed to the nearest microgram on a Cahn balance. Class A volumetrics were used for dilution and dilutions were conducted with hcxanc and volumetrics at 20° •+ 1. The error in this procedure was considered less than 1%. Samples were diluted in Class A volumetrics at 21°C +_ 1. After dilution the samples were placed next to the standards and given time to equalize in temperature with the standards. �CHROMATOGRAPHS a I-* to 2 /il #2 Standard, 48 pg//ll 24-6-73 3% OV 17 32x175 & 195°C 2 /il Imp 2-1- 2 Imp 2-1 = 200 ml Imp 2-1- 2 = 1 to 100 2 til Imp 2- 2 (243 ml) Figure D-9 2 Ul Imp 2-3 (243 ml) 2 pi Bypass Glass Rinse (102 ml) Run 2 2 Jil Probe Rinse (120 ml) Run 2 USAF EHL(M) �In view oJ' this brief error analysis, the mass determinations were not considered more accurate than _+ 15%. Mass recovery was considered complete if it fell between 85 and 115% of the mass vaporized, and the unconccntrated absorbent volume in the last impinger in the scries showed no more than a trace amount of contaminant. f. Sample Analysis. A series of four impingcrs charged with benzene was used in all experiments cither as the primary absorption system or as a backup system when Chromosorb 102 or activated carbon was used as the primary collection medium, To determine the quantity of esters collected in each individual impinger, the benzene volume was carefully measured and each impinger rinsed a minimum of 5 times with pesticide grade acetone. For' most experiments the rinsings were added to the benzene remaining in the impinger. This sample was diluted, if necessary, and a two microliter portion injected into the chromatograph and analyzed. For several runs, the acetone rinse was analyzed separately from the benzene in the impinger. This was done to obtain some insight into the collection mechanism. It was believed that the compounds principally absorbed in the benzene, but condensation on the frit was also an important mechanism. The benzene find acetone rinse from the third and fourth impingcrs often contained masses of each ester below the detection limit of the chromatograph. These solutions were never concentrated. The volume of benzene and acetone rinse from these impingcrs averaged 300 milliliters. Based on the detection limit of the gas chromatograph ( 5 picograms/ul), the mass con~ tained in these impingers could not have exceeded microgram quantity unless dilution was required. Since dilution was never required, the mass contained in these impingcrs never exceeded 0.1% of the total vaporized. The standard HFg methylation procedure was used to determine concentrations of the acids in the benzene. The benzene and acetone rinses from each impinger were concentrated by rotary vaporization and transferred to a 15 millilitcr conical centrifuge tube. The evaporation flask was rinsed with acetone and the rinse added to the tube. The tube content was dried with anhydrous Na2S04, and then concentrated to 0.5 milliliters in a hot water bath. After the concentrate cooled, 0.5 milliliters of 14% RI-'s in mcthanol was added and the mixture heated at 50°C for 30 minutes in a water or sand bath. After the mixture cooled, 0.5 millilitcr benzene and 4.5 millilitcr of 5% aqueous Na2S04 solution was added. After phase separation, the organic layer E-(D-13) �was removed and the surface washed with 1 milliliter bcn/.cne. The organic layers were passed through a micro cleanup column of florisil. Benzene was added to the column effluent to bring the processed sample volume to 5 millilitcrs. This prepared sample volume was then analyzed with an electron capture gas chromatograph. When Chromosorb 102 or activated carbon was used as the primary collection medium, the contaminants were extracted from the medium with acetone in a Soxhlet extractor at 30 cycles per hour. Again, samples were taken directly from the volume of acetone in the extractor, usually'200 millilitcrs, find analyzed for butyl esters. The solution was then concentrated, and, if acids had been collected, put through the mcthylation procedure. In two experiments where esters and acids were collected simultaneously, the samples were evaluated for butyl esters before and after the methylation procedure. This was done to determine the possibility of transesterification of the butyl esters to methyl esters in the methylation procedure. Significant (<3%) transesterification was not detected in this work or in similar studies at the Air Force Academy.(D~4) g. Findings and Discussion. Absorption of the butyl esters (2,4-D and 2,4,5-T) in benzene was evaluated in experiments 1, 2, 6, 8, 20, 22 and 23 (see Table D-2). The collection of the esters was complete in all experiments except 20 where the first impinger in the fritted series had been replaced with a standard impinger. The collection efficiency in this first impinger dropped from an average 93% with the fritted inpinger to 14% with the standard impinger. Also, the last impinger in experiment 20 had a 10% recovery while the last impinger in the other experiments never had more than a trace. Coarse frits were used in experiments 22 and 23 while fine frits were used in experiments 1, 2, 6 and 8. No trace of esters was found in the last impinger of experiments 1, 2, 6 and 8 while a trace was found in the last impinger of experiments 22 and 23. These results indicated a slight but insignificant loss of recovery efficiency with the coarse frits. Consequently, the field sampling unit was designed to use coarse frits because they operated under much less vacuum requirements than the fine frits (3"IIg vs 9"IIg) and significantly decreased the possibility of leaks in the system. Absorption of the acids in benzene was evaluated in experiments 10, 11, 20, 22 and 23. Results of 10 and 11 were discarded due to errors in analytical procedures, the less than complete recovery in 20 was due to the replacement of the $1 fritted impinger with a standard impinger. In 22 and 23 all impingers were fritted and recovery was complete. E-(D-H) �TABLE D-2 LABORATORY TESTING RESULTS 11 ORANGE" HERBICIDE PROGRAM NOV 1973 c Exp $ Overall Efficiency, Specific Components, % Efficiency Impinge r # -Other * 1 2 4 3 % Esters Acids Esters Acids Ssters Acids Esters Acids Esters Acids Esters Acids I 96 76 T ND ND 1 <1 105 104 ND ND 2 36 5 T 48 3 89 ND 4 46 ND T ND ND <1 • 52 99 <1 97 T ND ND 5 ND 98 <1 ND 6 106 3 90 1 T ND 7 1 103 99 T ND 115 113 2 8 x-n NE NE 98 ND 9 98 1 >1 ND 5 4 ND^ 10+ ND ND ND ND 11 + ND ND NE ~1 ND ND ~1 ND 12 *** 1 ND ND NE ND ND ND ND ND 13 ~1 ND NE 14 ~1 ND ND -1 ND ND AT ION 15 ;AMPL E LOST DUE Tj O COlv TAMUS 87 ND ND 87 ND ND 16 6 4 NE NE NE 17 NE 12 12 NE NE NE ND NE ND NE NE ND 22 NE 22 NE ND 18 15 97 37 13 13 8 19 62 13 39 21 32 15 89 14 32 38 18 10 10 20 80 35 ND 21 35 ND <1 86 7 <1 T T 90 83 4 ?.Z 90 <1 87 ^75 3 T T 23 13 89 ' 91 2 Mass T - Trace, None Quantitable ND - None Detected NE - Not Evaluated E f f i c i e n c y = Mass Recovered Mass Vaporized Glassware Washings Probe Bypas. s Esters Acids Ssters Acids i ND 20 T T T ND <2 12 <1 . <1 ND <2 ND ND ND ND ND ND ND ND ND ND ND ND <1 ND ND ND ND ND ND ND ND ND ND ND <1 ND Mass Measured to 0. 1 Milligram * Other Collection Medium X 100 4 Experiment results were discarded due to errors in analytical procedures. USAF EHL(M) �In experiment 19, the first impingor was a modified one charged with acetone. Recovery of acids was 95% while ester recovery was only 62%. Experiment 20 was a duplicate of 19 except the first impinger was charged with benzene. Recovery of esters improved while recovery of acids appeared to decline with the change to benzene. In both experiments, less than 85% of the esters and acids was recovered in the last impinger and recovery was therefore not considered complete. Adsorption of the butyl esters on 40/60 mesh activated carbon was evaluated in experiment 7. Carbon was spread evenly on a fiberglass filter and the assembly was maintained at 350°F in the filter section. The carbon effectively adsorbed the esters with less than 3% of the esters breaking through to the benzene impingers. The esters were not easily extracted from the carbon and twenty-four hours of Soxhlet extraction was necessary to achieve total ester recovery. This medium was not further evaluated for acid adsorption because of the later experience with adsorption on Chromosorb. A cold trap of acetone in an alcohol-dry ice bath was evaluated in experiment 17. The acetone was contained in a modified impinger. The impinger insert was a % inch inside diameter glass tube that extended to within % inch of the impinger bottom. After a sample volume of only 85 liters had been collected, the impinger insert became totally blocked with ice. Also, the collection efficiency in the trap was only 12%. This sampling technique was discarded due to the icing problem which would be severe in scrubbed effluent gas sampling and the low collection efficiency in the trap. Adsorption of butyl esters on Chromosorb 102 was evaluated in experiment 9 and for the esters, and/or acids in experiments 12, 13, 14, 15, 16, 18, and 21. The Chromosorb was packed in the bypass glassware in the filter section and maintained at 370°F during sampling. Even at this elevated temperature, the Chromosorb effectively adsorbed the butyl esters in experiments 9 and 16. Due to the negative recovery of the acids in experiments 12, 13 and 14, recovery of the butyl esters was not evaluated. In experiments 9 and 16, problematic extraction of the esters from the Chromosorb required sixteen hours of Soxhlet extraction at 30 cycles per hour to effect >85% recovery. Experiments 18 and 21 were conducted in an attempt to determine the reason for negative acid recovery in experiments 12, 13 and 14. Apparently chemical alteration of the acids was occurring on the Chromosorb due to the significantly elevated adsorption temperature. As a simple test, the Chromosorb was carefully weighed before and after adsorption of the acids. The weight gain indicated E-(D-16) �complete mass recovery and no acids were detected in the backup benzene train; however, the Chromosorb was discolored at the upstream interface and only 22 and 35% of the acids were recovered in experiments 18 and 21, respectively. The temperature in experiment 21 was 320°F compared to 370°F in experiment 18. A relationship between temperature and recovery of the acids was indicated during these Chromosorb experiments. In experiments 2, 6, 7 and 8 the acetone impinger rinse was evaluated separately from the benzene in the //I impinger. The percent of esters collected in the acetone rinse relative to the total collected in the impinger benzene was 12, 6, 30 and 44% respectively. In experiments 2 and 6 the impinger insert remained in the benzene for several minutes before the benzene was removed. This allowed the esters condensed on the frit to become dissolved in the benzene. In experiments 7 arid 8 the benzene was removed immediately after sampling ceased. These data indicated that condensation on the frit was an important collection mechanism. This procedure was not used in the acid experiments; however, condensation on the frit was indicated. The resistance in the sampling system increased or the sample flow rate decreased as sampling progressed. Also, the first acetone rinse percolated through the frit slowly. By the fifth rinse, the acetone passed through the frit freely. The only obvious cause of these anomalies was condensation of the acids on the frit. Since the acids had a much higher boiling temperature than the butyl esters, the condensation mechanism was important in acid collection and accounted for the excellent collection efficiency of acids in benzene even though the solubility of the acids was less than 1% in benzene. A caustic scrubber was simulated in experiments 4 and 5 by replacing the benzene in the first impinger with caustic solution. A standard impinger and a 10% NaOH solution was used in experiment 4 and a fritted impinger and a 2.5% Ca(OII)2 solution was used in experiment 5. The purpose of these two experiments was to evaluate the possible hydrolysis of the butyl esters in a caustic scrubber. In both experiments the hydrolysis, if it occurred, was less than 1%. The methyl esters that were detected could have been formed from transcsterification of the butyl esters remaining in the solution after extraction. No conclusions could be drawn from these experiments. Experiments 8 and 22 evaluated the presence of water vapor on sampling efficiency. Fifty milliliters of water were placed in the first impinger. The oven air used to generate samples was also saturated with water vapor by allowing a beaker of water to boil in the oven throughout the sampling period. The sampling efficiency was not degraded by this water. E-(D-17) �In the pyrolysis of the butyl esters large amounts of I1C1 would be produced. To test the effect that HC1 might have on the collection efficiency of the butyl esters, five milliliters of concentrated HC1 were poured through the first impinger frit just before sampling in experiment 6. As the data indicated, no effect was noticed. There was no reason to suspect that IIC1 would have any effect upon absorption of the 2,4-D and 2,4,5-T acids., h. Conclusions. Complete absorption (>85%) of the butyl esters and acids of 2,4-D and 2,4,5-T in benzene, using a series of four fritted Greenburg-Smith impingers, was documented. Test data were conclusive for contaminant concentrations between 0.1 and 50 ppm (by volume) and flow rates between 2 and 6 liters per minute (STP). Collection efficiency was not a functim of contaminate concentration or flow rate. Substitution of a standard impinger for the first fritted impinger in the impinger series decreased absorption efficiency to <85%. Test data were not sufficient to document the precise decrease in efficiency. TCDD, in view of its chemical similarities to the butyl esters, should be as effectively absorbed in the benzene-fritted impinger system as were the esters. Due to its extreme toxicity, impinger collection of TCDD was not tested in the laboratory. Water in the impingers and/or the sample gas did not degrade sampling efficiency. Test data verified this at benzene to water ratios of greater than 5 by volume. The presence of HC1 in the benzene did not affect the absorption of butyl esters and there was no reason to suspect that IIC1 would affect the absorption of the acids. In a very strong acid solution the esters could be hydrolyzed to their respective acids. If only the acids of 2,4-D and 2,4,5-T are detected in the field sampling impingers where IIC1 will be high, the sampling condition will be duplicated and further evaluated in the laboratory. 5. Sampling Procedure. Sampling was designed to monitor TCDD and the butyl esters and acids of 2,4,-D and 2,4,5-T simultaneously in the reaction tailpipe section upstream of the scrubber and in the scrubbed effluent gas stack downstream of the scrubber. This sampling scheme in combination with simultaneous scrubber water sampling provided data required" to perform certain material balances of the incineration process. E-(D-18) �a. Prior to Run; Minimi/ing potential contaminants that would interfere with gas chromatographic analyses was essential. All glasswfirc in the TCDD systems was soaked in hot, soapy water, rinsed 5 times with distilled water, and rinsed 5 times with pesticide quality acetone. The first four impingcrs were charged with 250ml pesticide quality benzene. The last two impingers were charged respectively with silica gel find activated charcoal and weighed. The entire train was then sealed with aluminum foil until sampling commenced. The particulate sampling train was prepared in accordance with procedures established in 40 CFK 60. Prior to sampling, all three sampling trains were leak tested in accordance with procedures recommended in 40 CFR 60. To verify that no leak occurred in the TCDD sampling train on the stack, the water collected during sampling was compared with the quantity of water collected in the particulate train during the same burn. The water collected in the reaction tailpipe TCDD sampling train was compared to the theoretical amount predicted by the contractor's calculations. b. During Run: Sampling was begun after herbicide combustion parameters in the incinerator had stabilized find remained so for a period of time, usually 45 to 60 minutes into the burn. All three sampling systems were activated as near the same time as possible. The two TCDD sampling systems were always activated within five minutes of each other to provide simultaneous samples pro- and post scrubber, The sampling system used at the reaction tailpipe section was operated at a sampling rate of 8 to 20 liters per minute and was constant for each burn. Loss of benzene due to evaporation necessitated the low sampling rate and also controlled the duration of sampling. The total sample volume for each burn usually exceeded 500 liters at conditions in the reaction tailpipe section. The particulate arid TCDD sampling systems used on the scrubbed effluent gas stack were operated isokinctically. The system used to sample for TCDD and the butyl esters and acids (of 2,4-D and 2,4,5-T) was not traversed across the stack. Movement of this system would have broken the unprotected glass probe, so it was necessary to conduct single point sampling. This was acceptable because temperature and velocity traverses across the stack showed uniform velocity and temperature profiles. The glass probe tip was sized to keep the sample flow rate between 4 and 6 liters per minute to prevent benzene loss. Sample volume for each burn was between 200 arid 400 liters at stack conditions. E-(D-19) �The particulatc sampling train was traversed across one diameter of the stack. Eight points, were sampled with a sampling time of 10 minutes at each point. Because of the presence of the other sampling train in the stack, it was impossible to sample along the other diameter. The average sample volume was 500 liters at standard temperature and pressure, and dry. This train was operated in accordance with procedures recommended in 40 CFR 60 for isokinetic stack sampling. c. After Run; Upon completion of the sampling run, the trains used to sample for TCDD and the butyl esters and acids (of 2,4-D and 2,4,5-T) were cleaned according to the following procedures. The final volume of benzene and water in each impingcr was measured. Each impinger was then rinsed five times with pesticide quality acetone followed by a deionized water rinse. The volume of this rinse was recorded and added to the benzene and water for that particular impingcr. All glassware from the probe tip to the first impinger was rinsed with about 200ml of acetone and the rinsings added to the liquid from the first impinger. This volume was also recorded. All glass connectors between impingers were rinsed into the preceding impingcr. Both impingers containing silica gel and activated carbon were weighed. This weight was used to determine the amount of benzene vapors that were adsorbed on the silica gel and carbon. If more benzene was lost from the impingers than was recovered, a sample volume adjustment was necessary. However, the data indicated that all benzene vapors were recovered in the adsorption media. The particulate train samples were handled in accordance with recommended EPA procedures. Additionally, a small sample of water from the first two impingers in this train was analyzed for hydrochloric acid and free chlorine by the Environmental Health Laboratory, Kelly AFB, Texas. After the particulate sample filter was dessicated and weighed the particulate matter was qualitatively and quantitatively analyzed by WCTS. 6. Field Sampling Results and Discussion a. Results. (1) Particulates. These data are presented in Table D-3, The Federal particulate emission standard for incinerators used in Federal government activities is 0.2 grains per standard cubic foot of dry flue gas corrected to 12% carbon dioxide (40 CFR 76). The particulate emissions in the incinerator's scrubbed effluent gases during these tests averaged 0 0 6 gr/scf (standard deviation = .7 0.035), and were thus well below the Federal standard. Also, these particulates, by visual observation, appeared to be mostly sodium salts that had been entrained in the scrubbed effluent gas during the scrubbing process in the caustic scrubber (see second paragraph, page G-7, Appendix G). E-( D-20) �TABLE D-3 SCRUBBED EFFLUENT GAS PARTICULATE SAMPLING DATA "ORANGE" HERBICIDE INCINERATION TESTS 12 - 30 NOV 73 STA CK Burn# Temp Dry Gas Fraction °F PARTICULATES Pressure Inches Hq Flow Dry @ Stp ft a /min Sample Voluime Dry @ Stp Ft3 Ibs/hr Gr/SCF @12%CO2 %Isokinetic* I 0.66 30.07 1551. 2/1211.8 22. 58 0. 72 0. 054 + 72 .7/ 93.1 II m i 161 166 0.62 30. 04 1465. 0/1256.2 13.66 0.64 0.051 + 93 .1/109.0 III 163 0.65 30. 09 1415. 4/1290.1 24.49 0. 39 0.032 + 86 .4/ 95.0 IV 163 0.65 29.96 1515. 9/1417.9 26.05 0.71 0. 055 0.055 85 .8/ 91.7 V 156 0.71 30.28 1719. 1/1269.1 27. 26 1.39 0. 095 0. 095 79 .2/107.0 VI 175 0.53 30. 20 1222. 5/1306.9 15.69 0.91 0.087 0. 087 85 .!/ 79.6 VII 170 0.59 30.12 1447. 0/1252.5 20.85 1.05 0.085 0. 082 71 .9/ 83.1 VIII 151 0.74 30.09 1589. 9/ 896.5 20. 28 1.98 0.145 + 63 .7/116.5 o 1 to Stack.Area: 1 0 . Square Inches. 038 Velocity is at stack conditions. *lst number is based on actual velocity pressure measurements/2nd number is based on velocities calculated from theoretical data (see Appendix I for discussion). +Not calculated due to erroneous C02 measurements during Burns I, II, III, and VIII. USAF EHL(M) �(2) Butyl Esters and Acids ( f 2,4-D and 2.4,5-T) and o. TCDD. Sample volume data are presented'in Table D-4. Neither TCDD, the butyl esters nor the acids (of 2,4-D and 2,4,5-T) were detected in any of the combustion or scrubbed effluent gas samples. Detection limits for these compounds during the different burns are presented in Tables G-2 and G--3 in Appendix G. Also see further discussion in Appendix I. (3) Hydrocarbons. Results and discussion of these data are presented In Appendix I. (4) CO, C02 and 02. These data arc presented in Tables D~5 and D-6. uoncentrations of CO, C02 and 02 in the scrubbed effluent gas for burns IV, V, VI and VII were indicative of efficient combustion. A sampling probe leak invalidated CO, C02 and 02 results for burns I, II, III and VIII. (5) Npx- These data are presented in Table D-5. NOX emissions fronTTncinerators are normally low due to the low combustion temperature ( 2 0 ° ) NOx emissions from the incinerator <90F. during "Orange" Herbicide incineration were low (<100 ppm) and in agreement with combustion temperatures and the excess nir. b. Discussion. (1) Particulates. Isokinetic sampling was difficult due to the low velocity pressure ( . 0 to 0.01 inch of water pressure^) 008 which could not be read more accurately than +_ 10% in the scrubbed effluent gas stack. A greater than 1 0 carbon recovery (Table D-6) 0% as calculated from measured gas velocity pressures and mole fractions of C02 and CO in the scrubbed effluent gas indicated that gas velocity pressures were read consistently high and that the scrubbed effluent gas velocities were greater than the actual velocities. To evaluate this possibility revised, scrubbed effluent gas velocities for each burn (see Table D-3) were calculated based on theoretical combustion data (Marquardt) and a chlorine mass balance. The ratio of measured/calculated scrubbed effluent gas velocities averaged 1.15 with a standard deviation of 0.14. Thus it was concluded that measured velocity pressures were read high. A thorough discussion of the revised, calculated scrubbed effluent gas velocities is given in Appendix I. The EHL(M) thermocouple used to obtain the scrubbed effluent gas temperature was reading 20°F too high (discovered during recalibration after this program). The dry gas fraction used to establish isokinetic sampling parameters had to be calculated from the water vapor saturation value of the scrubbed effluent gas at the sampling temperature. With the incorrect temperature, the indicated dry gas fraction was smaller than the actual. Calculations based on these data indicated that scrubbed effluent gas sampling had been performed at less than isokinetic flow. Fortunately, with the {aforementioned revised scrubbed effluent gas E-(D-22) �TABLE D-4 TCDD, BUTYL ESTER & ACID (OK 2,4-D & 2,4,5-T) SAMPLING VOLUMES, RATES, AND TIMES "ORANGE" HERBICIDE INCINERATION TESTS 12 - 30 NOV 73 Burn £ Sample SAMPLE VOLUME, Liters Meter Con'd Stack Con 1 d Dry @ STP Date Nov Start Time Duration RATE, Liters /Min Dry @ STP Stack Con'd CG SG 184.4 139. 3 512. 6 188. 3 137.4 106. 6 13 I 1445/61 1455/59 2. 25 1. 81 8. 40 3. 19 CG SG 45.0 158. 3 131. 1 228.5 34.0 120. 4 16 II 1550/17 1622/55 2.00 2. 19 7.71 4. 15 294.2 126.9 790.9 174. 8 223.2 97.?. 19 III CG SG 1432/64 1428/57 3.49 1. 70 12. 36 3.07 CG SG 334.0 176.2 956.9 242.7 250. 3 134.4 20 IV 1357/60 1345/60 4. 17 2. 24 15.95 4.05 7.9 145. 3 24.6 179.7 6.0 111. 1 27 V CG SG 1350/10 1356/60 0. 60 1. 85 2.41 3.00 CG SG 220.9 50.7 582. 1 81. 3 165.9 36. 3 28 VI 1158/31 1207/36 5. 35 1.01 18.77 2. 26 150.7 115. 5 437.2 165, 3 112. 15 82.6 29 VII CG SG 1007/23 1030/56 4. 89 1. 48 19.00 2.95 CG SG 169. 4 124. 0 615.0 142. 3 128.2 90.4 30 VIII 0952/33 0957/58 3.88 1. 56 18.64 2.45 m » W "" CG: Combustion Gas, Prescrubber (Reaction Tailpipe) SG: Scrubber Gas, Postscrubber (Scrubbed Effluent) Duration, in minutes USAF EHL(H) �TABLE D-5 CO, CO2, 02, H20 AND NOx SAMPLING RESULTS "ORANGE" HERBICIDE INCINERATION TESTS 12 - 3O NOV 73 Burn # Sample CONCENTRATION % BY VOLUME CO COS HgO °8 9. 1 9.7 ppm Temp OF 4.3 34 44.2 1875 161 36.9 30.07 4.5 38 43.3 1850 166 35.4 30.04 m o" to 5.4 35 50.6 1975 163 41.0 30.09 48.7 1840 163 35.9 29.96 44.8 2140 156 38. 1 30.28 46.3 1780 175 38. 1 30.20 95.9 2200 170 41.0 30. 12 100. 5 2160 151 32.8 30.09 <0. 01 I CG SG <0.01 II CG SG <0.06 III CG SG IV CG SG 0. 07 0.90 11.5 12.0. NA 4.8 5.4 35 V CG SG 0. 16 0.90 12.9 12.0 4.7 4.8 VI CG SG 0.03 0.90 11. 5 12.0 NA 4.8 6.1 29 5.4 47 VII CG SG 0. 14 0.90 12.7 12.4 4.9 4.8 6.0 41 0. 19 12.7 4.8 VIII CG SG 6.0 26 9.6 11.5 9. 1 6.6 NO* Inches Hg Pressure SG - Values are average of 4 measurements CG - Values are theoretical (see main report paragraph 2.6) NOTES: NA - Not available CG - Combustion gas pre-scrubber SG - Stack gas post-scrubber USAF EHL(M) �TABLE D-6 CARBON MASS BALANCE ON SCRUBBED EFFLUENT GASES "ORANGE" HERBICIDE INCINERATION TEST 12 - 30 NOV 73 Burn # Flow* Dry @ STP ftVmin CO, CO Volume % COa CO Mass as C Ibs/min Fuel Feed Rate Air Ibs/min Recovery** % IV 12.0 0.9 5.65/5.28 0 4 4.80 . 2 0. 01 126/119 V 1719.1/1269.1 12.0 0.9 64/.3 .147 04 . 8 5.45 0. 01 126/ 96 VI i a ro 1515.9/1417.9 1222.5/1306.9 12.0 0.9 45/.7 .648 0 3 4.80 . 4 0. 01 102/108 VII 1447.9/1252.5 12.4 0.8 55/.2 .748 04 .0 0.01 109/ 95 5.48 01 *First number based on measured velocity pressures/second number based on Marquardt theoVetical data, see discussion, Appendix I. **Does not include carbon mass as C02 removed by the caustic scrubber or the carbon mass as particulate matter and as hydrocarbor, gases escaping in the scrubbed effluent gas. USAF EHL(M) �velocities, recalculated isokinetic sampling flows were 96.9%(sa 12.9%) and no adjustments of particulate data were necessary. ( 2 ) Butyl Esters and Acids (of 2,4-D and 2,4.5-T)and TCDD. All sample volumes were "smTficienTto "'detect *5 ppo "oT^ Ihese compounds, except for the six liters of combustion gas sampled from burn V when the air cooled sampling probe clogged part way through the desired sampling period. Although the air cooled sampling probe clogged during burn II, a sufficient sample volume was obtained. A set of three identical sampling probes was used in burns I through V. The same probe was used in burns II find V. Since the clogging problem was isolated to one probe used in burns II and V, it seemed probable that the sampling conduit was crimped or the 90° bend was too sharp allowing particulate matter to build up. A new water cooled probe was used in burns VI, VII and VIII. This new probe had a 3/161 ID conduit versus the 1/8" ID conduit in the air cooled probe. The larger conduit allowed the high pressure in the reaction tailpipe section to be transmitted to the sampling train. The sample flow rate had to be increased to neutralize the positive pressure in the sampling train. (3) Hydrocarbons. See Appendix I. (4) CO, C02, 02. A sampling probe leak developed in burns I, II, III and VIII. The CO, C02 and 02 data for these burns were considered invalid. C02 and 02 concentrations in the scrubbed effluent gas of burns IV, V, VI and VII were in excellent agreement (even though C02 was absorbed in the scrubber) with the theoretical values calculated by The Marquardt Company. However, CO values were not in agreement. The measured concentrations of CO were significantly greater than the theoretical values (Marquardt). These data indicated that actual combustion efficiency was slightly less than theoretical efficiency. (5) NQx- These data were taken in anticipation of higher combustion teffipeYatures than were actually attained. NOX emissions from the incinerator were low (<100 ppm) and would not be expected to pose any environmental impact. 7. Definitions and Formulas Butyl Esters: Includes N-Butyl 2,4,5 Trichlorophenoxy-acetate and N-Butyl 2,4 Dichlorophenoxy-acetate. TCDD: 2,3,7,8 - tetrachlorodibenzo--p-dioxin. E-(D-26) �Acids: Free acids of 2,4,5 Trichlorophenoxy-acetate and 2,4 Dichlorophenoxy-acetate. STP; 70°F and 29.92 inches of Hg. Isokinctic Sampling; Extracting a gas sample from a flowing gas stream at the same velocity of the gas flow. Meter Conditions; Temperature and pressure of gas being measured by the dry gas meter. Stack Conditions; Temperature, pressure, and moisture content of the gas at the sampling point. DGF: Dry gas fraction, the mole fraction of dry gas in the sample volume. Gr/scf; Grains per standard cubic feet dry. 40 CFR 60; Code of Federal Regulations, Protection of the Environment, Part 60, Standards of Performance for New Stationary Sources. Conversion From Volume at_S_t_andard Conditions To Volume at S t acTTTbn'di t i oils'; T v stk = Vstp stk°R - ^530 2 9 . 9 2 1 P£tkT*n~Hg Conversion From Volume at^eter Conditions To Volume at St andar d Conditions; " v + Vstp - v m x 53"°H x 29092 V x Tm x Pm 8. References D-l. Incineration of Orange Herbicide, R. A. Callahan, July, 1972, USAF Environmental Health Laboratory, Kelly AFB, Texas D-2. An Assessment of Instrumentation and Monitoring Needs for Significant Pollutants Emitted by Air Force Operations and Recommendations for Future Research on Analysis of Pollutants, L. Parts, J. V. Pustingcr, W. D. Ross, A. D. Snyder, H. H. S. Yu, R. E. Sicvcrs and J. J. Brooks, to be published by the Air Force Aerospace Research Laboratory, Wright-Patterson AFB, Ohio in early 1974. E-(D-27) �D-3. Methods for Organic Pesticides in Water and Wastewater, EPA, 1971, Cincinnati, Ohio. D-4. A Rapid Method for the Determination of Several Phenoxyalkanoic Acid Herbicides in Soil Samples, E. L. Arnold and A. L. Young, USAF Academy, Colorado, D-5. Title 40, Code of Federal Regulations, Part 60 and Part 76.8 (C) ( ) 1. D-6. Perry's Chemical Engineers Handbook, 4th Edition, McGraw-Hill. D-7. Esterification of (2,4--Dichlorophenoxy) Acetic Acid A Quantitative Comparison of Esterification Techniques, J. Homer, S.S.Q. Hee, and R. G. Sutherland., Analytical Chemistry, Volume 46, No. 1, January, 1974. • D-8. Thermal Decomposition of Orange Herbicide, B. J. Stojanovlc, M. V. Kennedy, W. C. Shaw, June, 1972, State College, Mississippi. D-9. Controlled Test Atmospheres, Gary 0. Nelson, 1971, Ann Arbor Science Publishers, Inc. E-(D-28) �USAF ENVIRONMENTAL HEALTH LABORATORY Kelly AFB, TX 78241 APPENDIX E (TO APPENDIX E) SCRUBBER WATER MONITORING �(This page intentionally left blank) �APPENDIX E SCRUBBER WATER MONITORING Table of Contents Section 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. Page Introduction Cleaning of Sample Containers Description of Sample Bottles for Chemical Samples Sample Collection and Compositing EHL/K Methods and Equipment for Inorganic Analyses of Scrubber and Holding Pond Water Samples Analytical Results and Discussion of Scrubber Waters Inorganic QualIty Effect of Incinerator Operating Parameters on Spent Scrubber Water Inorganic Quality Scrubber Water Requirements and Recovery Removal of Iron From Spent Scrubber Water Mass Balance of System Chlorine, Sodium, and Hydroxide Effects of Spent Scrubber Water on Inorganic Quality of Holding Pond Water E-l E-l E-l E-l E-2 . E-5 E-16 E-21 E-24 E-24 E-24 Table E-l E-2 E-3 E-4 E-5 E-6 E-7 E-8 E-9 E-10 E-ll E-12 E-13 E-14 E-15 E-16 EHL/K Techniques of Analyses of Water Samples Equipment Used by EHL/K to Analyze Water Samples Summary of EHL/K Fresh Scrubber Water Analyses Summary of EHL/K Spent Scrubber Water Analyses - Burn I Summary of EHL/K Spent Scrubber Water Analyses - Burn II Summary of EHL/K Spent Scrubber Water Analyses - Burn III Summary of EHL/K Spent Scrubber Water Analyses - Burn IV Summary of EHL/K Spent Scrubber Water Analyses - Burn V Summary of EHL/K Spent Scrubber Water Analyses - Burn VI Summary of EHL/K Spent Scrubber Water Analyses - Burn VII Summary of EHL/K Spent Scrubber Water Analyses - Burn VIII— Quality and Chemical Loadings 1n Spent Scrubber Water for the Test Burns Percent of Caustic Feed Used to Remove C02 From Combustion Gases Scrubber Water Used/Recovered for Burn Conditions Total Iron Removal From Spent Scrubber Water Via Settling Caustic Material Balance for Sodium and Hydroxide for the E-3 E-4 E-7 E-8 E-9 E-10 E-ll E-12 E-13 E-14 E-15 E-17 E-23 E-26 E-27 Burns E-17 E-18 E-28 Chlorine Material Balance for the Burns Summary of EHL/K Holding Pond Water Analyses E-29 E-31 E-(E-I) �Table of Contents (contd) Figure E-l E-2 E-3 E-4 E-5 E-6 E-7 Page Relationship of Total Dissolved Sol Ids Measurements on Spent Scrubber Water - Standard Methods vs Meter Relationship of Caustic UsecTto"Tota1 Solids, Dissolved Sol Ids, and Chlorides 1n Spent Scrubber Water Relationship of Caustic Used to Chlorine Residual and Total Iron 1n Spent Scrubber Water Relationship of Caustic Used to Alkal1n1t1es and Sodium In Spent .Scrubber Water— Caustic Used Vs Percent C02 Removal and Percent of Caustic Used to Remove HC1 and C02 Relationship of Water Used/Discharged to Fuel/Air Ratios During Incineration of Orange Herbicide Effects of Spent Scrubber Water Discharge and Orange Herbicide Incinerated on Holding Pond Water Quality ME-II) E-6 E-18 E-19 E-20 E-22 E-25 E-32 �APPENDIX E SCRUBBER WATER MONITORING 1. INTRODUCTION: This appendix describes the equipment, procedures, and techniques used to collect scrubber water samples for chemical analyses and bloassay studies. Methods and results of chemical analyses performed by EHL(K) are also described, presented, and related to the combustion system operating parameters. 2. CLEANING OF SAMPLE CONTAINERS a. Containers for Chemical Samples: Upon receipt of the bottles from the manufacturer, EHL(K) waslied" aTTVottles~ and caps once with detergent and rinsed them thoroughly several times with hot tap water. Bottles and caps were then dried for about an hour 1n a 110°C drying oven. Dried bottles and caps were finally rinsed twice with pesticide grade quality hexane. New aluminum foil was likewise rinsed with pesticide grade hexane and then used to line all bottle caps before the caps were placed on the bottles. b. Containers for Bioassay Samples: The contractor provided reconditioned 55-gallon drums which had been steamecTcleaned. EHL(K) then rinsed these drums with a 25% by weight NaOH solution and then thoroughly flushed them with copious amounts of tap water. 3. DESCRIPTION OF SAMPLE BOTTLES FOR CHEMICAL SAMPLES: All water and residue samples collected for chemical analyses were composited and stored for analyses in new, especially cleaned glass bottles.. Dark amber, wide mouth glass bottles of 250, 1250, 1500, and 2000 ml capacity were used with molded black plastic caps lined with plastic ringlite. Clear, wide mouth glass bottles of three gallon capacity were also used and had metal screw caps lined with plastic ringlite. The clear bottles were always stored at room temperature in their cardboard shipping containers to keep light away from the collected samples. Bottle caps lined with new aluminum foil were used if the bottle contents were to be analyzed for herbicide and Its associated products. Aluminum foil was discarded and not used on the caps of other sample bottles because the alkaline samples would dissolve the aluminum and thus cause analytical interferences with the inorganic analyses. 4. SAMPLE COLLECTION AND COMPOSITING a. Fresh Scrubber Mater: A 1500 ml sample of fresh scrubber water was collected prior to commencing record burr tests I, II, III and IV. The supply tank had just been well mixed via agitation with shop air and the samples were taken from the tank's side port. b. Scrubber Water Discharge to Holding Tanks (1) Spent scrubber water samples were collected from a sample port downstream of the scrubber discharge pump, see paragraph 3.7 and Figure 6 of the report. Sampling was begun after a period 1n which incinerator operation had stabilized to equilibrium conditions and a cycle of accumulated spent E-(E-l) �scrubber water had been pumped from the bottom of the scrubber tank. This period was usually thirty minutes after the caustic scrubber water flow and herbicide Ignition had begun. The rate of spent scrubber water accumulation 1n the bottom of the scrubber tank was such that the float actuated discharge pump cycle was approximately seven minutes 1n the "ON" mode followed by about thirteen minutes In the "OFF" mode. This twenty minute pumping cycle varied ±2 minutes for all record test burns. The discharge pump was allowed to run about one minute and the sample port line was purged before a "pump cycle grab sample" was collected. (2) Grab sample volumes collected during each pump cycle were: 1500 ml for compositing Into a hourly composite, about 1300 ml for a reserve sample, and three to five gallons for compositing a drum of total burn period sample to be used for bloassay studies. A 1200 ml volume (or a proportional fraction) of each hourly composite was used to prepare a total burn period composite (TBC). c. Scrubber Water Collected From HpJdJjig_Tanks: After at least 24 hours of quiescent settling, a~l?DO"inrsampTe was coTTected from the side port on a holding tank. This sample was for EHL(K) chemical analyses. At the same time, the bottom valve on the holding tank was opened slowly and a 1500 ml sample of settled partlculates was collected. A fraction of this part1culate sample was analyzed by WCTS for hydrocarbons and the remaining fraction of this sample was kept by EHL(K) for any future analyses. d. Holding Pond Waters: Six two-quart grab samples were collected one foot below the surface and at equal distant points around the holding pond. These six grabs were blended to form a composited holding pond sample. The holding pond was so sampled once before my spent scrubber water had been discharged Into It. Spent scrubber water from the following groups of record test burns were then discharged Into the holding pond and a holding pond composite sample collected 24 hours after the last record burn's water had been discharged: I and II; III and IV; V, VI and VII. 5. EHL/K METHODS AND EQUIPMENT FOR INORGANIC ANALYSES OF SCRUBBER AND HOLDING POND WATER SAMPLES: Tables E-l and E-2 11st the techniques and equipment used by EHL/K to measure physical and analyze Inorganic chemical parameters of collected water samples. Additional comments are: a. The analyses of diluted samples for specific conductance were multiplied by two different factors to relate the two different dilutions back to the original sample strength. These factors were different because specific conductance readings are nonlinear with dilutions (see Table 154 of reference cited 1n Table E-l). Analyses of 1/99 dilutions were multiplied by 80.44 while 10/90 dilutions were multiplied by 8.73. b. Sol Ids analyses that required filtration were filtered through 0.6p glass fiber filter disks. Since the volatile sol Ids fractions from burns I and II were such an Insignificant fraction of their respective total sol Ids, the volatile solids were not analyzed 1n subsequent samples. c. Total dissolved solids were measured per Standard Methods (TDS-Ms) and with a meter (TDS-Mt) In order to compare the meter's results to the conven- E-(E-2) �TABLE E-l: EHL/K TECHNIQUES OF ANALYSES OF WATER SAMPLES Inorganic or Physical Parameter Temperature pH Specific Gravity Specific Conductance Total Solids (TS) Volatile Total Solids (VTS) Total Dissolved Solids (TDS) - Meas. Total Dissolved Solids (TDS) Meter Volatile Total Dissolved Solids (VTDS) Suspended Solids (SS) Volatile Suspended Solids (SS) Chlorides Total Chlorine Residual Free Available Chlorine Sodium j Iron, Total Total Alkalinity Hydroxyl Alkalinity Bicarbonate Alkalinity Carbonate Alkalinity FSW* N/A 100/0 . 250/00 1/99 10/0 NT 10/0 1/199 NT NT NT 1/99 2/0 2/0 1/2499 20/0 2/98 2/98 2/98 2/98 Volume of Sample Analyzed (ml) /Dilution Volume (ml) SG-P* HP* SSW* HT* 1 &2 N/A 100/0 250/0 10/90 10/0 10/0 10/0 1/199 10/0 100/0 100/0 1/99 1/249 1/249 1/999 20/0,1/249 2/98 2/98 2/98 2/98 N/A 100/0 250/0 10/90 10/0 10/0 10/0 1/199 10/0 100/0 100/0 1/99 1/249 1/249 1/999 20/0 2/98 2/98 2/98 2/98 N/A 100/0 250/0 100/0 10/0 NT 10/0 NT NT NT NT 100/0 2/0 2/0 1/9 20/0 100/0 100/0 100/0 i 100/0 NT ii it it ii ii ii ti ii ii ii 100/C 2/0 2/0 NT ii ii ii ii ii Reference to Procedures Followed** (pages /method) N/A 500 550 323-327 535-541 11 ii NA 535-541 ii ii 377/203B 385/204B ii 317/153A 211/129A 370/pH meter ii ii it 1 *See Appendix C for definition of these sample codes. NT - Not Tested **Standard Methods for the Examination of_ Water and Wastewater. 13th Ed, American Public Health Association, 1015 18th St NW, Washington DC 20036 (1971). USAF EEL/K �TABLE E-2: Measured Parameter Temperature pH Sp. Gravity Sp. Conductance TDS-Mt Chlorine Residuals Sodiusi Iron. Total Weights EQUIPMENT USED IT EHL/K TO ANALYZE WATER SAMPLES Equi t Deacription irsion Mercury thenoaeter Beckman Century SS pH Meter with combination 0-14 pH electrode. Meter Model 76. Standardized with pH buffers 4.0, 7.0. 10.0, and 12.45. Bydrometers: For liquids 1.000-1.200, and for liquids 1.200-1.400 Delta Scientific Conductivity Monitor/Recorder, Model 3314-01, Serial No. 2277. Total Dissolved Solids Meter, Model 512T5, Serial No. 062137, Myron L. Coapaay. Hellige Chlorine Comparator Atomic Absorption, Perkin Elaer, Model 403. Mettler Balance, Model H-lOTv, accurate to 0.1 USAF EHL/K �tional standard method. This was done because the standard method was very time consuming and subject to larger errors because of weighing and calculations based on a 10 ml sample. Figure E-l presents these different TDS values. Although the values differed by an order of magnitude, the meter values were acceptably correlated to the measured values. The error 1n correlation was acceptable considering the overall error (±15%) 1n measuring such high concentrations of hygroscopic sol Ids, I.e. sodium hydroxide and sodium salts. d. EHL/K chlorine residuals of burn I were verified by WCTS analyses using the lodometrlc method. Since acceptable agreement of these analyses was within ±20 mg/1, subsequent chlorine residual analyses were done using the HelUge chlorine comparator. e. Alkal1n1t1es were analyzed per the potent1ometr1c method using pH titratlon endpolnts of 10.0, 8.3, 4.5, and 4.2. All results were expressed as mg/1 as calcium carbonate. 6. ANALYTICAL RESULTS AND DISCUSSION OF SCRUBBER WATERS INORGANIC QUALITY a. Fresh scrubber water analyses 1n Table E-3 showed the quality of this highly caustic solution which was prepared to range from 8.7 to 15.5% by weight NaOH. From data In Tables E-4 through E-ll, spent scrubber water (SSW) quality was essentially constant between hourly composites, the TBC, and the holding tank sample for a given burn. The only Inconsistency was 1n burn VI when the applied caustic flow rate was Increased from 1.73 pps to 2.32 pps. This change 1n scrubber water quality 1n burn VI SSW-CTs Indicated the very strong effect that applied caustic had on the SSW quality. Chemical constituents in each burn's SSW holding tank were converted to total mass produced (pounds) and pounds per drum of herbicide burned. This last value was calculated so that the chemical constituents could be compared directly between burns and independent of the volume of scrubber/cooling water produced 'or the durations of the burns. b. Although the concentrations of SSW inorganic constituents changed between burns because of different applied caustic and herbicide fuel feed rates, the following concentrations were consistently within the following ranges and worth noting: (1) pH: 10.5 to 11.8. (2) Specific Gravity: 1.040 to 1.075 (3) Specific Conductance (xlO^vfliho/cm): 11.3 to 15.8 (4) Total Solids or Total Dissolved Solids - both being about equal (xlO3 mg/1): 61.0 to 87.0 (5) Suspended Sol Ids (mg/1): 56 to 97. As discussed in Appendix I, these sol Ids contained no hydrocarbons and were essentially carbon containing less than 10% by weight Iron. The volatile fraction of the suspended and total solids was considered Insignificant. The concentration of suspended solids Increased significantly to 500-800 mg/1 because of Iron content when applied caustic was decreased below two times theoretical requirements. E-(E-5) �-'Js T SI 13 y = -163408 + 5.86x 12 R 2 = 0.80 m en y = -32048 + 2.07x R2= 0.79 o rr> p •f. •n 3 •u c •-i 0.4 .5 0.6 0.7 0.8 0.9 4 Total Dissolved Solids - Standard Methods (mg/L xlO ) FIGURK E-l : liJJLATIONShIP OF TOTAL DISSOLVED SOLIDS MEASUREMENTS ds SPEL4T SCRUiJBiiR WATER - STANDARD METHODS vs METER l.'SAF EHL(K) �TABLE E-3: SUMMARY OF EHL/K FRESH SCRUBBER WATER ANALYSES SAMPLE NUMBER III-FSW B Time Collected (hrs) Date Collected (Nov 73) Date Analyzed (Nov 73) 1000 Mon 19 Sat 24 IV-FSW B 1450 Tue 20 Sat 24 AVERAGE VALUES Parameter (mg/1 unless noted) < Temp (Op) at time: ^ ( X w Collected 15 w Analyzed 66. 72. 13+ o pll Sp. Gravity Sp. Cond. (xlO\ y mho/cm) j rs (xio ) 63. 72. 13+ 13+ 1.149 65.9 174.77 1.154 68.3 189.37 1.151 67.1 182.07 ,_ VTS (x 103) EDS, Mt (xlO*) 50.0 CO p IDS, M — _ _ _ 50.0 .._ «. _ 0.014 0.014 0.0 0.0 0.0 o.o o_,o 97.5 1.45 o VTDS (xlO3) SS VSS _ 0.014 Ms (xlfl3) V) 97.5 1.61 97.5 1.53 195.8 198.0 196.9 193.3 0.0 2.5 196.3 0.0 1.7 194.8 0.0 2.1 USAF EHL(K) I/I Chlorides (xlO3) u h-1 Total Chi. Resld. tf 3 ** M Free Avail. Chi. Sodium (xlO3) Iron, Total VI -4 M 2 Total Alk (CaC03) OH-Alk (CaC03) (xlO3) (Xi03) 3 HCO-^ -A1K (CaCCh) (xlO ) 3 50.0 C03 -Alk ( . C 3 (X103) C i 0) E-(E-7) _ _ Q-° �TABLE E-4: SUMMARY OF EHL/K SPENT SCRUBBER WATER ANALYSES - BURN I I - SSW- GENERAL SAMPLE NUMBER Tine Collected ( r ) Bs TS ( ! 3 z0) VTS (x 103) IDS, Mt (xlO*) VTDS (xlO*) ss vss x0) w Chlorides ( ! 3 < Total Chi. Re. id. u c Free Avail. Chi. f ^ ^ 6 5odi.ua (xlO3) Iron, Total Total Alk (CaC03) (xlQ3) 2 OH-Alk (GaC0 ) (xlo3x 3 t- HC0 -Alk (CaC0 ) ^ ^ 3 3 > C03 -Alk (CaC03) 3) txlQ g 164. 73. 11.75 1.060 15.1 7^.28 4.11 13.3 164. 73. 11.60 1.060 14.8 75.77 6.05 14.1 164. 73. 76.35 6.78 74. <10. 17.5 281. 75.13 5.02 73. <10. 18.3 281. 76.82 7.23 70. <10. 17.9 281. 76.10 75.97 6.341 5.86 72. ao.o <10. 18.0 17.9 281. 280. 14.5 225. 281. 281. 281. 281. 225. 164. 72. 11.65 1.060 14.9 78.77 H.iU 3 8 IDS, Ms (xlO ) 1 C-3 16131647 Tue 13 . Wed 14 13.1 Date Collected (Nov 73) Date Analyzed (Nov 73) Paraaeter (iog/1 unless noted) leap ( F at time: °) Collected Analyzed PH Sp. Gravity Sp. Cond. (xlO* VBho/ca) V Ave. -l/C-3 14301647 Tue 13 Wed 14 C-2 15201555 Tue 13 Wed 14 C-l 14301503 lue 13 Wed 14 35.0 5.00 45.5 35.0 4.89 46.3 18.5 18.9 0,0 0,0 27.8 26.7 *Baaed upon concentration in TBC 11.70 1.060 14.9 74.94 4.75 13.5 35.0 4.01 46.8 35.0 4.63 46.2 17.6 0.0 29.3 sample. 18.3 0.0 27.9 TBC 14301706 Tue 13 Wed 14 1 HT-1 1045 Sat 17 Sat 17 . Ibs rr-i Ib/Drua ef Herbicide Burned 72. 75. 11.85 1.060 14.8 75.61 5. 82 13.1 11.50 1.055 14.0 71,23 2462.14 943.34 11.8 4078.80 1562.74 ^ 2626.02 1006,13* - 2.49 - 0.95* IBO. 35.0 4.88 45.6 18 = 2 0,0 27.4 32.0 0.99 44.3 17,1 0,0 27.2 _ - _ - 501.21 7.78 192.03 2.98 7.78 2.98 1106.11 0.17" 1531.28 591.08 0,00 940.20 * 423.79 0.06* 586.69 226.47 0.00 360.23 USAF EHL(K) �TAbLE E-5: SUMMARY OF EEL/K SPENT SCRUBBER WATER ANALYSES - BURN II II -SSW- GENERAL 1 SAMPLE NUMBER IS ( ! 3 s0) VTS (x 10J) IDS, Mt (xlO4) 3 TDS, Ms ( ! 3 x0) M 3 VTDS (xlO ) 15521633 Fri 16 Sat 17 164, 72. 15521831 Fri 16 Sat 17 TBC 15521831 Fri 16 Sat 17 163. 72. 163. 72. 72. 11.45 11.55 1.062 15.7 75.97 1.063 15.7 75.62 1.41 1.55 14.0 14.2 1.062 15.7 75.10 2.88 13.8 75.82 76.36 77.72 2.21 60.** <10. Total Chi. Resid. 18.5 250. 250. § l-i -^. M Sodium 3 (xlO ) 163. 72. 11.40 1.52 69.** <10. SS VSS CO Chlorides (zlQ3) 11.50 1.062 15.7 11.50 1.062 15.5 75.56 1.95 75.74 0.00 14.0 14.2 76.63 80.40 HT-1 OQOO Tue 20 Wed 21 72. 11.50 1.064 15-8 78.32 _ 14.3 _ _ 8.73 65.** <10. 18.1 260. 5.22 2.98 58.** "^ 62. <10. <10. 18.4 18.3 280. 263. 250. 16.0 225. 260. 280. 250. 225. 36.0 2.71 52.0 20.3 0.0 31.7 263. 37.0 36.7 3.29 3.79 3 Total Alk (CaC03) (xlO ) 52.2 52.0 3 OH-Alk (CaC03) (xlO ) 20.5 20.3 HC03 -Alk (CaC03Xxlo3) 0.0 0.0 C03 -Alk (CsC03)(xl03) 31. / 31.7 * Based upon concentration in TBC sample. ** Average of replicate samples. I Iron, Total 37.0 3.36 52.5 20.8 0.0 31.7 Ave. -l/C-3 C-2 C-3 165117511731 1831 Fri 16 Fri 16 Sac 17 , Sat 17 Free Avail. Chi. V. RLKALINITY m i Time Collected (Hrs) Date Collected (Nov 73) Date Analyzed (Nov 73) Parameter (mg/1 unless noted) Temp ( F at time: °) Collected Analyzed PH Sp. Gravity Sp. Cond. (xlO4 p mho/cm) C-l 18.3 37.0 3.29 52.5 20.8 0.0 31.7 HT-1 Ib/Drum of Herbicide Ibs Burned _ _ _ _ _ _ 2586.98 _ 862.08 _ 4723.41 1574.02 2655. £s 884.98* _ — - 2.15 - 0.72* - 528.49 7.43 176.11 2.48 7.43 36.0 1189.11 O.lt 0.73 51.6 1704.39 716.77 21.7 0.0 0.00 29.9 987.62 2.48 396.26 0.04* 567.97 _• 238.86 0.00 329.11 USAF EHL(K) �TAiLE E-6: SUMMARX 0? EHL/K SPEHT SCRUBBER WATER ANALYSES - BURN III III -SSW- GENERAL SAMPLE NUMBER Time Collected (Ere) Date Collected (Nov 73) Date Analyzed (Nov 73) Parameter (mg/1 unless noted) Temp ( F at tiae: °) Collected Analyzed PH . Sp. Gravity Sp. Cond. (xlO* V mho/cm) x(3 I TDS, Ms ( l > ) 3 • 4 C-3 16381718 Mon 19 Wed 21 :-i/c-3 14351718 Mon 19 Wed 21 TBC 14351718 Mon 19 Wed 21 11.9 61.64 164. 72. 11.55 1.050 11.9 81.06 163. 72. 11.60 1.048 11.5 65.21 164. 72. 11.60 1.049 11.8 69.30 9.80 68.29 _ 9.70 66.36 _ 9.77 67.32 _ 164. 72. 11.60 1.050 72. 11.60 1.050 11.6 66.02 9.80 67.01 _ Chlorides ( ! 3 z0) 76. <10. 20.1 Total Chi. Resid. 280. 81. <10. . 20.1 280. Free Avail. Chi. 280. 280. 81. <10. 20.0 280. 79. <10. 20.1 280. 78. =10. 20.1 280. 280. 280. 280. tft •» • V. Sodiuit fxl031 H Iron, Total Total Alk (CaC03) ( l 3 x0) g Z OH-Alk ( * 0 ) CC3 fxlo3> i,3 3 • HC03 -Alk (CaC0 ) ^ , ) 4 M C03 -Alk ( a 0 ) (xlQ3) CC3 HT-1 1000 Fuea 20 ted 21 , 1 ff-1 Ib/Drum of Herbicide Ibs Burned ] VTDS ( l ) zO ss vss V. C-2 15351616 Mon 19 Wed 21 9.80 _ TS <*103) VTS (x 103) IDS. Mt ( l * xQ) Cl Ave. C-l 14351519 Mon 19 Wed 21 28. 0 3.49 27.0 2.86 28.0 3.21 33 = 5 32.7 32.4 6.6 0.0 26.9 5_<J 0.0 J 26.8 fi n 0.0 26.4 *Based upon concentration in TBC sample. 27.7 24.0 3.19 32.9 3.37 32.9 & •) 0.0 26.7 A 9 0.9 26.7 72. 11.65 1.053 11.3 72.58 9.90 _ _ - - J2414.00 - 614.46 - in n 0.85 32.9 5.5 0.0 27.4 881 3.4 2228. ?5 _ 567.31* _ 2.5$ 19.6 £25. i 1225. J292.73 0.66* - • 651.89 165.93 7.48 7.48 1.90 1.90 i 997.80? 9,3! 1094.25 189. pi 0.00 911.32 253.98 0.03* 278.53 ift S6 0.00 231.97 USAF EHL(K) �TABLE S-7: SUMMARY OF EHL/K SPENT SCRUBBER WATER ANALYSES - BURN IV SAMPLE NUMBER IV -SSWAve. C-3 XL/C-3 13551609 1659 1659 Tue 20 Tue 20 ,Fri 23 Fri 23 HT-1 161. 72. 11.60 1.052 11.6 160. 72. 11.60 1.052 11.8 161. 72. 11.55 1.052 11.8 161. 72. 11.60 1.052 1.1,7 72. 11.55 1.052 11.8 72. 11.60 1.051 11.4 - 62.09 - 63.98 62.20 - 62.16 - 61.05 - 2140.25 - 545.73 - 10.00 9.90 9.93 9.90 10.00 3505.72 893.90 2200 . 54 561.10* - TBC 13551659 rue 20 Fri 23 1000 rfed 21 Fri 23 HT-1 Ib/Drum of Herbicide Ibs Burned .-SOLIDS . _ GENERAL 1 Date Collected (Nov 73) Date Analyzed (Nov 73) C-2 15051553 Tue 20 Fri 23 60.52 - Time Collected (Hre) C-l 13551445 Tue 20 Fri 23 Parameter (mg/1 unless noted) Temp ( F at time: °) Collected Analyzed PH Sp. Gravity Sp. Cond. (xlO4 p mho/cm) TS ( i 3 x0) VTS (x 103) TDS, Mt (xlO*) 9.90 _ TDS, Ms ( l > ) x(3 62.64 - 3 VTDS (xlO ) 64.71 SS VSS Chlorides ( ! 3 z0) 73. <10. 16.8 62. Total Chi. Resid. 280. Free Avail. Chi. 280. j 62.57 - 63.31 64. 62.77 - 70. <10. 16.6 - 56. <10. 16.5 <10. 280. 280. 280. 280. 16.1 225. .280. 280. 280. 280. 225. 16.7 16.7 ->» Sodiuffl a n Iron, Total Total Alk (CaC03) ( ! 3 x0) 27.0 3.07 i 34.7 OH-Alk (CaC03) (Xio3) \ 10.1 HC03 -Alk (CaC03) (xlo3j _ 0.0 C03 -Alk, ( a O ) . x O ) CCj. ( i 3 24.6 3 29.0 3.07 35.1 27.0 i. 2.57 34.8 27.7 2.90 34.9 27.0 2.86 34.7 31.0 0.74 33.9 9.5 0.0 25.7 10.0 0.0 24.8 9.9 0.0 25.0 10.3 0.0 24.4 9,9 0.0 24.0 *Based upon concentration in TBC sample. 2.45 - - 564.42 0.63 143.92 7.89 2.01 7.89 2.01 1086.78 o.to 277.11 0.03* 1188.44 303.03 347,07 0.00 841.37 88.50 0.00 214.54 USAF EHL(K) �TABLE E-8: SUMMARY OF EHL/K SPENT SCRUBBER WATER ANALYSES - BURN V V -SSW- GENERAL SAMPLE NUMBER Tine Collected (flrs) Date Collected (Nov 73) Date Analyzed (Nov 73) Parameter (ag/1 unless noted) leap ( F at ti»e: °) Collected Analyzed PH Sp. Gravity Sp. Cond. (xlO* pnho/ca) TS <*103) VTS (x 103) IDS, Mt ( 1 * «0) xQ) I TDS, Ms ( l 3 C-l 13441423 rue 27 Med 28 164. 72. 11.50 1.072 13.2 91.06 12.5 80.91 3 Ave. -l/C-3 1344 1614 Cue 27 rfed 28 TBC 13441614 Tue 27 Wed 28 166. 166. 165. 72. 72. 72. 11.55 11.45 11.50 1.074 1.073 1.073 13.1 13.4 13.9 87.14 86.99 88.40 13. 0 13.9 13.1 72. 11.40 1.072 13.2 86.33 - 83.68 _ 86.63 _ C-2 14421523 Tue 27 Wed 28 83.81 _ C-3 15421614 Tue 27 , Wed 28 82.87 _ 13.1 u VTDS (xlO ) 09 4 Sodium 12.7 _ _ _ 3 (xlO ) 97. <10. 94. <10. 93. <10. 87. <10. 23.4 500. 23.6 500. 23.4 500. 23.3 500. 22.2 438. 500. e ^^ 500. 500. 500. 500. 438. 33.0 4.36 § 1-1 Iron, Total x0) g Total Alk (CaCOi) ( ! 3 33.0 4.30 37.0 4.59 34.3 4.42 44,6 46,3 46.8 45,9 OH-Alk (CmC03) (xlO ) 11.6 11.8 11.6 11.7 H HC03 -Alk (CaC03) ^1Q^ 0.0 0.0 0.0 0.0 a C03 -Alk (CaC03) (Xi03) 32.8 35.2 34.7 34.2 *Based upon concentration in TBC sample. 3 ET-1 Ib/Drum of Herbicide Burned u 72. _ 11.45 1.070 _ 13.1 86.94 2592.50 " 23.2 500. Chlorides ( l > ) x(3 o Total Chi. Kesld. e Free Avail. Chi. Cl 1310 Wed 28 Thur 29 . Ibs — 89. <10. ss vss ' HT-1 - _ ^ _ 645.38 - }737 . 6 0 942.76 2583.25 _ 643.08* 2.59 _ 0.65* _ — 661.99 13.06 164.80 3.25 13.06 3.25 259. 82 0.03* 3S.O 3.78 35.0 0.93 043. S8 0.11* 45.6 11.8 0.0 33.8 44.6 11.8 0.0 32.8 329.94 351.87 00 .0 978.08 331.08 87.60 {LOO 243.48 USAF EHL(K) �TABLE E-9: • SUMMARY OF EHL/K SPENT SCRUBBER WATER ANALYSES - BURN VI* SAMPLE NUMBER Time Collected (Hrs) Date Collected (Nov 73) Date Analyzed (Nov 73) Parameter (ing /I unless noted) Temp ( F ac time: °) H Collected N Analyzed 3 H W P ^ Sp. Gravity Sp. Cond. (xlO^ y mho/ cm) VI -SSW- C-l C-2 D-l D-2 D-3 D-4 11081156 Wed 28 Thur 29 12131231 Wed 28 Thur 29 1111 Wed 28 Thur 29 1133 Wed 28 Thur 29 1156 Wed 28 Thur 29 1213 Wed 28 Ehur 29 167. _ 72. 11.40 11.40 i.oe: 72. 2.0 1.025 72. 72. 72. 11.3 11.3 11.3 1.050 1.060 TS (xlO ) 12.3 - 70,03 _ 3 - 85-. 43 _ _ - _ - 8.0 12.4 - - — - 50.95 78.94 - - 8.4 Thur 29 Thur 29 165. 72. 1.042 HT-1 - 72. - 1.062 1.051 - - _ _ - - VTS (xlO3) TDS, Mt (xlO*) c 3 h- TDS, . 11 Ms (xlO ) 0 CO VTDS 3 (xlO ) SS VSS to Chlorides (xlCP) h< Total Chi. Res id. -.0 Free Avail. Chi. nM (xlO3 51 SodiumTotal ) •<« Iron, £ Total Alk (CaCO-0 (xlO-*) M OH-Alk (CaC03) fvlct1) HC03-Allc (CaC03) (X103) rC03-Alk (CaC0 ) ( i 3) 3 x 0 d 1 - - 799. <10. 21.0 89. <10. 23.2 350. 350. 35.0 5.47 42.8 - 1A f> 38. 38. 22.0 303.57 19.5 4.1 0.0 15.2 0.0 - - - - - - - 28.2 — *A TBC was not prepared for this burn due to the distinct differences in SSW C-l and C-2. Also, a holding tank liquid sample was not collected because the tank did not fill to the sampling port, ^ctucu - i - - - - - - - - — U3AF EHL{K) �TABLE E-10: SUMMARY OF EHL/K. SPENT SCRUBBER WATER ANALYSES - BURN VII VI/VII -SSW- GENERAL VII -SSW- SAMPLE NBMBEK Time Collected (Bra) Date Collected (Nov 73) Date Analyzed (Nov 73) Parameter (mg/1 unless noted) Temp ( F at ti*s: °) Collected Analyzed PH Sp. Gravity Sp. Good. (xlO* y •ho/cm) TS («1Q3) VTS <z 1 3 0) IDS, Mt (xlQ*) £ IDS, Me ( L 3 *0) Ave. C-l C-2 094710471027 1127 Thur 29 Thur 29 Fri 30 Fri 30 , C-3 :-i/c-3 115009471227 1227 Thur 29 fhur 29 Fri 30 , Fri 30 166. 166. 73. 72. 11.30 11.30 1.07: 1.071 I _ 1 14.0 13.9 172. 168. 72. 72. 11.32 11.35 1.075 1.073 . _ - 3 M VTDS ( l ) xO ss vss _ 23.0 tr. Chlorides (xlO*) 4 Total Chi. Res id. t> 438. e Free Avail. Chi. e 438. _ 14.0 _ H 24.0 I 438. 438. • ^ (i Sodiua — 14.0 _ _ TBC 09471227 hur 29 Fri 30 72. 11.35 1.073 15.1 _ 87.31 14.0 82.08 _ ^ _ 438. 23.5 438. 438. 438. 23.6 38.0 36.0 (xlO3) 35.0 H Iron, Total 4.48 3.43 3.84 _ Total Alk (CaCC3) ( ! 3 x0) g _ _ OH-Alk ( a 0 ) (xi<)3) CC3 _ ^ ( HC03 -Alk (CaC03>, 3, 3 — C03 -Alk, (CaCOaJ . f d 0 | ..c. ) *Based upon concentration in TBC savple. 83. 14. 23.6 438. 438. 33.0 36.3 3,92 4.53 - ! 45.8 — — - - 12.6 0.0 j 33.2 HT-1 1230 Sat 1 DE Sat 1 Dec •% EIT-1 lb/Dnm of Herbicide Ibs Burned 72. 11.35 1.065 13.7 _ 81.67 3859.00 12.0 5670.13 _ 3878. 3$ _ _ 3.92 22.4 275. 275. 35.0 0.77 39.8 12.9 0.0 26,9 1058.42 12.99 12.99 _ 612.63 901 0.5 61 S.71* _ 0.62* 168.03 2.06 2.06 262.55 .653.79 0.03* 0.21 k.880.59 298.55 | 609. 54 96.77 ! 00 .0 0.00 fc.271.05J 201.78 USAF EHL(K) �TABLE E-ll: SUMMARY OF EHL/K SPENT SCRUBBER WATER ANALYSES - BURN VIII VIII -SSW- GENERAL 1 SAMPLE NUMBER Time Collected (Hrs) Date Collected (Nov 73) Date Analyzed (Nov 73) Parameter (mg/1 unless noted) Temp ( F at time: °) Collected Analyzed PH Sp. Gravity Sp. Cond. (xlO4 p mho/cm) TS (»lp3) VTS (x 103) TDS, Mt (xlO4) TDS, Ms (xlQ3) 1VTDS 3 V. (l ) zO V SS VSS Chlorides ( ! 3 z0) < Total Chi. Resid. o 1-4 c Free Avail. Chi. B ^ U 3 AlINIIVXTXJ Sodium (xlO ) Iron, Total Total Alk (CaC03) ( l 3 zQ) OH-Alk (CaC03) (xlO3) HC03 -Alk (CaC03) fxlo3lj C03 -Alk (CaC03) (X103^ C-l C-2 094611091041 1208 Fri 30 Fri 30 Sat 1 Dec Sat 1 Dec C-3 12321300 ri 30 at 1 Dec Ave. H[T-l TBC HT-1 -l/C-3 09460946Ib/Drum 1300 1300 1235 of Fri 30 Fri 30 at 1 Dec Herbicide. Burned at 1 Dec. 1 Dec Sat 1 Deo! Ibs sat 164. 72. 165. 72. 164. 72. 164. 73. 10.95 1.044 - 11.05 1.046 - 7.9 8.0 _ _ 9.05 1.041 - 10.35 1.044 7.4 7.8 _ - _ 72. 73. -10.80 1.044 8.9 82.06 - 10.80 1.041 8.5 68.01 L816.2H - 406.86 - 2002.86 448.68 1573.45 352.48* 7.9 58,92 7.5 _ _ 27.7 275. 27.6 275. 28.1 275. 27.8 »75. 560. <10. 27.9 275. — 26.7 138. ' 275. 275. 275. 275. 275. 138. 24.0 160.00 _ 25.0 191.96 _ 24.0 407.26 _ 24.3 253.07 _ 214.29 25.0 24. n 0.74 12.7 - _ - — *Based upon concentration in TBC sample. - 11.3 0.0 0,1 12.6 0.0 0,9 10.4 - - _ • 1.! 49 713.02 3.69 3.69 640.9? 5.72 301.76 0.00 24.03 277, 7^ 3.35* - 159.73 0.83 0.83 143.58 1.28* 67.60 0.00 5.38 62.22 USAF EHL(K) �(6) ChloHdts (103 x mg/1): 16.5 to 28.0. Chloride concentrations were Independent of applied caustic as long as applied caustic was two times theoretical. (7) Chlorine Residuals (mg/1): 250 to 500. There was no combined available chlorine and thus the free available chlorine residual equalled the total chlorine residual. (8) Sodium (103 x mg/1): 32 to 38. Sodium concentrations were directly related to the applied caustic. Burn VIII applied caustic averaged 0.054 pps (less than half the lowest rate of any other burn) to cause the SSW sodium concentration to average only 25.0 x Krmg/l even though Burn VIII applied water recovery (59.IX) was the lowest of all burns. Sodium masses were considered conservative through the scrubber system except for the minor fractions of sodium salts entrained and exhausted 1n the scrubbed effluent gases. (9) Iron. Total (mg/1): 3.0 to 5..0 except up to 400 when applied caustic fell below two times theoretical. Lack of adequate caustic allowed the HC1, Cl2» and any monatomlc chlorine of the combustion gas to react with the metal of the scrubber tank walls. (10) Total alkalinity as CaCOa (xlO3 mg/1): 32.0 to 52.5 except down to 12.0 (±0.7) when applied caustic was less than two times theoretical. As long as applied caustic was twice theoretical, carbonate alkalinity averaged 70(s«8)X of total alkalinity, the remaining alkalinity was hydroxyl, and no bicarbonate alkalinity was detected. At caustic less than twice theoretical, carbonate alkalinity Increased to 90(s*10)X of total alkalinity, the remaining alkalinity was bicarbonate, and no hydroxyl alkalinity was detected. 7. EFFECT OF INCINERATOR OPERATING PARAMETERS ON SPENT SCRUBBER WATER INORGANIC QUALITY a. Table E-12 presents the quality and chemical constituent loading In each burn's total SSW as a function of drums of herbicide Incinerated. Values for burns VI and VII were averaged Into the VI/VII column. Comparison of data 1n Table E-12 Indicated that all measured parameters except the relatively constant temperatures (x-164°F), specific gravities (x-1.057), and chlorides (x-167 pounds/drum burned) were directly related to &pp!1ed caustic and Independent of F/A or Percent Excess A1r. Multiple regression statistics were applied to these data and excellent correlation coefficients were obtained to relate these chemical product loadings to the ratio of applied caustic to that required to neutralize the theoretically expected amounts of HCI(NU/NT) - see Figures E-2 through E-4. Except as discussed 1n paragraph "t" below, all of these relationships were linear. b. The following reasoning substantiated why these correlations agreed so well with expectations: (1) Temperature was a function of combustion gas temperature, combustion gas volume, and total water volumes feed to the scrubber. Since all of these parameters were consistent In relative proportions and gas/water contact time In the scrubber tank was probably consistent, the effluent scrubber water E-(E-16) �TABLE E-12: QUALITY AND CHEMICAL LOADINGS IN SPENT SCRUBBER WATER FOR THE TEST BURNS BURN NUMBER I Unit Operations -Average NaOBused/NaOHtheory II III IV V VI/VII VIII 3.05 Fuel to Air Mass Ratio (F/A) % Excess Air 3.18 2.06 2.16 2.23 2.20 1.29 0.086 0.086 0.106 0.105 0.120 0.115 0.118 89. Spent Scrubber Water Holding Tank Physical Parameters Temp ( F @ Collection* °) PH Sp. Gravity Sp. Conductance (xlO y mho/ cm) 164. 11.50 1.055 14.0 Chemical Mass (Ibs) Per Drum of Herbicide Incinerated 943.34 Total Solids Total Dissolved Solids-MS* 1006.13 Suspended Solids* 0.95 192.03 Chlorides Free Available Chlorine 2.98 Sodium 423.79 0.06 Iron-Total* Total Alkalinity as CaC03 586.69 OH-Alkalinity as GaC03 226,47 HC03-Alkalinity as CaC03 0.00 C03-Alkalinity as CaC03 360.23 89. 52. 53. 34. 40. 37. 163. 11.50 1.064 15.8 164. 11.65 1.053 11.3 161. 1.0 16 1.051 11.4 165. 11.45 1.070 13.1 166. 11.35 1.065 13.7 164. 10.80 1.041 8.5 862.08 884.98 0.72 176. 11 2.48 396.26 0.04 567.97 238,86 0.00 329.11 614.46 567.31 0.66 165.93 1.90 253.98 0.03 278.53 46,56 0.00 231.97 545.73 561.10 0.63 143.92 2.01 277.11 0.03 303.03 88.50 0.00 214.54 645.38 643.08 0.65 164.80 3.25 259.82 0.03 331.08 87.60 0.00 243.48 612.63 615.71 0.62 168.03 2.06 262.55 0.03 298.05 96.77 0.00 201.78 468 0.6 352.48 3.35 159.73 0.83 143.58 1.28 67.60 00 .0 5.38 62.22 *Data/calculation based on analyses of total burn composite (TBC) sample. USAF EHL(K) �1000 900 rotal Dissolved Solids y = -27.14 + 301 ,29x R2= 0.92 800 i. a 253.57x q +J 700 T-> OJ ra s- ~^£ OJ 600 m i - OJ m ^^ 500 u +J -r- oi "£1 400 c 1•r- O .Chlorides y = 1.36.10 R2= 0.41 •a 5 300 3Q £ 200 13.63x A A-gr 100 0 2 3 NaOK Applied To Scrubber NaOH Theoretically Required To Neutralize 11C1 in Combustion Gases FIGURE E-2 RELATIONSHIP OF CAUSTIC USED TO TOTAL SOLIDS, DISSOLVED SOLIDS, AMD CHLORIDES IN SPENT SCRUBBER WATER USAF EHL(K) �Q_ 1 3 S- <u +J rt n OJ -t-> .-a icu c Free Available and Total Chlorine Residual= -0.089 + 0.90Sx R = 0.87 5- •.— 2 at a .a c a t- O u -o I I—1 IO 0 c a; .-r. a; = 2 c 4- •r- O TD 3 C S- Suspended Solids y = 10.36 -7.73x + 1. 3 Q O D-' R2= 0.98 Total Iron y = 3.96 - 3.09x + 0.59x2 R2 = 0.99 2 3 NaOII Applied To Scrubber SaOH Theoretically Required To Neutralize HC1 in Combustion Gases FIGURE E-3: RELATIONSHIP OF CAUSTIC USED TO CHLORINE RESIDUAL AND' TOTAL IRON IN SPENT SCRUBBER WATER USAF EI!L(K) �600 Total Alkalinity as y = -240.11 + 257.45x R2= 0.98 500 sGJ Q- QJ +J ^ s_ o , Sodium = -1812 + 134.I6x = 0.96 , «« 400 Carbonate Alkalinity,CaCO, y = -72.03 -f 136.16x 0.95 i <J - QJ c: -Q 1-1 .a 3 (L) u^ 300 00 O S0) •- 200 tn 5 -o s- C Q Eydroxyl Alkalinity as yo= -269.79 + 161.53x"1 Solid Line 2 = 0.98 J Only 100 i 2 3 NaOH Applied To Scrubber NaQH Theoretically Required To Neutralize HC1 in Co:=bustion Gases FIGL'RE E-4 : RELATIONSHIP OF CAUSTIC USED TO ALKALINITIES AND SODIUM IN SPENT SCRUBBER WATER L'SAr EHL(K) �temperature was relatively constant. (2) Specific gravity was dependent on these same parameters plus caustic feed. However, specific gravity 1s a relatively Insensitive measurement and would be expected to change only when the parameters on which 1t depended had changed more dramatically. (3) The slightly variable chlorides 1n pounds per drum of herbicide burned was apparently due to its following consistencies of: (a) Chlorine weight percent in the herbicide feed, (b) percent production of HC1, C"\2» the Incinerated chlorinated hydrocarbons, and ancl monatonric chlorine from (c) efficiency of the caustic scrubber to collect chlorine species as long as the applied caustic was greater than twice theoretical. Thus, these combined situations allowed collection of-chlorides almost indeaendent of any Ny/Ny radios greater than 1.1. (4) The inorganic loading of the fresh scrubber water into the spent scrubber water far outweighed any contributions that the herbicide combustion products (CO?, H20, any hydrocarbons) may have produced. Only the chlorine species of the combustion gases exerted any significant effects on Inorganic scrubber water loads, and their effects were Independent of Nn/Nr greater than 1.1. c. All but three of the correlated Inorganic parameters Increased directly over the range of NU/NT=! to Nn/Nj=3. Total Iron decreased rapidly to a constant value as N(j/Ny Increased from one to two. This was because at greater than 1.1 enough caustic was available to neutralize the HC1 which otherwise reacted with the scrubber tank walls to produce ferric precipitates. Suspended sol Ids responded in the same manner because the ferric precipitates v/ere a large fraction of suspended sol Ids when Nn/Nj was less than 1.29 (Burn VIII). The last exception was hydroxyl alkalinity which was zero at (1) NM/NT, Increased nonllnearly with Njj/Nj from one to two and then Increased directly when Ny/Ny was greater than two. Hydroxyl alkalinity approached zero at (1) Ny/Nj because it was depleted via reaction with the HCT in the combustion gases. For Nu/Nj between 1.0 and 2.0, excess hydroxyl Ions were present above HC1 requirements but they were being reacted with COo. Excess of hydroxyl ion rose steadily for Ny/Nj values greater than about two because all HC1 demands were met and the short water/gas contact time in the scrubber tank precluded any additional reaction with C0£. These relationships of hydroxyl utilization for HC1 and C02 reactions were very correctable to calculated data; see Figure E-5 which was plotted from the data in Table E-13. It was Interesting to note that an average of 10(±4)58 of the calculated C02 in the combustion gas was reacted with NaOH to produce carbonates. 8. SCRUBBER WATER REQUIREMENTS AND RECOVERY a. Caustic solution and cooling water mass flow rate requirements to cool E-(E-21) �100 50 Caustic Feed (as OK) Used to Remove CO2 40 y = -47.50 -5-69.54x - 13.27x2' R2= 0.87 80 60 E 3C -Caustic Feed (as OH) Used to Remove HC1 y = 139.69 - 67.72x +10.31x2 O) 10 •r) 20 40 10 20 Removal of C02 fron Conbustion Gases y = -11.24 + 12.62x - 1.41x2 R2= 0.95 0 NaOH Applied to Scrubber NaOH Theoretically Required To Neutralize HC1 in Combustion Gases FIGUREE-5: CAUSTIC USED vs PERCENT CO? REMOVAL AND PERCENT OF CAUSTIC USED TO REMOVE HC1 AND C02 USAF EHL(K) ra i-! n n �TABLE E-13: PERCENT Or CAUSTIC FEED USED TO REMOVE C02 FROM COMBUSTION GASES Scrubber Percent Removal of COg From Combustion Gases* "TWceril Of Caustic Feed Used To Remove CO^* VIII 15.3 13.8 9.8 9.1 10.2 8.5 2.6 39.6 41.0 44.2 39.9 43.3 36.3 19.3 3.05 3.18 2.06 2.16 2.23 2.20 1.29 Ave Std D. 9.9 4.1 37.7 8.5 2.31 0.64 Burn No. I II III IV V VI/VII *We1ght Percent N a°Hused N H a° Theory USAF EHL(K) E-(E-23) �and neutralize the combustion gases were based an estimates of combustion gas mass flows, chlorine composition, end temperature. These three parameters were dependent on the fuel to air mass ratios (F/A). see Appendix A. Consistent selection of scrubber water flow rates 1n relation to F/A were thus expected to produce correlations between scrubber water feed volumes, collected spent scrubber water volumes, and F/A. Excellent correlation of these variables are shown 1n Figure E-6 as plotted from the data In Table E-14. Even though total water flow Into the scrubber was comparable, scrubber water recovery from burns VI and VIII did not correlate to the other burns. The most likely reason for this poorer water recovery 1n VI and VIII was that the effective caustic strength of the scrubber water Into the venturl was lower and thus had a higher vapor pressure than 1n other burns. This difference of physical property allowed more scrubber water volatilization 1n burns VI and VIII than In the other burns. b. Evaluation of Figure E-6 showed that higher strength caustic stock solution (~15X by weight NaOH) was used to minimize total scrubber water requirements to 1200 (±50) gallons/drum of herbicide burned at F/A's of 0.115 (±0.005). Scrubber water recovery averaged about 75* or 1000 gallons/drum of herbicide burned. 9. REMOVAL OF IRON FROM SPENT SCRUBBER WATER: The color of spent scrubber water sediments Indicated the presence of partlculate Iron; particularly burns VI ad VIII. Iron concentrations fn well mixed SSW-TBC samples were compared with concentrations 1n settled holding tank supernatant. The average percent Iron removal after settling was 77.5 percent and Increased as Iron concentration In the SSW-TBC Increased. (See Table E-1S). Thus conventional settling tanks would effectively reduce the Iron to acceptable concentrations for discharge. 10. MASS BALANCE OF SYSTEM CHLORINE, SODIUM. AND HYDROXIDE a. These mass balances were based upon the Inorganic analyses of fresh and spent scrubber water and chlorine's theoretical average composition 1n the herbicide fuel. Considering the limited number of samples and the calculation errors Involved 1n determining masses for each burn, the average accountability of sodium (104.IX). hydroxide (95.4*), and feed chlorine (96.2%) attested to the overall accuracy of scrubber water collection and analyses. b. Data presented 1n Table. E-16 denote the fractions of hydroxide used to react with HC1 and CO?. Table E-17 shows that scrubber water analyses Indicated that about 98.7% of the herbicide chlorine was converted to HC1 and monatomlc chlorine while 1.3% was formed Into diatomic chlorine. 11. EFFECTS OF SPENT SCRUBBER MATER ON INORGANIC QUALITY OF HOLDING POND WATER a. Inorganic analyses of holding pond water were conducted on samples collected before and after Incremental volumes of spent scrubber water were dumped Into the 1.4 million gallon concrete wastewater reservoir. No other known Industrial wastewaters of any significant detriment were discharged to this reservoir during the sampling period. E-(E-24) �96 SO Percent Excess Air (+1%) 64 48 32 16 100 17CC - n v, o ^Caustic & Cooling Water Into Scrubber y = ( . - 30,9x + 87.6x2)1000 36 R2= 0.992 1600 • •H O c O •H 1400 l-l O 1300 I ro en 90 1500 - 30 1200 O Percent Water Recovery—• y = (1.7 - 16.6x + 72.1x2)10' 3.2= 0.79 1100 n cj 1000 K SJ O rj *-• rr ft fi 70 Scrubber Water Collected In Holding Tank y = (4.7 - 56.8x + 212x2)1000 R2= 0.977 o o 50 900 SCO A 700 £ Data fron Burns VI &VIII which did not fit to other data points and were neglected in the curve fitting. 50 O.C5 0.07 0.09 0.11 0.13 Ratio of Fuel To Air (?/A) JJhere Air Was 1.55 pounds/second And Fuel Was Undiluted "Orange" Herbicide Flow in pounds/second FIGURE E-6: 0.15 RELATIONSHIP 0? WATER USED/DISCHARGED TO FUEL/AIR RATIOS DURING INCINERATION 0? ORANGE HERBICIDE USAF EML(K) �TABLE E-14: Burn Numoer F/A Percent Excess Air SCRUBBER WATER USED/RECOVERED FOR BURN CONDITIONS NaOHUSed NaQHTheory TOTAL WATER Into Scrubber Recovered in Holding Tank (Gallons per Drum of (Gallons per Drum of Herbicide Incinerated) Herbicide Incinerated) Percent Recovery I 1650. 1397, 84.7 0.086 89. 3.18 1606. 1322. 82.3 0.106 52. 2.06 1353. 1013. 74.9 IV 0.105 53. 2.16 1364. 1073 = 78.7 V IN) 3.05 II I Ol 89. I I I 0.086 0.120 34. 2.23 1204. 892. 74.1 VI 0.106 52. 2.11 1342. 841. 62.7 VII 0,120 34. 2.26 1199. 934. 77.9 VIII 0.118 37. 1.29 1214. 717. 59.1 0.106 55. 2.27 1366. 1023. 74.3 0.014 23. 0.64 176. 234. 9.0 Average 5td. Deviation USAF EHL(K) �TABLE E-15: TOTAL IRON REMOVAL FROM SPENT SCRUBBER WATER VIA SETTLING Burn No.* I II III IV V VII VIII Average + Total Iron Concentration Into Holding Tank Holding Tank Supernatant (TBC - mg/1 ) (mg/1) Percent Removal (Based on Concentration] 4.88 3.29 3.37 2.86 3.78 4.53 214.29 0.99 0.73 0.85 0.74 0.93 0.77 0.74 79.7 77.8 74.8 74.1 75.40 83.00 99.7 3.79 0.84 77.5 *Burn No. -VI data were not evaluated becajse the holding tank did not fill enough to get a sample from the sampling port. + Based on Burns I, II. Ill, IV, V, and VII USAF EHL(K) E-(E-27) �TABLE E-16: Burn No. Sodium percent OT t-bw Feed Accounted For In Holding Tank CAUSTIC MATERIAL BALANCE FOR SODIUM AND HYDROXIDE FOR THE BURNS ^ used to React With HC1 co2 Hydroxide Percent of unusea ana In Holding Tank FSU Accounted For "abused Unaccounted *aUHTheory For I 26.8 39.6 24,9 91.3 8.7 3.05 I I 112.7 30.3 41.0 29.7 100.0 0.0 3.18 II I 105.2 44.8 44.2 8.9 97.9 2.1 2.06 IV m 101.3 109.4 37.2 39.9 16.1 92.2 7.8 2.16 V 100.5 41.7 43.3 15.6 100.6 0.0 2.23 i/I/VII 102.6 42.8 36.3 17.4 96.5 3.5 2.20 VIII 96.7 69.8 19.3 0.0 89.1 10.9 1.29 Ave. 104.1 41.9 37.7 16.1 95.4 4.7 2.31 Std 0. 5.5 14.0 8.5 9.8 4.5 4.4 0.64 USAF EHL(K) �TABLE E-17: CHLORINE MATERIAL BALANCE FOR THE BURNS Burn No. Percent~~oF Teear~CTiTorTne (Mass, Converted To * Accounted For ** HCI 1 (Cl) in 2 I I I II I IV V Vlt/VII VIII t 98.46 98.60 98.86 98.61 98.05 98.78 99.48 1.54 1 .40 1.14 1.39 1.95 1.22 0.52 110.09 100.91 94.96 83.00 94.98 96.. 81 92,77 Ave Std D. 98.69 0.44 1.31 0.44 96.22 8.21 Based on analytical measurements of spent scrubber water and assuming: *100% scrubbing efficiency. ** 29.78% weight chlorine in herbicide feed and all settled iron was as FeCl3. t Stack sampling crew could smell chlorine in scrubbed exhaust gases. USAF EHL(K) E-(E--29) �b. Analytical results are presented In Table E-18 and graphed In Figure E-7. The abscissa was double labeled and related the average gallons (1000) of spent scrubber water discharged per drum of herbicide Incinerated. The "freshwater" quality of the reservoir changed significantly 1n rising pH, total and carbonate alkalinity, sodium, chlorides, specific conductance, and total dissolved solids. The rise 1n pH from 7.4 to 9.7 was the most noticeable and easily measured parameter of change. The pH then slowly Increased to the equilibrium value of 10.4 for the bicarbonate-carbonate system. The fluctuating bicarbonate alkalinity Indicated the water system's attempt to equilibrate the carbonate alkalinity reactions. Total dissolved sol Ids content stabilized as the pH reached 10.0 — Indicating precipitating reactions had begun. Spent scrubber water caused no significant changes in any other measured parameters of the reservoir's water quality: specific gravity, total solids, chlorine residuals (0.0 mg/1), or hydroxyl alkalinity (0.0 mg/1 as CftC03). c. The elevated chemical concentrations 1n the holding pond would begin to decrease as the system slowly adjusts to a more natural equilibrium, with a pH of approximately 8. Exceptions to this natural adjustment would be the conservative sodium and chloride which would Increase the reservoir's salinity, but to a level much less than that of sea water. E-(E-30) �TABLE E-18: SUMMARY OF EHL/K HOLDING POND WATER ANALYSES Sample No: HP- Accumulative Holding Tanks Dumped to Holding Pond 1 NONE N/A Date Collected (Nov 73) Mon 19 Date Analyzed (Nov 73) Wed 2.1 GENERAL Date Holding Tanks were dumped (Nov 73) 2 I& II Mon 19 Wed 21 III & IV Tue 27 Thu 29 V, VI & VII Sat 24 Mon 26 Sat 1 Dec Wed 5 Dec Sat 1 Dec Wed 12 Dec Parameter (mg/1 unless noted) Temp ( F at time: °) Collected 72. 7.40 1.0005 PH. Sp. Gravity Tue 4 Dec. Mid 60 's 72. Analyzed 4 3 73. 9.70 1.0010 72. 10.00 10.40 1.0010 1.0020 Sp. Cond. ( l K y mho/cm) 0.06 x( 0.10 0.16 0.21 TS (xlO3) 1.48 0.85 _ 1.24 - 0.150 0.140 SOLIDS VTS (x 103) TDS, Mt (xlO4) 'CDS, Ms (xlO ) VTDS (x 103) VSS IONS/RADICALS — 0.065 _ 3 SS IALKALIHITY 0.40 0.035 _ _ _ — 0.0 Free Avail. Chi. LO.O 0.0 Sodium 85.0 0.48 77. OH-Alk (CaC03) _ __ 0.0 Iron, Total Total Alk (CaCQ3) — 88.0 Total Chi. Resid. _ — 26.0 Chlorides _ 170. 0.0 228. 0.0 220.0 0.68 0.0 370.0 0.58 0.0 >50.0 0.55 202. 365. J15. HC03-Alk (CaC03) 0.0 77. 53.5 C03-Allt (CaC03) 0.0 148.5 0.0 0.0 68.0 297.0 0.0 59. >56. USAF E-(E-31) EHL(K) �0.25 Specific Conductance"^ tal Dissolved Solids- i CO 10 0.05 0.00 U1UU 15 20 25 0 5 10 15 Accumulative Number of Druns of Orange Herbicide Incinerated Accunulative Gallons of Spenc Scrubber Water Discharged To Holding Pond 10 XOTS; 20 No significant changes occurred in other measured parair.sters; specific gravity, tocal solids, chlorine residuals (0.0 mg/1), or hydroxyl alkalinity (0.0 ng/1 as FIGURE E-7 : EFFECTS OF SPENT SCRUBBER WATER DISCHARGE AND ORAXGZ HERBICIDE IKCIXE-LMED ON HOLDING POND WATER QUALITY, USAF FHI (K) 25 �USAF ENVIRONMENTAL HEALTH LABORATORY Kelly AFB, TX 78241 APPENDIX F (TO APPENDIX E) DRUM CLEANING, DISPOSAL, AND ANALYSES OF DRUM RINSE SAMPLES �(This page Intentionally left blank) �APPENDIX F TABTE OF CONTENTS Page 1. Introduction F-l 2. F-2 Drum Cleaning Procedures 3. Drum Disposal ' F-3 4. EHL/K Procedures/Methods of Analyses of Drum Rinse Samples F-4 5. F-5 Analytical Results and Discussion of Drum Rinse Samples 6. Conclusions and Recommendations F-1.9 TAB1ES Pag;e F-l. Drum Draining/Dripping Data F-2 F-2. Summary of Herbicide Mass in Rinse Solution Drum Set A F-6 F-3. Summary of Herbicide Mass in Rinse Solution Drum Set B F-7 F-4. Summary of Herbicide Mass in Rinse Solution Drum Set C F-8 F-5. Summary of Herbicide Mass in Rinse Solution Drum Set D F-9 F-6. Accumulative Herbicide Mass Per Gallon of Rinse F-16 FIGURES Page F-l. Weight Percent of 2,4-D and 2,4,5-T Esters of Total Herbicide in Each Rinse F-10 F-2. Weight Percent of 2,4-D and 2,4,5-T Esters F-12 of Total Herbicide in Accumulated Drum Rinsings E-(F-j) �FIGURES (Continued) Page F-3. Mass of Accumulative Herbicide Esters in Rinses vs Accumulative Rinse Volumes and Rinse Numbers F-13 F-4. Mass of Total Herbicide Esters in Each Rinse vs Accumulative Rinse Volumes and Rinse Numbers F-14 F--5. Average Mass of Accumulated Herbicide Esters Per Gallon of Accumulated Rinse vs Rinse Numbers F-17 F-6. Average Mass of Accumulated Esters Per Gallon of Accumulative Rinse vs Accumulated Rinse Volumes F-18 F-7. F-20 Percent of Herbicide Mass Remaining in Drums vs Applied Rinse Volumes E-(F-ii) �APPENDIX F DRUM CTEANING, DISPOSAL, AND ANALYSES OF DRUM RINSE SAMPTES 1. Introduction This task was investigative in nature and was not designed necessarily for future use in any drum cleaning requirements,. The objective of this study was to assess the maximal removal of normal butyl esters of 2,4-D and 2,4,5-T from the drums. TCDD removal was not measured but estimates of its removal were made. This appendix describes the equipment and procedures used to clean and dispose of the drums. Methods and results of USAF Environmental Health Laboratory-Kelly AFT) (EHL/K) drum rinse analyses are also presented and discussed. 2. Drum Cleaning Procedures a. Drum cleaning operations were performed in the partially enclosed area north of Building 57. This area was curbed and hacl a sloped concrete floor with a catchment type drain (see Figure 9). b. Less than two quarts of "Orange" Herbicide were usually left in each drum after the drum's contents had been transferred to the fuel feed tank. Before each drum was rinsed, the contractor upended it and its contents were allowed to "free board" drain until steady dripping stopped. This drain time depended on the herbicide's drip rate, and the drain time ranged from six to nine minutes with an average of 7.3 minutes (s = 0 9 ) See Table F-1.. .0. Herbicide color and drip rate were subjectively observed and no consistent relationship was obtained between herbicide color and drip rate/total drain time. c. As specified by EHL/K, the contractor used the following procedure to clean the twenty-eight drums that had been drained per paragraph "b" above: (1) To a first set of seven random drums: (a) Five gallons of unused JP-4 were poured into a drum and the drum was recapped. (b) The drum was placed in a barrel rolling device for five minutes. (c) Drum contents were poured into a "rinse collection" drum as EHL/K personnel collected a 250ml sample of the rinse solution midway through this draining step. The 250ml sample container had been specially cleaned and the cap lined with aluminum foil per the procedure described in paragraph 2a, Appendix E. E-(F-l) �TABLE F-l: DRUM DRAINING/DRIPPING DATA 3 ttc 73 q O2 30-1625 hra) REHABKS HERBICIDE DRIP COLOR 4 Dfifi 73 DRAIN EHL(K) TIME DRUM fi?_i -J3SN1 8 73 EHL(K) DRUM NO. DRAIN TIME (WIN) 83 8 Dark Slow 88 6 Honey Fast 74 90 8 Dark Slow 82 6 Honey 71 6 81 fp£15-0845 hrs) REMARKS DRIP HERBICIDE RATE COLOR Light Slow 8 Light Slow 68 7 Light Slow Fast 75 7 Light Slow Honey Fast 62 9 Dark Slow 7 Dark Slow 91 8 Light Slow 92 7 Honey Fast 65 8 Light Slow 66 8 Dark Slow 76 8 Dark Slow 80 6 Honey Slow 63 9 Dark Slow 84 7 Dark Slow 64 7 Light Slow 70 6 Honey Fast 77** 8 Light Slow 86 7 Honey Fast 69 7 Honey Fast 78 6 Honey Fast 87 8 Dark Slow 89* 8 Dark Slow 85 7 Dark Slow t. > ** Drum 77 Was suspected of having 1(20 in it. However none was observed. (1) Average drain tine for all drums was 7.32 minutes, A * 0.90 (2) .Average ambient air temperature was 60°F during dralnings. * Drum 89 was a damaged Drum and was manually shaken. NOTES: USAF EHL(K) E-(F-2) �(d) Steps (a) through (c) above were repeated twice. (e) Drum was then recapped and stored for disposal. (2) To a second set of seven random drums, (1) above was accomplished except three gallons of unused JP-4 were used for each of the three rinses per drum. (3) To a third set of seven random drums, (1) above was accomplished except two gallons of unused JP-4 were used for each of the three rinses per drum. (4) To a fourth set of the seven remaining drums, (1) above was accomplished except that the following volumes of unused JP-4 were used for each rinse: five gallons for the first rinse, three gallons for the second rinse, and two gallons for the third rinse. 3. Drum Disposal a. EIIL/K inquired locally about public landfills which were approved by regulatory agencies for burial of hazardous materials. The Los Angelqs County "Class 1" Landfill Number 5 at Calabasas, CA was so approved and selected by EIIL/K for the drum disposal. Mr. Robert Van Huct, Los Angeles County Sanitation Office (213-484-1370) and Mr. Jack Johnson, Site Foreman of the Calabasas Landfill (213-889-1430), approved the drum burial after they had been briefed by EHL/K on the following characteristics of the drums: (1) Quantity and quality of the drums. (2) Herbicidal content of the drums and the method of drum cleaning that had been accomplished. (3) Requirement that the drums be crushed and buried to preclude any chance of them being salvaged and recycled for anyone1s use. b. The cleaned drums were loaded onto a flatbed truck, uncapped, and loaded with several cups of laundry detergent and about twenty gallons of tap water. This detergent solution sloshed around in the drums as the truck was driven to the landfill. This action of detergent rinsing was taken to stop any JP-4 vaporization and emulsify any residual JP-4/ herbicide that may have been in the drums. c. The uncapped drums were rolled from the truck bed into a pit freshly dug by the landfill operators. The drums were then immediately crushed, mixed, and compacted with other refuse, and buried while EHL/K personnel observed. E-(F-3) �4. EHL/K Procedures/Methods of Analyses ofJDrum Rinse Samples a. Equipment and Materials. (1) Gas Chromatograph - Tracer 220 equipped with flame ionization detector ( I ) FD. (2) Chromatographic column: 4 feet glass "U" tube packed with 3% ov-1 on Chromosorb W, 80/100 mesh. (3) Chromatographic operating conditions: (a) Injector temperature - 225°C. (b) Detector temperature - 175°C. (c) Column temperature: _1 Programmed initial temperature at 150°C for six minutes rising at 10°C per minute to a final temperature of 20C 0°. 2 Isothermal condition of 160°C. (d) Carrier gas - nitrogen. (e) Gas flow - 70 cc/minute. b. Standards. Standard solutions of nb 2,4-D and nb 2,4,5-T esters were prepared in JP-4. Standard curves were prepared for th,c nb 2,4-D and nb 2,4,5-T esters at three different concentrations: 6 ug/ul, 2 Ug/Ul, and 0.2 Ug/Ul. Linearity was obtained from 0.2 ug to 24 Ug but was lost above 24 ug for both the 2,4-D and 2,4,5-T nb esters. Standard curves were prepared by plotting peak height (cm) vs concentration of ester in micrograms (ug). c. Procedure. (1) Samples were injected into the gas chromatograph at an adjusted injection volume so that the concentration would be within the concentration of the prepared standard curves. Sample dilution was therefore unnecessary., (2) Samples from the first and second rinses were analyzed using the column temperature program. Samples from the third rinse were analyzed using the isothermal column temperature. This was done because samples from the third rinse had the lowest ester concentrations and the solvent interfered with the 2,4-D n-Butyl ester peak when using the temperature program. E-(F-4) �(3) Concentration of the samples was calculated using the standard curves. The value obtained was in micrograms per microliter which was then converted to milligrams per liter of sample. 5. Analytical Results find Discussion of Drum Rinse Samples a. Presentation of Analytical jtesults. (1) Analytical results were obtained for each individual nb 2,4-D and nb 2,4,5-T ester in each rinse sample (mg/L). These data were reduced to determine the: (a) Mass (gm) of each ester and the sum of both esters' masses in each rinse volume, (b) Accumulated (ace.) mass in grams of each ester and the sum of both esters' masses in the accumulated rinse volume , and (c) Fraction of accumulated mass of each ester find sum of both esters' masses in the accumulated rinse volume as a percent of the accumulated estcr(s) removed in all three rinses. (2) These reduced data as well as statistical qualities on them arc presented in Tables F-2 through F-5. The data points were highly variable with many standard deviations large when compared to a mean value, Whenever possible, statistical comparisons were performed on the data to determine the significance between data sets at or above the 90% confidence level. (3) TCDD was not analyzed in the rinse samples, but the samples were saved should any need arise. Since TCDD has similar solubility to 2,4-D and 2,4,5-T esters in organic solvents, its removal from the drums was based on the removal efficiencies found for 2,4-D and 2,4,5-T. b. Relative Removals of Each Ester. (1) Review of the data in Tables F-2 through F-5 revealed that the 2,4-D mass in a rinse was almost always greater than the 2,4,5-T mass in the rinse. This was expected since the blended herbicide analyses, Table G-l, showed that nb 2,4-D and nb 2,4,5-T esters, respectively, averaged 50.90 and 43.78 percent of the herbicide total weight. Figure F-l considers the 2,4-D and 2,4,5-T nb esters to be 100 percent of the total herbicide in the rinse and presents the average mass percentage of each of these esters in each rinse for all drums. Also shown is the mass percent of these esters when they are considered to be 100 percent of the herbicide total mass rather than their average 94.68 pcrpcrit. Similarily, E-(F-5) �TABLE F-2: SUMMARY OF HERBICIDE MASS IN RINSE SOLUTION - DRUM >a te Drum Set "A" EHL(K) Drum Numbers 63/64/74/75/76/77/91 Drain Dr?£ SAMPLE Time NO. (Min) A-63 9 A-64 7 A-74 8 A-75 7 A-76 8 A-77 8 A-91 8 Ave Std Ave Std (x) D. (4) (5) D. (-4) nb gm/ rinse 2 179.4 32.17 1 Rinses Gal/Rinse 24D ester Ace. gm/ rinse % Total 3 1 2 3 16.45 178.4 211 6 228.0 78.7 92 8 1.10 162.4 203 .5 204.6 79.4 99 5 6.25 176.0 l^i> .5 201.7 87.2 96 .9 7.12 128.3 US' .b 145.6 88.1 95 .1 6.66 173.7 ItW .2 195.9 86.7 96 .6 27.73 156.7 200 A 228.0 68.7 87 .8 7.31 135.1 14 } .2 154.5 87.4 95 .3 1 5 2 5 nb gin/rinse 2 173,7 27.82 1 153.3 33.50 166.9 10.03 131.7 4.92 169.2 7.38 151.0 30.66 139.7 6.06 24.87 10.37 158.8 183 .7 L94.0 155.1 13.89 8.90 20.2 28 .8 32.6 15.8 82.6 94 .8 3 .7 7.4 17.19 12.80 162.4 41.07 176.0 19.49 128.3 10.22 173.7 15.52 156.7 43.53 135.1 12.11 158.8 20.2 SET A Collectors : DILorenzo/Knerl • 3 :o Llectec p 3-4 Dec 73 Ja te 17 uec 7j - Chemists: Hodgkinson/Rodriguez 5 Vn,ilvzed . 8 Jan 74 245T ester nb Total Esters Ace. gm/ rinse Ace. gm/ rinse % Total ga/rinse % Total 1 1 2 3 2 3 3 1 2 3 173.7 201.5 211.4 353.1 60.0 26.3 353.1 413.1 439.4 9.88 82.2 95.3 80.4 94.0 0.62 153.3 186.8 187.4 315.7 74.6 1.7 315.7 390.3 392.0 81.8 99.7 80.5 99.6 2.21 166.9 176,9 179.1 342.9 29.5 £.5 342.9 372.4 380.9 93.2 98.8 90.0 97.8 2.6T 131.7 136.6 139.3 260.0 15.1 9.8 260.0 275.1 284.9 94.6 98.1 91.3 96.6 169. 21 176.6 179.0 342.9 22.9 2.42 9.1 342.9 365.8 374.9 94.5 98.6 91.5 97.6 .5.29 151.0 181.7 197.0 307.7 74.2 43.0 307.7 381.9 424.9 76. 7| 92.2 72.4 89.9 2.7S 139.7 145.8 148.5 274.8 18.2 LO.l 274.8 (293.0 303.1 94.0 98.1 90 .7j 96.7 5.12 5.38 155.1 172.3 177.4 313.9 42.1 15.8 23.0 25.6 35.8 26.6 88.1 97.3 i 7.6 2.6 15. 5 313.87 355.9 14. 2 35.8 51.6 85.3 96.0 7.5 3.2 371.4 58.0 USAF EHL(K) Ci �TABLE F-3: Drum Set "B" EHL(K) Drum Numbers 62/66/68/73/82/85/90 Drali or Drip SAMPLE Time NO, (Min) B-62 9 B-66 j 8 B-63 B-73 8 B-82 6 B-85 7 B-90 Ave Std Ave Std 7 8 () x D. ( ) 4 (5) D. (4) SUMMARY OF HERBICIDE Rinses Gal/Rinse 1 2 MASS SOLUTION - DRUM SET B Collectors: DiLorenzo/Knerl Da te : 3-4 Dec 73 3 Co Llected Ja te 17 Dec 73- Chemists: Hodgkinson/Rodriguez 3 kfl_alvzed: 8 Jan 74 ester 245T nb Total Esters Ace. gm/rinse Ace. gm/rinse % Total gm/rinse % Total 3 1 2' 2 1 3 1 2 3 3 1.67 68.1 150.4 156.8 72.8 74.4 136.9 13.5 6.3 136.9 91.5 97.8 87.3 96.0 0.49 86.0 86.5 175.8 11.2 1.4 175.8 187.0 188.4 81.8 99.4 73.3 99.3 94.6 2.46 149.9 172.0 174.5 308.0 58.1 7.9 308.0 366.1 374.1 82.3 97.9 98.6 85.9 0.41 97.4 100.6 101.0 201.0 8.5 1.1 201.0 209.5 210.6 96.4 99.6 95.5 99.5 0.39 86.5 89.2 89.6 168.3 6.9 1.2 168.3 175.2 176.4 95.4 99.3 99.6 96.5 1.23 65.4 73.7 74.9 128.1 23.5 4.4 128.1 151.6 156.0 98.4 82.1 97.2 87.3 0.23 110.4 117.1 117.3 233.0 17.9 0.6 233.0 250.9 251.6 92.6 99.7 94.1 99.8 3 3 24D ester nb Ace. gm/rinse ^m/ rinse % Total gm/rinse I 2 1 2 1 2 3 3 8.86 4.66 68.8 77. / 82.3 68.1 68.8 4.66 83.6 94. 3 7.04 u.yu 94.0 101.0 101.9 81.8 94.0 4.20 92.2 99.1 Jb.UU D.43 158.1 194. 1 199.6 149.9 22.14 l^B.i 79.2 97 3 D.34 G.b5 lOU.b 1UU. y 109.6 97.4 103. 6 3.18 94.5 99 4 4.2U u. 7o Ui.O 00 u 86.8 86.5 81.8 2.73 94.3 99 1 13. 2Z j.i2 bl. 1 77 .9 81.0 65.4 t>2. / 8.29 77.4 96 .2 122. b 11.24 u. 41 122. b 133 .8 134.3 110.4 6.70 91.3 99 .7 7.41 0.98 12.56 2.28 98.8 111 .4 113.6 94.2 98.8 6.78 0.84 10.99 2.11 32.2 41 .6 42.3 29.1 33.2 87.5 97 .9 2 .0 7.3 nb IN RINSE 94.2 101.6 102. d 193.0 34.7 35.1 62.1 29.2 99.0 92.3 0.8 4.3 20.0 17.8 3.3 193.0 212.9 216.3 2.7 62.1 76.0 77.2 89.8 98.4 1.4 5.9 USAF EHL(K) •o �TABLE F-4: Drum Set "C" EHL(K) Drum Numbers 71/81/83/86/88/89/92 Drain Drip SAMPLE Time (Min) NO. nb gin/rinse 1 2 G-71 6 82.2 6.59 C-81 7 55.0 5.00 C-83 8 105.4 9.84 C-86 7 104.5 15.29 C-88 6 80.8 7.80 C-89 8 L25.8 18.17 L07.2 13.93 C-92 7 i Ave Std Ave Std (x) D. (4) (i) D. (4) SUMMARY OF HERBICIDE MASS Rinses Gal/Rinse 2 AD ester Ace. gm/rinse Z Total 3 1 2 3 0.81 82.2 88. 8 89.6 91.7 99. 1 55.0 60. 0 61.2 1.2C 89.9 98. 0 2.45 105.4!ll5.2 117.7 89.6 97.9 1.7< 104.5 119 a 121.6 36.0 98 .6 80.8 88 .6 90.3 j 1.7( 89.5 98 .1 125.8 144 .0 145.4 | 1.42 86.5 99 .0 1.7C 107.2 121 .1 122.8 87.3 98 .6 94.4 , 10.94 1.5t 94.4 105.4 106.9 4.92 0.5] 23.3 27.9 28.1 23.3 88.6 98.5 2.1 0.5 1 2 2 2 nb gm/rinse 1 2 75.9 3.86 49.5 2.80 99.0 5. S3 97.7 9.24 74.0 4.47 119.9 16.35 102.2 8.93 88.3 23.3 i 7.35 4.67 IN RINSE SOLUTION - DRUM SET C Collectors : DiLorenzo/Knerl )a t.e :o Llected .3-4 Dec 73 ia te 17 Dec 73- Cheadsts: Hodgkinson/Rodriguez 2 \n.alvzed: 8 Jan 74 245T ester nb Total Esters Ace. gm/rinse Ace. gm/rinse Z Total go/rinse % Total 1 3 1 2 3 2 1 3 2 3 10.5 1.2 158.1 168.6 169.8 79.8 80.2 75.9 0.43 93.1 99.3 94.7 99.5 7.8 1.8 104.5 112.3 114.1 0.64 99.5 52.3 52.9 [L09.5 91.6 98.4 98.8 93.5 1.26 99.0 104.8 106.1 Z04.4 15.7 3.7 204.4 220.1 223.8 91.3 93.3 98.8 98.3 iZOZ . 2 Z4.3 /.> 202.2 226.7 229.4 97.7 106.9 107.9 0.91 88.1 98.8 99.2 90.6 0.90 74.0 78.5 79.4 154.8 l2.3 Z . b 154.5 167.1 169.7 91.2 98.5 93.2 98.9 0.74 119.9 136.3 137.0 J4b. ; 3*. 5 Z . Z 245.7 280.2 282.4 87.5 99.5 87.0 99.2 102.2 111.1 112.0 zuy .4 22. y Z.t> £09.4 232.3 234.9 0.90 99.2 91.2 89.2 98.9 i a ii58Tr 0.83 0.26 88.3 23.3 92.0 2.4 95.7 96.5 L82.7 27.5 27.6 46.6 99.1 0.3 18.3 9.5 1 2.4 0.8 182.7 201.0 203.4 46.6 55.3 55.6 90.2 ! 98.8 0.4 2.2 USAF EHL(K) OD �TABLE F-5: SUMMARY OF HERBICIDE MASS IN RINSE SOLUTION - DRUM SET Collectors: DiLorenzo/Knerl 5a te [: 3-4 Dec 73 Drum Set "D" EHL(K) Drum Numbers Rinses 1 2 3 Co Llected Ja te Chemists: Hodgkinson/Rodriguez I/ Dec / } . 65/69/70/78/80/84/87 Gal/Rinse 5 3 2 \n alvzed : 8 Jan 74 nb 24D ester nb 245T ester Drain nb Total Esters or Ace. gm/ rinse Ace. gm/ rinse Ace. gm/ rinse SAMPLE Drip gm/ rinse gm/ rinse % Total gm/ rinse % Total % Total Time 1 2 NO. (Min) 1 3 1 2 2 3 2 2 3 1 3 1 1 2 3 3 109.0 113 .0 114.2 211.2 217.6 219.4 102.2 104.6 105.2 D-65 3.97 1.20 95.5 98 .9 100.0 102.2 8 109.0 211.2 6.4 1.8 2.38 0.63 99.4 96.3 99.2 97.1 138.5 146 .9 147.5 265.7 279.0 279.9 127.2 132.1 132.4 D-69 7 138.5 8.40 0.60 93.9 99 .6 4.88 0.28 265.7 13.3 0.90 127.2 94.9 99.7 99.8 96.1 9H.8 112 .7 114.1 191.9 213.6 215.8 93.1 100.9 101.7 D-70 6 98.8 13.85 1.43 86.6 98 .7 191.9 21.7 2.2 7.84 0.76 88.9 99.0 93.1 91.5 99,3 227.. 1. 238 = 3 239.7 118.1 125 .1 126.0 109.0 113,2 113.7 D-78 7.04 0.89 93.7 99 .3 6 118.1 227.1 11.2 1.4 94.7 99.4 4,20 0.48 109.0 99.6 95.9 320.2 338.1 340.4 163.5 174 .7 176.2 156.7 163.4 154.2 D-80 6 163.5 ! 11.24 1.49 92.8 99 .2 94.1 99.3 320.2 17.9 2.3 156.7 6.70 0.78 95.4 L 99 = 5 308.9 352.3 354.5 159.0 185 .6 187.0 149.9 166.2 167.5 D-84 7 159.0 26.57 1.46 85.0 99 .2 87.1 99.4 308.9 43.4 2.2 149.9 16.81 0.77 89.5 99.5 120.4 1/6 .0 177.5 237.4 344.4 346.6 L17.0 168.3 169.1 D-87 8 120.4 55.64 1.45 67.8 99 .2 237.4 L07.0 2.2 117.0 51.32 0.79 68.5 99.4 69.2 99.5 kve Std &ve Std m Q) D. ( ) 4 (5) D. (4) 129.6 24.8 18.10 18.08 1.22 129.6 147 .7 149.0 122.1 0.35 24.8 31 .4 31.5 23.9 87.9 99 .2 9.7 0.3 i 13.45 17.34 0.64 0.20 L22.2 135.6 136.3 251.8 31.0 30.2 30.3 48.6 35.8 23.9 99.5 90.7 0.2 9.9 1.9 0.5 251.8 283.3 285.2 48.6 61.5 61.7 89.2 99.3 0.2 9.7 USAF EHL(K) �Averege 24D weight »ere««t IB undiluted 75 65 •H U OQ 55 — 53.76 45 - 46.24 nb 2,4,5-T ester i 35 25 ^Average 245T weight percent In undiluted haftiolde 1 2 3 4 Hu«ber of Rinses FIGURE F-fc WEIGHT FE1CEVI OF 2,4-D AND 2,4,5-T ESTERS OF TOTAL HERBICIDE IN EACH RINSE USAF EHL(K) E( -F-10 : �Figure F-2 gives, for all drums, the average accumulative mass percentage of each of these esters in the accumulative rinses. (2) An evaluation of Figures F-l and F-2 indicated that slightly more of an original mass of nb 2,4,5-T ester was removed from a drum during its first rinse than was the nb 2,4-D ester. This better proportional removal of an original 2,4,5-T mass appeared independent of the solvent volume used in the initial rinse. Apparently, in the competing solubilities, 2,4,5-T was absorbed more rapidly than 2,4-D in an initial rinse of JP-4. The proportion of 2,4,5-T decreased markedly in successive rinses because a larger fraction of it had already been removed. The accumulative three-rinse effect of this phcnomenac was less dramatic than the individual rinses but still showed a proportionately higher average removal ( 0 % of original masses of 2,4,5-T than 16) 2,4-D, respectively, from the drums. c. Estimate of Herbicide Mass in Drum. (1) The average accumulative mass of total esters in the accumulative rinses and the average mass of total esters in each rinse are plotted for each drum set in Figures F-3 and F-4, respectively. The curves in both figures were fitted by regression analyses and found to best fit power equations (Figure F-3) and exponential decay equations (Figure F-4). Data in both figures indicated that ester mass removal in the rinses was controlled by a first order absorption isotherm. There was no significant difference iri the total herbicide mass in drum set "B" and "C" ri,nses which was only 70 to 80 percent of the mass in drum set "A" and "D" rinses. (2) Drum set "A" rinses contained significantly higher amounts of total herbicide mass on a per rinse basis and on an accumulative basis. Drum set "A" rinses removed more herbicide from the drums and this set's data were used to estimate the average total herbicide mass originally in the drums. Applying the principle of first order decay, the seventh rinse or 35th accumulative gallon of rinse should remove an estimated 99 plus percent of the drum's herbicide mass. The equations of best fit were then used for the seventh rinse and 450 ( 25) grams of herbicide ^ were concluded to be the best estimate of original mass of herbicide in drum. d. Herbicide Removal Per Gallon of Rinse Used. (1) Table F-6 presents the accumulative herbicide mass per gallon of accumulative rinse for each drum in all drum sets. The data in Table F-6 were statistically compared with each other for herbicide mass per accumulated gallon of rinse. At the 95% confidence level, these comparisons showed that: �35 /•Average 24D n«TCMit in undiluted t parctat In the accurtulfttlvt a i-t H? u u 50 *Ji >H o • l! S3 nb 2,4,5-T Mter 243T parcant in th« rin«aa (4-0.60) "M.24, 243T iMdf>t parcant in undiluted harticiia 45 of RiMea 'FIGUUF-2: WEIGHT PHUCBR OF 2»4-D and 2,4,5-T KITBLf OF TOTAL HttJEClDl XI ACCUMULATED DRUM IXMOMI. USAf EHL(K) E( F-12 ) �S«t A, gal JP-4/rinae - 5/5/5 500 - - - Set D, O O " - 5/3/2 Set B, Set C. " " - 3/3/3 - 2/2/2 400 300 2« O 0 .£ i 100 D 5 10 15 20 Accumulative Rinse Volume (gal JP-4) m T9 r->. 01 25 1 2 3 4 Rinse Number FIGURE F 3 HASS OF ACCUMULATIVE HERBICIDE ESTERS IN RINSES vs ACCUMULATIVE RINSE VOLUMES AND RINSE NUMBERS -: USAF EHL(K) �500 Set A, gal JP-4/rinse - 5/5/5 Set D, " = 5/3/2 m 1 FIGURE F-^: MASS OF TOTAL HERBICIDE ESTERS IN EACH RINSE vs ACCUMULATIVE RINSE VOLUMES AND RINSE NUMBERS IJSAF FHI (K) �(a) Variances of herbicide mass per accumulated gallon of rinse for the following cases were: J. Equal for rinse gallon combinations of 5,3,5, and 2/2 and the pooled variance of these rinse gallon combinations was unequal to any other single or pooled variances. Note range of rinse gallons: 3 to 5 gallons. 2 Equal for rinse gallon combinations of 5/5, 3/3, 5/3, and 2/2/2" and the pooled variance of these rinse gallon combinations was unequal to any other single or pooled variances. Note range of rinse gallons: 6 to 10 gallons. 3 Equal for rinse gallons combinations of 5/5/5, 3/3/3, and 5^/3/2 and the pooled variance of these rinse gallon combinations was unequal to any other single or pooled variances. Note range of rinse gallons: 9 to 15 gallons. _4 Unequal for any rinse gallon combinations or their pooled variances when compared to the single rinse of 2 gal1 ons. (b) Means of herbicide mass per accumulated gallon of rinse for the following cases were: jl Equal for rinse gallon combinations of 5,3,5, and 2/2 and the pooled mean of these rinse gallon combinations was unequal to any other single or pooled mean. Note range of rinse gallons: 3 to 5 gallons. 2 Equal for rinse gallon combinations of 5/5, 3/3, 5/3, and 2/2/2" and the pooled mean of these rinse gallon combinations was unequal to any other single or pooled means. Note range of rinse gallons: 6 to 10 gallons. 3^ 3/3/3, and 5/3/2 and tions was unequal to of rinse gallons: 9 Equal for rinse gallon combinations of 5/5/5, the pooled mean of these rinse gallon combinaany other single or pooled means. Note range to 15 gallons. 4^ Unequal for any rinse gallon combinations or their pooled means when compared to the single rinse of 2 gallons. (c) Rinses with smaller volumes caused significantly higher variances in performance. The three gallon rinses had dramatically less variance than the two gallon rinses. (2) Considering these statistical evaluations, the data of Table F-6 were plotted in Figure F-5 against rinse number arid in Figure F-6 against accumulative rinse volume. Interpretation of these figures indicated that: E-(F-15) �TABLE F-6: Accumulative Herbicide Mass Per Gallon of Rinse Ace. Mass of Herbicide Esters Per Ace. Gal. Rinse (gm/gal) Drua Set A Rinse Number/ Ace. Rinse Volume (gal JP-4) -Si B 'f X s S2 41.31 3.3 90 37.24 27.51 36.58 38.19 29. 3O 35.59 5.16 26.64 2/6 3/9 25.07 31.17 61.02* 34.92 2.0 92 25.27 41.82 17.42 2.3 09 41.57* 2.0 34 19. 6O 17.33 2.6 79 .57.95 31.24 63 .8 4O.67 21. 1O 40 .6 1.8 64 C 2.6 47 1/3 Set 2.9 92 26.13 25.39 1.9 89 2.9 49 28.33 2O.21 62.77 7.16 51. 3O Rinse Number/ Ace. Rinse Volume (gal JP-4) Drum 3/15 45.63 58.60 102.67* 67. OO 56. 1O 4.0 27 77.67 s S2 2/10 7.2 06 63.14 6.8 85 52. OO 68.58 61.54 5.6 49 X Ace. Mass of Herbicide Esters Per Ace. Gal. Rinse (gm/gal) 1/5 13.11 171.79 3/6 1O4.7O 42.15 2 . 08 8 55. 03 5.8 66 41.78 7.5 00 5.8 80 2.0 83 1.2 90 37. 3O 38.23 2.8 82 4.7 70 39.15 91.36 23,30 529 4.9 5O.26 13.82 110 9.9 33.91 9.27 85.95 1/5 2/8 3/10 27.20 3.8 48 2.0 67 2.9 97 21.94 2.9 79 21.58 23.97 4.6 22 : 3.4 40 4.8 74 4.4 40 4.5 30 35.45 3.6 46 50.35 9.72 94.57 35.42 ! 28.52 6.17 76 .9 59.15 38.11 > 79. 05 52.25 1O2.2O 1O1.10 77. 4O ! x" s 38 .6 S2 14.93 i 2/4 1/2 D 128 2.5 42.24 53.14 3.8 : 83 45.42 6.4 40 61.78 X 1 s2 s : i ! *Considered to be a possible outlier and not used in statistical calculation. USAF �FIGURE F-5: CO IH Average Mass of Accumulated Herbicide Esters Per Gallon of Accumulated Rinse vs Rinse Numbers Set A, gal JP-4/rinse = 5/5/5 Set D, " = 5/3/2 Set B, " = 3/3/3 Set C, " = 2/2/2 •- Mean Value for Sets A, B, and D 110 CO/—s 10O •H e o Eft 0> CO C -P Ti C3 Oi •H -P 3 05 u o o 90 80 7O GO 0 03 O 01 5O aa 4O mo e> SH >o 30 20 10 0 1 2 Rinse Number 0 Rinse Number USAF EHL(K) �110 en •p <B/—\ Set A, gal JP-4/rinse Set D, Set B, Set C, 1OO W i-l CO fl> 5/5/5 5/3/2 3/3/3 2/2/2 9O O •H .0 it Oi om M C 8O •rt •OK o> 7O M-P am 6O CB o^ •a; o u o OQ «H O m o) c 13 © 5O 4O So 0>iH (BO h CO Si > O 0:0. 3O ^ 20 O 4 6 8 10 12 14 16 Accumulative Rinse Volumes (gallons JP-4) FIGURE F-6: Average Mass of Accumulated Esters Per Gallon of Accumulative Rinse vs Accumulated Rinse Volumes USAF EHL(K) �(a) Herbicide removal per gallon of solvent was essentially independent of any two applied rinse volumes whose accumulative total volume was <5 gallons, 6 to 10 gallons, and 11 to 15 gallons. However, a more consistently average pcrformancc could be expected if volume per rinse were maximized within each of these volumetric groupings, i.e., use a single rinse of 5 gallons if total rinse volume is <5 gallons; use two rinse volumes of 3/3, 4/4, or 5/5 gallons if total rinse volume is between 6 and 10 gallons; etc. (b) The difference in average performance diminished between rinse sets on the third rinse because 350% of the herbicide had been removed from the drum and each rinse set had approached its respective plateau for herbicide removal per rinse (see Figures F-3 and F-4). c. Estimate of Herbicide Removal Efficiency. (1) The accumulative mass of total herbicide in each rinse volume was compared to the estimated 450 grams of total herbicide in each drum. Percent removal of this estimated amount of herbicide after two rinses was 79.1% for "A", 63.0% for "D", 47.3% for "D", and 4 . 7 for "C." Regardless of rinse 4.% volume used, the third rinse improved the overall herbicide removal efficiency by less than 3%. (2) Percents of original herbicide remaining in the drum were calculated for each drum set and plotted against accumulative rinse volume in Figure F-7. The five gallon rinses left 15 to 30 percent less herbicide in the drums than did any other rinses. It was thus concluded that given two or three rinses whose total volume was less than 10 gallons, the optimal removal efficiency (79.1% for the total gallons used) was achieved using two rinses of five gallons each. 6. Conclusions and Recommendations a. Herbicide mass removal from the drums using JP-4 appeared to be dependent upon the applied rinse volume and to follow a first order absorption isotherm. b. Accumulative mass of herbicide in the accumulative JP-4 rinses were fitted quite well to exponential curves which were used to estimate the original mass of total herbicide in the drained drums: 450 (+^ 25) grams. c. Based upon the original weights of 2,4-D and 2,4,5-T esters in the herbicide, proportionately more 2,4,5-T ester mass than 2,4-D ester mass was removed in the first JP-4 rinse. These proportions reversed during the following rinses, but the accumulative effect was that about 106 percent more 2,4,5-T ester mass was removed than was the 2,4~D ester mass. E-(F-19) �90 a c Set Set Set Set 80 faO 70 (S 60 CO (0 CO 5O S> A, gal JP-4/rinse = 5/5/5 D, " = 5/3/2 B, " = 3/3/3 C, " = 2/2/2 4O E •a to o 5O 0> 20 c 0) o 10 S-. £ O O 6 8 10 12 14 16 Rinse Volumes (gallons JP-4) FIGURE F-7: Percent of Herbicide Mass Remaining in Drums vs Applied Rinse Volumes USAF EHL(K) �d. Removing drum ends and spraying the rinse downward through an open drum would provide.better herbicide removal efficiency per gallon of rinse used. This is because successive rinses could be thoroughly drained from the drum. Since such draining could not be achieved in this test program, 10 to 25 percent improved results could be expected depending on rinse volumes used. c. Depending on ultimate drum disposal, desired drum cleanliness, and availability of rinse (JP--4), this program concluded that under the following two constraints, separate rinse procedures could be used to obtain maximum results: (1) Limited supplies of JP-4 rinse (-5 gallons per drum) and some cleaning desired. Use the five gallons in a single rinse to obtain minimal variation of drum cleanliness. Any volumetric rinses totaling five gallons per drum would remove about the same herbicide mass but would be more variable in performance. (2) Up to 10 gallons of JP-4 rinse available per drum and optimal drum cleaning required—use two rinses of 5/5 gallons to remove the most herbicide from the drum, i.e., 79% compared to 45 to (>3% for the rinse volumes of 2/2/2, 3/3/3, or 5/3/2 gallons. (3) A third JP-4 rinse equal to or less than 5 gallons would not improve the overall removal efficiency by more than 3%. .f. No evidence exists to indicate that contaminated JP-4 could not be used to achieve the same drum cleaning performance as unused JP-4. g. Calculations based on an average TCDD concentration of 13.25 mg/kg of herbicide showed that the mass of TCDD in these drained drums was 5.96 mg. This calculation of TCDD mass in the drum before and after rinses presented the worst case for all herbicide stocks because the TCDD in these 28 drums was 7 times greater than the average TCDD concentration in the Air Force stock (see paragraph 2.2). If TCDD removal efficiency was equal to the herbicide esters, then 1.25 mg of TCDD would have been in the drums after two JP-4 rinses of 5/5 gallons. Rinse samples were not analyzed for TCDD but were saved for analyses should they be needed to select a final drum disposal method. h. The data of this study can be used to determine the volumetric rinses of unused or contaminated JP-4 needed to meet any prescribed drum cleaning requirements. E-(F-21) �(This page intentionally left blank) �WEST COAST TECHNICAL SERVICE, INC. APPENDIX G (TO APPENDIX E) ORGANIC ANALYSES OF BLENDED HERBICIDE, COMBUSTION AND SCRUBBED EFFLUENT GASES, SPENT SCRUBBER WATER, AND RESIDUES �APPENDIX G TAHI.E OF CONTENTS Paragraphs Page; I Procedures G-l II Calibration 0-2 [II Recovery Efficiency G--3 IV Work Up and Analysis of Sample G-4 V General Comments G-6 VI Results G-8 Tables Page G-1 Composition of 111 ended Herbicide Feed (weight percent except as noted) G- 9 G-2 Composition of Combustion Gas Sampling Train Impingcr Samples (micrograms per total sample as compound except as noted) G-1Q G-3 Composition of Scrubbed Effluent Gas Sampling Train Impingcr Samples (micrograms per total sample as compound except as noted) G-18 G-4 Total Quantity of Material Present on Particulate Sampling Filters (micrograms per total sample as compound except as noted) G-26 G-5 Composition of Gas Sampling Probe Rinses (micrograms per total sample as compound except as noted) G-28 G-6 G-30 Composition of Miscellaneous Samples Related to Gas Sampling (micrograms per total sample as compound except as noted) G-7 Extractables from Fresh and Spent Scrubber Water (inicrograms/liter of compound except as noted) G-33 G-8 Composition of Sediment fron Spent Scrubber Water Holding Tank (micrograms as compound except as noted) G-35 G-9 Compositionof Combustion Chamber Residue (micrograms of compound per 100 grams of residue) G-36 E-(G-i) �WEST COAST TECHNICAL SERVICE INC I 17605 FAB RICA WAY, SUITE D / CERRITOS. CA 90701 REPORT Oate/ February 1, 1974 P-o- no-/ Prepared Dr. R. P. Babbitt Job DO./ 5252 805137-1 for/ The Marquardt Company 16555 Satlcoy Street Van Nuys, California 91409 The samples from the combustion of liquid herbicide have been analyzed by gas chromatography, combined gas chromatographymass spectrometry, and/or atomic absorption. The various samples were processed prior to analysis by one of the procedures described below. In addition, extraction efficiency, sensitivity and detection limits for the various compounds were determined. These data are given below: I Procedures A. Equipment 1. Mass Spectrometer A DuPont Model 490 Mass Spectrometer was used for identification of the various components. The mass spectrometer was connected to the gas chromatograph ' through an all glass jet separator. All spectra were taken at an ionizatlon voltage of 70e.v. The spectra were recorded on a recording oscillograph. 2. Gas Chromatograph A Varlan Model 2700 Gas Chromatography equipped with a flame lonizatlon detector was used for separation and quantization of all volatile components. The operating parameters were as follows: Column -10 ft. x 1/8 inch stainless steel packed with 5% OV-17 on Chromsorb G (AW DMCS) Detector - 325° C Injector - 310°C Flow Rate - 22cc/minute Column Temperature - 165° - 310°C at 10°C/minute 3. Atomic Absorption A Perkin-Elmer Model 403 Atomic Absorption Spectrometer was used for determining the iron content of certain samples. The aqueous solutions were run against standard iron solutions. The iron content of the blended herbicide was determined by diluting the sample with xylene and running against an organo-lron standard dissolved in xylene. Tnie report pertains only to the samples Investigated and does not necessarily apply to other apparently Identical or similar materials. This report to submitred tor tho exclusive use of the client to whom It Is addressed. Any reproduction of this report or use of this Laboratory's name far advertising w publicity purposes without written authorization Is prohibited. �WEST COAST TECHNICAI/SEIWCE INC. The Marquardt Company Dr. R. P. Babbitt February 1, 1974 J/N 5252 Pago 2 II Calibration A standard solution containing th« following material was prepared in benzene. This solution was used for calibration and determination of recovery efficiency. The solution contains 500 mlcrograms of the following compounds per mlUlllter of solution. 2, 2, 2, 2, 2. 2, -dlchlorophenoxy acetic: acid , 5-trlchlorophenoxy acetic acid, -dlchlorophenoxy acetic acid butylester . 5-trichlorophenoxy acetic acid butylester , 5-trlchlorophenoxy acetic acid octylester -dichorophenol In addition, the standard contained 51 micrograms of 2,3,7,8tetrachlorodlbenzo-p-dicxin per millillter of solution. The standard solution was treated with dlazomethane to convert the acids and phenol to the esters and ether. The sample was then diluted to volume and injected into the gas chromatograph, and the response of the various components determined. The detection limit for these compounds was determined. Since all test samples were taken to a final volume of 25 mlcrollters. the absolute detection limits for the various components were calculated based on this volume. These limits are, therefore, the limit for the quantity present in the total sample. The detection limits for the components of the standard solution were as follows: Detection Limit Nanograms/Total Sample 3 2,4-dichlorophenoxy acetic acid (methylester) 2,4,5-trlchlorophenoxy acetic acid (methylester) 2,4-dichlorophenoxy acetic acid butylester 2,4,5-trlchlorophenoxy acetic acid butylester 2,4,5-trichlorophenoxy acetic acid octylester 2,4-dlchlorophonol (methylethor) ' 2,3,7,1-telrachlorodibenzo-p-dioxin 22 21 23 21 19 29 22 Previous calibration and stability tests show the detection limit to be valid to * 10% of the value. E-(G-2) �WEST COAST TECHNICAL SERVICE INC. The Marquardt Company Dr. R. P. Babbitt February 1, 1974 J/N 5252 Page 3 III Recovery Efficiency The efficiency of extraction for the various compounds from a water solution was determined as follows: * 1.00ml of the standard solution described in II above was pipetted into a 1 liter beaker. The benzene was removed under a nitrogen stream at 40°C. 500ml of tap water was added and the solution mixed. The water solution was then added to a separating funnel, made acid-pH-2, and extracted four (4) times with 50ml portions of diethylether. The ether extracts were combined, dried over anhydrous sodium sulfate, filtered and evaporated to a volume of 5cc. Excess diazoinethane in ether was added and allowed to stand for 15 minutes as the solution evaporated under nitrogen at 40°C. The extract was then diluted to 1.00ml with benzene and analyzed by gas chrorr,atography. A 1.00ml volume of the standard solution was evaporated to dryness and treated with excess diazomethane for 15 minutes. The ether was then removed and the mixture diluted to 1.00ml with benzene. This solution was then analyzed by gas chromatography. The recovery efficiency was calculated as the percentage of the standard components extracted from the water solution relative to that from the esterfled standard solution. The recovery efficiency of the standard components were found to be as follows: Efficiency of Recovery 2,4-dichlorophenoxy acetic acid. 2,4,5-trichlorophenoxy acetic acid 2,4-dichlorophenoxy acetic acid, butylester 2,4,5-trichlorophenoxy acetic acid butylester 2,4,5-trichlorophenoxy acetic acid octylester 2,4,-dichlorophenol 2,3,7,8-tetrachlorodibenzo-p-dioxin E-(G-3) 92% 92% 96% 98% 97% 72% 93% �WEST COAST TECHNICAL SERVICE INC, The Marquardt Company Dr. R. P. Babbitt February 1, 1974 J/N 5252 Page 4 IV Work Up and Analysis of Sample A. Analysis of blended herbicide samples 0.5ml of the blended herbicide was tested with excess diazomethane to convert any acid or phenol present to the more volatile methyl derivation. The ether was removed at 40*C under a stream of nitrogen. The samples were then chromatographed and the composition of the mixture determined. The identity of the various components was determined, on the first sample by a use of the combined gas chromatography-moss spectrometry. Subsequent samples were analyzed by gas chromaitography only using the retention time from the original gas chromatography-mass spectrometry run for Identification. B. Analysis of combustion, scrubbed effluent)and miscellaneous gas implnger samples The quantity of the benzene solutions was determined and recorded.. The benzene was removed by distillation. The residue was treated with excess dlaxomtthaiM in ether for IS minutes and the ether removed at 40* C under a stream of nitrogen. The residue was then diluted to 25 microliters with methylenechlorlde and analyzed by gas chromatography. Combined gas chromatography-mass spectrometry was used to identify the various compounds in the first sets of samples. Subsequent samples were analyzed by gas chromatography using the retention time data for identification. The water layer from those samples which contained water were acidified to pH-2 with hydrochloric acid and extracted four (4) times with ether. The ether was dried over anhydrous sodium sulfate. The ether extract was then added to the corresponding benzene solution or treated with diazomethane and processed in a corresponding manner. E-(G-4) �WEST COAST TECHNICAL SERVICE INC. The Marquardt Company Dr. R. P. Babbitt February 1, 1974 J/N 5252 Page 5 C. Analysis of fresh and spent scrubber waters 500ml of the scrubber water sample was acidified (pH-2) with concentrated hydrochloric acid. The water solution was then extracted four (4) times with ether. The ether was than dried and evaporated. The extract was treated with excess diazomethane after which the solvent was evaporated and the residue diluted to 25 microliters with methylenechloride and analyzed by gas chromatography. Combined gas chromatography-mass spectrometry was used to identify the various components from the first runs. Subsequent samples were analyzed by gas chromatography using the retention time data for identification. The presence of 2,3,7,8tetrachlorodibenzo-p-dioxin in sample III SSW TBC was confirmed by gas chromatography-irass spectrometry. D. Analysis of combustion chamber residues The hard carbonaceous reside was pulverized. A 100 gram sample was then extracted four (4) times with a boiling mixture of 75% benzene -25% methanol. The extracts were combined and the solvents removed by distillation. The residues were treated with excess diazomethane, concentrated and diluted to 25 microliters with methylenechloride. The residues were analyzed by gas chromatography. Combined gas chromatography-mass spectrometry was used to identify the various components. Five grams of the carbon residues were ignited in a platinum crucible. The ash was treated with hydrochloric acid and diluted to 25ml. The acid solution was then analyzed for iron by atomic absorption. The ash content was determined by thermogravimetric analysis in air. The sample began to lose weight (undergo oxidation) at approximately 525°C. The carbon was completely oxidized by 725°C. E. Analysis of spent scrubber water sediment The dark precipitate from the scrubber water sample was separated by filtration through one micron glass filter and washed with 60ml of deionized water. The residue was air dried and weighed. The residue was then treated in the same manner as the combustion chamber deposit. E-(G-5) �WEST COAST TECHNICAL SERVICE INC. The Marquardt Company Or. R. P. ^abbitt February 1, 1974 J/N 5252 Page 6 F. Analysis of paniculate filter samples The filters were extracted four (4) times with hot benzene. The benzene was then removed by distillation. The residue was treated with excess dlazomethane and the solvent evaporated. The residue was then diluted to 25 mlcroliters with methylenechloride and analyzed by gas chromatography. Combined gas chromatographymass spectrometry was used to identify the various components. The benzene insoluable material was then extracted with hot 5% hydrochloric acid. The extract was then diluted to 25ml and analyzed for iron by atomic absorption. V General Comments The presence of ionol and dldecylLphthlate in several of the samples is most probably due to contamination. Since these compounds are used extensively as an anti-oxldant and plasticlzer, respectively, in plastics, then presence is quite frequently encountered. These compounds could have been picked up from the sample bottles, screw caps, plastic tubing or from the work area atanonphere. / The absence of blphenyl in the combustion gas and scrubber water while seen in other samples, raises certain questions. It is possible that the blphenyl was not observed In the combustion chamber gases as a result of peak interference. Its absence from the spent scrubber water is most probably due to its being removed by the hot water vapors. Since the blphenyl has a very low solubility in water and the presence of the salt and caustic further reduce this solubility, there Is no driving force to retain it in the water phase. The detected biphenyls were unchlorinated. The presence of butylalcohol was specifically monitored in the spent scrubber water and scrubbed effluent gas since it is a hydrolysis product of the principal herbicides. It was possible that some butylesters of the herbicide would survive the combustion and react with the hot caustic solution. Saponification could then occur producing the acid salt and butylalcohol, The absence of butylalcohol therefore eliminates the possibility dt the ester reaching the scrubber and being hydrolyzed. E-(G-6) �WEST COAST TECHNICAL SERVICE INC. The Marquardt Company February 1, 1974 Dr. R. P. Babbitt J/N 5252 Page 7 There was no evidence for the presence of aldehyde in the combustion gases. This was substantiated by the fact that the several peaks Identified as aliphatic and aromatic hydrocarbons occurred both in the combustion gas and spent scrubber water samples. If aldehydes had been present in the combustion chamber, they would have undergone further reactions in the presence of hot aqueous caustics and not been detected in the spent scrubber water. The bulk of the residues on the paniculate sampling filters appeared by visual examination to be sodium chloride. The only analysis which was carried out on these residues was for iron and volatile organic compounds. It is difficult to fully explain the presence of the phenoxyacetic acid in sample III RACC-2, combustion chamber residue. It would appear that it arises directly from the blended herbicide feed since it is present as the butylester in the range of 0.02% to 1.64%. It would therefore appear that the compound exhibits a higher stability than the other products in the zone where the carbon deposit occurs. No attempt was made to identify the positional isomers of the monochlorophenol or the dichlorophenol. It is reasonable to assume that the monochloro derivitive is a mixture of ortho and para isomers, since these are the normal products from the preparation of chlorophenol. It is also reasonable to assume that the dichlorophenol is 2,4-dlchlorophenol since it is a reactant in the preparation of 2,4-dichlorophenoxy acetic acid. The identity of specific aromatic and aliphatic hydrocarbon was not undertaken. The mass spectrometry of these materials showed them to contain no chlorine. The aromatic hydrocarbons were distributed around the C^ substituted benzene derivation. These compounds also appeared to have saturated sldechain. The amount of these aromatic hydrocarbons was therefore .calculated as butylbenzene. The aliphatic hydrocarbons in the system spanned the range of Cy through Cjg. The preponderance of them was centered at CJQ. These compounds were therefore calculated as C 1(^32 even though many of them appear to be unsaturated. E-(G-7) �WEST COAST TECHNICAL SERVICE INC. The Marquardt Company Dr. R. P. Babbitt February 1, 1974 J/N 5252 Page 8 VI Results The results of the various analyses are given in the following tables. If we can be of any further assistance, please do not hesitate to contact us. Respectively submitted, WESTSCOASMEOHNICAL SERVICE INC. fisher, Ph.D. (dent-Technical Director HDF/lp P.S. Reported values were not adjusted for analytical recovery efficiencies but all the reported detection-limits were. E-( (3-8 ) �TABLE G-l COMPOSITION OF BLENDED HERBICIDE FEED (weight percent except as noted) I BH 62/63 64/65 Dichlorophenol T richlorophe nol Phenoxy acetic acid butylester 2,4-dichlorophenoxy acetic acid 2,4.5-trichlorophenoxy acetic acid 2.4-dichlorophenoxy acetic 71 acid-butylester n Monochlorophenoxy acetic jo. acid-octylester 2,4,5-trichlorophenoxy acetic acid-butylester 2,4,-dichlorophenoxy acetic acld-octylester 2,4,5-trichlorophenoxy acetic acid - octylester 2,3,7,8-tetrachlorodibenzop-dioxin Iron Total n BH 76/77/91 HI BH 78/80/ 89/92 IV BH 86/87/90 V BH 71/81 82/84 VI BH 66/83 85/88 vn BH vm BH 69/73 68/70 74/75 1.86 .61 .63 .03 .78 .08 .82 .09 .52 .55 2.97 1.64 2.00 1.16 2.13 1.12 .02 .08 ,33 .38 .28 1.27 .85 .79 .53 .44 .33 .33 .14 1.47 1.64 .96 .48 .37 .28 .32 .24 .94 .72 .82 50.35 52.02 53.14 52.99 52.71 47.59 49.25 49.15 .43 .34 .27 .29 .00 .76 .66 .60 44.46 45.30 44.41 44.29 45.21 41.23 42.15 .77 .73 .32 .31 .32 .06 1.24 1.13 .49 .06 ,04 .19 .00 .09 1.25 1.15 12ppm* 7.2ppm* 14ppm* 6.7ppm* 12ppm* 12.3ppm* 13ppm* 6.2ppm* 14ppm* 9.1ppm* 100.00 100.00 100.00 100.00 100.00 llppm* 8.2ppm* 99.98 16ppm* 14.3ppm* 100.01 14ppm* 7.6ppm* 99.97 43.21 * ppm by weight (mg/kg) WEST COAST TECHNICAL SERVICE INC. �TABLE G-2 OOMPOSmON OF GOhBUSTKM GAS SAMPLING ' O4PINGER SAMPLES icrograras per total sample as compound except t Detection Units* ICG-1 Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dichkiroDhenoxy acetic add Gnetnyiester} 2,4,5-trichk>rophenoxy acetic acid fcsethyiester) 2.4,-dlcnloropnenoxy * acetic acid - butytester 2.4,5-trichlorophencDcy acettc add - butytester lonol Didecylphtnlafe Biphenyl 2.3,7,8-tetrachlorodlben p-dtoodn calculated calculated calculated calculated K3G-3 ICG- 3.2 4.1 51.9 2.1 2.9 2.7 m^^^^^^m D.lf 0.18 as as as as ND ND ND 0.18 ND 146 ND ND ND ND ND ND ND ND ND ND 0.18 0.22 0.22 ND ND ND ND S.1S ND ND ND ND 0.15 ND ND ND ND 0.17 ND 1.67 14 ND ND 3.2 1.5 ND ND 4.3 1.5 ND ND 4.9 0.6 ND 0.15 0.18 0.18 0.18 ND ND ND ND 0.16 647 Total volume of solution (ml) (1) (2) (3) (4) 362 83 ICG-2 249 272 213 ND •c Based on flow data furnished by EHL/li butylbenzene decane dichlorobenzene CiH^Cl2 (TABLE G-2 cont'd WEST COAST TECHNICAL SERVICE INC. following seven pages) �TABLE G-2 (cont'd) COMPOSITION OF COMBUSTION GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) ncc-1 (1) Aromatic hydrocarbons Aliphatic hydrocarbons ( ) 2 Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4 dichlorophenoxy acetic acid (methylester) er) 2,4,5-trichlorophenoxy acetic acid (methylester) er) 2,4, -dichlorophenoxy acetic acid - butylester 5r 2,4,5-trichlorophenoxy ST acetic acid - butylester lonol Didecylphthlate Biphenyl 2,3,7,8-tetrachlorodibenzop-dioxin calculated calculated calculated calculated nCG-2 HCG-3 HCG-4 Detection Limits* nanograms/liter 8.2 6.2 6.1 1,2 0.6 1.0 0.74 0.74 as butylbenzene as decane as dicnlorobenzene as ND ND ND ND 0.74 ND ND ND ND ND ND ND ND ND ND ND 0.74 ND 0.88 0.88 ND ND ND ND 0.65 ND ND ND ND 0.62 ND ND ND ND 0.67 ND ND 37.3 ND 2.2 ND ND 67.2 7.3 ND ND 121.2 223 1.4 ND 0.62 0.94 0.74 0.74 ND ND ND ND 0.65 781 Total volume of solution (ml) (1) (2) (3) (4) 314 29.3 ^ 368 320 324 1.2 * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC �TABLE G-2 (coot'd) COMPOSITION OF GOftmWSTION GAS SAMPLING TRAIN IMPINGE* SAMPLES <naerograms per ra1*1 •«••*• as compound iexcept as no«90) Detection Limits* mcG-i Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2 , 4-dichlorophenoxy acetic acid {methyiester) 2.4, 5-tricnloropbenoxy acetic add (methyfester) to 2,4, -dichlorophenoxy acetic add - butylester 2,4, 5-trfchlorophenoxy acetic add - butylester lonoi Didecylphthlate Bipbenyl 2 3 7 8tetucMorodfefnzo~ p~*dloxin Total volume of solution (ml) (1) (2) (3) (4) calculated calculated calculated calculated as butylbenzene as decane as dichlorobenzene as ZHCG-2 1DCG-3 mcG-4 100. 201. 3.2 27.1 4.3 11.2 2,5 .5.9 0.11 0.11 ND ND ND ND 0.11 ND ND ND ND ND ND ND ND ND ND ND ND 0.11 0.13 0.13 ND ND ND ND 0.10 ND ND ND ND 0.10 ND ND ND ND 0.10 ND 12.5 16.2 ND ND 0.6 • .3 ND ND 0.5 3.1 ND ND 0.6 0.2 ND 0.10 0.11 0.11 0.11 ND ND ND ND 0.10 446 360 352 410 — ~ • i i i n a a i •• • fm1m»ir tfOftO^ff vBCBr ^sWv * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-2 (cont'd) COMPOSITION OF COMBUSTION GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) IVCG-1 (1) Aromatic hydrocarbons Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichiorophenoi 2,4-dichlorophenoxy acetic acid (methylester) 2,4,5-trichlorophenoxy acetic acid (methylester) 2,4, -dichlorophenoxy acetic acid - butylester 2,4,5-trichlorophenoxy acetic acid - butylester lonol Didecylphthlate Biphenyl 2,3.7.8-tetrachlorodibenzop-dioxin Total volume of solution (ml) (1) (2) (3) (4) calculated calculated calculated calculated IVCG-2 IVCG-3 0.7 0.27 0.4 0.45 0.3 0.23 IVCG-4 0.2 0.2 Detection Limits* nanograms/liter 0.10 0.10 ND ND ND 0.10 ND ND ND ND ND ND ND ND ND ND ND ND 0.10 0.12 0.12 ND ND ND ND 0.09 ND ND ND ND 0.09 ND ND ND ND 0.09 ND 0.3 2.4 ND ND 09 : 0.6 ND ND 36.2 8.2 ND ND 1.4 ND 0.09 0.10 0.10 0.10 ND ND ND ND 0.09 524 as butylbenzene as decane as dichlorobenzene as ND 286 228 388 16.9 * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-2 (cont'd) COMPOSITION OF COMBUSTION GAS SAMPLING TRAIN MPINGER SAMPLES (micrograms per total sample as compound except as noted) VCG-1 Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dlchlorophenoxy acetic acid jaethylsster} 2,4,5-tricblorophenoxy acetic acid (metbylester) 2,4, -dtenlorephenoxy acetic acid - batytoster 2,4,5-trichlorophenaxy acetic acid - butytester lonol Didecylphthlate Biphenyl 2,3,7,8-tetrachtorodibenzop-dioxln Total volume of solution (ml) (1) (2) (3) (4) calculated calculated calculated calculated 2.7 2.5 butylbenzene decane dichlorobenzene C7H4C1? 8.7 0.3 VCG-3 VCG-4 Samples not submitted by EHL/M for analysis. Detection Units* nanoqraats/Bter 4.2 4.2 ND ND ND ND ND ND ND ND 4.2 5.0 5.0 ND ND 3.7 ND ND 3,5 ND ND 3.1 ND 5.6 7.2 ND ND 1.7 2.9 ND 3.5 4.2 4.2 4.2 4.2 3.7 ND 576 as as as as VOG-2 312 * Based on Sow data furnished1 by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-2 (cont'd) COMPOSITION OF COMBUSTION GAS SAMPLING TRAIN IMPINGER SAMPLES (mlcrograms per total sample as compound except as noted) VIOG-1 (1) Aromatic hydrocarbons Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2.4-dichlorophenoxy acetic acid (methylester) er) 2,4,5-trichlorophenoxy acetic acid (methylester) er) 2,4, -dichlorophenoxy acetic acid - butylester jr 2,4,5-trichlorophenoxy acetic acid - butylester sr lonol Dldecylphthlate Biphenyl .2,3,7,8-tetrachlorodibenzop-dloxln calculated calculated calculated calculated 2.6 0.4 0.3 VICG-3 0.3 0.3 VICG-4 0.1 0.2 Detection Limits* nanograms/liter 0.15 0.15 as butylbenzene as decane as dichlorobenzene as ND ND ND ND 0.15 ND ND ND ND ND ND ND ND ND ND ND ND 0.15 0.18 0.18 ND ND ND ND 0.13 ND ND ND ND 0.13 ND ND ND ND 0.14 ND 27.1 21.7 ND ND 3.6 2.9 ND ND 1.3 2.2 ND ND 2.1 0.8 ND 0.13 0.15 0.15 0.15 ND ND ND ND 0.13 570 Total volume of solution (ml) (1) (2) (3) (4) 29.0 VICG-2 325 315 295 * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABU G-2 (cont'd) coiiPosmoN OF ooraurriON GAS SAMPLMG TBAIN MPINGEll SAMPLES per total sanpte as compound except as noted) VHCG-1 Aromatic hydrocarbons (1> Aliphatic hydrocarbons (2) Chlorinated aroBattc hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chtorophanol Dtchlorophenol 2. sattc 2.4. S-trlchioroBtmwxy aceHc scM «a«1hylester) 1.4,-dlchiarophsnagcy aoettc acid - swcytaster 2,4. i-trtchksropfceaoKy Bid - btrtyitstor Total votuoM of solution fcsl) calculated calculated calculated calculated 1.3 07 . VBCG-3 O.C 0.5 VHCG-4 0.3 0.2 Detection Undts* >r as butylbenzene as decane as dichlorobenzene as ND ND ND ND 0.22 0.22 S 0.22 ND ND ND ND ND ND ND ND ND ND ND ND 0.22 0.27 0.27 ND ND ND ND 0.20 ND HD ND ND 0.19 ND ND ND ND 0.21 ND 19. 5 0.5 ND ND 1.0 1.4 ND ND 1.1 0.4 ND ND 0.4 0.3 ND 0.19 0.22 0.22 0.22 ND ND HD ND 0.20 €35 Bipfaenyl 2.3,7.»-letrachioTodiben«op-dtaxin (1) (2) (3) (4) 7.0 1.9 VBCG-2 315 310 295 * Based on flow data furnished by EHL/M WEST COAST TECtgnCAL SERVICE INC, �TABLE G-2 (cont'd) COMPOSITION OF COMBUSTION GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) vnicG-i Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dichlorophenoxy acetic acid (methylester) 2,4,5-trichlorophenoxy acetic acid (methylester) 2,4,-dichlorophenoxy acetic acid - butylester 2,4,5-trichlorophenoxy acetic acid - butylester lonol Didecylphthlate Biphenyl 2,3,7,8-tetrachlorodibenzop-dioxln calculated calculated calculated calculated 1.0 2.3 vmcG-3 0.3 0.7 vincc-4 0.2 0.3 Detection Limits* nanograms/liter 0.20 0.20 as as as as butylbenzene decane dlchlorobenzene C2H Cl ND ND ND ND 0.20 ND ND ND ND ND ND ND ND ND ND ND ND 0.20 0.23 0.23 ND ND ND ND 0.17 ND ND ND ND 0.16 ND ND ND ND 0.18 ND 72.8 495. ND ND 13.6 8.6 ND ND 1.3 1.0 ND ND 1.8 0.3 ND 0.16 0.20 0.20 0.20 ND ND ND ND 0.17 490 Total volume of solution (ml) (1) (2) (3) (4) 19.2 10.8 vmcc-2 290 285 285 Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �iTABLE G-3 COMPOSITION OF SCRUBBED EFFLUENT GAS SAMPLING TRAIN IMPINGER SAMPLES (mlcrograms per total sample as compound except as noted) BG-1 calculated calculated calculated calculated KG-4 Detection Limits* nanograms/liter 1.2 1.1 1.1 0.9 0.9 0.5 0.23 0.23 ND ND ND ND 0.23 ND ND ND ND ND ND ND ND ND ND ND ND 0.23 0.28 0.21 ND ND ND ND 0.21 ND ND ND ND 0.20 ND ND ND ND 0.22 ND S.4 35.2 0.25 ND 3.0 2.4 0.21 ND 0.* 0.7 0.01 ND 0.6 0.3 0.50 0.20 0.23 0.23 0.23 ND ND ND ND 0.21 448 Total volume of solution (ml) (1) (2) (3) (4) ISG-3 2.7 1.6 Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2 , 4-dichtorophenoxy acetic acid (Bethyfester) 2.4, 5-irichlarophfriKHcy acetic add (aethylester) 2.4, -dichiorapheBoxy acetic acid - butylester 2.4. S-trfehtorephenoxy acetic arid - butylester lonol Didecylphthlate Biphenyl 2.3.7, t-tetrachtorodlbeniop~dtoocin ISG-2 361 350 276 * Based on flow data furnished by EHL/M as butylbenzene as decane as dichlorobenzene as WEST COAST TECHNICAL SERVICE INC. (TABLE G-3 cont'w VB following seven pages) �TABLE G-3 (cont'd) COMPOSITION OF SCRUBBED EFFLUENT GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) HSG-1 (1) Aromatic hydrocarbons Aliphatic hydrocarbons ( ) 2 Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dichlorophenoxy er) acetic acid (methylester) 2,4,5-trichlorophenoxy acetic acid (methylester) er) 2,4,-dichlorophenoxy jr acetic acid - butylester 2.4,5-trichlorophenoxy acetic acid - butylester sr lonol Didecylphthlate Biphenyl 2,3,7,8-tetrachlorodlbenzop-dioxin calculated calculated calculated calculated HSG-3 IISG-4 Detection Limits* nanograms/liter 0.5 1.1 0.5 0.8 1.2 1.0 2.1 1.5 0.21 0.21 as butylbenzene as decane as dicnlorobenzene as C C l ND ND ND ND 0.21 ND ND ND ND ND ND ND ND ND ND ND ND 0.21 0.25 0.25 ND ND ND ND 0.18 ND ND ND ND 0.17 ND ND ND ND 0.19 ND 2.8 5.7 C.69 ND 1.5 6.0 0.39 ND 8.2 3.5 0,41 ND 17.9 2.4 0.56 0.17 0.21 0.21 0.21 ND ND ND ND 0.18 626 Total volume of solution (ml) (1) (2) (3) (4) HSG-2 342 394 380 * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-3 (cont'd) COMPOSITION OF SCRUBBED EFFLUENT GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) mSG-1 m Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2.4-dichlorophenoxy er! acetic acid (roethylester) 2.4,5-trichloropheaoxy er) acetic acid (raethylester) 2,4, -dlchlorophenoxy 9T acetic add - butylester 2,4.5-trlcnk»rophenoxy tr acetic acid - butylester lonol Didecylphthlate Biphenyi 2,3,7, l-tetrachlorodlbenzop-dioxln calculated calculated calculated calculated 1.7 4.1 IIISG-3 2.2 1.2 mSG-4 Detection Limits* nanograms/liter 1.9 1.1 0.26 0.26 as butylbenzene as decane as dlchlorobenzene as ND ND ND ND 0.26 ND ND ND ND ND ND ND ND ND ND ND ND 0.26 0.31 0.31 ND ND ND ND 0.23 ND ND ND ND 0.21 ND ND ND ND 0.24 ND 11.6 19.5 0.63 ND 2.1 1.5 0.10 ND 1.3 0.4 0.07 ND 0.4 0.3 0.12 0.21 0.26 0.26 0.26 ND ND ND ND 0.23 534 Total volume of solution (ml) (1) (2) (3) (4) 9-9 6-7 IDSG-2 468 362 340 * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-3 (cont'd) COMPOSITION OF SCRUBBED EFFLUENT GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) IVSG-1 Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dichlcrophenoxy acetic acid (methylester) 2,4,5-trichlorophenoxy acetic acid (methylester) 2.4, -dichlorophenoxy acetic acid - butylester 2,4,5-trichlorophenoxy acetic acid - butylester lonol Didecylphthlate Biphenyl 2,3,7,8-tetrachlorodlbenzop-dioxln calculated calculated calculated calculated 1.7 1.9 IVSG-3 0.3 0.7 IVSG-4 0.2 0.6 Detection Limits* nanograms/liter 0.19 0.19 as as as as butylbenzene decane dichlorobenzene CJI.C1, ND. ND ND ND 0.19 ND ND ND ND ND ND ND ND ND ND ND ND 0.19 0.22 0.22 ND ND ND ND 0.16 ND ND ND ND 0.16 ND ND ND ND 0.17 ND 53.4 50.3 0.80 ND 3.1 29.7 0.07 ND 2.9 3.8 ND ND 3.2 16.4 ND 0.16 0.19 0.19 0.19 ND ND ND ND 0.16 492 Total volume of solution (ml) (1) (2) (3) (4) 6.1 3.2 IVSG-2 406 354 324 * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-3 (cont'd) COMPOSITION OF SCRUBBED EFFLUENT GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) VSG-1 71 Si 2, i Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dlchloropnenoxy acetic acid fwethyfeeter) 2,4.5-tiichlcropteaoxy acetic acid (aethylester) 2,4,-dichioroplteaaxy acetic acid - butylester 2,4. 5-trichlorophenoxy acetic add - butylester lonol Didecylphthlate Biphenyl 2.3,7. t-tetrachtorodibenzop-dtoxin Total volume of solution (ml) (1) calculated as butylbenzene (2) calculated as decane (3) calculated as dichlorobenzene (4) calculated as VSG-2 VSG-3 VSG-4 Detection Limits* nanograms/Uter 1.1 0.4 0.7 0.6 0.7 0.6 0.6 0.23 0.23 2.3 ND ND ND ND 0.23 ND ND ND ND ND ND ND ND ND ND ND ND 0.23 0.27 0.27 ND ND ND ND 0.20 ND ND ND ND 0.19 ND ND ND ND 0.21 ND 2.7 15.3 4.18 ND 5.2 33.9 09 .0 ND 4.9 4.5 0.30 ND 5.8 8.5 ND 0.19 0.23 0.23 0.23 ND ND ND ND 0.20 610 250 424 330 * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-3 (cont'd) COMPOSITION OF SCRUBBED EFFLUENT GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) VISG-1 f 10 Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dichlorophenoxy acetic acid (inethylester) 2,4,5-trichlorophenoxy acetic acid (methylester) 2,4, -dichlorophenoxy acetic acid - butylester 2,4,5-trichlorophenoxy acetic acid - butylester lonol Didecylphthlate Biphenyl 2,3,7,8-tetrachlorodibenzop-dioxin 2.3 4.2 calculated calculated calculated calculated 1.9 3.7 VISG-3 0.8 2.0 VISG-4 0.7 1.2 Detection Limits* nanograms/liter 0.69 0.69 ND ND ND 0.69 ND ND ND ND ND ND ND ND . ND 0.69 0.83 0.83 ND ND ND ND 0.61 ND ND ND ND 0.58 ND 'ND ND ND 0.63 ND 5.7 11.0 0.98 ND 7.3 39.4 2.17 ND 1.7 1.5 1.67 ND 6.2 2.9 1.29 0.58 0.69 0.69 0.69 ND ND ND ND 0.61 520 as as as as ND ND ND ND 335 335 285 ^ Total volume of solution (ml) (1) (2) (3) (4) VISG-2 butylbenzene decane dichlorobenzene CZH Cl Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-3 (cont'd) COMPOSITION OF SCRUBBED EFFLUENT GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) Total volume of solution (ml) (1) calculated as butylbenzene (2) calculated as decane (3) calculated as dichlorobenzene (4) calculated as C.H.C1, A 4 * ND ND ND ND 0.30 ND ND ND ND ND ND ND ND ND ND ND ND 0.30 0.36 0.36 ND ND ND ND 0.27 ND ND ND ND C.25 ND ND ND ND 0.29 ND 0.6 0.4 2.05 ND 1.9 0.8 0.42 ND 0.5 0.5 0.04 NC 0.5 0.1 0.03 0.25 0.30 0.30 0.30 ND ND ND ND 0.27 450 Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dichlorophenoxy acetic acid (methylester) 2,4,5-trlchlorophenoxy acetic acid (methylester) 2,4, -dicbJcropnenGxy acetic add - butylester 2,4,5-trlchlorophenoxy acetic add - butylester lonol Didecylphthlate Blphenyl 2,3,7,8-tetrachlorodibenzop-dioxin VHSG-2 395 410 295 1.3 0.8 VIISG-3 1.0 1.1 vnsc-4 Detection Limits* nanograms/liter vnsG-i 1.1 1.1 0.2 0.7 0.30 0.30 * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-3 (cont'd) COMPOSITION OF SCRUBBED EFFLUENT GAS SAMPLING TRAIN IMPINGER SAMPLES (micrograms per total sample as compound except as noted) vmsG-i Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichioropheiiol 2,4-dichlorophenoxy acetic acid (methylester) 2,4,5-trichlorophenoxy acetic acid (methylester) 2,4, -dichlcrophenoxy acetic acid - butylester 2,4,5-trichlorophenoxy acetic acid - butylester lonol Didecylphthlate Biphenyl 2,3,7,8-tetrachlorodibenzop-dioxin calculated calculated calculated calculated 1.3 0.7 vmsG-3 0.5 0.2 VniSG-4 0.5 0.2 Detection Limits* nanograms/liter 0.28 0.28 as butylbenzene as decane as dichlorobenzene as ND ND ND ND 0.28 ND ND ND ND ND ND ND ND ND ND ND ND 0.28 0.33 0.33 ND ND ND ND 0.24 ND ND ND ND 0.23 ND ND ND ND 0.25 ND 4.9 2.2 4.37 ND 2.5 1.1 1.21 ND 0.5 0.4 0.87 ND 0.9 0.4 0.02 0.23 0.28 0,28 0.28 ND ND ND ND 0.24 470 Total volume of solution (ml) (1) (2) (3) (4) 7.0 2.2 vmsG-2 350 400 320 '* * Based on flow data furnished by EHL/M WEST COAST TECHNICAL SERVICE INC. �TABLE G-4 TOTAL QUANTITY OF MATERIAL PRESENT ON PARTICULATE SAMPLING FILTERS (nlcrograns per total sample as compound except as noted) Detection Limits mlcrograms I-P Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2.4-dfchlorophencxy acetic acid (aethylester) 2,4.5-trichlorophenoxy acetic acid (methylester) 2.4. -dlchlorophenoxy acetic add - butylester 2,4.5-trichloropnenoxy acetic add - butylester Sonol Dldecylphthlate Biphenyl 2.3,7,8-tetrachlorodibenzop-dtoxln Iron Total paniculate mass (x 103) (data furnished by EHL/M) (1) (2) (3) (4) calculated calculated calculated calculated as as as as butylbenzene decane dichlorobenzene r, H Cl n-p m-p IV-P ND 11.3 ND 4.2 ND 3.1 Sample lost in transit. ND ND ND 0.025 ND ND ND ND ND ND ND ND ND 0.025 0.030 0.030 ND ND ND 0.022 ND ND ND 0.021 ND ND ND 0.023 ND ND 0.5 ND ND ND 0.3 ND ND t ND 0.1 ND 0.021 6.025 0.025 0.025 ND 76 8. ND 69 6. ND 1016, 0.022 N/A 79.6 44.9 51.1 92.9 0.025 0.025 N/A WEST COAST TECHNICAL SERVICE INC. (TABLE G-4 coot'd next page) �TABLE G-4 (cont'd) TOTAL QUANTITY OF MATERIAL PRESENT ON PARTICIPATE SAMPLING FILTERS (micrograms per total sample as compound except as noted) Detection Limits micrograms V-P I f § Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dichlorophenoxy acetic acid (metliylester) er) 2,4,5-trlchlorophenoxy er) acetic acid (methylester) 2,4, -dichlorophenoxy »r acetic acid - butylester 2,4,5-tr ichlorophenoxy »r acetic acid - butylester lonol Didecylphthlate Biphenyl 2 "3,7,8-tetrachlorodibenzoizop-dioxin Iron Total paniculate mass (x 1O3) (data furnished by EHL/M) (1) calculated as butylbenzene (2) calculated as decane (3) calculated as dichlorobenzene (4) calculated as C H C 1 VI-P Vn-P VIU-P ND 1.3 ND 9.3 ND 3.7 ND 6.2 0.025 0.025 ND ND ND ND 0.025 ND ND ND ND ND ND ND ND ND ND ND ND 0.025 0.030 0.030 ND ND ND ND 0.022 ND ND ND ND 0.021 ND ND ND ND 0.023 ND ND 0.1 ND ND ND 0.6 ND ND ND 1.1 ND ND ND 1.2 ND 0.021 0.025 0.025 0.025 ND 1720. ND 400. ND ND 659. 1070. 0.022 N/A 167.8 88.4 114.4 191.O N/A WEST COAST TECHNICAL SERVICE INC. �TABLE G-5 COMPOSITION OF GAS SAMPLING PROBE RINSES (micrograms per total sample as compound except as noted) Detection Limits micrograms ICG-ACP Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2.4-dichlorophenoxy acetic acid (methylester) 2.4,5-trichk>rophencKy acetic add (methylester) 2,4, -dichlorophenoxy acetic acid - butytester 2.4,5-trichlorophenoxy acetic acid - butylester lonol Didecylphthlato Biphenyl 2.3.7,8-tetrachlorodibenzop-dioxln Total volume of solution (ml) (1) (2) (3) (4) calculated calculated calculated calculated HCG-ACP IHCG-ACP IVCG-ACP 66.7* 1.7 1.3 2.8 1.7 Sample rinsed into IVCG-1. ND ND 0.025 ND ND 1.38 ND ND 0.7 0.025 0.030 0.030 ND ND 0.022 ND ND 0.021 ND ND 0.023 ND ND ND ND ND ND ND ND 0.021 0.025 0.025 0.025 ND ND 0.022 265 as butylbenzene as decane as dichlorobenzene as 242 0.025 0.025 280 * Light lubrication oil; material masked other possible compounds present. WEST COAST TECHNICAL SERVICE INC. (TABLE G-5 r.ont'd next page) �TABLE G-5 (cont'd) COMPOSITION OF GAS SAMPLING PROBE RINSES (micrograms per total sample as compound except as noted) VCG-ACP f to Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2,4-dichlorophenoxy acetic acid (methylester) 2,4,5-trichlorophenoxy acetic acid (methylester) 2,4, -dlchlorophenoxy acetic acid - butylester 2,4,5-trichlorophenoxy acetic acid - butylester lonol Didecylphthlate Biphenyl 2,3.7,8-tetrachlorodibenzop-dioxin Total volume of solution (ml) (1) (2) (3) (4) calculated calculated calculated calculated VICG-WCP Sample Sample not rinsed into submitted VICG-1. by EHL/M VnCG-WCP VIIICG-WCP 0.40 0.26 1.8 0.73 0.025 0.025 ND ND 0.025 ND ND ND ND ND ND 0.025 0.030 0.030 ND ND 0.022 ND ND 0.021 ND ND 0.023 ND ND ND ND ND ND ND ND 0.021 0.025 0.025 0.025 ND ND 0.022 118 as butylbenzene as decane as dichlorobenzene as Detection Limits micrograms 415 WEST COAST TECHNICAL SERVICE INC. �TABLE G-6 COMPOSITION OF MISCELLANEOUS SAMPLES RELATED TO GAS SAMPLING (micrograms per total sample as compound except as noted) IP-1&2 Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophe nol 2,4-dichloropnenoxy acetic acid (methylester) 2,4.5-trichlorophenoxy acetic acid (methylester) 2,4,-dichlorcphenoxy acetic acid - butylester 2,4,5-trkrhtoropnenoxy acetic add - butylester tonol Didecylphthlate Bipnenyl 2,3,7, S-tetrachlorodlbentop-dk>xln Total volume of solution (ml) (1) (2) (3) (4) calculated calculated calculated calculated IIP-U2 72.1 7.4 51.2 45.6 0.025 0.025 NO ND 0.025 ND ND ND ND ND 1.3 0.025 0.030 0.030 ND ND 0.022 ND ND 0.021 ND ND 0.023 ND ND ND ND ND ND ND . ND 0.021 ND Samples not submitted IVP-1&2 ND 0.022 •(I.. ',* 65 as as as as butylbenxene decane dichlorobenzene C H Cl Detection Limits mlcrograms IHP-1&2 a. 025 0.025 0.025 400 WEST COAST TECHNICAL SERVICE INC. (TABLE G-6 cont'd next two pages) �TABLE G-6 (cont'd) COMPOSITION OF MISCELLANEOUS SAMPLES RELATED TO GAS SAMPLING (micrograms per total sample as compound except as noted) VP-1&2 Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2.4-dichlorophenoxy acetic acid (methylester) 2,4,5-trichlorophenoxy acetic acid (methylester) 2,4, -dichlorophenoxy w acetic acid - butylester 2,4,5-trichlorophenoxy acetic acid - butylester lonol Didecylphthlate Biphenyl 2,3,7,8-tetr achlorodibe nzop-dioxin f Total volume of solution (ml) (1) (2) (3) (4) calculated calculated calculated calculated butylbenzehe decane dichlorobenzene C2K C12 vnp-i&2 vmp-i&2 Detection Limits micrograms 34.7 32.1 16.2 1.7 ND ND 0.025 ND ND ND ND ND 0.10 0.025 0.030 0.030 ND ND 0.022 ND ND 0.021 ND ND 0.023 ND ND * . ( ND ND ND ND ND ND 0.021 0.025 0.025 0.025 ND ND 0.022 475 as as as as VIP-1&2 Samples not submitted. 0.025 0.025 280 WEST COAST TECHNICAL SERVICE INC. �TABLE G-6 (cont'd) COMPOSITION OF MISCELLANEOUS SAMPLES RELATED TO GAS SAMPLING (micrograms per total sample as compound except as noted) IVCG-CT through Detection Limits ICG-CT IICG-CT mCG-CT VIIICG-CT microqrams Aromatic hydrocarbons (1) Aliphatic hydrocarbons (2) Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dichlorophenol 2.4-dtehlorophenoxy acetic acid (methylester) 2,4. S-tr ichlorophenoxy m JL. acetic acid (Mthylester) f 2.4,-dtehloropnenoxy g acetic acid - butylestor -— 2.4.5-trlchioropnenoxy acetic acid - butylester fonol Didecylphthlate Btphenyl 2,3.7, 8-tetrachlorodibenzop-dloxin Total volume of sohition (ml) (1) (2) (3) (4) calculated calculated calculated calculated 12.6 0.3 16.0 32.0 Samples not submitted 0.02S 0.025 ND ND ND 0.025 ND ND 1.2 ND ND 0.1 ND ND 0.1 0.025 0.030 0.030 ND ND ND 0.022 ND ND ND 0.021 ND ND 0.023 6.5 ND ND ND •ND ND ND ND ND ND ND ND 0.021 0.025 0.025 0.025 ND ND ND 0.022 6.70 640 as butylbenzene as decane as dichlorobenzene as 0.9 70S 637 WEST COAST TECHNICAL SERVICE INC. �TABLE G-7 EXTRACTABLES FROM FRESH AND SPENT SCRUBBER WATER (micrograms/liter of compound except as noted) ISSWTBC Aromatic hydrocarbons (1) 191.5 Aliphatic hydrocarbons (2) 107.6 Chlorinated aromatic 524.1 hydrocarbons (3) Chlorinated aliphatic ND hydrocarbons (4) 52.7 Chlorophehol ND Dlchlorophenol 2,4-dichlorophenoxy acetic acid (methylester) ND er) 2,4,5-trichlorophenoxy er) acetic acid (methylester) ND 2,4, -dichlorophenoxy sr ND acetic acid - butylester 2,4,5-trichlorophenoxy -r ND acetic acid - butylester 6.3 lonol 16.9 Didecylphthlate ND Biphenyl 2,3,7,8-tetrachlorodibenzoizoND p-dioxin Butylalcohol ND (1) (2) (3) (4) calculated calculated calculated calculated NOTE: as as as as butylbenzene decane dichlorobenzene C2H Cl nssw- nissw- TBC . TBC IVSSWTBC VSSWTBC 121.0 97.2 56.4 112.5 5.1 6.2 1.2 9.6 465.1 32.3 7.2 ND 14.1 ND ND 0.2 ND ND VIISSWTBC vmssw- Detection Limits TBC pg/1 7.8 9.7 6.2 9.8 0.05 0.05 3.2 1.1 2.2 0.05 ND 0.2 ND ND 0.1 ND ND 0.1 ND ND 0.1 ND 0.05 0.08 0.08 ND ND ND ND ND 0.048 ND ND ND ND ND ND 0.046 ND ND ND ND ND ND 0.048 ND 2.6 7.2 ND ND 3.8 7.1 ND . ND 2.2 6.3 ND ND 0.5 4.1 ND ND 1.2 3.6 ND ND 0.3 7.2 ND 0.043 0.05 0.05 0.05 ND ND 0.25 ND ND ND ND ND ND ND .^ ND ND 0.047 0.05 WEST COAST TECHNICAL SERVICE INC. A VI-SSW-TBC sample was not prepared or submitted by EHL/K. (TABLE G-7 cont'd next page) �TABLE G-7 (cont'd) EXTRACTABLES FROM FRESH AND SPENT SCRUBBER WATER (micrograms/liter of compound except as noted) IFSWA Aromatic hydrocarbons (1) 13.5 Aliphatic hydrocarbons (2) 4.0 Chlorinated aromatic ND hydrocarbons (3) Chlorinated aliphatic ND hydrocarbons (4) ND ChkkTophenol ND Dlchlorophenol 2.4-dichlorophenoxy er) acetic acid (methylester) ND 2,4,5-trichlorophenoxy er) acetic acid (methylester) ND 2,4, -dichlorophenoxy it ND acetic add - butylester 2,4,5-trichIorophenoxy er ND acetic add - butylester ND lonol ND Didecylphthlate ND . Biphenyi 2.3,7,8-tetrachlorodlbenzcizoND p-dioxin ND Butylalcohol (1) (2) (3) (4) calculated calculated calculated calculated NOTE: as butylbenzene as decane as dichlorobenzene as IIFSW- mssw- A * Detection Limits Cl IVSSWCl VSSWCl VESWCl VISSWC2 1.7 3.6 0.6 0.5 15.0 0.7 5.3 2.0 1.4 1.9 0.05 0.05 0.8 0.9 1.0 0.6 0.2 O.05 ND 0.2 ND ND 0.1 ND ND 0.1 ND ND 0.1 ND ND 0.1 ND 0.05 0.08 0.08 ND ND ND ND ND 0.048 ND ND ND ND ND 0.046 ND ND ND ND ND 0.048 ND O.S 9.6 ND ND 3.4 3.5 ND ND 11.4 10.5 ND ND 8.4 8.5 ND ND 2.7 7.1 ND O.043 O.OS 0.05 0.05 ND ND ND ND ND ND ND ND ND ND O.047 0.05 M9/1 * Sample not analyzed by agreement between WCTS & EHL/K due to aluminum contamination. WEST COAST TECHNICAL SERVICE INC. No !/!!/¥!!/ or VIII SStf-Cl samples were submitted by EHL/K. �TABLE G-8 COMPOSITION OF SEDIMENT FROM SPENT SCRUBBER WATER HOLDING TANK (micrograms as compound except as noted) isswHT-2 nssw- inssw- HT-2 HT-2 Sample Aromatic hydrocarbons (1) Sample (2) apparently not Aliphatic hydrocarbons lost . submitted . Chlorinated aromatic hydrocarbons (3) Chlorinated aliphatic hydrocarbons (4) Chlorophenol Dlchlorophenol 2,4-dichlorophenoxy er) acetic acid (methylester) 2,4,5-trichlorophenoxy er) acetic acid (methyiester) 2,4, -dichlorophe noxy 5r acetic acid - butylester 2,4,5-trichlorophenoxy * sr acetic acid - butylester lonol Didecylphthjate Biphenyl 2,3,7,8-tetrachlorodibenzoizop-dioxin . Total residue (grams) of f ND ND IVSSWHT-2 ND ND vsswHT-2 Sample not submitted . vi/vn vmsswHT-2 ND ND Detection Limit- jig ND ND SSW-HT-2 0.025 0.025 - •>•' ND ND ND ND 0.025 ND ND ND ND ND ND' ND ND ND ND ND ND 0.025 0.030 0.030 ND ND ND ND 0.022 ND ND ND ND 0.021 ND ND ND ND 0.023 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.021 0.025 0.025 0.025 ND 11.3 ND 8.6 ND 9.6 ND 12.2 0.022 N/A 80600. 99200. 55700. - sample submitted Iron (micrograms/gm. of residue) (1) (2) (3) (4) calculated calculated calculated calculated as butylbenzene as decane as dichlorobenzerie as .- P 44000. N/A WEST COAST TECHNICAL SERVICE INC. �TABLE G-9 COMPOSITION OF COMBUSTION CHAMBER RESIDUE (micrograms of compound per 100 grams of residue) IRACC-2 HRACC-l HRACC-2 163.5 Samples not Aromatic hydrocarbons <1) 86.8 received Aliphatic hydrocarbons (2) at Chlorinated aromatic ND WCTS hydrocarbons (3) Chlorinated aliphatic ND hydrocarbons (4) ND ChJorophenol ND DlchJorophenol 2,4-dlchkxrophenoxy acetic add (methylester) ND 2,4.5-trichlorophenoxy acetic add (methylester) ND 2,4. -dichlorophenoxy ND acetic acid - butylester 2.4,5-trichlorophenoxy ND acetic acid - butylester ND fonol ND Didecylphthlato 9.5 Biphenyl 2,3,7.8-tetrachlorodlbenzoND p-dioxin 2.4-dtahlorophenoxy ND acetic add-octylester 2,4, S-trichlorophenoxy ND acetic add-octylester 103 Iron Not requested Ash (%) ND Phenoxyacetic acid (1) calculated as butylbenzene (2) calculated as decane (3) calculated as dichlorobenzene (4) calculated as NOR: No VIII RACC-1 s«ple was submitted by SML/K. mRACC-2 IVRACC-2 2.7 512.6 16.2 7.6 Detection Limits V/VIRACC-2 micrograms/ IQOgms. 33.9 31.4 0.025 0.025 ND ND ND 0.025 0.5 ND 6.8 ND ND 5.6 ND ND ND 0.025 0.030 0.030 2.5 ND ND 0.022 2.4 ND ND^ 0.021 551 ND ND 0.023 542 ND ND 6.2 ND ND ND ND ND ND l.C 0.021 0.025 0.025 0.025 ND ND ND 0.022 ND ND 0.020 ND 0.05 - ND 12.5 0.04 1.5 ND ND 0.020 N/A N/A 0.025 0.2 0.6 127 17.1 25.0 0.06 WEST COAST TECHNICAL SERVICE INC. �APPENDIX H (TO APPENDIX E) SAFETY AND HANDLING 1.0 GENERAL Due to the potential health hazard related to handling arid incineration of "Orange" Herbicide, special safety requirements were established per the contract and TMC safety standards. In general, the items discussed in the following paragraphs were established to insure that: • Personnel were protected against any contact with the herbicide or its possible hazardous combustion products. • No herbicide was released to the environment. • Medical surveillance of applicable personnel was provided. As applicable, many of these same safety precautions were also observed in the handling of caustic solution. 2.0 DRUM MONITORING An Inspection Log Sheet was established for each drum of "Orange" Herbicide received from the Air Force. This sheet was maintained by a TMC Safety Engineer and all information regarding the drum during its stay was recorded. Information included initial receipt data, receipt condition, results of daily inspection, transfer data, cleaning operations, and final disposal. All drums were received in good condition and no rcdrumming was required. These records are available at TMC. 3.0 PHYSICAL EXAMINATIONS Complete physical examinations were performed on all TMC personnel directly involved in herbicide operations of unloading, transfer, incineration, operations and drum cleaning. Examinations were performed just prior to TMC receipt of the "Orange" Herbicide, and repeated after the program was completed. Although intermediate examinations were authorized if warranted by exposure problems, none were required. Examinations included a routine history and physical, chext x-ray, and special attention directed to skin and liver. Laboratory procedures included complete hemogram including hematocrit and platelet count, prothrombin time, serium lipids, S-GOT, S-GPT, serium bilirubin, blood glucose, and complete urinalysis. Examinations were conducted at the Van Nuys Medical Clinic, Panorama City, California and the records will be maintained at TMC until at least November, 1976. E (H-l) �4.0 EQUIPMENT AND FACILITIES 4.1 Personnel Protective Gear The following gear was worn by personnel during transfer or other operations where direct contact with the herbicide was possible: • MSA Cyralon Gloves • MSA Yellow Plastic Suits • Tingley 10" Neoprene Boots • MSA Face Shields Personnel requiring gas masks (including AF) were issued MSA Rocket Propellant Masks No. EF-86847 with Cannisters, Type GMC-S, P/N 05-84908, suitable for use with "Orange" Herbicide, phosgene, or HC1. MSA hard hats were also issued and required in the test area. «• 4.2 Special Equipment » In addition to the normal equipment used in this type of facility operations, the following special items were provided: • "Orange" Herbicide drums were transported with a fork lift drum handling fixture. This fixture was securely attached around the drum's entire circumference, and allowed the drum to be rotated for draining. • Barrel pumping was performed with a pneumatic device which forced the fluid through a hose assembly. This device removed all but about two quarts of "Orange" Herbicide from the drum while the drum was in its normal upright position. • A specially constructed funnel was placed in the run tank for receiving the "Orange" Herbicide from the drum pump hose. This funnel had a closed top to prevent splash or spray and included a filtering screen. • Steam cleaned 55-gallon drums were available for possible redrumming of any leaking drums. • Drums of JP-4 were stored in' the drum storage area and in the test cell area for use to wash down any spillages. • Scalable cardboard drums were available for storing any accumulated contaminated materials. • The Aero Thermo Laboratory and the drum storage area were equipped with fire protection equipment and emergency eye baths and showers. £-(H-2) �5.0 GENERAL SAFETY PROCEDURES The following paragraphs present other general safety requirements employed during this program: • Only authorized personnel (TMC personnel with physical examinations or required AF personnel) were permitted to conduct test program operations and be present in the test area during actual* testing. • The test area was bounded by safety ropes during operations. Access to the area was strictly controlled by the Test Engineer. •* All personnel within the test area during tests were required to have an approved gas mask and cannister attached to their person and available for immediateuse. • Warning signals were prearranged to notify personnel to don gas masks and evacuate the test area during the testing. • During testing the test area was monitored for the presence of phosgene gas with an MSA Model 1 kit, Universal tester (P/N 0883500) using MSA phosgene gas sampling tubes (P/N 8 8 0 . Moni99) toring was conducted in the control room, on the scrubber stack sampling platform, and within a 100-foot radius of the test «area. • Visual contact between operators and the test system was maintained at all times. • All "Orange" Herbicide transfer and cleaning operations were performed within diked areas. Drums were placed on a grounding plate during transfer. • The protective clothing described in paragraph 4.1 were required to be worn by personnel involved in all operations which directly exposed them to the herbicide or caustic solution. "*• • All spills or drips were immediately mopped up with JP-4 soaked rags. • All utensils (funnels, hoses, beakers, etc.) contacted by the herbicide were rinsed in JP-4 after each use and stored in covered containers. • All materials contaminated with "Orange" Herbicide were stored in sealed containers and disposed of by the Air Force. 6.0 INDOCTRINATION A meeting was held prior to initiating the test program to acquaint all TMC and USAF personnel with the operations to be conducted and the applicable safety requirements and hazards. Facility safety procedures were defined. Gas Masks, face shields, and hard hats were issued and their operations demonstrated. t E-(H»3) �(This page intentionally left blank) �USAF ENVIRONMENTAL HEALTH LABORATORIES Kelly AFB, TX 78241 McClellan AFB, CA 95652 APPENDIX I (TO APPENDIX E) EVALUATION AND DISCUSSION OF ORGANIC ANALYSES OF BLENDED HERBICICE, SCRUBBER WATER, COMBUSTION GAS, SCRUBBED EFFLUENT GAS, AMD RESIDUES �APPENDIX I TABLE OF CONTENTS Section 1. 2. Page 10. 11. Introduction Analyses of "Orange" Herbicide Incinerated During this Program lonol and Didecylphthlate in EHL Samples Combustion and Scrubbed Effltent Gas Volumes Per Burn Comparison of Collected Sample Data for Replicate Burns— Hydrocarbon Mass Penetration Through the TCDD, nb-Ester and Acid (of 2,4-D and 2,4,5-T) Sampling Trains Relative Pyrolysis Efficiencies of "Orange" Herbicide Incineration % Effects of Incinerator Operating Parameters Hydrocarbon Mass Penetration Through the Caustic Scrubber and Collection in the Scrubber Beckman 109A Data Compared With RPE's Herbicidal Compounds Detected in Gas Samples and 12. 13. Herbicide in Burn III EHL Samples Discussion of Conflicting Data 3. 4. 5. 6. 7. 8. 9. Related Equipment , 1-1 1-1 1-2 1-2 1-4 1-8 1-11 1-12 1-16 1-19 1-21 1-24 1-25 Table 1-1 Carbon Material Balance -'Orange" Herbicide Program 12-30 Nov 1973 1-2 1-3 1-4 1-5 1-6 1-7 1-3 Chlorine Mass Balance - Measured Vs Theoretical Values "Orange" Herbicide Program - 12-30 Nov 1973 Scrubbed Effluent Gas [x 10^ Liters/Burn) - Measured (M) Vs Calculated (C) - "Orange" Herbicide Program 12-30 Nov 1973 '..... Comparisons of Combustion System Parameters and EHL Sample Data for Replicate Burns - "Orange" Herbicide Program - 12-30 Nov 1973 Hydrocarbon Mass Collection in the TCDD Sampling Trains "Orange" Herbicide Program - 12-30 Nov 1973 Relative "Orange" Herbicide Pyrolytic Destruction "Orange" Herbicide Program - 12-30 Nov 1973 Hydrocarbon Mass Penetration Through the Caustic Scrubber (CGH vs SGH) - "Orange" Herbicide Program 12-30 Nov 1973 1-8 1-9 1-5 1-6 1-7 1-9 1-13 1-17 Summary of Hydrocarbon Compounds Collected in Spent Scrubber Water - "Orange" Herbicide Program - 12-30 Nov 73, 1-18 Comparison of Hydrocarbon Data - Beckman 109A (Scrubbed Effluent Gas), CGH, and SSWH - "Orange" Herbicide Program - 12-30 Nov 1973 1-20 •E-(I-I) �APPENDIX i EVALUATION AND DISCUSSION OF ORGANIC ANALYSES OF BLENDED HERBICIDE, SCRUBBER WATER, COMBUSTION GAS, SCRUBBED EFFLUENT GAS, AND RESIDUES 1. INTRODUCTION: This appendix contains an evaluation and discussion of all organic analyses of EHL samples; see Appendix G for data. Relationships were established between: a. Measured and theoretical combustion gas volumes. . .; b. Sample data from replicate burns. c. Combustion and scrubbed effluent gas hydrocarbon mass concentration. d. Penetration and collection of hydrocarbon mass 1n the caustic scrubber. e. Beckman 109A hydrocarbon data and TCDD sampling train hydrocarbon data. f. Hydrocarbon mass collected 1n the TCDD sampling train and hydrocarbon mass Incinerated. This.relationship was used to calculate relative pyrolysls efficiencies (RPE) for each burn. These RPE's were used in various comparisons. * 2. ANALYSES OF "ORANGE" HERBICIDE INCINERATED DURING THIS PROGRAM •• " " ' ! " a. The twenty-eight 55-gallon drums of "Orange" herbicide Incinerated during this program were from the USAF stocks at Gulfport MS. The drums were all from FSN 6840-926-9095, original Air Force Transportation Control Number of FY94617165-0001AA, and Air Force Analysis Sequence Number 18. b. Blended samples of herbicide were taken from the fuel feed tank prior to each burn. WCTS's analyses of each sample are presented 1n Table G-l, Appendix G, with reference to the EHL/K drums from which the fuel feed tank was filled. Composition of each sample was consistent with no significant variations. The 2,4-D acetic acid-butyl ester content averaged 50.9025 by weight and met Air Force procurement specifications for this compound. The 2,4,5-T acetic acid-butyl ester content,, however, averaged only 43.78% by weight and was 10% below its A1r Force procurement specification. The average weight percent of "contaminant" compounds were, in decending order, as follows: * (1) Dlchlorophenol - 1.46% plus trlchlorophenol of 0.66% to yield total phenolic contaminants of 2.12%. 1.44%. (2) 2,4-D, 2,4,5-T, and monochlorooctyl esters had a total average of (3) Acids of 2,4-D and 2,4,5-T were 0.73% and 0.52%, respectively, for total acids of 1.25%. (4) TCDD concentration averaged 13 mg/kg (ppm) of total herbicide weight (s=2 mg/kg). This composition of TCDD was 1n very close agreement with other laboratories' TCDD analyses of other herbicide samples taken from drums of Analysis Sequence Number 18. E-(M) �(5) Iron concentration averaged 9.0 mg/kg of total herbicide weight (s=2.9). Iron was considered a minor and Insignificant "contaminant" which was slowly leached from the drum walls or from materials during the manufacturing process. c. Neither 1onol nor dldecylphthlate was detected 1n the blended herbicide samples even though these compounds consistently appeared as mlcrogram quantities in nearly all EHL gas and liquid, samples. Their, presence in these samples 1s discussed in paragraph 3, this appendix. 3. IONOL AND DIDECYLPHTHLATE IN EHL SAMPLES a. lonol (2,6-d1-tert-butyl-4-methyl phenol) and dldecylphthlate [C6H4(COOCioH2l)z] were not considered products of "Orange" herbicide Incineration. Both compounds are associated with tygon tubing and plastics (plasticizers and antloxidants) which had been extensively used in the laboratory areas where gas and water sample containers were prepared for sampling. b. These compounds were not found in the blended herbicide samples, fresh scrubber water, combustion chamber coke deposits, holding tank sediment samples, the miscellaneous gas sample probe and cold trap rinses, or the "blank" benzene and acetone used in filling or cleaning the impingers. However, the compounds appeared in nearly all the gas sampling 1mp1nger liquids and spent scrubber water liquids. Their concentrations were random and could not be related between-, implngers in a series, applied caustic strength, or incineration parameters. c. Based upon factors in paragraphs 3a and b and the lack of a likely precursor mechanism for these compounds in the "Orange" herbicide incineration process, it was concluded that these compounds were contaminants not associated with "Orange" herbicide pyrolysisj see Paragraph V, Appendix G. 4. COMBUSTION AND SCRUBBED EFFLUENT GAS VOLUMES PER BURN a. The scrubbed effluent gas velocity pressures were too low (0.008 to 0.010 inches of water pressure; to be measured accurately. The error in the velocity pressure measurement was estimated by calculating carbon mass balances for burns IV, V, VI, and VII. The calculated carbon masses were 102 to 136X greater than the carbon feed into the system. (See Tables D-6 and 1-1.) This carbon Imbalance indicated that the measured effluent gas velocity pressures were inaccurate and could not be reliably used to calculate the total effluent gas volumes for each burn. b. Consequently, an alternative method for determining the total burn combustion gas volumes was to evaluate Marquardt's computer predictions of combustion gas products and gas velocities through the incinerator. In this evaluation, a carbon mass balance could not be used for the combustion or scrubbed effluent gas because neither CO? nor CO were measured in the combustion gases, the scrubber absorbed various amounts of CO?, per burn depending on the applied mass of NaOH, and the measured C02 and CO in the scrubbed effluent,. E-U-2) �TABLE 1-1: ! CAHEBS MATERIAL BALANCE "CS/.i:GiH EE33ICIDE PP.OGRAM 12-30 SOV 1973 OUT -Si'j SYdi±l Co_-;-=;tcr 1 Coke t Into CoicDusLor Holding Ta-X. •{eraicide Air Deposit ' Carbonate -articles ,'"" Ibs Ibs lei las 1 %T %T Ibs J.T %X 1 1 736.74 754.33 99.68 2.41 0.32 7.9 1.C4 112.8 14.9 2.49 0.33 239.94 j 2o9.01 0.94 O.S2 1 3.03 43.22 t 809.95 289.90 Bum So. I II III t IV Total 1= Ibs •' 99.68 £67. li 289.06 !ll3S.40 i 1135.42 2S9.77 j 2S9.U1 2.V8 0.26 0.76 12.9 1.13 3.23 2.99 -0.26 0.76 11.01 0.97 2.81 100.96 25.74 3.00 0.26 0.74 12.7.37 29.22 3.50 0.19 0.56 152.53 24.22 3.3SJ3.70 2.59 0.20 33.33 j 7.47 0.5S 2.56 J9.23 t t m i H-• >i? 99.74 1163.65 289.63 1160.96 289.01 99,77 t Vl/VII 1824.93 2SJS..63 1320.51 2S9.01 99.76 1293.18 ! 239.68 i 1290.12 289.01 99.76 Ave * 239.77 Std. +. 0.11 3. : 269.02 jy.73 O.J2 P.J; v i • VIII 2.70 0.67 0.23 4.43 0.70 0.24 3.06 0.69 I 0.24 1 "" I 10.05 2.59 |0.22 5.36 5.96 77.37 539.27 "" 225.77 _ i 0.20 .0.53 _ " i _ 17.28 942.57 2J9.92 6.23 951.29 ' 83.71 70.72 242.56 13.03 6.22 136.1 72.53 38.0f- 6.23 136.7 98.9ail31.44 7.2ob.552.73 85.08 112.52 20.87; j 246.50 17.86 _ _ - {U60.68 89.75 87.34 i 260.02 19.57 i i ; \ 1333.4 6.17 115.0 i 8.72 117. 33| 99.12 340.00 25.27 82.30 ^ 70.95 IS. 06 i 1365.33 j 117.33 102.24 I 8.79 • 96S.13 339.83 i 0.65 1S06.57 286.80 _ 0.71 2.07 1 i 44.35 17. CO 'ees.75 79.17 51.34 ~ 0.23 i 2.45 f O . 2 2 C.63 8.88 Ferce=: 31. Trial A c e 1 tea Jor byMeasure Scribed E f f l u x - : Stack. • Per Measurement i kzr Caicul. 3alar.ce C07 CO CO,* CO* Ibs 5.T Ibs ZT XT Ibi Ibs 2T 229.52 109.3561 9.61 2.59 !0.£6 27.84 1133.46 289.01 SYS'iZy 0.23 1.9C 0.66 99.74 1136.45 289.77 01' _ 118.51 ; 13.6 39.50 i 9.02 1.04 3.01 2.77 0.32 0.92 1 ; 25.45 83. 2C 241,00 _ 6.76 _ 2.00 0.69 0.77 |C.27 O.li 0.04 ! 1.29 0.45 i 28.17 i 11.59 i 9.72jO".89 J O . 31 l 1 i • 3.99 !G.54 .0.13 347.38 119.90 62.46 i 21.57 I i 9.23 240.76 2.65'i 0.9: 11.25 26.39 i : or. ;ssu=?ticr. ;;.sc 93:i o; C 2.r. eifluent g&ses was zs C02 par Bums IV, V, VI, and VII ?-r drira of htrjicida iriCiLerateu curing Bum. KOTS: All carbon spcciss expressed in pounds as carbon. %T denotes that species carbon as a percent of total carbon Into the system. 83.081 17.98 i 3.90t : C.82 6.23 0.29 USAF EKL(K) �gases could not be conveniently related to what may have been present In the combustion gases. Therefore, this evaluation was based on a chlorine mass balance of the system which considered that no chlorine as HC1, Cl2, or (Cl) escaped 1n the effluent gases and that these chlorines 1n the combustion gases were completely absorbed Into the scrubber water. This was a reasonable basis of evaluation since none of these chlorines were detected In the effluent gases—except for short periods during burns VI and VI11 when slightly less than the required amount of NaOH was applied to the scrubber. c. The total HC1,C12 and (Cl) predicted by Marquardt's theoretical analyses never exceeded 0.03 mole fraction of thi combustion gases and these gases had a calculated volume always exceeding a million liters per burn. Thus, If total calculated chlorine mass production per burn from Marquardt's theory was comparable to measured chlorine mass 1n the scrubber water, then volumes of combustion gas production per burn as calculated from Marquardt theory could be accepted. These volumes could then be used to calculate dry scrubbed effluent gas volumes which would be more accurate than those calculated from measured effluent gas velocity pressures. Table 1-2 presents the calculated and measured chlorine mass balance for each burn. The ratio of measured to calculated chlorine mass for each burn averaged 0.947 over the eight burns and had a standard deviation of 0.057. These balances were acceptably close for all burns. Marquardt's theoretical data were therefore used to calculate total dry combustion and dry scrubbed effluent gas volumes for each burn. The mass of C0£ removed In the caustic scrubber was calculated from the mass of carbonate alkalinity measured 1n the spent scrubber water. The mass of carbonate alkalinity was converted to the equivalent volume of C02* and this volume plus the volumes of HCl,(Cl), Clo and HgO were subtracted from the combustion gas volume to obtain dry scrubBed effluent gas volume. Table 1-3 presents the measured and calculated dry scrubbed effluent gas volume for each burn. Excluding burn VIII. the ratio of measured/calculated dry scrubbed effluent gas volumes per burn averaged 1.15 and had u standard deviation of 0.14. *• d. All gas volumes used 1n this report are dry volumes at standard conditions of 70°F and 29.92" of mercury pressure. 5. COMPARISON OF COLLECTED SAMPLE DATA FOR REPLICATE BURNS a. A review of Table 2 showed that burns I and II could be considered a set of burns which were conducted with poppet nozzles under nearly Identical operating parameters. Similarly, burns V and VII could be considered a different set of near-replicate burns which were conducted with radial slot nozzles under nearly Identical operating parameters. b. Each burn's datum 1n Table 1-4 compared favorably and within accuracies of measurement with Its respective replicate burn datum. The only exception to these comparable values was burn V's CCiH of 0.90 versus burn VII's CGH of 0.10. This difference was attributed to Burn V's combustion gas sample volume of only six liters versus an average of 150 liters for other burns. This small sample volume was less representative and contained hydrocarbon mass near the analytical detection limit. Since all these burns operated with very minor fluctuations of operating parameters, the comparisons of Table 1-4 data lend credence to the repllcabiHty of Incineration products as determined by reproducible sample collections and analyses. Ml-4) �TABLE 1-2 BURN NUMBER EHL(K) Measured Cl as HC1 Pounds % of Total Cl as Cl£ Pounds % of Total Cl Total Pound* EHL(M) Calculated* Cl as HC1 Pounds % of Total ui CHLORINE MASS BALANCE - MEASURED VERSUS THEORETICAL VALUES "ORANGE" HERBICIDE PROGRAM 12-30 NOV 1973 Pounds and Percent of Total I II III IV V VI/VII STATISTICS VIII MEAN STD D. 451.7 520.1 655.6 570.5 668.5 1064.9 714.9 98.5 98.6 98.9 98.6 98.1 98.8 99.5 98.7 7.4 35.0 116.8 35.5 39.0 67.5 7.1 2.0 1.5 1.4 1.4 1.2 0.5 1.3 1.1 458.8 527.5 690.6 687.3 704.0 1103.9 782.4 0.4 , 408.5 499.2 635.9 694.2 638.8 1001.1 706.5 91.5 86.4 84.0 87.5 86.8 85.9 85.1 46.3 97.0 113.7 111.8 157.2 134.1 14.9 7.0 8.5 13.2 14.1 13.6 16.0 12.5 439.4 545.5 732.9 807.9 750.6 1158.3 840.6 93.0 Cl as Clo& Cl Pound:t 30.9 % of Total Cl Total Pounds Measured/ Calculated Totals as Percent 0.4 104.4 96.7 94.2 85.1 93.8 95.3 93.1 3.4 3.4 94.7 |5.7 *EHL(M) calculated based on Marquardt theoretical as predicted by computer program. USAF EHL(M) USAF EHL(K) �SCRUBBED EFFLUENT GAS (xlO6 LITERS/BURN)* MEASURED (M) VERSUS CALCULATED ( ) C» "ORANGE" HERBICIDE PROGRAM 12-30 NOV 1973 TABLE 1-3 I I I II I MEASURED 8.38 9.04 9.14 10.12 CALCULATED 6.55 7.75 8.58 RATIO M/C *** 1.28 1.17 1.07 BURN NUMBER * Dry, at 70°F and 29.92" Kg pressure. ** Based on Marquardt's theoretical data. v VI 10.36 4.71 8.72 16.02 9.47 7.65 5.03 7.55 8.76 1.07 1.35 0.94 1.16 1.83 IV L VII VIII x 1.23 A = 0.27 For burns I thru VIII x 1,15 4 = 0.14 excluding burn VIII EHL(M) �TABLE 1-4 COMPARISONS OF COMBUSTION SYSTEM PARAMETERS AND EHL SAMPLE DATA FOR REPLICATE BURNS "ORANGE" HERBICIDE PROGRAM 12-30 NOV 1973 BURN NO. I II btay lime (sec) F/A 0.086 006 .8 2273 2286 Fuel Temp OF (±1) CGH SGH 0.16 0.15 65 97 4.02 9.59 0.081 SGBH SSWH SSWC CCD/D NOZZLE 0.6 .03 3.5 18.6 8.59 6.38 0.89 3.03 0.68 3.01 Poppet Poppet 0.90 0.055 0.10 0.076 75.7 36.5 0.13 0.22 0.62 0.60 Slot Slot Replicates ft ! V 0.120 VII 0.120 Replicates 2734 2772 0.14 0.15 99 105 0.74 0.75 CGH - Sum of aliphatic and aromatic hydrocarbons as carbonmass per liter (^g/1) in sampled combustion gas, See Table 1-6. SGH - Sum of aliphatic and aromatic hydrocarbons as carbon mass per liter (Vg/1) in sampled scrubbed effluent gas, See Table I-?. SGHB - Beckman 109A hydrocarbon data (ppm) from scrubbed effluent gas, See Table 1-9. SSWH - Total aliphatic, aromatic, and phenolic hydrocarbons as carbon mass (gms) collected in the total volume of spent scrubber water, See Table 1-8. SSWC - Carbon particles in spent scrubber water, pounds per drum of herbicide burned. CCD/D - Combustion coke deposit in combustion chamber, pounds per drum of herbicide burned. USAF EHL (K) AND (M) �6. HYDROCARBON MASS PENETRATION THROUGH THE TCDD, nb-ESTER AND ACID (OF 2,4-D AND 2,4,5-T) SAMPLING TRAINS '. a. The TCDD, nb-ester and add sampling train (TCDD sampling train) was developed and tested specifically for the mass collection of the nb-esters and acids of 2,4-D and 2,4,5-T (See Appendix D.). The collection of TCDD in the sampling trains was not tested in the laboratory. However, TCDD's vapor pressure and solubility similarities to the nb-esters of 2,4-D and 2,4,5-T were sufficient to conclude that TCDD would be collected as effectively 1n the sampling train as the nb-esters. This same reasoning could not be applied to the mass collection of nonchlorinated aliphatic and iionchlorinated aromatic hydrocarbons. However, sufficient data were collected during the field sampling program so that an assessment of hydrocarbon mass penetration (collection) through the sampling trains could be made. b. Table 1-5 presents, for each burn, the hydrocarbon mass collected in all four Impingers, the mass collected only 1n the last one of the four serial impingers, and the percent of the total mass that was collected in the last implnger. The combustion gas samples and the scrubbed effluent gas samples were grouped respectively as sets because the physical conditions (temperature, pressure, etc.) of these sampled gases were quite different. * (1) The following observations of the data in Table 1-5 were made: (a) The averages of the aliphatic and aromatic hydrocarbon masses collected 1n the last Implnger were nearly equal in both sample sets. (b) The averages of the total masses collected in all four Impingers varied significantly between sample sets. (c) The total mass collected in all four Impingers varied significantly within each sample set. (d) The mass collected in the last Implnger did not vary significantly within each sample set (relative to the variance of mass collected in all four impingers). (2) From these observations, It was concluded that hydrocarbon mass collection in the last implnger (in the series of four Impingers) was Independent of: (a) Mass loading in the first three Impingers. (b) Hydrocarbon mass concentration in the sampled gas. c. For nonchlorinated aliphatic and aromatic hydrocarbon mass collection In the last Implnger of this serial Implnger collection system to be independent of mass loading and Independent of mass concentration in the sampled gas, the mass collection efficiency 1n the first three Impingers necessarily was good for those hydrocarbons collected or It was near 0% in all Impingers. Since collection efficiency was obviously not OX, collection efficiency 1n the first three Impingers was good (for those hydrocarbons collected). However, since hydrocarbon mass was found in the last Implnger, collection efficiency 1n the Implnger sampling train was not 100%. '£-(1-8) �TABLE 1-5 HYDROCARBON MASS COLLECTION IN THE TCDD SAMPLING TRAINS "ORANGE" HERBICIDE PROGRAM 12-30 NOV 1973 COMBUSTION GAS SAMPLE SET BURN NO. I I I II I IV V VI VII VIII Total Mass (y g) Collected in all 4 Impingers Aliphatic Aromatic C6H5 (C4H9) C10H22 MassUg) Collected in Last Irnpinger Aliphatic C H 10 22 Aromatic C6H5 (C^g) 91.9 37.7 245.6 1.2 2.8 3.4 3.3 14.1 440.0 329.0 110.4 1.6 3.4 29.8 9.2 20.7 2.7 1.0 5.9 0.2 0.3 0.2 0.2 0.3 2.9 0.6 2.5 0.2 0.7 0.1 0.3 0.2 X 50.0 118.0 1.3 0.9 4 84.9 170-7 2.0 1.1 ' Aliphatic C1QH22 Aromatic c6H5 (C4H9; 1 3 3 2 17 11 6 6 2 6.2 0 2 13 21 o. 3 1 5.1 *Exclud1ru burns IV and V 5.3 3.7 7..7 1.2 V- 9 x * 4 * % of Total Mass Collected in Last Impinger 1,2 SCRUBBED EFFLUENT GAS SAMPLE SET I I I II I IV V VI VII VIII X & x ** 4 ** 4.1 4.4 13.1 6.4 4.3 11.1 3.7 3.3 5.9 4.3 15.7 8.3 2.7 5.7 3.6 9.3 0.5 1.5 1.1 0.6 0.6 1.2 0.7 0.2 0.9 2.1 1.9 0.2 0.6 0.7 0.2 0.5 12 34 8 9 14 11 19 6 15 49 12 2 22 12 6 5 6.3 3.7 6.9 4.2 0.8 0.4 0.9 0.7 14 9 11.3 4.3 16 15 10.6 6.8 ** Exclud- ng Burn II . USAF EHL/M HI-9) �d. Two potential causes for penetration of hydrocarbon mass to and through the last impinger were considered: (1) A specific nonchlorinated aliphatic and aromatic hydrocarbon or a specific group of hydrocarbons was relatively Insoluble In the benzene or, (2) a specific hydrocarbon or group of hydrocarbons was bleeding (movement of the compound down the Impinger series) due to high vapor pressure (volatility) and low concentration 1n the sampled gases. e. Solubility was dismissed as the potential cause for penetration of hydrocarbons to the last Impinger since nonchlorinated aliphatic and aromatic hydrocarbons are generally very soluble 1n benzene. f. Bleeding of a specific hydrocarbon or group of specific hydrocarbons was considered the most probable cause of mass penetration to and through the last Impinger. Discussion of this consideration Is as follows: (1) Since a gas confined (as 1n a bubble) 1n contact with a liquid will dissolve In the liquid (if soluble) until "...Its partial pressure above the liquid 1s In equilibrium with the gas dissolved in the liquid..."1 any hydrocarbons that existed 1n the sampled gas and had a significant vapor pressure at -50^ (benzene temperature during sampling) would not have appreciably dissolved (absorbed) in the benzene at concentrations less than several 1000 ppmv/v and would have bled. Since aromatic hydrocarbons with molecular weights <132.2 have vapor pressures >0.0001 mm of mercury pressure at ~50°F (100 ppm at 760 mm of mercury pressure and at saturation), these hydrocarbons would have bled (penetrated the sampling system) substantially. (2) However, nonchlorinated aromatic hydrocarbons with molecular weights greater than 200 generally have freezing points near ~50°F (temperature of benzene in the 1mp1ngers during sampling) and the corresponding vapor pressures are extremely low (<0.00001 mm mercury pressure). Thus, these compounds would have been effectively collected 1n the TCDD sampling train. An exact number for the collection efficiency of these heavy hydrocarbons (>200) was Impossible to determine objectively, however, a subjective evaluation based on previous laboratory work was made and the collection efficiency was considered =9035 for hydrocarbons with molecular weights >200. For hydrocarbons with mw<200 the collection efficiency becomes a function of their vapor pressure and mass concentration In the sample gas. A similar argument was used for aliphatic hydrocarbons. (3) At this point, two dependent conclusions were made that the hydrocarbon mass collected In the TCOD sampling trains: JPatty. Frank A., fnclustrlal Hygiene and Toxicology. Volume I, 2nd Edition, page 153. E-(I-IO) �(a) did not Include lightweight hydrocarbons (row <132) and was thus not representative of a total hydrocarbon mass 1n the sampled gas, but (b) was representative of the degree of "Orange" herbicide pyrolytlc degradation to unchlorinated hydrocarbon compounds which were considered to have no significant herblddal or toxic properties even though they were herbicide pyrolyzates. (4) This latter conclusion, 1n conjunction with the fact that hydrocarbon collection efficiency in the TCDD sampling train remained equal for all burns, permitted the hydrocarbon mass data from the TCDD sampling systems to be used as an Indicator of the relative degree of pyrolysis of Orange herbicide. Thus, relative pyrolysis efficiencies (RPEs) were calculated for each burn. The collection efficiency of specific hydrocarbons in the TCDD sampling trains did not vary between burns since the trains were operated in a consistent manner under similar sampling conditions. An RPE calculation was based on tie mass of hydrocarbons as carbon collected in a TCDD sampling train at the reaction tailpipe versus the mass of Orange herbicide as carbon Incinerated. Although these calculated efficiencies were relative to hydrocarbon mass collected rather than an absolute quantitation of all potentially existing combustion gas hydrocarbons, they provided a means of evaluating and comparing the different burns. g. The existence of nearly the same hydrocarbon mass in the last impinger from all sample trains was probable due to a combination of factors: (1) analytical accuracy decreased as the hydrocarbon mass in the sample volumes approached the detection limit, (2) hydrocarbon gas chromatographic peaks were more susceptible to Interferences, when hydrocarbon mass 1n the samples was lowest, (3) potential production of intermediate weight Orange herbicide pyrolysis products (those hydrocarbons having molecular weights between 132 and 200 and being only partially collected) may have been produced 1n a relatively constant mass concentration during all burns, h. Essentially the same hydrocarbon mass was collected in each burn's scrubbed effluent gas sampling train. This was probably caused by a relatively consistent mass of light and intermediate weight hydrocarbons (mw <200) which penetrated the scrubber and were collected by the scrubbed effluent gas sampling train. 7. RELATIVE PYROLYSIS EFFICIENCIES OF ORANGE HERBICIDE INCINERATION a. Relative pyrolysis efficiencies (RPE) of Orange herbicide were calculated for burns I through VIII and are presented in Table 1-6. Presented data are described as follows: (1) Total combustion gas volume per burn (liters) as discussed in paragraph 4, this appendix. E-(I-ll) �(2) Total hydrocarbons detected 1n combustion gas samples, divided Into two categories: the monochlorophenol and aliphatic hydrocarbons (nonchlorinated) and aromatic hydrocarbons (nonchlorinated), expressed as the: (a) actual mass of each per liter of sampled combustion gas (b) carbon mass of each per liter of sampled combustion gas (c) actual mass as carbon for each in the total burn (g). (3) Five herbicide compounds (2,4-D and 2,4,5-T nb-esters and acids and TCDD) that were undetected but could have existed without detection In a combustion gas sample — expressed as the: (a) mass of each compound as the compound per liter of sampled combustion gas (yg/1), (b) mass of each compound as carbon per liter of sampled combustion gas (yg/1), and burn (g). (c) total masses for all five compounds as carbon for a total The undetected masses of these herbicide compounds were calculated based upon an average detection limit of 22x10~9 gms per total sample for all flye compounds. This detection limit was divided by the burn's combustion gas sample volume to find the minimum combustion gas mass concentration that was necessary for detection of each of these compounds. This value was then multiplied by the total burn combustion gas volume* the average percent carbon content of these compounds, and five in order to determine the total possible undetected mass of these compounds in the combustion gas of each burn. This procedure assumed that the undetected total mass of these compounds and the detected masses of the other hydrocarbons existed evenly throughout the burn. (4) Herbicide fuel feed mass expressed as carbon mass that was injected into the combustion chamber during a burn period. (5) lonol and dldecylphthlate were not Included in Table 1-6 combustion gas sample masses since these compounds were not considered products of Orange herbicide incineration (see paragraph 3, this appendix). (6) Relative pyrolysis efficiency (RPE) was based upon the analytical values presented for each burn. (See Appendix G for analytical values.) b. One could double the total combustion gas hydrocarbon masses as carbon per burn and decrease the fuel feed herbicide carbon by 5% to test the significance of the digits of the RPE in Table 1-6. These worst case conditions would represent pooling of errors for nonrepresentatlve sampling, errors of sample analyses, and errors 1n calculating total burn volumes. This exercise concluded that the second decimal place was significant for all burns and that the third decimal place was significant only for Burns IV through VIII. 8. EFFECTS OF INCINERATOR OPERATING PARAMETERS a. Effects of various incineration operating parameters on the RPE's E-d-12) �TABLE 1-6 RELATIVE "ORANGE" HERBICIDE PYROLYTIC DESTRUCTION "ORANGE" HERBICIDE PROGRAM 12-30 NOV 1973 BURN NUMBER Combustion Gas Volume (Liters /Burn)1 I I I 6 6. 79x1 06 8. 02x1 O II I IV V VI 8. 89x1 O6 9. 79x1 Q6 7. 98x1 O6 5.21xl06 VII 7. 87x1 O6 VIII 9. 03x1 O6 Aliphatic HC2 (Unchlorinated) Hg/1 as Ci0H22 0:57 1.11 1.10 <0.01* 0.47 0.02 0.03 0.09 Vl as C g/Burn as C 0.56 3.80 0.92 7.38 0.92 8.18 <0.01 <0.01 0.39 3.11 0.02 0.10 0.03 0.24 0.09 0.81 Aromatic HC2 (Unchl ori nated )** Vl as C6H5 (C4H9) 4.26 9.68 0.49 <0.01 0.57 0.18 0.08 0.16 3.46 23.49 8.67 69.50 0.44 3.91 <0.01 <0.01 0.51 4.07 0.16 0.83 0.07 0.55 0.14 1.26 0.00013 0.00019 0.00017 0.00006 0.00009 0.00008 0.000 0.004 0.004 0.79 585776. 2.07 585714. 1 di c V g/Burn as C Herbicide HC^ - H}/1 as HC/compound 0.00016 0.00065 0.00009 0100008 0.00366 Hj/1 as C/compound 0.00008 0.00033 0.00005 . 0.00004 0.00180 0.003 0.013 0.002 0.002 27.29 342466. 76.89 393670. 12.09 515480. <0.01 * 514590. g/Burn as . C/c§mpounds TOTAL CARBON g/Burn Combustion Gas g/Burn Input * 0.072 7.25 527076. 0.93 529992. % Kelative 99.99 99.99 >99.999 99.998 99.999 99.999 99.999 99.98 Pyrolysis Efficiency 1. Based on Marquardt theoretical calculations (5ee Appendix A ; *See Discussion of Conflic 2. Calculated from hydrocarbon mass found in combustion gas impinger samples. " ting Data, page 1-25. 3. Based on the maximum mass that could have existed in the combustion gas without ** T _-I..J .ui .u—,. being detected (Sum of TCDD and the butyl esters and acids of 2,4-D and 2,4,5-T), detectedin Burn I. USAF EHL/M �of Table 1-6 were evaluated by comparing those burns that were replicate except for a change 1n only one operating parameter. Since the RPE's were almost Identical 1n value, they were not used to assess effects of changed operating parameters. Instead, the following measured/calculated data are defined and were used 1n the comparisons: (1) CGH - (See definition on Table 1-4) (2) SSWH-(See definition on Table 1-4) (3) CCD/D - (See definition on Table 1-4) (4) SGHB - (See definition on Table 1-4) (5) Contaminate mass of hydrocarbons found in the combustion coke deposit (CCH) expressed as ug/100 gms, see Table G-9, Appendix G. b. As selected from Table 2 of this report, the following burns were compared in relation to their one different operating parameter. (1) "Orange" Herbicide Preheat - Burns III and Jl (a) "Orange" herbicide fuel was preheated to 178°F (±2) in burn IV but only to 91<>F(±1) in burn III. The CGH was two orders of magnitude greater in III than IV. The SSUH of III was 2.42 gms or about ten times (on order of magnitude) the SSWH of IV (burn duration of III and IV were about equal.) Additionally, the spent scrubber water of III contained 0.25 vg/1 of TCDD which along with any of the other original herbicide compounds were undetected in any scrubber water samples. The CCD/D was 2.81 pounds for burn IV compared to 3.28 pounds for burn III. Burn Ill's CCH was 1132.6 and contained the methyl and butyl esters of 2,4-D and 2,4,5-T while burn IV's CCH weighed 542 and no methyl/butyl ester of 2,4-D or 2,4,5-T were detected. (b) A small improvement of effluent quality due to herbicide oreheating was also noted between replicate burns I and II, see Table 1-6. Although comparisons of Table 1-6 values did not show significant Improvement, the trend toward better RPE's was evident. (c) From these comparative observations it was concluded that: 1. Burn IVs RPE appeared at least one order of magnitude better than burn Ill's, and 2_. Preheating of "Orange" herbicide to ~180°F was an important operating" parameter which Improved burn IV's RPE. (2) Central Poppet Nozzle Versus Radial Slot Nozzles - Burns III and_VI: Burns ill and VI wer,e IdentlcaTIn operaffng parameters" except tTie central poppet nozzle was used in burn III while the radial slot nozzles were used in 1 burn VI. Burn Ill's CGH was about one order of magnitude greater than burn VI s CGH. The SSWH for burn III was 2.42 while burn VI's SSUH would have been 0.06 for a total burn period equal to Ill's. Burn Ill's CCD/D was �3.28 pounds versus 0.85 pounds for burn VI. As previously cited, Burn Ill's CCH was 1132.6 and herblddally contaimlnated while burn VI's CCH was only 66.9. These data demonstrated that radial slot nozzles produced significantly oetter incineration results than poppet nozzles when both nozzles were operated under identical parameters and a medium range F/A of 0.106. (3) Process Flow Rates - Burns VII and VIII; Burns VII and VIII were replicates except that the air and herBidde fuel feed mass flow rates of burn VIII were only 66% of burn VII's: 1.05 pps air/0.123 pps fuel for VIII and 1.55 pps air/0.186 pps fuel for VII. Burn VIII's CGH was about twice that of Burn VII's CGH; however, both concentrations were near the analytical detection limit and thus not sufficiently different, to allow a definitive conclusion about which set of process flows was better. Compared to equal burn durations, the SSWH and CCD/D of burns VII and VIII were very nearly equal. Analyses of combustor coke deposit from these burns were not made but there was no reason to believe their qualities differed. These comparisons showed no differences in RPE or effluent quality between these identical burns which had different air and fuel mass flow rates but identical F/A ratios. Thus without any differences, the higher process flow rate could be chosen to minimize incineration time. : (4) Fuel to Air Mass Flow Ratios and Different Nozzles - Burns I and II Versus Burns V and VII (a) As discussed in paragraph 5, this appendix, burns I and II were replicates of each other as were burns V and VII. As shown in Table 1-4, the EHL sample data values of Burns V/VII were all at least ten percent less than those for burns I/11 -- particularly noteworthy was that burns V/VII's CGH, SSWH, and CCD/D values were one order of magnitude less than burns I/II's values. The only exception was SBGH, and its Inverse relationship to RPE is discussed in paragraph 10, this appendix. (b) From these comparative observations it was concluded that the radial slot nozzle handled higher mass flow rates than the poppet nozzle and yet produced RPE's and incineration effluent quality generally one order of magnitude better. (c) Effects of Temperature on RPE 1. The relative degree of "Orange"herbicide destruction in the combustion process was not expected to be a simple function of temperature (heat energy). Other parameters such as burn velocity (stay time), burner pressure, air and fuel preheat, process flow rates, and method of fuel injection were all expected to be interrelated parameters. The following analysis of the relationship of temperature and the relative degree of "Orange" herbicide pyrolysis indicated the complexity of these interrelationships. £. For example, the average temperature (TCy\VE column 16, Table 2 and discussion, paragraph 7.2) for burns I and II was 22800 p and the TCAVE for burns V and VII was 2753° F. The RPE's in burns V and VII were significantly better than in burns I and II, 99.999 vs 99.99%. However, burn VI had an RPE comparable to that in burns V and VII, but the TCy\vE was F-fl-lfi * �2454°F, about 300°F less than in burns V arid VII and only 174°F greater than the TCAVE 1n burns I and II. In yet another case, burn IV had the highest RPE of all burns but the TCAVE was only 2508°F, 245°F less than 1n burns V and VII and only 228<>F greater than 1ri burns I and II. 3_, From these observations one might have concluded that the RPE was not Improved by Increasing TCAVE above 2454°F. In these burns and from a temperature standpoint, this conclusion would be correct. However,, other combustion parameters were changed In the burns and one could not conclude that destruction efficiency would not nave Improved with an Increase 1n temperature had different operating parameters existed. 9. HYDROCARBON MASS PENETRATION THROUGH THE CAUSTIC SCRUBBER AND COLLECTION IN THE SCRUBBER a. Table 1-7 presents each burn's CGH and SGH data. Penetration of hydrocarbon mass through the caustic scrubber Increased as the burn's RPE Improved. Similar to the discussion 1n paragraph 6 of this appendix, hydrocarbon mass penetration through the caustic scrubber was expected to be a function of hydrocarbon vapor pressure (condensability) since the detected hydrocarbons were only slightly soluble In caustic solution. The hydrocarbon collection mechanism 1n the caustic scrubber was probably 1mpact1on (entralnment) rather than absorption. Heavier, less volatile hydrocarbons were expected to condense from the combustion gases In and downstream of the venturl since the venturl pressure drop and Injected caustic solution provided very rapid cooling of the combustion gases. The degree of this rapid cooling was rather consistent between burns, I.e. from an average combustion gas temperature of 1990°F (s*158) exiting the reaction tailpipe, passing through the venturl at 400 ft/sec, and dropping to an average scrubbed effluent gas temperature of 163°F (s«8). b. Once these condensed hydrocarbons were entrained 1n the caustic solution, they were either dissolved to their solubility limits and retained or desorbed and entered the scrubbed effluent gas if their vapor pressures were significant 1n the spent scrubber water's average temperature of 160°F. As the burn's RPE Improved, the combustion gas contained less of these heavier hydrocarbon compounds. The hydrocarbon mass collected 1n the spent scrubber water decreased with the decreasing difference 1n hydrocarbon mass collected In the combustion and scrubbed effluent gas TCDD sampling trains. Scrubber water "efficiency" of total hydrocarbon collection decreased more rapidly than that of the TCDD sampling trains because of the much higher collection of low vapor pressure hydrocarbons in benzene at ~50<>F. c. Table 1-8 presents the detected hydrocarbon (grams) 1n each burn's total spent scrubber water volume. As discussed in paragraph "b" above, the detected hydrocarbon masses decreased in proportion to increased RPE; I.e. one order of magnitude decrease when the third decimal of the RPE became significant. Except for burns I, II and III, which used poppet nozzles and had the lowest RPE's and KAVE'S, all detected hydrocarbons were less than 20 yg/1 in the spent scrubber water'. Of this total hydrocarbon mass per liter of SSW, less than 1.5% could have been the total undetectable TCDD and acids/esters of 2,4-D and 2,4,5-T listed in Table 1-8. E-d-16) �TABLE 1-7: HYDROCARBON MASS PENETRATION THROUGH THE CAUSTIC SCRUBBER (CGH vs SGH) "ORANGE" HERBICIDE PROGRAM 12-30 NOV 73 I Burn Number II ii r V IV Scrubbed Effluent 6.55xl06 7.75X106 8.58xl'06 9.47xl06 Gas Volume (Liters)* VI 7.65xl06 5.03xl06 VI II VII 7.55xl06 8.76xl06 * i Aliphatic HC** ug/1 as CioH22 yg/1 as C g/burn as C 0.038 0.032 0.210 0.037 0.031 0.240 0.135 0.113 0.969 0.048 0.040 0.379 0.039 0.033 I 0.252 0.306 0.255 1.283 0.045 0.037 0.279 Aromatic HC yg/1 as C6H5(C4Hd) yg/1 as C g/burn as C 0.055 , 0.049 0.321 0.036 0.032 0.248 0.162 0.145 1.244 002 .6 0.056 0.530 ,0.024. 0.022 0.168 0.157 0.141 004 .4 0.103 0.092 0.709 0.039 0.294 Biphenyl HC yg/1 as Ci2Hio yg/1 as C g/burn as C 0.017 0.017 0.016 0.016 0.102 • 0.132 009 .0 009 .0 0.048 0.046 0.348 0.168 0.158 0.031 0.029 0.218 0.072 0.067 0.589 j ! Herbicide HC | j yg/1 as HC/compoundj 0.000211 0.00018 yg/1 as C/compound ( 0.00010; 0.00009 g/burn as C/5 com- } 0.003 • 0.004 } pounds , 0.006 0.006 0.076 ! 0.061 i ! 0.00023 0.00016 0.00011 0.00008 0.005 i 0.004 i Total Carbon j 0.974 2.289 g/burn Scrubbed Gas S 0.636 0.624 7.9 68 12.09 <0.01 g/burn CombustionGe! 27.29 i 0.81 18.93 Penetrati on .Percent 2.33 99.98 . 99.99 99.99 >99.999 : Relative Pyrolysis Efficiency .Percent i *Drys at 7QOF and 29,92" Hg pressure* From Table 1-3. **HC - hydrocarbon tFrom Table 1-6 ; p 0.796 0.037 0.031 0.272 . 086 .0 ; i 0.00020 0. 00060T j 0.00026 0.00024 . O.OOOlOj 0.00030 0.00013 0.00011 0.007, 0.004 •.0 0 0 4 0.005 f • 1 0.772 7.25 10.65 99.998 2.795 0.93 99.999 0.79 1.672 0.79 2.07 100. 80.8 "99.999 [99.999 1 USAF EHL(M) u �TABLE 1-8: SUMMARY OF HYDROCARBON COMPOUNDS COLLECTED IN SPENT SCRUBBER WATER "ORANGE" HERBICIDE PROGRAM 12-30 NOV 1973 wJ* r BurnTLitersJ §P«in1 Sc'rubBer Wai er Tot Y YoT 15693 14996 15100 15916 13538 7185 14267 T2TO I I "ITT i VI VIII IV V VII BURN NUMBER •+ Detected Hydrocarbons (gms) Miphatic Hydrocarbon as C1QH22 1.689 1.458 1.699 0.099 0.130 0.014 0.138 0.119 1.407 1.215 1.415 0.082 0.108 0.012 0.115 0.099 3.005 1.815 0.852 0.081 0.001 0.024 0.111 0.075 as C 2.692 1.626 0.763 0.073 0.001 0.022 0.099 0.067 Hchlorobenzene as C6H4C12 8.225 6.975 0.488 0.115 0.043 0.003 0.016 0.027 as C 4.030 3.418 0.239 0.056 0.021 0.001 0.008 0.013 0.827 0.211 0.003 0.003 0.001 0.001 0.001 0.001 0.463 0.118 0.001 0.001 0.001 0.001 0.001 0.001 as C Aromatic Hydrocarbon as CgHgC^Hg tonocnlorophenol as CgH^lOH as C Total Weight of Above (gms) " " " as C (gms) .042 0.266 0.222 13.744 10.459 3.042 0.298 0.175 8.592 6.377 2.418 0.212 0.131 0.035 0.223 0.180 Maximal Undetected Components of Blended Herbicide Feed (mgm) TCDD TCDD as C 2,4-D acid (butyl ester) 11 ' as C 0.74 0.33 0.75 0.43 0.71 3.78* 0.32 1.69 0.72 0.72 0.42 0.42 0.75 0.34 0.76 0.44 0.64 0.29 0.65 0.37 .34 0.68 0..58 .15 0.30 0,25 .34 0.68 0.58 .20 0.40 0.34 2,4,5-T add (butyl ester) 1 as C 0.63 0.29 0.60 0.28 0.60 0.28 0.63 0.29 0.54 0.25 .29 0.58 .13 0.26 2,4-D add (methyl ester) n n M n as C . 0.75 0.34 0.72 0.33 0.72 0.33 0.76 0.35 0.65 0.30 .34 0.68 0..58 .16 0.32 0..27 2,4,5-T acid (methyl ester) as C 0.67 0.27 0.64 0.26 0.64 0.26 0.67 0.27 0.57 0.23 .30 .12 0.60 0.24 0.51 0..20 3.54 3.39 6.46 3.57 3.05 .62 3.22 2.74 1.66 1.61 2.98 1.69 .44 .76 1.51 1.28 Total Undetected Weight of Above (mg) as C (mg) Grand Total of all Hydrocarbons (gms) 13.748 10.462 3.048 0.302 0.178 " as C (gms) 8.594 6.379 ,,421 0.214 .132 *0nly one of these compounds detected 0,49 0,22 .044 0.269 0.225 .036 0.225 0.181 1n any spent scrubber water samples. -(I-18) E USAF EHL(K) I �d. The unchlorlnated aliphatic and aromatic hydrocarbons of Table 1-8 were considered as pyrolyzates which were trapped and slightly dissolved in the scrubber water. The detected chlorinated hydrocarbons were considered hydrolyzates formed by reaction of the aromatic hydrocarbons and chlorine species 1n the combustion gases as they cooled and mixed with the caustic in the scrubber (see paragraph 11, this report). As the RPE's increased (burns IV through VIII), the mass of the chlorinated hydrocarbons in the SSW decreased faster than the mass of the aromatic hydrocarbons. This was because the mass of the former was dependent on the latter, and the latter decreased 1n the combustion gas as RPE-increased. e. Table 1-8 also presents the maximal mass of components of blended herbicide (mgm) that could have existed undetected in each burn's total spent scrubber water volume. These values were based on the detection limits and analytical recovery efficiencies of each compound in 500 ml of collected SSW TBC that was analyzed. These calculated masses were therefore all relative to the total spent scrubber water volume except for TCDD in burn III. This TCDD was the only one of these herblcidal component compounds detected in any SSW-TBC or SSW-C1 samples, see discussion in paragraph 12 of this appendix. f. Suspended matter 1n the SSW were analyzed from concentrated sediment samples collected after each burn from the bottom of the SSW holding tank. Analytical results presented in Table G-8, Appendix G, showed that no detectable hydrocarbons were extracted from any of the sediments. These sediments were thus considered as carbon with less than 9.0% iron content. The carbon was a pyrolytic product but the iron came from combustion gas adds leaching the metal of the scrubber tank. 10. BECKMAN 109A DATA COMPARED WITH RPE's a. Table 1-9 was presented to demonstrate that scrubbed effluent gas hydrocarbon data measured with the Beckman 109A total hydrocarbon analyzer (SGBH) was not an Indicator of the relative pyrolysis efficiency (RPE) of "Orange" herbicide. b. Burns I and II had the lowest SGBH of all burns. If SGBH was a good indicator of RPE, burns I and II would have had the best RPE in the set of eight burns. However, the CGH and SSWH was greater in burns I and II than in all other burns and the RPE of burns I and II was less than in all other burns. c. Burns VII and VIII had a greater RPE than burns I and II, but their SGBH readings were greater than in burns I and II. In burns III through VI, the SGBH had no apparent Inverse or direct relationship to RPE. d. During the incineration of "Orange" herbicide, the CGH and SSWH were related. This was anticipated since the heavier, but not completely combusted hydrocarbons, (pyrolyzates) would be more effectively collected 1n both the TpDD sampling trains and the caustic scrubber than the light molecular weight pyrolyzates. In burns that had a poorer RPE (burns I and II) the heavy pyrolyzates were more effectively collected in the caustic scrubber and were not �TABLE 1-9: COMPARISON OF HYDROCARBON DATA - BECKMAN 109A (SCRUBBED EFFLUENT GAS), CGH, AND SSWH "ORANGE" HERBICIDE PROGRAM 12-30 NOV 73 I II V VI III IV BurnNumber 3.5 29 £. y 18.6 5.8 CGH 4.02 9.59 1.36 SSWH v (g/bum) 8.59 6.38 2.42 SGHBt x (ppm) s (vg/i) • ^ 395* 1450.0 1258.9 79.5* 151.7 22.6 VII VIII 75.7 23.1 36.5 17.1 0.90 0.21 0.18 0.10 0.23 0.13 0.04 0.22 0.18 •Measured during the same time period of CGH sampling. "'"Four (4) values used for x. For definition of SGBH, CGH, and SSWH, see Table 1-4. rsj O USAF EHL(M) and (K) �detected by the Beckman l69A. In burns that had better RPE's (burns IV through VIII) the light pyrolyzates were not collected in the scrubber but were detected by the Beckman 109A, arid thus higher SGBH values were observed even though the RPE's were higher. \ 11. HERBICIDAL COMPOUNDS DETECTED IN GAS SAMPLES AND RELATED EQUIPMENT a. The nb-esters of 2,4-D and 2,4,5-T were detected in the rinse from the Beckman 109A cold trap used in burn I Monochlorophenol was detected in the first impinger'of the combustion gas sampling train from burn I. Dichlorophenol was detected in the rinses from the Beckman 109A cold traps used in burns I, II and III, in the air cooled sampling probe rinses from burns II and III, and in the mixed (one and two impingers) water of the particulate source sampling train impingers from burns IV and VI. b. The butyl esters found in the cold trap rinse from record burn I could have been deposited during either of two checkout burns made before record burn I (see Marquardt Test 4 and 5). The first attempt at record burn I was aborted 16 minutes into the burn due to fuel injection problems caused by the high viscosity of "Orange" herbicide. Since the incineration of "Orange" herbicide during these checkout burns was not as carefully controlled as during all successful record burns, and since the cold trap was not rinsed after the two checkout burns it was concluded that the cold trap rinse from record burn I was not representative. No butyl esters were found in the cold trap rinses from record burns II and III. The cold traps used in burns IV through VIII were rinsed but not analyzed. c. The dichlorophenol found in the Beckman 109A cold trap rinse from burn I was considered unrepresentative for reasons given in the previous paragraph. d. Dichlorophenol was found in the Beckman 109A cold trap rinses from burns II and III and in the combustion gas air cooled sampling probe rinses from burns II and III. However, the compound was not detected in the combustion gas impinger samples that were downstream of the air cooled probes or in the spent scrubber water samples from these burns. (1). Dichlorophenol has a high irelting and boiling point (113°F and 403°F for 2,4). The caustic scrubber (caustic solution at 160°F in collector tank) was expected to collect a significant fraction of compounds as condensable as dichlorophenol (monochlorophenol was collected in the scrubber). Since dichlorophenol was not detected in the combustion gas impinger samples (detection level = 0.88 xlO~9 grams/liter) downstream from the air.cooled probes or in the spent scrubber water (detection level = 0.08 x!0'b grams/liter) from these burns, the existence of dichlorophenol in the combustion gas was doubted. (2) Since no dichlorophenol was detected in the impingers downstream of the air cooled probe, it was supposed that the probe collected all of the dichlorophenol. Based on this conclusion, the apparent combustion gas concentration was 40 xlO"9 grams per liter (1.38 ug/34 liters). If this E-U-21) �concentration existed throughout the burn, the caustic scrubber was exposed to 320 mg over the total burn. The volume of the spent scrubber water from burn II was 14996 liters. Based on the detection limit of dichlorophenol in the spent scrubber water (0.08 ug/1), 1.2 mg of dichlorophenol 1n the spent scrubber water would have been detected. The 1.2 mg needed for detection was only 0.37% of the 320 mg available if the 40 xlO'9 grams/liter existed throughout the burn. The caustic scrubber was expected to collect a significantly greater fraction of dichlorophenol than 0.37% (see Table 1-7). (3) From these observations, the following possibilities were considered. That, (a) dichlorophenol did not exist at a mass concentration of 40 xlO'9 grams/liter throughout burn II, and (b) the dichlorophenol was formed in the air cooled sampling probes and 1n the Beckman 109A cold traps from reactions of Cl2 and (Cl) with the nonchlorinated aromatic hydrocarbons detected 1n the combustion gas (these reactions are favorable between 500 and 700°C, slower at <500°C and almost nonexistent >70QOC; the combustion gas was cooled from ~1040°C to 150°C rapidly in the air cooled probe; the environment was favorable to formation of dichlorophenol), or (C) the dichlorophenol was chemically altered to the monochlorophenol in the caustic scrubber. Monochlorophenol and dlchlorobenzene were detected in all spent scrubber water samples. The monochlorophenol-dichlorophenol equilibrium could have been shifted to monochlorophenol in the caustic scrubber. e. The spent scrubber water from burns II and III contained 211 mg and 3 mg of monochlorophenol respectively. The (apparent) total burn production of dichlorophenol was 320 mg and 26.7 mg for burns II and III respectively. There appeared to be a relationship between (apparent) dichlorophenol in the combustion gas and monochlorophenol in the caustic scrubber. However, since dichlorophenol and monochlorophenol could have been formed in the venturi of the caustic scrubber (rapid cooling of combustion gas from ~1040°C to 72°C), to account for the monochlorophenol detected, and the existence of mono and dichlorophenol in the combustion gases was unfavorable (temperature), the conclusion was made that dichlorophenol did not exist in the combustion gas but was generated in the air cooled probe and in the cold trap. This conclusion was supported by the fact that dichlorophenol was not detected in these probes and traps of burns IV through VIII when the mass concentration of unchlorinated aromatic hydrocarbons was low. f. The dichlorophenol found in the water implngers in the particulate sampling train sample from burns IV and VI was concluded to be contamination not associated with "Orange" herbicide incineration. This conclusion was based upon the following observations: (1) In burn IV. the dlehlorcphenol mass concentration in the scrubbed effluent gas that was necessary to produce the mass collected in the particulate sampling train was greater than the detection limit in the TCDD sampling train, i.e., 1.3 pg was collected from a sample volume of 737.2 liters for an apparent mass concentration of 1.76 xlO"9 grams/liter but the detection limit in the TCDD sampling train was 0.22 xlO-9 grams/liter. Therefore, dichlorophenol should have1 been detected'ir. the TCDD sampling train. E-(l-22) �(2) In burn VI; 0.1 ug was collected from 444.0 liters for an apparent mass concentration of 0.22 x 10~9 grams/liter. However, the detection limit in the TCDD sampling train was only 0.83 x 10-* grams/liter. The apparent mass concentration in the scrubbed effluent gas was below the detection limit of the TCDD sampling train if the collection efficiencies in the particulate and the TCDD sampling trains was assumed to be equal. However, dichlorophenol collection efficiency in the TCDD sampling train was greater than in the particulate train water impingers and dichlorophenol should have been differentially collected in the TCDD sampling train because: (a) Dichlorophenol is soluble in benzene but only slightly soluble in water. (b) Fritted impingers, as used in the TCDD system are more effective gas and aerosol collectors than modified impingers used in the particulate train. (c) A series of four Impingers was used in the TCDD sampling train but only two were used in the particulate train. (3) The water Impingers used 1n the particulate train were packed in sponge rubber and styrofoam for shipment. They had been used in numerous particulate source'sampling projects prior to this work. Since it was not anticipated that they would be used for hydrocarbon collection, they were not properly washed for herbicide analysis but merely rinsed with distilled water. Contamination of these Impingers with dichlorophenol could have occurred in numerous cases and rinsing with distillled water would not have removed contamination. Also two Impinger sets were alternated and the same implnger set (potentially contaminated) was used In burn IV and VI while a different (uncontamlnated) set was used in burr III and V. (4) The water in the Impingers and the particulate sampling train from burn III and V did not contain'dlch'lorophenol even though burn III was less efficient in relative pyrolysis of "Orange" herbicide than burn IV and VI. Burn V had a comparable RPE to burn IV and VI. If dichlorophenol was being produced during "Orange" herbicide Incineration 1t would have been produced and detected in burn III and V as well. (5) Dichlorophenol was not detected in the spent scrubber water (detection limit < equal to 0.08 xlO~6 grams/liter) in any of the burns, and as discussed in paragraph lld(l) the caustic scrubber was expected to collect a significant fraction of dichlorophenol. If dichlorophenol was being produced throughout the burn at the rate indicated by the water implnger samples in burn-IV (1.76 xlO'9 grams/liter) then (1.76 xlO'9 grams/liter times 9.47 x 10° liters) 16.67 milligrams would have been produced. If 1.27 milligrams (7.6% of 16.67 milligrams) of dichlorophenol had been collected by the caustic scrubbers it would have been detected. g. Based upon the fact that dichlorophenol should have been differentially collected in the TCDD sampling train but was not, contamination of the water impingers with dichlorophenol was possible, and no dichlorophenol was detected E-(I-23) �in the caustic scrubber, the conclusion was made that dichlorophenol found 1n the water 1mp1ngers 1n burn IV and VI was extraneous contamination. 12. HERBICIDE IN BURN III EHL SAMPLES a. Only two of all the EHL samples'contained any of the following nine herbicide compounds: nb 2,4-D and 2,4,5-T esters and adds, octyl 2,4-D and 2,4,5-T esters and adds, and TCDD. Both of these samples occurred 1n burn III. First, the combustion chamber coke deposit contained 1100.20 yg of these esters and adds per 100 gms of deposit; of which 551 yg was nb 2,4-D ester and 542 yg was nb 2,4,5-T ester. Theije esters produced the characteristic "Orange" herbicide odor which was detected 1n burn Ill's coke deposit. Neither this odor nor any of the aforementioned nine herbicide compounds were detected 1n coke deposits from any other burns. Second, the total burn scrubber water composite (SSW-TBC) sample contained 0.25 yg/1 of TCDD but none of the other eight herbicide compounds. Suspended matter 1n burn Ill's SSW-TBC or from any of the other burns contained none of the nine herbicide compounds. None of these compounds were detected 1n burn Ill's first hour spent scrubber water composite (SSW-C1) or any other burn's SSW-TBC or SSW-C1. b. The total TCDD mass 1n the spent scrubber water was calculated as 3775 yg for the total burn. If this TCDD mass had been evenly distributed throughout the burn's combustion gas, the sampled combustion gas would have contained about 4.5 times the TCDD mass concentration needed for TCDD detection. However, no TCDD was detected in the combustion gas sample which was initiated 51 minutes Into the burn and continued for 64 minutes. Additionally, no TCDD was detected 1n the SSW-C1 which was Initiated 54 minutes Into the burn and completed 44 minutes later. Thus, the TCDD must have passed through the Incinerator during the last 120 minutes of burn III. The TCDD probably passed through the Incinerator 1n a relatively short period since no noticeable changes in burn Ill's operational parameters were ever observed. c. Unlike any other burns, the appearance of burn Ill's coke deposit Indicated very poor combustion and that lower temperatures occurred around the deposit. Although no TCDD was detected in the deposit, it could have been present in concentrations up to about 15 yg/100 grams of deposit. This value was calculated under the assumption that TCDD was present 1n the 1100.2 yg of esters and adds in the same proportion as it was in the blended herbicide. The 15 yg/100 grams of deposit would have been below the analytical detection limit for that size sample. d. Earlier comparisons of CGH and SSWH showed no reason to believe that the overall RPE of burn III was significantly less than RPE's in burns I and II. However, burn Ill's quantity and quality of coke deposit, SGH quality, and TCDD 1n the SSW-TBC were significantly different than burn I, II, or any other burns. These comparative observations lead to the conclusion that combustor coke chips, 175 grams or more, broke loose from the combustion chamber deposit and, combusted well enough during incinerator dwell time to destruct the herbicide esters and adds but not the TCDD, and then Intimately mixed and settled in the scrubber tank. Even though not appreciably soluble in water, enough TCDD must have leached from the coke to produce 250 nanograms per liter of collected SSW-TBC. E-(I-24) �13. DISCUSSION OF CONFLICTING DATA a. Burn IV: (1) In burn IV, the scrubbed effluent gas hydrocarbon mass concentration (S6H) was greater than the corrbustion gas hydrocarbon mass concentration (see Table 1-7). In all other burns, as expected, the reverse was true. (2) The mass of hydrocarbons collected In the scrubber (SSWH) during burn IV was comparable to that collected In burns V, VI, VII and VIII. Since caustic scrubber characteristics were not significantly different In burn IV from those in burns V, VI, VII and VIII,one must consider that burn IV combustion gas contained hydrocarbon mass concentrations comparable to burns V, VI, VII, and VIII, or that a combination of two things occurred, (a) a slug of pyrolyzates occurred during startup (before sampling to account for the hydrocarbon mass 1n the scrubber) and (b) the combustion gas and scrubbed effluent gas samples were reversed in the recovery or analytical steps. (3) Since gas chromatographic peak Interferences were possible in the burn IV combustion gas samples,the first consideration was concluded to be the most probable. Therefore, the CGH in burn IV was considered equal to or greater than the CGH in burns V, VI, VII and VIII, but less than the CGH in burns I, II and III. b. Burn VI; In burn VI, the SGH aliphatics were greater than the CGH allphaticslThis conflict was concluded to be due to: „. (1) gas chromatography peak interferences, or (2) analytical accuracy as the detection limit was being approached. c. Biphenyls in SGH: Biphenyl (unchlorlnated) was not detected in the CGH (Tables G-2 and G-3). Also, it was not detected in the SSWH (Table G-7). The conclusions were made that biphenyl was: (1) present in the CGH but hidden by gas chromatographic peak interferences (Appendix G, paragraph V), (2) not collected in the SSWH due to its relatively high vapor pressure (1n the scrubber water temperature, 160-170°F) and low solubility 1n the caustic solution, (3) detected in the SGH because of fewer gas chromatographic peak interferences. E-(I-2S) �(This page intentionally left blank) �USAF ENVIRONMENTAL HEALTH LABORATORY Kelly AFB, TX 78241 APPENDIX J (TO APPENDIX E) NOISE f'ONITORING �(This page intentionally left blank) �APPENDIX J NOISE MONITORING 1. Introduction This appendix presents the noise measuring equipment used, octave band analyses of the noise produced by one incinerator, and the location where noise measurements were made. Data arc discussed, particularly as regards the occupational hazards of the noise to exposed operators and estimates of noise intensities expected by more than one incinerator. 2. Results and Discussion a. Octave band sound level measurements of the incinerator noise, equipment used, and environmental conditions arc presented in Table J-l. Locations where noise measurements were made are shown in Figure J-l. b. "A" weighted octave band sound levels could not be summed any closer than +_ 2 decibels (db) of the overall dbA. These minor inaccuracies of measurement were acceptable for meeting the objectives of the study. The following unavoidable environmental conditions caused the measurement errors: (1) Except for location "7", positions of equipment within the area required that all measurements be taken relatively close (10 - 15 feet) to the incinerator in order to get "line-of-sight" measurements. Consequently, the measurements were influenced by "near field" effects. (2) Many metallic surfaces around the incinerator contributed reverberation noises. (3) Background noises were present from a commercial airport 100 - 200 yards away as well as industrial noises from within the contractors facility. However, measurements were taken only when these background noises were at a minimum. c. The incinerator was not considered a point source of noise. The noise was steady state. The overall sound level averaged 91 dbA and 91 dbC at points twelve feet around the incinerator. Such close values of overall dbA and dbC were in agreement because most of the noise level was produced in the higher frequencies, 2000 8000 Hertz. At twenty-four feet from the incinerator, overall average noise levels decreased to 85 dbA or 87 dbC because the E-(J-l) �TABLE J-l: SU£®Burner Noise Survey-Octave Band Analyses R Location^ ' Angle (ft)- "A" Wei qh ted Slow Resoonse Octave Band Level (dB) Reference 0.0002L'bars/M^ for Oc ave-Band Center Frequency in Hertz 8000 125 4000 16000 31.5 250 500 1000 t>3 2000 "r." "A" All Pass All Pass 1* 2* — -- 12 12 72 76 79 80 72 72 71 74 74 79 78 82 82 84 88 89 84 85 73 74 92 93 91.5 92 3* 4*&5* — — 12 12 78 75 83 85 77 79 79 80 83 84 84 83 88 86 84 80 71 65 92 91 92 92 6* — 12 74 83 80 77 77 84 79 77 79 83 77 62 88 91 7* — 24 68 74 69 68 69 76 80 84 78 65 8* — 15 — — — — — — — — — — 87 64 86.5 65 1** — 12 71 81 71 73 74 77 81 85 81 72 88 89 2** — 12 78 79 77 74 78 83 83 88 84 74 91 91 6** — 12 — .«_.„ -_tlliB — — — — 84 87 7** — 24 — 68 69 70 76 80 74 60 83 83 XI 2 3 4 5 91. 91. Xfi.7 85. 87. 10 r — 70 75 \ 71 Instruments Used: General Radio Uctave Band Analyzer Type 1558-PB(Serial No. 2473) with General Radio Microphone 1560-P6 with wind shield (Serial No. 2680).Calibrated with General Radio Calibrator Type 1562-A (Serial No. 2579) Burn VII Date of Survey: *20Nov **29Nov surveyor: Capt.C.W. Bullock Operational Mode of Burner: Burn IV Dashed lines indicate that measurements were not taken. (1) For location of measurement, see Figure j-i. 0 USAF EHL(K) rtind conditions during survey:* Fftom 120-160°, 9mph, Temp=62°F. **Calm, Omph.Temp=62uF. �Exhaust Tower I 65' to Holding Pond Reaction Tailpipe Scrubber Water Holding Tanks Control Bldg 48 Combustion Chamber Bldg 92 Herbicide Feed Tank SCALE: 1"= 10' Numbers in square blocks denote location of noise measurements FIGUREJ-1 LOCATIONS OF NOISE MEASUREMENTS DURING TEST BURNS USAF EHL(K) E( J-3 ) �higher frequency noises had begun to dissipate and the lower frequency components were contributing more significantly to the overall noise level. d. The incinerator octave band experienced control building effectively attenuated exterior noise to an overall level of 64 dbA. Although analyses were not made, no speech interference was inside the control building. e. Operators occupationally exposed to the noise within a fifty foot radius of the incinerator should be provided car muffs and be monitored via a hearing conservation program. The noise data can be used with various hearing protection criteria to determine limited exposure periods in which an unprotected operator could be exposed without risk of developing any hearing loss. f* Table J-2 below presents estimated overall sound levels with increasing numbers of Incinerator units. Appropriate adjustments of hearing conservation protection requirements around the incinerator(s) can be made depending on the number of incinerators and the distance from them to the workers. TABLE J-2: ESTIMATES OF OVERALL SOUND LEVELS AT VARIOUS DISTANCES FROM ONE TO EIGHT INCINERATORS Number of Incinerator Units Overall Sound Level (Reference 0 0 0 u foars/M2) .02 At Twenty-four Feet At Twelve Feet dbA or dbC dbC dbA 1 91 85 87 2 94 88 90 4 97 91 93 8 100 94 96 E-(J-4) �APPENDIX K .(TO APPENDIX E) REFERENCES ,; MAIN REPORT (1) THERMAL DECOMPOSITION OF ORANGE^HERBICIDES, Mississippi Agricultural and Forestry~Experiment Station and Plant Science Research Division of the USDA, Cooperative Agreement No. 12-14-100-10, 673(34), to USAF, AFLC/SAAMA, Kelly AFB, Texas (1 June 1 7 ) 92. (2) INCINERATION OF ORANGE HERBICIDE, USAF Environmental Health Laboratory Technical Report EHL700 72-7, USAF EHL(K), Kelly AFB, Texas (July 1972). (3) REPORT ON THE FEASIBILITY OF DESTROYING IlERBIC IDE ORANGE BY INCINERATION USifllTTHg MAT^^ATUPT'SUE^ BU'RNER, Report S-122^, The Marquardt Company, VluTNTiys, CaiifornTaT Prepared under Contract No. F04611-72-C-0087 for Air Force Rocket Propulsion Laboratory (AFRPL), Air Force Systems Command, Edwards, California (August 1972). APPENDIX B (4) Private Communication, The Marquardt Company, Van Nuys, California and Air Force Rocket Propulsion Laboratory (AFRPL), Edwards, California ( 9 2 . 17) APPENDIX D (See Reference.'* on Page D-27) E (K-l) �(This page intentionally left blank) �APPENDIX F THE ECOLOGICAL CONSEQUENCES OF MASSIVE QUANTITIES OF 2,4-D and 2,4,5-T HERBICIDES SUMMARY OF A FIVE YEAR FIELD STUDY �(This page intentionally left blank) �•£ THE ECOLOGICAL CONSEQUENCES OF MASSIVE. QUANTITIES OF 2,4-D and 2,4,5-T HERBICIDES SUMMARY OF A FIVE YEAR FIELD STUDY* Young, A.L., C.E. Thai ken, W.E. Hard and W.J. Cairney Department of Life and [Jeh.ivioral Sciences United States Air Force Academy, Colorado In support of programs testing aerial dissemination systems, a one square mile test grid on Test Area C-52A, Eglin AFB Reservation, Florida received massive quantities of military herbicides. The purpose of these test programs was to evaluate the capabilities of the equipment systems, not the biological effectiveness of the various herbicides. Hence, it was only after repetitive applications that test personnel began to express concern over the potential ecological and environmental hazards that might be associated with continuance of the Test Program. This concern led to the establishment of a research program in the fall of 1967 to measure the ecological effects produced by the various herbicides on the plant and animal communities of Test Area C-52A. This report documents six years of research (1967 - 1973) on. Test Area C-52"A and the immediately adjacent streams and forested areas. This report attempts to answer tha major questions concerned with the ecological consequences of applying massive quantities of herbicides (345,117 pounds), via repetitive applications, over a period of eight years, 1962 - 1970, to an area of approximately one square mile. Moreover, the report documents the persistence, degradation, and/or disappearance of the herbicides from the Test Area's soils and drainage waters "and their subsequent effects (direct or indirect) upon the vegetative, fauna I, and microbial communities. The active ingredients of the four military herbicides (Orange, Purple, Hhite, and Blue) sprayed on Test Area C-52A were 2,4-d'ichlorophenoxyacctic acid (2,4-D), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 4»amino-3,536-trichloropicolinic acid (picloram), and dimethy'larsinic acid (cacodylic acid). It is probable that the 2,4,5-T herbicide con-' tained the highly teratogenic (fetus deforming) contaminant 2,3,7,8-tetrachlorodibonzo-p-dioxin (TCDD). Ninety-two acres of the test grid received 1,894 pounds 2,4-D, 2,4,5-T per acre in 1962 to 1964, while anothc-ir 92 acres received 1,168 pounds per actr in 19M to 1%S. In the period from 1966 to 1970, a third distinct ar.:a of over 240 acres received 343 pounds per acre of 2,4-D an>i 2,-1,5-1, 6 pounds per acre picloram, and in 1969 to 1970, H3 poi.nds p.-:r aero cacodylic acid (?tt pound: per acre of arsenic -::r, tlr: orounic pentnvalcnt form; calculated on weight of Blue applied nor acre). From the rates of herbicides that wore: applied during the years of testing spray equipment,r it was obvious that TesL Area C-R2A offered a uninufi opportunity to ,tudy herbicide persistence and soil leaching. Yet Lh(! problem of how best to assess the levol of herbicide residue was to the Weed Sciences Society of America, 14 February 1974, Us Vcnv>, Nc'vjda. Abstract No. 164. F-l �a difficjlt one. The herbicides could be chemically present bub because of soil binding might not be biologically active. Thus, both bioassay techniques and analytical analyses were employed. The Mrsf. major bioassay experiment was conducted in April 1970. By considering the flightpaths, the waber sources, and the terracing effects, it was possible to divide the one-square mile test, grid into 16 vegetation arsas. These areas formed the basis for the random selection of 4u 3-foot soil cores. Soybean bioassays indicated Liiat 27 of the 43 cores were significantly different from control cores (95^i probability level). The results indicated that soil leaching or penetration was much more prevalent along the dissemination flight paths than in other areas of the test grid. Efforts to quantitate (chemically) the bioassay v;ere confined to only the top 6-inch increment because of within-core variations. By considering that all phytotoxic effects were from Orange (2,4-D and 2,4,5-T) the average value for the top 6 inches of soil core for the eight cores showing greatest herbicide concentration was 2.82 ppm (parts per million) herbicide. Chemical analyses of soil cores collected from the eight sites shewing greatest phytotoxic concentrations were performed in December 1970. Results indicated that the maximum concentration of either 2,4-D or 2,4,5-T was 8.7 ppb (parts per billion). A 1970 analysis of soil cores for arsenic, from areas receiving greatest quantities of Blue, indicated maximum levels of 4.70, 1.30, and 0.90 ppm arsenic for the first three 6-inch increments of the soil profile, respectively. These same increments were again collected and analyzed in 1973: levels of arsenic were 0.85, 0.47, and 0.59 ppm for the three consecutive 6-inch increments. Leaching of the arsenical from the soils may have occurred. Picloran analysis in November 1969 of soil cores from areas receiving greatest quantities of White indicated that maximum levels of 2.8 ppm picloram were present in the 6 to 12-inch depth increment. Analysis of the same sites performed in 1971 indicated the picloram had leached further into the soil profile but concentrations were significantly less (ppb). Analysis of soil cores in 1971 showed no residue of TCDD at a minimum detection limit of less than 1 ppb, even in soil previously treated with 947 pounds 2,4,5-T per acre. However, data from soil analysis (via mass spectrometry) of four total samples collected in June and October 1973 indicated TCDD levels of <10, 11, 30, and 710 parts per trillion (ppt), respectively. These levels were found in the top six inches of soil core. The greatest concentration (710 ppb.) was found in a sample from the oren that received 947 pounds 2,4,5-T in tlio 1962 - 1964 test period. A comparison of vegetative coverage and occurrence of plant species on the one-square mile grid between Jjne 1071 -md June 1973 has indicated Lnrt areas with 0 to 60" vegetotivi cover in 1971 had a coverage of 15 to 85/i in June 1973. Tho':.r areas having 0 to 5',:- coverage in 1971 (areas adjricont to or under flightp<Uh.s iist-d during htjrbicide-nquipment testing) h.vi 15 lo 54" coverage. The race or charge; in coverage seemed to be dependent upon soil type, toil moisture, arid v/ind. There was no evidence to ind'iccvi.0 tlmt the existing vegetative coverage was in any way related to herbicide residue in the soil: dicotyledonous or broadleaf plants that are F-2 �normally susceptible to damage from herbicide residues occurred throughout the entire one square mile grid. The square-foot transect method of determining vegetative cover indicated that the most dominant plcnts on the test area were the grasses, switchgrass (Panicum virgatum), woolly panicum (Panicum lanuginosurn), and the broadleaf plants rough buttotiwced (Diodia tcrcs), poverty weed (llvpericuni gentianoides), and common polyprcmum (polypremum procumbens). In 1971, 74 dicotyledonous species were collected on the one square mile grid; in 1D73, 107 dicotyledonous species were found. ATI of the plant species collected wore pressed, mounted, and placed in the Eglin AFB Herbarium. An evaluation of the effects of the spray-eqjipment testing program on faunal communities was conducted from May 197D to August 1973. The extent of any faunal ecological alterations was measured by assessing data on species variation, distribution patterns, habitat preference and its relationships to vegetative coverage, occurrence and incidence of developmental defects, as well as gross and h'istologic lesions in post mortem pathological examinations. A total of 73 species of vertebrate animals (mammals, birds, reptiles, and amphibians) were observed on Test Area C-52A and in the surrounding area. Of these 73 species, 22 species were observed only off the grid, 11 species were observed only on the grid, and 40 species were observed to be common to both areas. During the early studios no attempts were made to quantitate animal populations in the areas surrounding the grid; however, in 1970, preliminary population studies by trap-retrap methods were performed on the beach mouse (Peromyscus polionot.us) population for a GO day period to confirm the hypothesis that it VMS the most prevalent species on the grid. The hypothesis was supported by the capture of 36 beach mice from widely distributed areas on the grid, except in areas with less than BA vegetation. Eight pairs of eastern harvest, mice were taken to the laboratory and allowed to breed. Six of the eight pairs had litters totalling 24 mice. These progeny were free from any gross external birth defects. During February - May 1971 'population densities of the beach mouse were studied at eight different locations on the grid along with two different areas off the grid which served as controls. Populations were estirna;ed on the basis of trap-retrap date.. There was no difference in mouse population densitites in herbicide treated and control areas affording comparable habitats. All indications were that any population differences in other animal species between the test area and the surrounding area were due to differences caused by the el initiation of certain plants and, therefore, certain ccolociical niches, rather than bein'j duo to any direct dntri:nc;Hta'l er'foct of the herbicides on the animal population present on TA C-52;\. "luring the last day of l!iO U7I sf'hly, 9 :,iice were captured and taken Lo t ic laboratory for posi. i;"irty:n p;.V.ho logical exai'iination. There were no ivitdnces of cleft palate or othur do f on;: i tic-:.. Ilistologically, liver, ki'ln?y and gonaclal tissues from L!ie5(? aniii'als appeared normal, In the l'J/3 stu'.ly several different, specie; of animal", were caught, both on and : F- 3 �off the test grid. These included beach mice, (P£rpjny_scus_ PP.Up].iptyrL), cotton mice, (Pejorny_scus_ c_qs_sypi_nus_), eastern harvest mice, (RpHJinxfpji hujnuVijjJ, hispid cotton rats, (S_iJ3npdpn_ h|_sp_idus_), six-lined race-runner's, TCnemi'dpphorus sexlineatus), a toad, (_Bufp/_ainerkaiuj_sj, and a cotLoiniiouth water" nToccaTin, C^£tj5tro_cp_n pjsjflyp.ry.C) • A "total" of 89 animals v.'ere submitted to The Armed" Forces Tnstituffe"of Pathology, Washington, D.C. for complete pathological examination including gross and microscopic studies. Liver and fat tissue from 70 rodents were forwarded to the Interpretive Analytical Services, Dow Chemical U.S.A., for TCDD analyses. The sex distribution of the trapped animals was relatively equal. The ages of the animals varied, but adults predominated in the sample. No gross or histological developmental defects were seen in any of the animals. Several of the rats and mice from both groups were pregnant at the time of autopsy. The stage of gestation varied considerably from early pregnancy to near term. The embryos and fetuses were examined grossly and microscopically, but no developmental defects or other lesions were observed. Gross necropsy lesions were relatively infrequent ond consisted primarily of lung congestion in those animals that had died from heat exhaustion prior to being brought to the laboratory. The organ weights did not vary significantly between the test and control animals when an animal with lungs end kidneys showing inflammatory pathological lesions was removed from the sample. Histologically, the tissues of 13 of the 26 control animals and 40 of the 63 animals from the test grid, were considered normal. Microscopic lesions were noted in sonie animals from both groups. For the most part, these were minor changes of a type one expects to find in any animal population. One of the most common findings was parasites. A total of 11 controls and 9 grid animals were affected with ore or more classes of parasites. Parasites may be observed in any wild species and those in this population were for the most part incidental firidinps that were apparently not harmful to the arimals. There were exceptiors however. Protozoan organisms had produced focal myositis in one rat, ard were also responsible for hypertrophy of the bile duct epithelium in a six-lined raceruriner. Moderate to severe pulmonary congestion and edema were seen in several rats and mice. All of these animals were found dead in the traps before reaching the laboratory, and the lung lesions were probably the results of heat exhaustion. The remainder of the lesions in both groups consisted principally of inflammatory cell infiltrates of various organs and tissues. They were usually mild in extent and although the etiology was not readily apparent, the cause was not interpreted as toxic. The analyses of TCUD from the rodents collected in June and October 1973 indicated, that 1CDD or a compound chemically similar to TCDD accumulated in the liver and fat of rodents collected from an area receiving massive quantities of 2,4,5-T. However, b?sed on the pathological stud'lfcs there was no evidence that the herbicides and/or contaminants produced any c-evelopmental defects or other specific lesions in the animals sampled or ir Lhe progeny of those that were pregnant. The lesions found v.'ere interpreted to be of a naturally occurring type and were not considered related to any specific chemical toxicity. F-4 �In 1970 beach mice were not found on the more barren sections of the grid (0-5% vegetative cover). There were, however, some areas of tlic grid which had population densities exceeding those of the spec ins preferred habitat as reported in the literature. In an attempt to correlate distribution of tha beach mouse with vegetative cover (i.e., habitat preferance) a trapping-retrapping program of 8 days duration was conducted in 1973. The majority of <;nimals (63) were found in areas with 5','i to 607, vegetative cover: Within this range, the 1greatest number of animals trapped (28) was from an area with 40?j to 602 cove ". A similar habitat preference has been observed along the beaches of the Gulf Coast. In this study, it appeared that the beach mouse used the seeds of switchgrass (Panicurn virgatum) and wooly panicum (Pa n i c urn 1 a n u g i no s urn) as a food source. Trapping data from 1971 was compared to trapping data collected in 1973 to determine whether an increase in the population of beach mice had occurred. The statistical evidence derived from that study showed that the 1.64 beach mice per acre population (based on the Lincoln Index for 1973) was slightly higher than the 0.8 and 1.4 mice per acre reported for a similar habitat. The population of beach mice was also higher in 1973 than in. 1971 in the area of the test grid. The apparent increase in beach mouse population on the grid in 1973 over 1971 was probably due to the natural recovery phenomenon of a previously disturbed area (i.e., ecological succession). Some areas of the test grid have currently exceeded that preferred percentage of vegetative coverage of the beach mouse habitat, and other areas were either ideal or fast developing into an ideal habitat. If the test grid remains undisturbed and continues toward the climax species, a reduction in the number of beach mice will probably occur simply due to decline of preferred habitat.. A 1973 sweep net survey of the Arthropods o~ Test Area C-52A resulted in the collection of over 1,700 specimens belonging to 66 insect families and Arachnid orders. These totals represented only one^ of five paired sweeps taken over a one-mile section of the test grid. A similar study performed in 1971 produced 1,803 specimens and 74 families from five paired sweeps of the same area" using the same basic sampling techrnq~ues. A much greater number of small"to minute insects were taken in the 1973 survey. Vegetative coverage of the test a^ea had increased since 1971. The ;wo studies showed similarities in pattern o? distribution of Arthropods in relation to the vegetation, number of A'-'thropod spncies, and Arthropod diversity.. Generally, the 1973 study showed a reduction of tho extremes found in the above parameters in the 1971 study. This trend was expected to continue as the test area stabilizes .inn! develops further plant cover, thus allowing a succession of insect populations to invade the recovering habitat. There are two classes of .viinHc areas assor.interl with the Test Area; ponds actually on the square ri'ilo area and strcai:s which drain the area. Most of the ponds are primarily of the "wH weather" typo, drying up once in the last five years, although one of th^ ponds is spring fed. Three major stream:; and two minor strearrs drain the te:>t area, the combined F-5 �annual flow of the fivo streams exceeds 24 billion gallons of water. Seventeen different species of fishes have been collected from the major streams while three species have been collected from the spring-feel pond on the grid. Statistical comparisons of 1969 and 1973 data of fish populations in the three major streams confirm a chronologically higher diversity in fish populations. However, the two control streams confirm a similar trend in diversity. Nevertheless, from examining all of the aquatic data, certain observations support the idea that a "recovery" phenomenon is occur v "irig in the streams draining TA C-52A. These observations are difficult to document because of insufficient data. For example, in 1969, the Southern Brook Lamprey (Jcjitjiypmyzqn. ca_gei_) was never collected in one of the streams immediately adja'cont'to" the"*area of the grid receiving the heaviest applications of herbicides; however, in 1973 it was taken in relatively large numbers. These observations may or may not reflect a change in habitat due to recovery from herbicide exposure. Residue ana"yses (1969 to 1971) of 558 water samples, 68 silt samples and 73 oyster samples from aquatic coirmunitites associated with drainage of water from Test Area C-52A showed negligible arsenic levels. However, a maximum concentration of 11 ppb picloram was detected in one of the streams in June 1971 but dropped to less than 1 ppb when sampled in December 1971. TCDD analysis of biological organisms from streams draining Tost Area C-52A or in the ponds on the test area vwere free from contamination at a detection limit of less than 10 pa 'ts per trill ion. In analyses performed 3 years after the last, application of 2*4-0 and 2,4,5-T herbicide the test grid exhibited population levels of soil microorganisms identical to that in adjacent control areas of similar soil and vegetative characteristics not exposed to herbicides. There were increases in Actinomycete and bacterial populations in some test site areos over levels recorded in 1970. This was possibly due to a general increase in vegetative cover for those sampling sites and for the entire test grid. No significant permanent effects could be attributed to exposure to herbicides. Data on aquatic algal populations from ponds on the one square mile grid (previously exposed to repetitive applications of herbicides) indicfi'';ed that the genera present wore those1 expected in warm, acid (pll 5.5), set.'nag.--:, or standing wafers. F-6 �APPENDIX G FIELD STUDIES ON THE SOIL PERSISTENCE AND MOVEMENT OF 2,4-D, 2,4,5-T, AND TCDD �(This page intentionally left blank) �FIELD STUDIES ON THE SOIL PERSISTENCE AND MOVEMENT OF 2,4-D, 2,4,5-T, and TCDD* ; A.L. Young, E.L. Arnold and A.M. Wachinski Department of Life and Behavioral Sciences USAF ACADEMY, COLORADO 80840 INTRODUCTION Concern over the level of contamination of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) herbicide by the teratogen 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) may result in the disposal of selected inventories of this herbicide. A potential disposal method is that of soil incorporation. The soil incorporation method is based on the premise that high concentrations of phenoxy herbicide and TCDD will be degraded to innocuous products by the combined action of soil microorganisms and soil chemical hydrolysis. It has been known for several years that the rate at which herbicides disappear from the soil is largely dependent Lpon their susceptibility to metabolism by soil microorganisms. Much of the information available on the biological breakdown of the phenoxy herbicides cornes from laboratory studies and is very useful for predicting what might happen when relatively high concentrations of phenoxy herbicides are applied to a soil incorporation site. Conversely, a certain amount of caution must always be used when extrapolating laboratory data to a field situation. Data on the field persistence of TCDD is extremely limited primarily due to the low levels of contamination in commercial formulations, the rate of application of such formulation, and the lack of a sensitive analytical method for the detection of TCDD. This report documents current field research on the soil degradation of a TCDD-contaminated phenoxy formulation when incorporated in the soil at massive rates of application. METHODS-AND MATERIALS In August 1972, a site for the soil incorporation of phenoxy herbicides was selected on the Air Force Logistics Command Test Range Complex, Hill Air Force Base, Utah. The potential site was characterized as being relatively flat and having a uniform, surface without rock outcrops or areas of marked deflation or dunes., Sediments in this area are lacustrine in origin and were deposited when ancient Lake Bonneville covered this region of the Great Basin. Sediments consist of clays interlaced irregularly with sand lenses and remnant stream 'sands; the clays predominanting.. The undifferentiated clays contain various amounts of dissolved salts. Table 1 shows an analysis of the top two *Presentation to the Weed Science Society of America, 13 February 1974., Las Vegas, Nevada. Abstract No. 226, G-l �TABLE 1. Soil analysis of the top two six-inch soil increments from the soil incorporated plots, Air Force Logistics Command Test Range Complex, Hill Air Force Base, Utah3 Inches pH Organic Carbon Electrical Conductivity (EC x in3)b 0-6 7.8 0.82 28.0' 23.7 3.9 6-12 7.9 0.95 31.0 23.8 3.9 a Silt (*) Clay 13.4 27 53 20 31.1 13.2 26 52 22 34.2 K Moisture at Saturation (*) Determined by Soils Laboratory, Utah State University, Logan, Utah, and the Soils Laboratory, Kansas Agricultural Experiment Station, Garden City, Kansas. Electrical conductivity in millimhos per cm at 25 C. C75 Sand (%) Ma meq/lOOg soiIT Ca/Mq �six-inch increments (0-6, 6-12 inches) of the soil profile. The annual rainfall of the area is less than ten inches taking into consideration the water equivalent of snowfall. Ground water of the area varies from 16 to 20 fee" below the surface. It is supplied primarily by the precipitation fallinq on-the nearby mountains. . The small amount of water which percolates through the existing clays moves laterally westward towards the salt flats, picking up chemical matter from these clays. As A result, the ground water contains up to 1,000 parts per million (ppm) sodium chloride. The annual mean daily minimum temperature is 33.5 F and the annual mean doily maximum temperature is 64.7 F. The experimental area has a vegetative cover of 15 percent and is dominated1 by fourwing saltbush, A£n_p_lqx_ cane seen s (Pursh) l\utt,; halogeton, Rlorosratus^ (M. Bieb.) C.A. Mey; "and" "gr'a'y"molly, Koch i a vestita. Six field plots, each 10 x 15 feet, were established on the Air Force Logistics Command Test Range Complex on 6 October 1972. To simulate subsurface injection (incorporation), three equally-spaced trenches, 6 inches wide and 10 feet in length were dug to a depth of 4-6 inches in each plot. The rates of herbicide selected for incorporation were 1,000, 2,000, and 4,000 pounds active ingredient per acre (Ib ai/A) 2,4-D plus 2,4, 5-T. Two replications (plots) per rate were included in the experiment. The quantity of herbicide required for each rate was divided into three equal parts and sprayed, as the concentrate, into each of the three trenches per plot, respectively. A hand sprayer with the nozzle removed was used to spray as uniformly as possible an approximate two-to-three-inch band of herbicide in the center of the 6-inch by 10-foot trench. The trenches in each plot were then covered by use of a handshovel , tamped, and levelled using a handrake. The herbicide formulation used for these simulated incorporation experiments was an approximate 50:50 mixture of the n-butyl esters of 2,4-D and 2, 4, 5-T. One gallon of this formulation contains 4.21 pounds of the active ingredient of 2,4-D and a. 41 pounds of the active ingredient, of 2, 4, 5-T. The formulation was originally specified to contain: n-butyl ester of 2,4-D free acid of 2,4-D n-butyl ester of 2, 4, 5-T free acid of 2, 4, 5-T inert ingredients (e.g., butyl alcohol and ester moieties) 49.40% 0.13% 48.75% 1.00% 0.62% Some of the physical, chemical, and toxicoloqical properties of the herbicide formulation are: Specific Density (25 C) 1.202 Viscosity, centipoise (23 C) 43 Molecula7' mass 618 Weinht of Formulation (Ibs/oal) 3.63 Soluble in water no Specific toxicity for female 566 white -"Qts (mg formulation/ kg body weight) G-3 �A 200 ml sample of the formulation was removed from the container of herbicide used on these plots, placed in a hexane-acetone-rinsed ulass jar and shipped to the Interpretive Analytical Services Laboratory, Dow Chemical U.S.A., Midland, Michigan, for analysis of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The results of the analysis indicated a concentration of 3.7 parts per million (ppm) TCDD. The first initial soil samples were to be taken the following day after incorporation of the herbicide. However, because of adverse wc.ather initial samples were not obtained. Beginning in January 1973 soil samples were collected routinely every 2-3 months. Sampling was done by using a 3-inch by 6-inch hand auger. Each row (trench) in each plot was sampled once by removing 6-inch increments to a depth of 36 inches. Each depth was uniformly mixed per plot (i.e., the three rows per plot were mixed for each depth), placed in sample containers, and shipped under dry ice to the laboratory for herbicide analysis. In all cases, the soil cores were obtained as accurately as possible -From the center of the 6-inch wide row (trench). In the laboratory, each sample was analyzed for 2,4-D acid, 2,4,5-T acid, 2,4-D n-butyl ester, and 2,4,5-T n-butyl ester by the gas chromatographic procedure of Arnold and Young (jn press, Analytical Chemistry, 1974). RESULTS AND DISCUSSION The results of the analysis of soil samples taken from the test plots are displayed in Tables 2-4. Table 2 illustrates the loss of total active herbicide frcn the upper 12' inches of soil increment over a period of 440 days (6 Oct 1972 - 14 Dec 1973). Assuming normal climatological conditions this period represents 7 months of relatively cold temperatures and 7 months of relative warmth. The percent loss of herbicide over just the 330 day sampling p_er_iod_ (from 110 to 440 days) was 78.22, 75.2% and 60.8% for the 1,000, 2,000, and 4,000 Ib ai/A plots, respectively. If the theoretical values for herbicide concentration at day 0 are used, percent loss of herbicide during the entire experiment was 87.8%, 85.3?; and 82.6%, respectively. These deta tend to indicate a decreased degradation of herbicide with increased application rate. However, the unusually low rate calculated for 4,000 Ib ai/A application over the 330-day period is likely a result of low valoe of herbicide measured in the first sample (110 days) rather than a difference in degradation rate. If a strict exponential decay curve is assumed, the half life for the total herbicide ranges from 146 to 155 days depending on application rate. Tables 3 and 4 illustrate the individual loss Df each of the herbicides (2,4-D and 2,4,5-T) contained in the original formulation. Except at the lowest rate of applicaton, no significant difference was seen in the rate of degradation of the individual components in this formulation. At the anplication rate of "000 lb.s/A, there was a 7.5% difference (rate, 2,4-D = 81.22; 2,4,5-T = 73.7%) in deoradation rates. It was originally thought that this was due to laboratory error, however, further sampling has tended to confirm this difference. It should be n.oted at this G-4 �TABLE 2. Soil concentration, part per million, of 2,4-D and 2,4,5-T herbicide at selected sampling periods, days, following soil incorporation. Application Rate of Formulation (Ib ai/A)b Sampling Time After Incorporation (Days) Oc nO 1,000 10,000 5,580 2,000 20,000 11,877 4,670 2,944 4,000 40,000 17,729 8,489 6,944 220 282 440 1,216 1,876 Data represent an average of two replications with the duplicate samples of each replication: the total value for depths 0-6 and 6-12 inches of soil increment. b Pounds active ingredient per acre. c Theoretical concentration at time <of application based on a two-inch spray at heoretical swath at a depth of 4-6 inches within the soil profile. G-5 �TABLE 3. Soil concentration, parts per million, of 2,4-D herbicide at selected sampT'ng periods, days., following soil incorporation. Approximate3 rate Df 2,4-D (Ib ai/A) Sampling Time After Incorporation (Days) 0C 110 220 976 500 5 ,000 3,280 1,000 10,000 7,261 2,000 20,000 10,545 232 440 616 2,370 4,829 1,844 —- 4,112 Rate of herbicide per acre was based on the oricn'nal specification of the formulation (i.e., a 50:50 n-butyl formulation containing 8,63 pounds active ingredient per gallon). Data represent an average of two replications with two duplicate samples of each replication: the total for depths 0-6 and 6-12 inches of soil ricrement. Theoretical concentration at time of application based on two-inch spray • swath at a depth of 4-6 inches within the soil profile. G-6 �TABLE. 4. Soil concentration, parts per million, of 2,4,5-T herbicide at selected sampling periods, days, following soil incorporation. Approximate3 Rate of 2,4,5-T (Ib ai/A) Sampling Time After Incorporation (Days) Oc 110 /* 220 282 440 500 5,000 2,300 1,000 10,000 4,616 2,300 1,100 2,000 20,000 7,184 3,734 2,832 900 604 Ra'ce of herbicide per acre was based on the original specification of the formulation (i.e., a 50:50 n-butyl formulation containing 8.63 pounds active ingredient per gallon). Data represent an average of two replications with two duplicate sanples of each replication: the total for depths 0-6 and 6-12 inches of soil increment. Theoretical concentration at time of application based on two-inch spray swath at a depth of 4-6 inches within the soil profile. G-7 �[joint that while it was originally assumed that the formulation which was applied contained equal anounts of each herbicide, data obtained from soil analysis tended to contradict this assumption. On the first sampling date the soils contained an average of 66.9» 2,4-D and only 33.1% 2,4,5-T*. This ratio was approximately maintained throughout the study. A sample of the herbicide formulation was analyzed by gas chromato^raphic-mass spoctron'etry techniques and found to contain approximately 6Q% ?,4-D and 40?t 2.j4,5-T In addition to the butyl esters, the formulation also contained relatively large amounts of octyl and iso-octyl esters of both components. A great deal of difficulty was encountered in our attempt to accurately measure the rate of herbicide loss in these field samples. Without averaging, loss rates calculated varied over a rather large ranqe from sample to sample. Even with averaging a few samples which were analyzed were not included in the da';a due to extreme vernations in herbicide concentration, i.e. much higher or lower than previous samples. We attribute these variations to a number of uncontrollable variables, the most significant of w'n'ch was a variation in application rates within the test rows. When the test plots were established, the herbicide was sprayed into the rows with a hand sprayer and it appears likely that there were originally concentration differences at various points due to this method of application. A second source of error is attributable to the moisture content of the soil samples. On some of the sampling dates, the samples received were extremely wet due to snow drifts over the plots while others were relatively dry. This variation in moisture tended to change the consistency of the soil and -'n many cases made the obtaining of a uniform sample impossible. A third source of variation occurred due to the composition of the herbicide sample which was originally applied. As was previously mentioned in addition to the expected n-butyl esters of 2,4-D and 2,4,5-T, a portion of the formulation of the sample was made up of n-octyl and iso-octyl esters of the two herbicides. No attempt was made to analyze for these esters in the soil samples; consequently, the effect of these compounds on the overall degradation pattern would only be noted after they had been hydrolyzed to the free acid. Since the rates of hydrolysis of these compounds may be different than that of n-butyl esters, this is another possible source of variation in the data obtained on early sampling dates. In order to minimize variations in the data, on February 1, 1973, small amounts of soil (200 g) from the field plots were analyzed and placed in glass stoppered bottles. These bottles were then placed in a constant temperature incubator at 83 F to be analyzed periodically at later dates. The analytical data from these samples are presentee' in Table 5. Average percent loss/day values calculated from these samples were 0.42%/day for 2,4-D and 0.48£/day for 2,4,5-T. Half lives for 2,4-D and 2,4,5-T calculated from these data are 119 days and 104 days, respectively. In these Scinples it appears that the rate of degradation decreases with time since, in most samples, the loss of herbicide was greater from day 0 to 02 than between days 82-156. Apparently initial concentration had little effect on the degradation rate. The average rates of loss for the 6 samples with the highest initial concentrations, were .43 and .48 .vhile those for the 6 G-8 �T. TABLE 5. SaT.pl 0 Number 1 Loss of herbicide (ppm) from field samples incubated iri the laboratory at 83 F. 0 Da s y_ . Total loss/ day (p crcent) 156 Days 82 1Day?. 2,4-D 2,4,5-Tb 2,4-D 1 2740 1980 2300 1178 868 480 .44 .44 2 2440 1500 1412 695 680 320 .46 .50 3 3220 2380 1340 82.0 840 488 .47 .51 4 2360 1500 1260 750 784 440 .43 .45 5 5704 4220 3148 1640 2000 1124 .42 .47 6 5484 3388 2408 1350 '1852 920 .43 .47 7 3260 2100 1540 760 1164 632 '.41 .*5 8 2980 2200 1162 547 1300 720 .36 .43 9 9680 7080 4584 2408 3552 1740 .41 .48 10 11000 7720 4644 2388 3590 1902 .43 .48 n 2820 1820 1500 700 1032 608 .41 .43 12 3320 . 2440 1448 895 1028 500 .44 .51 AVG. 4584 3194 2229 1178 1558 823 '.2 '4 .43 TOTAL 55,008 38,328 26,746 14,131 18,690 . 9,879 a 2,4,5-T 2,4-D 2,4-D 2,4,5-T 2,4,5-T i* a Total value for esters ar.d acids of 2,4-D. Total value for esters and acids of 2,4,5-T. 6-9 �samples of lowest concentration were .42 and .46, respectively, and are therefore not significantly different. One observation that was apparent in all degradation studies which have been performed is the relatively rapid hydrolysis of the n-butyl esters of the herbicide due to coitact with the alkaline Utah soils. Table 6 gives the percentage saponification of the n-butyl esters of 2,4-D and 2,^,5-t to the acids over a period of 282 days for two different application rates. It was found that in all samples, the rate of hydrolysis of n-butyl 2,4-D was greater than that of n-butyl 2,4,5-T. Moreover, it is likely that at the higher concentrations (e.g., 4,000 Ib ai/A), the acid salts formed could not be removed at a sufficiently rapid rate (via degradation and/or penetration), causing the chemical equilibrium to shift to the left. Data concerning herbicide penetration in Utah soils are shown in Table 7. Samples from lower soil increments were taken from those plots where it was expected that herbicide concentrations would be most likely to penetrate into the 'soils. With one Exception, both 2,4-D and 2,4,5-T residues were found at all levels sampled. In all cases the total herbicide concentration in levels greater than 18 inches was made up entirely of the free acids. Butyl esters were not detected at depths greater than 12 inches for 2,4-D or 18 inches for 2,4,5-T. It is also interesting to note that the penetration of 2,4-D is greater than that of 2,4,5-T. Apparently this is due to the greater water solubility of the free acid of 2,4-D. This may also explain why 2,4-D appeared to degrade more slowly in laboratory samples where there was no loss from the sampla due to penetration. In June 1973, a composite soil core froir one of the 4,000 Ib ai/A plots was selected for TCDD analysis,. The Interpretive Analytical Services Laboratory, Dow Chemical U.S.A. performed the analysis using e. modification of the nethod developed by Baughman and Meselson (published in Environmental Health Perspectives, Experimental Issue. No. 5, September 1973). The following data were obtained: \ _^ 2,3,7,8-tetrachlorodibenzo-p-dioxin Sample parts per trillion parts per billion Control (0-6 inc'ies) <10 <10 Plot 5 (0-6 incnes) 15,000 15.00 3,000 90 120 3.00 0.09 0.12 Plot 5 (6-12 inches) Plot 5 (12-18 inches) Plot 5 (18-24 inches) Thus, within the four samples from the plot 5 core (4,000 Ib ai/A) a total concentration of 18,210 ppt (18.21 parts per billion - ppb) was found. Undoubtedly the lower two depths (12-18 and 18-24 inches) represent contamination from the upper two increments, via the use of the hand auger. G-10 �TABLE 6. Percentage saponification of the n-butyl esters of 2,4-D and 2,4,5-T at selected time periods, days, followinq soil incorporation in alkaline soils. Application Rate of Formulation 1,000 Ib ai/Ab Esters Acids 4,000 Ib ai/A Esters Acid a Days After Incorporation a 0 110 220 282 100 24 13 3 0 7(5 87 97 100 77 40 32 0 23 60 68 Data are the percent acid and esters of herbicides found in top 0-6 of soil profile. Ib ai/A = pounds active ingredient per acre. G--11 �TABLE 7. Herbicide (2,4-P and 2,4,5-T) penetration (ppm) in the 4,000 Ibai/A plots 282 days after soil incorporation. 2/-D a (ppm) 2,4 s 5-T a (ppm) Percent of total Herbicide 0-5 4262 2982 72.4 6-12 1093 752 18.4 12-18 126 TOT 2.3 DeDth (inches) i 18-24 70 2.7 25-30 230 50 2.9 30-36 a 158 161 21 1.8 Data are an average of two analyses and represents the total of both the es*er and acid components. G-12 �Since the TCDD concentration of the formulation was known (see Methods), and since its determination in the soil core was performed by the same laboratory and instrumentation, an estimation of the degradation of TCDD can be obtained by comparison to the expected value based on the known concentration of herbicide at time of sampling. Subsamplos of the soil core analyzed for TCDD were also analyzed for 2,4-D and 2,4,5-T. the total concentration of herbicide in the 0-6 anc 6-12 inch increments was, approximately 14,000 ppm. Therefore, the actual concentration should have been approximately 51.8 ppb TCDD (14,000 x 3.7 x 10-3 = El. 8) vf degradation of the TCDD was at the same rate as 2,4-D and 2,4,5-T. If the. theoretical values for herbicide concentration at day 0 (time of incorporation) are used, then the initial concentration of TCDD would have been 148 ppb (40,000 x 3.7 x lO"3 = 148 ppb). The percent loss of TCDD over a period of 265 days was 87.7% (18.21/148 = 12.3?;; 100% 12.3% = 87.7%). The value 87.7% would represent 3 half-lives for TCDD persistence. Therefore a rough estimate for the half-life of TCDD would be 88 days in. these alkaline sojljs_, under desejrt conditions^ and in the presence " ' .......... These preliminary data suggest that TCDD degrades at a more rapid rate than 2,4-D or 2,4,5-T. Moreover, the movement of the TCDD to the 6-12 inch depth probably represents co-movement with the missive 'amounts of esterified herbicide, rather than independent penetration into the soil profile. G-13 �(This page intentionally left blank) �APPENDIX H JOHNSTON ISLAND DATA �(This page intentionally left blank) �APPENDIX H - JOHNSTON ISLAND DATA Page 1. BACKGROUND INFORMATION a. b. History of Johnston Island Location arid Size—- c. Geology - H-l H-6 ' - H-16 d. Hydrography-— e. Tides and Currents- —-— H-21 H-22 f. Climatology H-24 1 2 3 4 5 6) Climate Temperature Precipitation Relative Humidity Surface Winds Trophospheric Circulatior 7 Stratospheric Circulatior 8 (9 — - - --. H-24 H-24 H-27 H-27 H-27 H-27 H-3<1 Sky Cover Historical Data H-31 H-31 - g. Surrounding Land and Water Use and Ownership h. Facilities- H-31 H-35 (1) Transportation H-35 « Sea Transport [b) Air Transport (c) Ground Transport (2) Comnuni cations (3) Utilities a b c d *•• ** • H-35 H-37 H-38 • • H-38 H-38 * Water Supply SystemElectrical Power System Sanitary Sewerage System Storm Drainage System H-38 H-38 H-39 H-39 - (4) Housekeeping H-39 (a 'Housing (b Messing c Recreation d Dispensary e Miscellaneous :— (5) Storage (a (b (c H-39 H-39 H-40 H-40 H-40 H-40 Warehouses Open Storage POL/LOX -H-i - H-40 H-40 H-40 �Page (6) Construction H-41 i. Terrestrial and Marine Flora and Fauna (1) Vegetation (2) General Animal Life H-41 • - H-41 H-41 (a) Mammals —- (b) Birds • H-42 (c) Reptiles (d) Amphibians • • H-42 H-42 (e) Fish • - (f) Insects and Other Arthropods—'(g) Land Crustaceans and Mollusks H-ii H-41 H-42 - H-42 H-43 �LIST OF TABLES Table ^ ~ ~ ~ r H-l Ownership and Control of Johnston Atoll H-2 Johnston Island Acreage H-3 • Mean Number of Days of Thunderstorms, Johnston Island H-7 H-14 - H-25 H-4 Climatic Brief - Johnston Islard H-32 H-5 Frequency of Occurrence - Atmospheric Stability Classes - Johnston Island H-33 Frequency of Occurrence of All Stability Codes vs Wind Direction - Johnston Island H-34 H-6 LIST OF FIGURES Figure Page H-l Central Pacific Ocean H-10 H-2 Map of Pacific Ocean H-1'I H-3 Changes in the Land Area of Johnston Island H-12 H-4 Johnston Atoll - U.S. Naval Survey Map No. 83637,1966 — H-13 H-5 Central Pacific Submerged Mountain Ranges H-15 H-6 Johnston Island Atoll Showing Reefs ar.d Depths H-18 H-7 Profiles of Two Reef Types H-20 H-8 Mean Monthly Air and Sea Temperatures, Johnston Atoll — H-26 I--9 Mean Monthly Precipitation, Johnston Atoll, 1931-1972 -— H-28 H-10 Wind Speed, Johnston Atoll, 1931-1972 H-29 H-ll Percent Frequency of Wind from E and ENE, and ESE and NE H-30 Port Facilities at Johnston Island H-36 H-12 H-iii �(This page intentionally left: blank) �1.. BACKGROUND INFORMATION a. jrf_Johnston Isjand • History" ~ "—' • (1) Johnston Atoll has had a varied history. ' It is one of the most isolated atolls in the entire Pacific Ocean. Originally it consisted of two small, insignificant islands, a partial coral reef to the west and northwest and a rather large, shallow lagoon to the east and south. This lagoon is dotted by numerous patch reefs and coral heads. It is new a large Department of Defense (DoD) complex. Johnston Atoll was originally discovered by the American brig "Sally" out of Boston on September 2, 1796 (Bryan, 1942)(Wetmore, 1963). However, no landing was made. On December 1, 1807 the HMS "Cornwallis" under the command of Captain Charles James Johnston visited the atoll (Marshall, 1825). Today the atoll bears this discoverer's name. Since 1858, Johnstor Atoll has been the undisputed possession of the United States. Prior to that date it was claimed for short periods of time by the Kingdom of Hawaii (Bryan, 1942). In 1892, Great Britain filed a claim that Johnston Atoll was being considered as a possible relay station for a transoceanic communications cable (Bauer, 1973). Johnston Atoll is not now and never has been a part of the State of Hawaii. It is presently an unincorporated territory which is distinguished from an incorporated territory, i.e., it is a territory to which the constitution of the United States has not been fully and expressly extended (U.S. Department of State, 1965). Birds have in the past and continue at present to play an important part in the history of the atoll. Following passage of the Guano Act of 1856 by the United States Congress there were transient guano mining efforts in 1858-1860. The first scientific visit in July 1923resulted largely from interest in the bird population (Wetmore, 1963). As a result of this visit, the atoll was made a Federal bird refuge on July 29, 1926 by Executive Order No. 4467 signed by President Calvin Coolidge. Initially the atoll was under the jurisdiction of the Department of Agriculture but in 1940 this responsibility was transferred to the Department of the Interior.. This executive order remains in force although subsequent executive orders have given jurisdiction over the atoll to the Department of Defense, see Appendix B. (2) Because of its strategic military location, President Franklin D. Roosevelt, on December 29, 1934, by Executive Order No. 6935, placed the atoll under the Department of the Navy. From 193^- to 1939 infrequent visits were made to Johnston Atoll by Pacific Fleet units. In the fall of 1939 the Navy awarded a contract for construction of a small naval base. A lagoon seaplane landing area with headquarters on Sand Island was initially constructed (Bauer, 1973). In February 1941, by Executive Order No. 8682, the airspace above and the water witlrn the 3-mile marine .bouncary were designated as the Johnston Island'Naval Airspace Reservation and the Johnston Island Naval Defense Sea Area, respectively, see Appendix B. On August 15, 1941, the Naval Air Station was commissioned. On December 15, 1941, eight days after the attack on Pearl Harbor, Johnston island was shelled for a short time by Japanese surface vessels. Again on December 21, 22, and 29, 1941 both Johnston and Sand Islands were shelled; one Japanese submarine was reported sunk by American gunfire. There were no injuries to personnel but the shelling caused considerable damage to various facilities. Construction continued until April 1942. Channel approaches and a seaplane landing area were dredged. Other construction included bomb shelters, living quarters, runways, parking aprons, storage sheds and gun emplacements (Bauer, 1973). H-l �(3) During early World War II, patrol submarines used the atoll as a refueling station. By 1944, and throughout the rest of the war, it became a major transport terminal for the Pacific area, servicing aircraft going to and from the Pacific battle fronts (Abend, 1942). After World War II, the Navy continued to operate the Naval Air Station at reduced strength. The status was later reduced to that of a Naval Air Facility. Sand Island was abandoned in 1946. By order of the Secretary of the Navy, operational cortrol of Johnston Atoll was transferred to the U.S. Air Force on July 1, 1948. The Navy retained technical jurisdiction. During the Korean airlift in 1951 and 1952, Johnston Island again assumed major military importance,, The airstrip was enlarged by dredginc and new buildings and improved utilities were added (Bauer, 1973). ^ (4) On January 25, 1957, the Treasury Department was granted a permit for the U.S. Coast Guard to operate a LORAN (Long Range Air to Navigation) transmitter on Johnston Island. On September 13, 1957, the Department of Commerce began operation of a Weather Bureau facility on the island. On April 22, 1958 operational control of Johnston Atoll was assumed by the commander of Joint Task Force Seven. As part of Operation Hardtack, two missiles carrying thermonuclear devices were fired from Johnston Island into the stratosphere to obtain information on the effects of nuclear detonations at high altitudes. These were the first megaton devices detonated in the stratosphere by the United States. The Pacific phase of Operation Hardtack lasted until August 19, 1958. Operational control of Johnston was assumed by Joint Task Force Eight and the Atomic Energy Commission on January 17, 1962 for the purpose of conducting additional high-altitude nuclear tests. The Secretary of Defense granted permission on Uecenber 10, 1959 to relocate the U.S. Coast Guard LORAN-A and -C Station to Sand Is'and. Completed in 1961, the U.S. Coast Guard facility presently maintains a staff of approximately 25 men. Sand Island is still a bird sanctuary under the jurisdicition of the Department of Interior (Bauer, 1973). (5) By August 1960, Air Force retention of Johnston Island seemed assured, and a survey was made to ascertain the scope; of work required to restore base facilities to minimum operational condition. Extensive engineering activity continued throughout 1961. Also, during this period the LORAN station on Sand Island and the U.S. Weather Station authorized by JCS Document 1910/10 were finished. Important contracts were let for modification and alteration, airfield pavement repair and emergency runway lighting. Repair of the old distillation system and installation of new equipment was accomplished. Several construction projects continued with a deadline of 15 March 196E, necessitated by 19b2 Pacific Atomic Tests (USAF Hist, 1959-1963). Joint Tas< Force Eight and the Atomic Energy Commission entered into an operational agreement with the Department of the Air Force on 17 January 1962 to take control of Johnston Island. Additionally a memorandum of understanding was executed between Commander, Joint Task Force Eight and Commander in Chief, Pacific Air Forces on 18 January 1962. As part of this agreement, support of both the Coast Guard LORAN Station and the Weather Bureau Station, previously a commitment of Pacific Air Force Base Conmand, was undertaken by Commander, Joint Tas< Force Eight. Major construction projects in support of the test series were completed in May 1962; however, numerous minor projects continued throughout the test period. All existing facilities were aigmented to the fullest extent possible, but were subject to the limitations imposed by useable estate and available time (Bauer, 1973). H-2 �(6) Commander, Joint Task Force Eight proposed in his message 26030Z of October 1962 to the Chairman, JCS, that steps be taken'for preservation on the island of certain test assets there and to return operational control of the island to Commander in Chief, Pacific Air Forces providing there were no plans for additional nuclear tests prior to mid-1964. The JCS generally concurred; however, because of plans for possible use of Johnston Island during calendar year 1963, by their message 071837Z of November 1962", requested that the plan be reviewed in light of this development. While this review was being conducted, further direction by JCS message JCS 7654 011648Z of December 1962 was received. It directed Commander, Joint Task Force Eight to retain control of Johnston Island pending further guidance. On 16 January 1963, Commander, Joint Task Force Eight, proposed that the control and support arrangements for Johnston Island be maintained until at least 1 April 1963. Additional plans and guidance for the Task Force were received from tha JCS through their Paper SM373-S3 of 19 March 1963. It was clear at this time that the most efficient procedure would be for Comrrander, Joint Task Force Eight to retain operational control of Johnston Island at least through the completion of the 1964 test plans. The proposal was affirmed by JCS Paper SM-758-63 Df 11 June 1963. Later in 1963 the mission and the future of Johnston Atoll were to be guided by the national requirements for possible continuation of nuclear tasting in the atmosphere. The significant influence for ratification of the Limited Test Ban Treaty of 1963 was President Kennedy's assurance to Congress that four safeguards would be estaalished and maintained to keep the U.S. from falling behind in nuclear technology. One of the safeguards, Safeguard III, was the development of the ability to resume testing promptly in those environments prohibited by the treaty in the event of Russia's abrogating the treaty or if such test should be deemed essential to national security. Thus, by Safeguard III, the future of Johnston Atoll was estaDlished as an overseas nuclear test base. Plans for the 1964 tests were later cancelled; however, CJTF-8 continued to maintain Operations control of Johnston Atoll (until 1970) under the direction of the Director, Defense Atomic Support Agency (DASA), now the Defense Nuclear Agancy (DNA) (Bauer, 1973). (7) During the latter part of 1964 and early 1965, an advanced state of readiness was developed at Johnston Atoll in support of the National Nuclaar Test Readiness Program (NNTRP), a prompt response testing program, prepared by both the Atomic Energy Commission (AEC) and DoD (DoD-AEC a., 1965) (DoD-AEC b., 1965) to satisfy the Safeguard III requirement. This readiness posture, which included an extensive building program on Johnston Atoll, was maintained until 1970. Annual exercises conducted by JTF-8, commencing in 1964, evaluated the capability of the AEC and DOD agencies to initiate nuclear testing within specified reaction times. These full scale exercises at Johnston Atoll commenced with Operation Crosscheck in 1964 and continued with Operation Rcundup in 1965. Operation Windlass in 1966 and Operation Paddlewheel in 1967 (the last JTF-8 readiness-to-test exercise) included in addition to the previous years activities, a series of coordinated rocket firings from Johnston Atoll. The Department of the Interior approved the title "Johnston Atoll" to be used henceforth and forevermcre as a fitting recognition of the importance of the Johnston Island complex and its environs. Further, it was proposed that the two man-made island, created within the surrounding barrier reef, be named Akau and Hikina, Hawaiian words meaning north and east. On 20 May 1965, these names were officially assigned to the two islands. Extensive building of testing and support facilities, including airfield improvements and the installation of the Pacific Missile Range tracking complex, continued during 1965 to 1967. An Air H-3 �Force Ba<er-Nunn space camera station was constructed on Sand island and was functioning in 1965. It has continued to remain in full operational status. An agreement between AEC and DoD (AEC-DoD, 1971) in 1965 provided the basis for the necessary contractual arrangements for engineering, construction, maintenance, and operations services. The build-up program consisted of laboratories, shops, rocket launch pads, rocket assembly buildings, storage bunkers, control and monitoring facilities, sampling and tracking facilities, photo and optical stations, and weather facilities (AEC-CoD, n.d). A significant portion of the readiness-to-test capability is the THOR launch complex developed by the USAF which was used for launching nuclear paylcads during the test series (Dominic/Fishbowl) of 1962. Since then this complex operated by Program 437, a USAF R&D space program, made 15 scheduled THOR launches from 1965 to 1970. Since that time only crew training (operations terminated short of actual launch) continues. Launch crews are provided by the 10th Aerospace Defense Squadron under the control of Aerospace Defense Command. Improvements to the communications system in 1965 included the installation of a submarine telephone cable from Johnston Atoll to Oahu with additional cables connecting Johnston Island to Sand, Akau and Hikina Islands (Bauer, 1973). "(8) During the years of the Vietnam conflict, Johnston Atoll continued to support the flow of air traffic enroute to and returning from Southeast Asia. Formations of tactical aircraft made use of Johnston Atoll's refueling facilities since they were dependent upon enroute stops and/or the use of inflight refueling tankers. Due to increasing derrands for additional jet commercial routes to the various Pacific Islands, particularly to the Trust Territories, the Defense Department allowed the Civil Aeronautics Board to authorize commercial aircraft to make refueling stops at Johnston Atoll. This resulted in Air Micronesia service to Jo'hnston Atoll on 17 May 1968 (Bauer, 1973). (9) In late 1969, national decisions were made to reduce the leve" of support to the readiness program and to revise the NNTRP. These decisions included the inactivation of JTF-8 and the transfer of operational and funding responsibility for Johnston Atoll to the USAF (AEC-DcD, n.d). Effective 1 July 1970, operational control of Johnston Atoll was transferred to USAF, with continuing readiness planning responsibilities assumed by Director, DNA (Sec Def, 1969). The JTF-8 designator and records were retained by Director, DNA for utilizations as required. Operations and maintenance of Johnston Atoll was assumed by the 6486th Air Base Wing (PACAF), which was renamed the 15th Air Base Wing on 1 November 1971 with no change in mission. The population of Johnston Atoll, which had been approximately 1200, was reduced to approximately 600 by the end of 1970, with about one-half military and one-half civilian contract personnel. The responsibilities of Director, DNA concerning readiness facili-,. ties and the siting thereof at Johnston Atoll are defined in Dep Sec Def Memorandum for Director, DNA (Program/Budget, 1969). The relationships and responsibilities for the 15th Air Base Wing (PACAF) and the DNA (JTF-8) at Johnston Atoll concerning readiness natters were delir-eated. in a support agreement (Sec Def b, 1970). Concurrently, the emphasis within the technical and experimental readiness related programs of the AEC and DoD laboratories was shifted to address high altitude phenomenology and effects. A high altitude development test, planned and funded prior to the decision to phase down, was carried forward to execution. In September 1970, the AEC/DNA development test was conducted at Johnston Atoll utilizing a THOR booster mated with an AEC developed non-nuclear high altitude test vehicle (HATV). The successful THOR/HATV launch was conducted by a JTF-8 organization developed for this particular test. H-4 �(10) The decision was made during IS 70 to remove U,S. chemical munitions from Okinawa; however, their retention as part of the national stockpile was necessary., Political pressure which ultimately resulted in forbidding relocation of these munitions, designated RED HAT, to any point on CONLS or Alaska caused the selection of Johnston Atoll as the storage siteMovement of the RED HAT toxic .chemicals (MUSTARD, GB and VX) by ships, from Okinawa to Johnston Atoll, started in early 1971 and was completed in mid-May 1971. On Johnston Atol"! they were placed under the custody and control of the U.S. Army 267th Chenical Company. The construction of storage facilities for RED HAT in the southwest quadrant of Johnston Island occupies a 41-acre area. Just prior to movement of the chemical munitions to Johnston Atoll, the Surgeon General, Public Health Service, reviewed the shipment and the Johnston Atoll Storage plans and caused the Secretary of Defense in December 1970 (DNAPACAF, 1971) to issue instructions restricting missile firirgs and all air--craft flights to the island except essential military flights to support the island's mission. As a result, Air Micronesia service was immediately discontinued and rocket missile firings suspended (Bauer, 1973). Again, early in 1972, another politically unpopular problem arose with the phasing down of the Vietnam conflict which necessitated the movement of herbicice Orange (a USAF defoliant spraying mixture)from Vietnam. As a result of Congressional and citizen interest in disposal problems, the Department of Defense (DoD) decided to move one and one-half million gallons (26,300 55-gallon drums) to Johnston Atoll for storage to await a means of future disposal. By April 1972, herbicide Orange was in storage at Johnston Atoll (Sec Def a, 1970) on the southwest peninsula. As a result of a DNA Joint Hazards Evaluation Group study (DNA, 1972) conducted in July 1972, concerning the hazards to both transient and island personnel from commercial aircraft ise imposed by the storage of RED HAT, the commercial flight restrictions to Johnston Atoll were conditionally lifted. Air Micronesia was allowed to resume air service to Johnston Atoll on 29 April 1973. (11) Durinc mid-August 1972, a tropical storm, Celeste, located southeast of the Hawaiian Island, had blossomed into a full scale hurricane. Observation of Celeste's track for several days, it became apparent that Johnston AToll woul be in the path of the hurricane. The decision was made to evacuate the island and by 18 August all personnel had been flown to Hickam AFB, HI. This was the first known time ths island had been completely evacuated of personnel since the Navy commenced its construction progra.ni in 1939. On 19 August, Celeste struck Johnston Atoll at approximately 1400 hours local time. The atoll was subjected to sustained winds of 100 knots with gusts up to 130 knots. The heavy surf primarily affected the north, northeast, and south sides of the island. On 22 August a seaborne cadre, consisting of an Army RED HAT checkout team and an Air Force/H&N team, were put ashore at Johnston Atoll from the Navy destroyer USS Lloyd Thomas to initiate restoration of life support activities (Bauer, 1973). (12) In June 1973, the Deputy Secretary of Defense approved a USAF plan for the transfer of host manager responsibility of Johnston Atoll to DNA which was formulated into a joint USAF/DNA agreement (Joint Hazards, 1972) with an effective date of transfer of 1 July 1973 (DAF-DNA, 1973). H-5 �(13) Remaining still in effect, down through the years, is the executive order which origianlly designated Johnston Atoll a bird sanctuary. The bird scene today, principally at Sand Island, shows little if any effect by the numerous activities which the atoll has been committed to during its years of development. (14) A summary of ownership and control of Johnston Atoll is shown in Table H-l. (15) Through the past decade Johnston Atoll (environment, flora, fauna) has been the subject of numerous studies and surveys. Periodically, the Smithsonian Institution has investigated the bird life of Sand Island (bird sanctuary), its most recent effort being in 1969 when a research biologist spent several months there. Earlier studies commenced in 1963 (Bauer, 1973) by the Hawaii Marine Laboratory of the University of Hawaii, to investigate the effects on marine growth from the extensive dredging and buildup of the atoll, have continued tc this day. A land management plan (Support Agreement, 1973), prepared at the request of CJTF-8 in 1964, was used as a guide for developing plant life on the atoll and for control of erosion from wind and water. Surveys corducted in 1965 for the Naval Oceanographic Office (DNA-AEC, 1973) obtained detailed information about the water flow regime around the island. Another environmental program, continuous since 1966 by the Laboratory of Radiation Ecology, College of Fisheries, University of Washington, has been to obtain information for predicting &nd evaluating the biological consequences of a possible nuclear test series at Johnston Atoll. Reports on this program are submitted to the AEC annually. (16) As a result of Executive Order numbers 4467 and 6935 and their effect on the possible disposal of herbicide Orange on Johnston Island, the opinion of the General Counsel, Department of the Air Force, was requested. b. Location and Size (Land Surface) (1) Located at latitude 16 degrees 45 minutes north and longitude 169 degrees 30 minutes west, Johnston Atoll is one of the most isolated atolls in the Pacific. The closest reef is French Frigate Shoals, approximately 450 miles to the north. Honolulu, Hawaii is approximately 717 miles to the northeast, while the nearest land to the southeast: is Palmyra Island., about 750 miles away. The Marshall Island Group is the closest: land mass to the west at a distance of about 1,300 miles, see Figures H-l and H-2 (POBSP, 1964) (Thorp, 1960)(Navy Hydro a, 1959 and Navy Hydro b, 1959). 4 i (2) Johnston Atoll consists of a pair of low sand and coral islands, Johnston and Sand Islands, plus two entirely man-made islets, Akau (North) and Hikina (East) Islands within a shallow lagoon partially enclosed by a semicircular reef to the north and west. The southern arid eastern portions of the fringing reef, however, are made up of numerous discrete fragments spread over a large area to the south and east of the main lagoon. If one uses the 4-fathom line as indicating the outer boundaries of the atoll, Johnston Atoll has a circumference of somewhat more than 21 miles. This particular depth was used since it apparently correlates aVuost exactly with tie outer limits of the exposed reefs, with the line lying only a few yards to the seaward of the most southerly of the reefs. The atoll is roughly lens-shaped, with the long axis running on H-6 �TABLE H-l OWNERSHIP AND CONTROL OF JOHNSTON ATOLL Psriod "Owner" Operational Control Purpose of Document Authority ,923 Dept of Agriculture Agriculture Plant and sealife surveys, *Executive Order 4457 1934 Dspt of the Navy USN Pacific defense *Executive Order 6935 Established Naval Defense Sea Area for military sea and air operations ^Executive Order 8682 n 1941 n n n USN 1944 USN 1948 Jul 1 USAF 1949 Jun 1 I! II II II Bird refuge (Executive Order June 2SS 1225} Became Johnston Island Naval Air Station Defense of area; Air Transport Command operations; Oceanic Air Traffic Control USN 1947 Event/Use Secretary of the Navy Transfer of operational control to USAF Became a Naval Air Facility Agreement Pacific Air Command (MATS, ARS, AACS, Ai'/S Dets) (SecNav ordered transfer to USAF) USAF *Executive Orders are still in effect; have net been amended or rescinded so as to affect "ownership" Pacific Air Command inactivated; Pacific Division MATS took over, �TABLE. H-l (Cont'd) Purpose of Document Period "Owner" Operational Control 1951-52 Dapt of the Navy USAF Korean a i r l i f t support USAF USAF granted Treasury Department five year use for USCG Loran Station USAF. USAF granted Department of Commerce five year use for U . S . Weather 3ureau 1957 Jan 25 " 1957 Seo 13 " " 1958 Apr 22 CD " " " " " !1 " CJTF-7 Jul 24 " " " " USAF 1959 Sap 23 II <! !! M USAF 1959 Oun 30 II II Jl II USAF Authority Agreement Event/Use Atomic tests in Pacific area until August I S , 1S5S; then roll-up. Formal meeting in Hawaii to propose transfer of operational control to Amy for the Nike-Zeus test program, i To transfer • operational con. trol to Army Proposed agreement sent to higher headquarters Secretary of the Treasury asked Secretary of Defense for • Sand Island as Loran S t a t i o n , to be under operational control of Commander in C h i e f , P a c i f i c . �TABLE H-l Period Operational Control "Owner 1362 Jar. 17 Dept of tha Navy 1962 Jan 18 II li II II 1970 Jul 1 II II 1973 Jul 1 " " Purpose of Document Authority Event/Use CTOF-8/AEC Agreement USA" signed Operations Agreement for 1962 nuclear tests, CJTF-8/AEC Agreement Commander in Chief, Pacific signed agreement with Germander Joint Task Force EIGHT, CJTF-8/AEC1 1963 Jun 11 (Cont'd) Joint Chiefs of Staff reaffirmed operation control of Joint Task Force EIGHT. — M II USAF Transfer of operational control to USAF " " DNA (FCDMA) Transfer of operational con trol to DNA JTF-8 inactivated. Deputy Secretary of Defense Memorandum to Secretary of Air Force for transfer of JA to USAF Agreement Department of the Air Force signed agreement with Defense Nuclear Agency �--H-H—. i .!. J ' __. I ' _—,_. ,._J—I—,_.. ' I I r " !'"' I O '.' ~j \ \ I • i i i g •\ r J ! '. ', I I ; i ?• " ' i—i—:— 3- r~T~ , i ! I i i I * ; • ' !<j r 1 . -: ( W— — ft F^ F 1 • — : I ? : j [ ' 2 £' I ' i' . : ' . l ; ! r-y-p FIGURE H-l T1 ~J 7'^L.ILI I ' l l • ; : ' .i ^ • : ' _ ! • : ' : 1-,--.' ' i I I I ! i -—i---iJ ,—;- -h-4—^-h-—r -I-..4-J -_.:_.._. TAKEN FROM THE PRELIMINARY BIOLOGICAL SURVEY OF SAND ISLAND - JOHNSTON ATOLL (POBSP, 1964) �PAC'FIG OCEAN in." .no1 IOT : ./ i../ '* | I \ '«%: ! '—tf \ __ —' i^".;.._ ; '. -V^V'2 I jfi-^ I ^rt-St i ! • 1 .-KuMf i 1 'fiui . : "1 ->V*•'—T,s4-<- f**°rs • p^.4s-s— ^•SlwLf I:- .n ' I j ^-teS^S^S ^«.<LX^"!=' *i 2^vXi*rr^N I It -L' i -*.NU i —r—h--h- 47* 3OUTH iitrCAsr izcr FIGURE H-2 "'" '"io- MAP OF PACIFIC OCEAN no- \Xf ucr tar fff vf cv \KTJT �ORIGINAL LAND AREA 1959 LAND AREA 0 FIGURE | |3 IOO 200 300 4OO 5OO YARDS CHANGES IN T!!E LAND AREA OF JOHNSTON ISLAND (Bryan, 1942) (Navy Hydro a, 1959) �\:/' *s\ \ ?; '' * '/'•; °<" % ' A / ** .N ^ *{**""•/-,*& * |."'|"»\m^** 'do ""/'"'|»P ' *0 / a l V 1 v FIGURE H-4 24 JOHNSTON ATOLL U.S. NAVAL i SURVEY MAP NO. 83637, 1966. ; SCALE 1: 50,000 H-13 �a line almost exactly northeast to southwest (POBSP, 1964). Johnston Island, the larger of the two island, has had its area considerably modified by human activity. Figure H-3 reveals the original area of Johnston Island with the area in 1959. Originally the island was 2,850 feet long at its greatest extent. The width of the island varied from 500 to 800 feet. The original area of the island was about 40 acres or 0.06 square mile (Emery, 1956). Since 1949, however, Johnston Island has been more than tripled in size, as the lagoon was dredged with new land fills being developed at the periphery.. At present {1959} the long axis of the island stretches 6,150 feet,, with a greatest width of about 1,500 feet at the center of the island near the airstrip control tower. The total area, of Johnston Island in August 1959, was about 0.33 square mile. None of the original shore line remains, and the addition of fill all around the original island has tended to produce an artifically smooth shore line except in the northeastern quarter where the quays and piers of the harbor area jut into the lagoon. The original rectangular orientation of Johnston has been retained, however., except for this1 northeastern portion of the island, see Table H-2 (Thorp, 1960)(Navy Hydro a, 1959)(Navy Hydro b, 1959). The following table depicts the major changes i'i the Johnston Atoll acreage as a result of the dredge and fill programs: TABLE H-2 JOHNSTON ISLAND ACREAGE Acreage 1963 198 0 0 TOTAL 648 25 18 198 Johnston and Sand North (Akau) East (Hikina) 1973 691 (3) Sand Island (originally known as Agnes Island) is a small coral islet located 1,900 yards to the northeast of Johnston Island. It is roughly triangular in shape, and has not been greatly modified by man in its outline. "The dimensions of Sand Island are about 600 feet by 1,500 feet, with an area of about 10 acres or about 0.016 square mile. A causeway has been built which runs about 500 yards west from Sand Island to a fill area of several acres which is adjacent to the seaplane landing area in the lagoon. The causeway, the fill area, and the original islet are locally thought of as being one unit, and "Sand Island" is used as a designation for the entire complex. Johnston Island -"s located a bit southwest of the center of the atoll. It is more than a mile south of the northern barrier reef, while almost abutting the first of the southern reefs. Sand Island is nearly at the center of the long axis of the atoll*, but it is more than 2-1/2 miles south of the main barrier reef, while at the same time about 1-1/4 miles to the north of the first southern.reefs, see Figure H-4 (Thorp, 1960). H-14 �FIGURE H-5. CENTRAL PACIFIC SUBMERGED MOUNTAIN RANGES (P013SP, 1964) H-15 �c. Geology (1) The original surface of Johnston Island was a mixture of sand, coral, and coral-derived rocks. The island rose from the southern beaches northward to a continuous sandy ridge (of an average height from 8 to 10 feet) extending along the northside of the island from end to end. This range connected Summit Peak, at the eastern end of Johnston Island, with an unnamed heignt of 13 feet at the western end of the island. Summit Peak, with an elevation of 44 feet, was the highest point in the atoll. At present the average height of the island is under eight feet, since both ridges and the two hills were leveled during the heavy construction which started in 1940 and changed the outline and surface of the island. Sand Island had no original height greater than eight feet, but it too has been leveled, since even a small relative relief such as that encountered on these two islands nay produce a fairly rough and hummocky topography when the base material is sand under constant agitation by the prevailing winds (POBSP, 1964) (Thorp, 1960). (2) The Central Pacific Ocean is dotted with a number of island groups, most of which are products of coral construction on worn-off volcanic upheavals. The Hawaiian Ridge stretches for a distance of some 1500 nautical miles from 20 N at 155 W to 30°N. The Mid-Pacific mountains intercept this chain from the west but support only one small coral atoll, namely Johnston Atoll. South of the Hawaiian Ridge and Johnston Atoll are located the Line Islands, also known as the Northwest Christmas Island Ridge and the Phoenix Islands, see Figure H -5. There is indirect evidence that Johnston Atoll is intermediate in age between the Line and Hawaiian Islands, rather than between the older Mid-Pacific Mountains and the Line Islands, between which Johnston Atoll lies physically (Thorp, 1960). If this is the case, then Johnston Atoll" probably has existed for slightly mere than the 24-million years which is thought to be the minimum age of the Hawaiian Islands, or somewhat less than the 60 to 70million years since the Mesozoic-Cenozoic boundary when the Line Islands were thought to have formed. If, however, Johnston is more closely allied geologically with the Mid-Pacific Mountains, it could be older, perhaps dating from the middle Cretaceous Age or approximately 100-million years ago (Amerson, 1973). Ashmore (1973) considers Johnston Atoll as a northernmost extension of the Christmas Ridge and suggests that "the terraces at Johnston Atoll probably were formed with falling sea levels at the end of the Sangamon Interglacial, or with rising levels at the end of the Wisconsin Glaciation..." If the terraces fonr-ed at the end of the Sangamon Interglacial Age they have been exposed to approximately 65,000 years of subaerial weathering and erosion. The terraces.... appear to be much too we.ll preserved to have withstood erosion and solution fcr that length of time. A more recent formation would seem indicated. If the possibility of Wisconsin interstadials is neglected the time of formation would be within the last 10 to 12 thousand years, Holocene period. Ashmore (1973) believes that the tilting hypothesis explains the northwestern reef and the submerged rim, but fails to explain many of the other atoll features. He favors a sea-level-change, which assumes that lowered sea levels during some glacial period allowed portions of the original atoll to be removed. He presents evidence that this hypothesis accounts for the -60 foot terrace and -30 foot level with its sinkholes. He does acknowledge the possibility of a combination of the tilting and sea-level-change hypothesis to explain the present day configuration of the atoll. H-16 �(3) The surface of Johnston Island is mainly coral sand, with an admixture of fine.coral fragments. The original shoreline of the island had several outcrops of massive beach rock. The beach rock occurred especially on the northwestern tip of the island and on the south central shore. These outcrops have been covered over by the fill which was used to expand the area of tha island. However, beach rock of the same type may still be seen in some places around the shore of the island. The beach rock is composed of coral sand and coral gravel loosel-y cemented together by calcium carbonate. Originally it was exposed in the form of smooth platforms, but with age, its surface has been eroded biochemically to form a series of irregular solution basins and srnooti water-level terraces (Thorp, 1960). Records from the Corps of Engineers have oeen kept-of 56 borings, with a maximum depth of 36 feet, that were made for tne heavy construction foundations of 12 buildings on the central and northeastern parts of Johnston Island. In addition, drill logs were kept of six deep wells which ranged from 86 to 191 feet below mean sea level. In general, a fairly thin layer (or layers) of beach reck was found a few feet below the surface under a pure sand layer. Below this sandstone (or beach rock layer) was another area of pure sand alternating with sand mixed with coral fragments. These layers ranged from 10 to 50 feet in thickness and were usually followed by the solid coral bedrock of the island which extends below drilling depths. In view of the results obtained'from deep drilling on other low islands in the Pacific, it seems probable to assume that the noncalcareous bedrock may be encountered as deep as 700 to 1,000 feet (Thorp, 1960). Under parts of the island there is apparently a narrow second layer of beach rock, according to the recordings.in the drill logs. In 18 of the holes, the driller hit beach rock which was between 1 and 2\ feet above mean low water, and which extended to an average of 0.7 foot below mean low water. This strata apparently correlated with the beach rock still exposed on Sand Island. It is thought that the upper layer may be correlated with the widespread occurrence of beach rock in the wave-washed zone between high and low tides on most of the low coral islands of the Pacific. The origin of the deeper layer is more complex, but samples of beach rock were collected .eight feet below sea level along the bases of the fragmented reef which extends from Johnston Island to Sand Island. Emery (1956) hypothesized that the unusual straightriess of the oatch reefs is the result of the various types of coralline algae atop the outcropping edges of this recently submerged beach rock. The deeper parts of the wells show alternating sand, loose coral, and sand and coral with no possibility of correlatipn from well to well. There were several small inclusions of mud in the wells from unknown origns. (4) There is no noncalcareous rock found on Johnston Island other than that brought by man, with the exception of pumice stone found on the beaches and one erratic piece of fine-grained rhyo'lite about 10 inches in diameter which was found in situ in the beach rock on Sand Island. The pumice which floated onto the beaches, especially in 1953, was thought Jo have corns from the volcanic eruptions at San Benedicto Island near Mexico. Emery (1955) stated that this was probably the result of driftwood transport, since large individual pieces such ds this one could be more readily carried by floating trses than by other plants or animals, while transport by icebergs or kelp is ruled out by the tropical location. The coral bedrock weathers down to a fairly coarse-grained white sand. There is no solid soil cover on Johnston Island, nor was any reported prior to the alterations of the environment by man. Since, as noted abovei bedrock does not crop out on the surface of the two islets, it is necessary to build foundations to extra depths for any buildings which have a heavy bearing load. . - H-17 �169*33' 169*30' 169*87' 169*24' 169*21' 48 48' 4 S. MILES CONTOUR INTERVAL - 4 FATHOMS 100 FATHOM CONTOUR ADDED 16-1 145' I 00 16* f42'l wl _L 169*33' FIGURE H-6. 169*30' 169*27' 169*24' JOHNSTON ATOLL SHOWING REEFS AND DEPTHS (AFTER EMERY, 169*21' �The 56 borings for foundation piers (mentioned previously) averaged 10 feet iri depth, of which the extreme depth was 36 feet. Another difficulty encountered in heavy construction work results from the porosity and toughness of the coral, which makes it hard to remove in large quantities either by blasting or bulldozing. (5) The original shore lines of Johnston and Sand Islands were about evenly divided between sandy beaches and exposed coral formations which were usually the "beach rock." The beaches were between 50 feet and 100 feet wide generally, and they had a sand or beach rock cover, But they have all been modified, except fo:" parts of Sand Island, with the result that'the present shore lines tend to end abruptly in the water with little or no beach remaining (Thorp,1960). It is estimated that the total area of these reefs which are exposed at low tide is about two square miles, but because of the numerous small patch reefs no exact measurements have ever been made. If it were necessary to compute their area, an air photo taken at low tide could provide a fairly accurate base from which to compute the total expanse of reef exposed. Probably more than one-half of the total area of reef which lies above sea level at slack water is in the main northwestern reef, which forms an arc a'most 11 miles long if one includes the brea< of about one mile near the northeastern end of the reef and its northeastern outlier which continues for another half mile. This latter section of reef is kpown locally as Small Island, although this name does not appear on the official charts. (6) The depth in the shallow "lagoon" area to the south of the main reef ranges from 3 to 40 feet. It is in this area that the elongated and subcircular patch reefs attain their greatest concentration. To the south of Johnston Island these patch reefs serve to define the southeastern boundaries of the lagoon area (Thorp, 1960). Profiles of the two reef types are shown in Figure H -7. The main outer reef has a gentle slope to the seaward (at least for the first few hundred feet) cut by narrow surge channels. An algal ridge forms the outer edge of the reef about one to three feet above mean sea level. However, this area is periodically inundated by waves or high tides especially during storms. On the lagoon side, there is a reef flat from 100 to 500 feet wide composed chiefly of coralline algae and small corals of various species. This reef flat has numerous potholes and narrow channels left behind as the reef migrated seaward. The lagoon edge of the reef is a fairly steep slope consisting of mainly living coral to a depth of about 15 feet. Below this, dead coral and fragments of dead coral ("coral gravel") form a more gentle slope to the fairly flat sand bottom which reaches its greatest development at from 20 to 25 feet below the surface. This flat expanse of bottom is broken repeatedly by coral heads, a few yards in diameter, which rise just as abruptly but may be several hundred feet long. Characteristically, these patch reefs are toppec by an irregular, overhanging surface of coralline algae just below the low-tide level. On the sides and locally are irregular masses, of branching coral, mostly composed of different species of Acropora. The lower slopes are mainly a talus of loose pieces of dark dead coral ancTcbralline algae which extends to the sandy bottom at about a 45 angle. There were no natural bays or harbors at Johnston Atoll, since none of the entrances into the lagoon area originally had a safe depth of more than three or four feet. There were no features on the interior of either Johnston Island or Sand Island. H-19 �80% CORALLINE ALGAE A X A SAND TALUS OF DEAD CCfcAL AND ALGAE 90% CORALLINE A i r A I Oirv.4 ALGAE \ ALGAL RIDGE o g 90 % CORAL A.—Isolated patch reef about 1 mile northwest of Johnston Island. B.—Outer reef at Small Island, FIGURE H-7. PROFILLS OF TWO REEF TYPES (EMERY, 1955) H-20 �(7) Topography appears to be no particular problem for the installation of any type of equipment which does not require a large area. At the present time most of the surface of Johnston Island is completely utilized by existing facilities. It is necessary to spend considerable time in the construction of foundations because of the shift from sand to bedrock, and any underground installations required special water-proofing treatment because of the high water table £.nd the permeability of the porous coral bedrock. -9 d . Hydrography (1) There are no natural permanent freshwater bodies on Johnston Atoll. This lack of surface water is primarily due to the ccarse texture and extreme permeability of the coral sand and rubble which make up the first few feet of the regolith, as well as to the porous nature of the coral bedrock. Uther factors contributing to the absence of any fresh water on Johnston Island are the small size of the land area, the geographic location and the narrowness of the two islets as compared to the total length (Thorp, 1960). The lagoon inside the main atoll is about 14,000 yards long at its axis, which runs southwest from Small Island through the centre of both Sand and Johnston Islands. At its widest point, just east of Sand Island, the lagoon extends about 3,500yards from northwest to southeast. West of Johnston Island the lagoon narrows to a few hundred yards in width before coming almost to a point at the extreme southwestern corner of the atoll. East of Sand Island, as mentioned above, the boundaries of the lagoon are indistinct, as the main reef breaks down in-;o an intricate series of linear reefs and numerous isolated patch reefs, which are usually awash at high water. The total area of the lagoon within the reef is approximately 13 square statute miles. An exact measurement is impossible unless one uses a depth curve for the boundary of the lagoon because of the difficulty of measuring the exact line of demarcation between the lagoon proper and the extensive coral flats which form the southeastern part of the atoll (Thorp, 1960) (Navy Hydro a, 1959) (Navy Hydro b, 1959). The natural depths within the lagoon (except for the dredged portions) va^y from a few inches to about 40 feet, because of the presence of coral heads and patch reefs. The greatest area lies between 15 and 25 feet underwater at mean sea level. At the extreme northeastern corner of the lagoon, south of the opening between the main reef and Small Island, there is an area of deeper water in which average depths of more than 4U feet have been reported, but the bottom still has many irregularities and numerous coral heads which almost broach the surface. Artificial dredging in the lagoon has left the seaplane landing area with a depth of eight feet cleared of obstructions, while the harbor and the entrance channel were originally dredged to 23 feet and have been swept to 14-1/2 feet (Thorp, 1960). H-21 �e - Tides and Currents (1) The tidal range at Johnston Island, 1n common with other mid-Pacific islands, is relatively small, and the effects of the tides upon the atoll are correspondingly minor. The absolute tidal range during the year (the difference between the lowest and highest tides of the year) is only 3.4 feet, the lowest low is minus 0.5 foot in June, while the highest high is plus 2.9 feet, also in June. The mean spring high tides are plus 2,2 feet while the mean spring low tides are ninus 0,2 foot. The mean neap tides are plus 1.6 feet, while the mean neap low tides are plus 0.4 foot (Thorp, 1960) (Navy Hydro, 1959) (Wennekens, 1969). The time of the tidal crests and troughs is only slightly later than those of Honolulu, the nearest point for which a full tide table is available. High tides are 29 minutes later at Johnston Island than at Honolulu, while the low tides are 23 minutes later. The high-water interval from full tide to the change of tide is three hours and 15 minutes. Inside the lagoon, the tides have a range only slightly less than in the open waters outside the lagoon, since the structure of the reefs permit water to flow through them as well as over them. The permeability of the coral bedrock is shown by the fact that the water level in all six of the deep wells on Johnston Island rises and falls with the tides (Thorp, 1960) (Wennekens, 1969). (2) Ocean currents in the vicinity of Johnston Island run from the east to the west at a speed of about 1/2 knot or from 10 to 15 miles per day. Johnston Island is approximately in the center of the North Equatorial Current which extends in breadth several hundred miles both to the north and to the south of the island and has a fairly constant velocity. The tidal currents at Johnston Island, within the lagoon, show a variation. The normal current flows with average velocities of 1/2 knot to the northwest. However, usually for a short time at high tide the current flows at one knot to the southeast. According to Emery (1955) the current pattern influences the distribution of sand to the south of the lagoon: "These patch reefs block the current, causing the sand to be deposited against the currentward side and leaving a depression where the water speeds through the gaps between the patch reefs. Examination of several such areas showed depths in the gaps to be about half a .fathom deeper and floored with coarser sediment than that of the adjoining areas." (3) The underwater platform on which Johnston Island is located is similar to those connected with many Pacific atolls. Like most other low islands in the Pacific the main outer reef has a typical cross section, which includes surge channels, an algal ridge, and a reef flat, with coral heads rising abruptly in the deeper waters to the south and east of the main reefs. Between 16 and 100 fathoms the outer slope is quite steep, usually less than one-half mile in linear distance, with an average slope of 19°. The platform on which Johnston Atoll rests stops fairly abruptly at about the 16 fathom line at most points around the circumference of the atoll as the bottom begins to slope steeply down (Thorp, 1960) (Navy Hydro b, 1959) (Wennekens, 1969). (4) The shallow lagoon area and its Dorclering reefs together form roughly the northwester quarter of the triangular-shaped platform on which the atoll rests. At the deeper eastern end of the platform the submerged contours suggest the outline of earlier peripheral reefs. It has been suggested by Emery (1955) that some early reefs may have been submerged as a result of the tilting of the whole base structure of the atoll to the southeast. Since the reef-f ox-mi ng corals grow slowly, and since they will not grow at all in water H-22 �below approximately 25 fathoms, a fairly rapid tilting might "drown" the coral ridges faster than they could build up. The main difference between Johnston Atoll and other Pacific islands is the lack of continuous reef around the atoll. The main outer reef extends around less than one-fourth of the circumference of the platform. In addition, there is an extensive zone of shallows to the south of the main reef which is also an unusual feature. As noted previously, it is this zone of shallows which contains most of the patch reefs, Johnston and Sand Islands and the two islets which make up the land area of Johnston Atoll. This suggested tilting of the whole atoll would account for this area of shallows to the northwest, since this area of the atoll would be raised as the opposite side, and most of the main reef sank. This theory has been moderately received, with the result that Johnston is considered one cf the "raised" atolls, even though it does not have the typical outward features of one (cliffed beaches, dry center depression, comparatively good water supply, etc.) (Thorp, 1960) (Ashmore, 1973). An alternate theory, which would account for the unusual reef formation at Johnston Atoll is the early removal of the windward reef by wave erosion, is not generally accepted. According to this theory the original outer ridge to the east was the most exposed to waves and hence eroded away, probably at some time when a climatic change or a lowering in sea level had temporarily halted the growth of the reef. The main objection to this theory is the fact that, today, the most vigorous growth of a reef is to be found on the side of an atoll because the agitation of the water provides a greater supply of nutrients for the coralbuildings organisms. It would seem that a temporary interruption in reef building would be compensated for, once conditions reverted to normal (Ashmore, 1973). It has been hypothesized that Johnston Atoll may be structurally related to the Line Islands (Christmas Island, Palmyra Island, Jarvis Island, etc.). Although they are mainly raised islands also, this theory has yet to receive any confirmation (Emery, 1956). (5) The waters around Johnston Island have not been completely surveyed, but the deepest point on H.O. Chart 5356 (Navy Hydro a, 1959) is 1,051 fathoms, which is located about 14 nautical miles southeast of the center of Johnston Island and about five miles south of the 100-fathom line. This indicates a descent of one foot in every 4-1/2 *eet horizontally. (6) The Japanese word "tsunami" is the term used to describe long gravity waves in the central and western Pacific Ocean areas. These waves are more commonly known as tidal or seismic waves and are caused by submarine earthquakes, landslides and plutonic activity and spread annularly from an epicenter. They are "shallow water waves,51 i.e., a wave in which the length of the wave is long when compared to the wa:er depth. The velocity of the Pacific Tsunami ranges between 375 and 490 nautical miles per hour. The Tsunami Research Center of ESSA and the Institute of Geophysics of the University of Hawaii maintain historical records of tsunami events in the Pacific. The largest amplitude wave recorded appears to have been about 3.4 feet as a result of the Chilean earthquake generated tsunami on May 23-24, 1960. The second highest, slightly over three feet, followed the Alaskan earthquake of March 28-29, 1964. Past records reveal that the crest of a tsunami at Johnston Atoll resenbles a 'progressive rise in sea level with the maximum depth being reached in about 25 to 30 minutes. The period of tsunami waves at Johnston Atoll is between 45 and 60 minutes. "Historical records indicate that, so far, no large breaking waves or bases have been experienced at the island from a tsunami." H-23 �' I •••„ The steep off-shore slope does not enhance incoming tsunami waves and the island is partially protected by an awash fringing reef along the western and northern periphery and by numerous coral patches scattered along the southern and eastern sectors of the island platform. "Historical records and the analysis of certain unusual environmental factors indicate that the effects of a tsunami at Johnston Island should be minimal, consisting of transient rise in water levels, occasional breakers to higher than normal levels, and local flooding of low areas. Backup of water in storm sewers and drainage ditches can be expected, and some erosion of the fill material can take place when the water drains out..." (Wennekens, 1969). Past history indicates that no large breaking wave is likely to occur on the island. f. Climatology (1) Climate (a) The climate of Johnston Atoll is marine and tropical in nature. Weather records are available from about 1931; however, standardized data are available only since 1952. These latter records show a climate with little variation in temperature and wind speed, but great variability in rainfall. Weather data are from Joint Task Force Seven (1959), U.S. Dept of Commerce (1972), and Shelton (ms. in prep), USAF .Environmental Technical Applications Center Report 7057. Because Johnston Atoll has a maximum elevation of less than 10 feet, a land area of about one square mile, and is surrounded by shallow waters in all directions, there is little difference in climate conditions from one part of the atoll to another <(Amerson, 1973). (b) Johnston Island is under the influence of tradewind weather 98% of the time. The normal weather during this period is scattered to broken Cumulus bases normally 2000 ft, tops 70.00 to 9000 ft. Scattered showers in the area will occasionally drift over the island causing light precipitation to fall. This can be axpected any time during the day or night as there is no apparent diurnal variation in the showers. Occasionally cloud tops wi'l build to 11,000 f=et, seldom exceeding 15,000 feet due to easterly perturbations in the area. Scattered Altostratus are in the area during this time and an increased amount of shower activity occurs until this perturbation passes. Due to the size of the island, w.iich is about two miles long and approximately one-half mile wi.de, convect^ve type clouds due to heating do not build. Even if they were influenced by the warm land they would be far off shore before they reached shower producing proportions. (c) Severe storms in the area are limited to thunderstorms, tropical storms and hurricanes. Thunderstorms occur infrequently in the area. The mean number of days during which thunderstorms occurred over a 26 year interval (1945-1970) are listed in Table H-3 . The + indicates less than one-half day. (2) Temperature: The mean annual temperature is 79.3°F. Temperatures are slightly"higher from June through November (80°-80°F) than from December through May (770-79°F) (Fig H-8). Daily ranges are normally only 70 or 8C'F, and the daily maximum and minimum temperatures vary only a few H-24 �TABLE H--3 MEAN NUMBER OF DAYS OF THUNDERSTORMS JOHNSTON ISLAND MONTH JAN FF.B MAR APR MAY OUH JOHNSTON ISLAND + + + t + + MONTH JUL AUG SEP OCT NOV DEC YEAR Note: Plus indicates less than one-half day. AWSP 105-4, Vol IX H-25 JOHNSTON ISLAND + + + + + 1 1 �~v High Extreme (Air) .•••• •..V •.. Mean Daily Maximum- 7 axmum — (Air) ^.'" Mean (Air)-^ .•• / •---• . . _£• LU Mean Daily Minimum (Air) Q- 70°F UJ Extreme (Air) A M S 0 N D FIGURE.H-8. MEAN MONTHLY AIK AND SEA TEMPERATURES, JOHNSTON ATOLL, ADAPTED FROM SECKEL (1962) and'U.S. DEPARTMENT OF COMMERCE (1972). H-26 �degrees throughout the year. The extremes range from a low of 62°F (December 1964) to a high of 89°F (October 1968, July and November 1969). This is lower than the daily range frequently encountered in continental areas. This constancy of temperature results from the fact that air masses passing over the atoll having been modified by close contact with the ocean for thousands of miles. Thus the air temperature is near that of the water temperature. Sea surface temperatures vary little from clay to day and change only slowly with the seasons (Amerson, 1973). i (3) Precipitation: Precipitation of 0.01 inch or more occurs 162 mean number of days each year. The mean annual rainfall is 26.11 inches, but year-to-year variation is great. For example, the total for 1968 was 42.27 - the wettest year on record - while 1969 was only 17.11, next to the lowest yearly total recorded (12.86 inches in 1953). There is little monthly mean rainfall variation (Fig H.-9); rainfall averages 2.75 inches monthly from December through March and 1.87 Inches monthly from April through November. Year-to-year monthly variation is, however, great (Amerson, 1973). (4) Relative Humidity: The annual mean relative humidity Is 75 percent, being highest aF 0100 hours (78 percent) and lowest at 1300 hours (69 percent). Monthly rrean relative humidity values vary little throughout ' the year, but January and February values are definitely lower (Amerson, 1973). (5) Surface Winds: The mean annual wind speed is 15.1 miles per hour with very little variation throughout the year (Fig H-10) (monthly means = 13.6 to 16.0 mph). Monthly extremes (excluding 1972) range from' 35 mph in July to a high of 49 mph in March and November (mean monthly extremes = 43 mph). On 19 August 1972, however, the wind speed hit an all time high of 104 mph when hurricane Celeste, which spawned off the southern coast of Mexico some 3,000 nautical miles to the east nearly two weeks earlier, passed only about 25 miles to the northeast of Johnston Atoll. Damage to the island was minor. Observations from weather satellites Indicate that tropical storms in the Johnston Atoll arsa, although infrequent, may not be as unusual as was once supposed. Surface trade winds are dominant at all times of the year (Fig H-ll). Winds from between NE and E are experienced 62 percent or more of the time in every month, with the annual average being 85 percent, see F1g H-10 and H-ll, (Amerson, 1973) (Bauer, 1973). Basically, two seasons can be distinguished. The first extends from December through March when the wind is from trade directions (NE through E) only 20 percent, or less, of the time. During this period, light, variable winds and westerlies occ.ur, occasionally, as organized disturbances. These disturbances bring in cooler, less humid, less stable air, which results In more cumulus buildup and heavier, more frequent precipitation. From April through November, winds are from trade directions 80 percent, or more of the time (Amerson, 1973). (6) Trophospheric Circulation: The trophospheric winds are readily divided into two~3ist1nct currents — the Trade Winds, and the Upper Westerlies — by the lower zero isopleth of zonal components. The Trades are largely zonal and quite persistent all months of the year and are at a maximum in depth, speed, and steadiness during the summer. The Upper Westerlies occupy the remainder of the trophosphere and are separated from the stratospheric easterlies by the second zero isopleth at approximately 55-60,000 feet. They are also quite persistent during all months of the year, but reach a H-27 �- 16 15 14 13 12 II 10 9 OT W U 8 7 6 • 5 - 4 • 3 M M N D Figure H-9 Mean monthly precipitation, Johnston Atoll, 1931 - 1972; means (solid line), extremes (dashes). Adapted from U.S. Department of Commerce (1972). H-28 �105 N/ 50 ' S 8 40 ' \/\ A / V V \' \^ V w ^ H 30 ' 20 • - 10 ' 0 F M A M J A S N D Figure H-10 Mean monthly wind speed, Johnston Atoll, 1931 - 1972; means (solid line) upper extremes (dashes). Adapted from U.S. Department of Commerce (1972). H-29 �100 • ^— * X" 90 • 80 • 70 60 . H W 50 • U Of! W 40 • X X^ 1I xx x; -^ *£_ ? x: § _^ ^ 1 g ^^™ X X X X ^ X fx X X ^L ^ X X X X •"^ -^ ^ 30 . 20 10 - 0. M Figure H - l l ;r M o N Percent frequency of wind from. E and ENE (open bar) and ESE and NE (striped bar), Johnston Atoll. (AMERSON, 1973) H- 30 �definite maximum in speed, steadiness, and depth during March and April. The November winds are nuch lighter in general ard westerlies and the easterlies tenc to cancel each other out leaving only a small south component in the mean, while in the winter there is a fairly strorg northerly component reaching a maximum in February (Amerson, 1973). (7) Stratospheric Circulation: The mean stratospheric circulation over Johnston Atoll is dominated by"th~e krakatoa Easterlies, but surprisingly shows greater seasonal variability than the trophospheric circulation. The winter is characterized by relatively light winds generally with east predominating in the lower stratosphere, west in the mid-regions, and east again at levels above 110,000 feet. A fairly rapid transition occurs in spring to strong steady easterlies reaching a maximum in July and August. There is a sharp transition in the fall back to light and variable winds (Amerson, 1973). (8) Sky Cover: Mean monthly sky cover, sunrise to sunset only, averages 6.0 on a scale of 0 to 10. There is little variation throughout the year. During an average year (again, sunrise to sunset) there are 75 mean clear days/172 mean partly cloudy days, and 118 mean days (Amerson, 1973). (9) Historical Data: Table H-4 shows a climatic brief for the period 1945-1970; Table H-b shows the frequency of occurrence of different stability classes from ::949 to 1958, 86,190 observations; Table H-6 shows the frequency of stability vs wind direction for the period of Table H-5 g. Surrounding Land and Water Use and Ownership: NOTE: THE FOLLOWING INFORMATION WAS PROVIDED LARGELY BY THE LOGISTICS PLANNING GROUP, HOLNES AND NARVER, INC., LAS VEGAS, NEVADA 89114. (1) There are no cities or incorporated communities on Johnston Atoll. There are approximately 600 personnel currently living on the atoll. These consist for the most part of employees of Holmes and Marver, Inc., Pacific Test Division, P.O. Box 9186, Honolulu, Hawaii, 96820. This firm, operating under contract AT(29-2)-20 with the AEC, provides for general construction, maintenance and general operations on and around the atoll. The atoll is under the control of the Field Command, DNA and is currently under the command control of the USAF. There are a liirited number of Holmes and Narver, Inc., subcontractor personnel. The United States AEC; U.S. Weather Bureau; 10th Aerospace Defense Squadron, Det 1; 18th Surveillance Squadron., Det 2; 2675th Chemical Company, USA; 2194th Communications Squadron; and USAF Logistics Command (SMAMA) maintain small detachments. At times a very limited number of personnel from other organizations such as the Smithsonian Institution, Sandia Corporation, USAF Space and Missile Organization, The University of Hawaii, etc., may be present on the atoll. (2) A bird sanctuary still exists on Sand Island under the provisions of Executive Order No. 4467, dated July 29, 1926. (For detailed information regarding the present day bird population see Appendix A) H-31 �TABLE H-4 CLIMATIC BRIEF-JOHNSTON ISLAND CO ro JAN FEE MAR APR MA Y |J -J.N 1JV I 36 37 87 «s ]_.5o "5'ZTP — i 88 ~ u r 1 89 *IJV i 89 (DK^J 88 A.NLS S3 81 82 73 74 75 1i 83 _7^. 1 84 7? 1 85 86 73 i 78 i 85 77 ! 85 76 I 83 74 82 75 i 83 AWSP 105-4, Vol IX 67 67 C« r'-.Q 70 70 71 3.9 1. 5 2. 3 2. 3 u 1.0 0,8 1. 3 2. 3 2._4 66 3. 3 63 i 2.1 62 3.0 62 26. 2 9.8 4. 2 3. 8 3. 9 A. 6 rtS o ^ ENE 14 ENE 14 ENE! is ENE 15 ENE 14 i.l ENE MS 2. 0 ,E-N!E_j 14 8. 0 ENE 1.4 4.0 ENE 14 9 . 5 ENE 14 2.8 iENE 15 9 . 2 ENE 15 9. 8 BNE 14 55 46 54 46 47 46 43 F 46 48 43 48 58 58 Relative Humidity (%) ' o o & w 'A o C H-r in 7^ • i-« •4-1 C 0 •H 3 O o o "v 0 0 o CO r—1 79 71 79 70 79 71 Si 72 72 81 80 70 80 70 80 70 70 79 71 80 80 72 79 77. 80 71 ^ & S " o & s rtn o £1 .il O > 68 , 6 9 | 08 68 70 71 71 72 73 73 73 71 70 71 Cloufls (Teiivh.s) SH T3 Prevailing Direction 35 o o Maximum ia 24 hours Extreme Minimum Mean Daily Minimum 73 | 63 88 , 81 bV "S":"" 73 64 :;ri_£-9 AUtr Mean Daily Maximum Month Extreme Maximum 1 _• I—1 Mean 1 Wind (KT) Extreme f Peak J Speed V G u s t / precip (IN) - Temperature (°F) 5 • h'J u / o .69 ! . f4 . 76 .76 .79 . 82 .32. . 82 .76 . 74 .76 ! 5 6 6 5 5 t \ '-> : 6 6 5 5 5 �TABLE H-5 FREQUENCY OF OCCURRENCE - ATMOSPHERIC STABILITY CLASSESJOHNSTON ISLAND Stability A MAR APR MAY JUN JUL AUG SEP OCT NOV DEC ANN ANNCALM A B C D E F C D E .0033 .0029 .0026 .0023 .0019 .0014 .0033 .0017 .3024 .3044 .3000 .0021 .0024 .0012 JAN FEB B .0254 .0253 .0257 .0195 .0137 .0157 .0174 .0109 .0205 .0195 .0038 .0113 .0175 .0009 .0748 .0775 .1121 ,1097 .1258 .1470 ..1423 .1481 ,,1352 ,1017 .0370 .0477 ,1362 .0304 .7272 .7656 .7703 .8009 .8095 .7596 .7653 .7719 .7306 .7688 .8962 .8377 .7821 .0002 . 1 1 42 .0907 .0692 .0527 .0399 .0611 .0624 .0611 .0944 .0857 .0455 .0842 .0718 .0000 - F .0551 .0380 .0200 .0150 .0093 .0150 .0093 .0064 .0168 ' .0199 ' .0175 ' .0170 .0199 .0048 Extremely Unstable Moderately Unstable Slightly Unstabls Neutral Slightly Stable Moderately Stable USAF Environmental Technical Applications. Center Report 7057 H-33 �TABLE H-6 FREQUENCY OF OCCURRENCE WIND DIRECTION JOHNSTON ISLAND N NNE NE ENE E ESE SE SSE . 0097 . 0247 . 1244 . 3665 .3625 .0661 .0159 . 0066 S SS W SW WSW W WNW NW NNW . 0038 . 0030 . 0030 . 0024 .0031 .0019 .0032 .0033 USAF Environmental Technical Applications Center Report 7057 H-34 �(3) There is no commercial fishing in the immediate area of Johnston Atoll. Recreational fishing is extensive and is, in fact, one of the principal forms of recreation. A wide variety of species are present within the lagoon but extreme caution is advisable since some are hazardous on physical contact (sharks, barracuda, rnoray eel, turkey fish, stone fish, etc.) and others are very poisonous if ingested. Other forms of recreation include scuba diving, swimming, boating, basketball, bowling, golf, tennis, softball, pool, movies, library, hobby shops, clubs and gymnasium. h. Facilities (1) Transpcrtation (a) Sea_Jransj3ort: Johnston Atoll is under the administrative control of the DoD, DNA and~ls a Naval Defense Sea Area and Airspace Reservation. All private vessels must apply for entrance prior to their arrival except in emergencies. Unauthorized landing or tie violation of other regulations governing admission to the island are grounds for Federal prosecution. Johnston Atoll is accessible from all directions, although it is distant from all supply ports except Honolulu, Hawaii. This presents a problem since any supplies not brought in from Hawaii must be scheduled sufficiently in advance to allow for extra travel time for mainland supply ports. Otherwise a smooth flow of supplies is not maintained, and this often results in the use of expensive "airlifts" of bulk supplies which could be handled more economically by ship. There is no commercial shipping which makes Johnston Atoll a port of call. All supplies brought by ship are handled by the Military Sea Transport Service. Johnston Harbor (Fig H-12 ) is an artificially dredged turning basin and harbor area inside the lagoon and located to the north of Johnston and Sand Islands. The navigable width of the channel is from 170 feet to 190 faet, and it has a minimum charted depth of 35 feet and is 400 feet wide. The harbor and turning basin vary in width from 1200 to 2000 feet, 35 feet deep and about 1.2 miles long. A 300 foot wide, 17 foot deep channel around the west end of the island continues to deep water. Separate channels 120 feet wide and 8 feet deep connect Akau and Hikina Islands to the harbor area. At one point H.O. Chart 5356 (Navy Hydro a, 1959) shows a least depth of 13 feet. Vessels which are too large for the entrance channel may anchor in the channel approach area south of the channel entrance between the southernmost channel buoy, which is moored in 62 feet of i/vater about 2,750 yards bearing 148° from the Johnston Island Aviation Light, and the 100-fathorn line, about four miles to the south of the Island (Bauer, 1973) (Navy Hydro a, 1959) (Navy Hydro b, 1959). All channels are outlined with boundary lights, and pile dolphins are located within the harbor for ship moorage. LCM boats are available to assist with docking. Two ship-to-shore radio communications channels are provided. These are Harbor Common on 2716 KH^ and Local Boat Control on 32.8 KHZ. A bulkhead wharf, a 360-foot long wooden pier, and a small boat pier with an adjoining wharf (approximately 450 feet long) are located on the north side of Johnston Island. These facilities are served with freshwater lines,a saltwater fire protection System, fuel lines, power, and lighting. The bulkhead wharf provides over 180,000 square feet of dock area, "here is also a bulkhead wharf at the west end of the island with 14,000 square feet of dock area, but its usefulness is irnpared by silting in the channel. Small boat*piers and wharves are located on the smaller islands. All the wharves and piers are equipped with H-35 �169*31' 169^31'30" "T l-i.-^^uri^J-i-i.. AO / {•. :;•-,..( TURNING '* O .;•'' \ ••., -..*""•» .X " x" V' o J^-7 •S •••'• ••• -:• *""• 16" 45' 16° 44' 30" B FIliJRE H-12 . 31'30" PORT FACILITIES AT JOIJNSTON ISLAND (Navy Hydro a, 1959) ' H-36 �protective fenders (Bauer, 1973) (Navy Hydro b, 1959). Other facilities associated with the harbor are a repair shop (Bldg 126), trar.sformer building (Bldg 128), harbor control (Bldg 110), and marine shop (Bldg 127). 4 (b) Air Transport: A major activity on Johnston Island is in connection with the airstrip which is operated by the United States Air Force. There is one cornnercial airline providing services to Johnston Atol",. A rurway on Johnston Island is oriented in a northeast-southwest direction (true bearing of 65° 13' 30") along the southern side of the island. It is approximately 9,000 feet long and 150 feet wide ar.d has shoulders 150 feet wide on each side. The first 500 feet of the west end is concrete, and the remainder is paved with asphaltic concrete. The runway weight bearing capacity for aircraft with twin wheel type landing gear is 200,000 pounds, and for aircraft with twin tandem wheel type landing gear is 350,000 pounds. Turnaround areas, blast pads and overruns adjoin each end of the runway. The north taxiway and parking area are closed; however, there are small parking areas north and south of the,west end of the runway and a large parking area (140.,000 square yards) south of the middle of the runway. The runway is equipped with standard frangible type lights and with visual guide indicators for approaches from the west. Traffic signals on the isi and's perimeter road control the movement of vehicles across flight paths. Runway lighting control equipment is housed inBuilding oOl which has a 75-KW standby generator for emergency power. AGE, personal equipment, and parking areas are also lighted. Air/ground communications facilities include a control tower (Bldg 505) located north of the runway near its midpoint, air/ground tactical communications (Bldg 507), antenna tower (Bldg 506), and a generator shed (31dg 508). Airfield navigational aids are a base beacon tower (Bldg 635), a low frequency base beacon (Bldg 901), several aircraft obstruction lights, and a Tactical Air Navigation (TACAN) unit. The tower and UHF/DF are normally operational 30 minutes prior to and after all departures, and 30 minutes prior to an ETA until landing and parking of all arrivals, A newly constructed air passenger and freight terminal (Bldg 285) is located east of the aircraft parking area on the south side of the island. It is 14,000 square feet in Area, and contains a freight handling area, waiting area, baggage and ticket offices, lounges, restrooms, and a security briefing area. The island is currently serviced by both commercial and Military Airlift Command flights on a regularly scheduled basis. Since 1966, Johnston Atoll has adhered to USAF safety regulations, and approved waivers theretc, pertaining to airfields and their surrounding airspace. Current and future planning of new facilities will conform to the dimensions, clearances, and transitional slopes stipulated in these regulations. The seaplane base at Johnston Island has landing aprons and ramps on the north side of the island; a dredged landing area in the lagoon north of the boat turning basin and harbor area. The longest; runway in the lagoon is 11,000 feet, running from the northeast to the southwest. There are also two shorter runways running north and south and northwest and southeast, with lengths of 6,000 and 4,000 feet respectively. The entire seaplane landing area has been swept to a minimum depth of eight feet. The first facility on Johnston Atoll was originally based on Sand Island; the causeway and fill to the west of Sand Island were constructed for this original seaplane base in the late 3 0 ' s . The seaplane base is little used today, since, with the cominc of the long-range land plane to the Pacific, the flying boat lost much of its utility and is at present being used mainly for air-sea rescue operations (Bauer, 1973). In the interest of ' H-37 �completeness and to provide information not contained in the Holmes and Narver report, Change 12, U.S. Naval Oceanographic Office Publication, H.O. Pub. 80 (formerly No. 166) "Sailing Directions for the Pacific Islands" Vol. Ill, pages 354a - 375, 6th Ed., 1952 is included in Appendix (T. (c) Ground Transport: There are several miles of roads on Johnston Island including a perimeter road .which varies from 20 to 26 feet in width. Some sections are paved with asphaltic concrete and others are compacted coral. The road network is excellent and allows easy access to all major facilities (Bauer, 1973). (2) Communications: In addition to those discussed previously under Sea and Air Transport, tEeire are numerous other communications facilities. A 1080 automatic dial telephone exchange provides on-a-.;oll administrative telephone service, and off-island dialing to Oahu through a submarine cable. The Defense Communications Agency furnishes worldwide tele-communications services on a 24-hour, seven-day week, again through the submarine cable, and there is a backup communication link provided by a long haul radio trunk to Hickam AFB,HI. On-islar.d there is a non-tactical VHF/FM mobile radio system with enough stations activated to meet local requirements. There are also from one to three civilian amateur radio stations, an Armed Forces Radio Station, a television station, a MARS station, a public address system, a disaster control system, and a fire alarm system (Bauer, 1973). (3) Utilities (a) Water Supply System: Johnston Atoll's Water system uses both fresh and salt water. Raw sea water is pumped from the lagoon through a traveling screen to the Salt Water Pump House (Bldg. 3). From there it is pumped to the Distillation Plant (Bldg. 45), arid also into the salt water distribution system where it is used for sanitary purposes, fire protection, air conditioning condenser units, power plant waste heat dissipation, distillation Plant (Bldg. 45) which houses twelve distillation units and related equipment; the Freshwater Treatment Plant (Bldg. 44) with a pump station, sodaash treatment area, and a chlorination room; the Freshwater Pump House (Bldg. 650); an Auxiliary Freshwater Pump House (Bldg. 649); and, storage facilities for approximately 740,000 gallons. The fresh water system is designed to support a population of approximately 4,500. Its total rated capacity is 318,000 gpd, but, allowing for maintenance and miscellaneous downtime, about 240,000 gpd can be expected. Fresh water for Akau, Hikina and Sand Islands is barged there in tank trucks (Bauer, 1973). (b) Electrical Power System: The Power Plant (Bldg. 48) contains seven diesel-driven generators, e"ach" rated at 1400 kw with an 80 percent power factor. Outgoing power of 4160 volts is distributed through thirteen feeders. Two feeders serve the power plant's auxiliary equipment and utility load, two serve the smaller islands, one serves the LOX plant, and the remainder serve Johnston Island through approximately eighty substations. The distribution system consists of a network of underground duct banks in a modified loop radial configuration, and submarine cables which carry power to Akau, Hikina and Sand Islands. Although a loop tie-in arrangement provides 100 percent power back-up for the small islands, each also has one or more standby generators. H-38 �(c) Sanitary Sewerag^ System: Johnston Island has insufficient relief to permit use of a gravity s'ewage coTTiction system; therefore, a forced system employing pumps arid lift stations is used. The force main is a series of 3" to 16" cast iron arid asbestos cement pipes in parallel runs along the north and south shores w:th connecting laterals. Raw effluent is discharged on the ocean bottom at a depth of 25.6 feet through a 10" pressure outfall pipeline which extends approximately 520 feet out from the southwest peninsula of the island. Sewage on the three smaller islands is collected in septic tanks, and the effluent ~~rom the septic tanks drains by gravity into the sea (Bauer, 1973). (d) Storm Drainage System: The drainage system consists of inlets, french drains, and ditches which discharge into the lagoon. It is separate from the sewage system and does not use piping o~ any kind except for culverts under roads, runway, and taxiways and where ditches-drain through outfalls into the ocean. Drainage is adequate for normal conditions, but problems may arise after heavy prolonged rainfall or severe storms (Bauer, 1973). (4) Housekesping (a) Housing: Johnston Atoll housing can be classified as enlisted men's, officer/professional, and VIP. Dependents are not authorized; therefore, there is no dependent housing. Enlisted men's quarters are provided by six 4-story reinforced concrete barracks and two 3-story concrete block barracks. The former contain dormitory type accommodations (two-man cubicles) with a centrally located latrine on each floor. Each has a recreation lounge on the first floor and storage, janitorial,and eqjipment space. Each floor of the latter has twenty-four two-man rooms, a centrally located latrine, or recreational lounge, and laundry facilities. Eacn barrack also has storage, janitorial and equipment space. Total design capacity for the eight EM barracks is 1808. Two 4-story reinforced concrete professional barracks and twelve 2-story concrete block apartment buildings provide accommodations for officers and professional type personnel. The barracks have two-man bedrooms with each room accessible from an outside balcony. Each two bedrooms are connected by a latrine and closet area. Space is provided for storage, janitorial supplies, and equipment, and a recreational lounge is located on the first floor. Each apartment building contains six apartments with three bedrooms, a kitchen, combination liying/dir-ing area, and a bathroom. Total design capacity for officer/professional personnel is 824. There are four small cottages on Johnston Atoll which are reserved for use by the Commander and other VIPs. These contain kitchens, bathrooms, living and dining areas, and three bedrooms. Total capacity of the VIP quarters is 12 (Bauer, 1973). (b) Messjmg: There are two mess halls on Johnston Atoll, Building 519 (Mess HairNo. 1) and Building 4 (Mess Hall No. 2). Mess Hal". No. 1 is of concrete block construction with a built-up roof and a concrete floor. It can seat 1000 men for either family or cafeteria style meals and can be turned three times during each dining period for a serving capacity of 3000. Mess Hall No. 2 is constructed of concrete blocks with a precast roof. It was designed to seat 500 men, but it is not operational at the present time. One dining wing is now serving as a chapel and the other as the Officer's Club (Bauer, 1973). H-39 �(c) Recreation: Because of the remot eness of Johnston Atoll, its physical characteristics, and its use, emphasis ias been given to providing excellent and varied recreation facilities. Indoor fac ilities include a bowliny alley, gymnasium, hobby shops, library, pool and NC 0, Officers and civilian clubs. Outdoor sports available are basketball, boatin g, fishing, golf, scuba diving, softball, swimming, tennis and volleyball. The re is also an outdoor theater which seats approximately 1,000 men (Bauer, 1973). (d) Dispensary: Medical facilities sjimilar to those of a clinic or small hospital are located in Building 405, an underground structure of reinforced concrete with approximately 6,600 square feet of useable floor space. Included are rooms for minor and/or emergency surgery, axarnination and treatment, x-ray and associated darkroom equipment, isolation, 20-ied ward, offices, laboratory, storage, waiting room, library, latrine, and a dental operating room and laboratory. Two medical doctors and one dentist ars normally on the island; however, treatment is generally confined to minor or emergency type ailments while patients with major problems are air-evacuated to Hawaii (Bauer, 1973). Facilities associated with the dispensary but located ii separate structures are a decontamination station (Bldg 404), air conditioning equipment (Bldg 407), oxygen storage (Bldg 409), and emergency power (Bldg 416). (e) Miscellaneous: In addition to the above, there is a post office, base exchange, barber shop, tailor shop, laundry, and fire station. All of -;hese are adequate to support an island population of 4,500 personnel, if necessary. (5) Storage (a) Warehouses: Twelve steel frame buildings on the north side of Johnston Island, two similar structures near the south aircraft parking area, and Building 400, a wood frame structure with metal siding, provide a total of over 74,000 square feet of warehouse space. However, the latter (Bldg 400) was severely damaged during a recent hurricane and replacement facilities are being planned. There are also numerojs storage facilities throughout the island designed and used for the storage of various types of munitions, and there are facilities reserved for special useage which are now used for storage. (b) Open Storage: Open storage areas are located east of the north aircraft parking area, north of Bldg 390, and along the northwest shore of Johnston Island. Because of corrosion caused by the high humidity and blowing coral, the type of supplies which can be placed in outdoor storage is limited unless such supplies are enclosed in weather resistant packaging or coatings. (c) POL/LOX: Petroleum, oil and lubricants (POL) stored in bulk include aviation gasoline (AVGAS), jet fuel (JP-4), motor gasoline (MOGAS), and diesel fuel. There are also storage facilities associated with the liquid oxygen (LOX) plant. MOGAS and diesel fuel facilities are located in the northeast portion of the island. Tanker-delivered fuels are conveyed to a 13,500 gallon diesel fuel tank near the power plant, and to six 25,000 gallon tanks (two fo'" diesel and four for MOGAS) near the distillation plant. Associated facilities are a tank truck .loading area and a vehicle fuel pumping station. The aircraft POL installation is located in an isolated area in the southeastern H-40 �part of the island. It includes a 13,500-barrel storage tank and a 1 ,500-barrel ready tank for AVGAS, and the same for JIM. This complex also has a tank truck loading assembly area, an electrical equipment shop, a pump complex, and a propellent and lube storage area (Bauer, 1973). The .LOX plant, located on the northwest corner of the island, has two 28,000-gallon tanks for liquid oxygen storage, and a 28,000-gallon tank and 13,500-galloi tank for liquid nitrogen storage. (6) Cons_tructjj)ji: Construction of new facilities and modification of existing facilities is normally accomplished by the support contractor under a Cost-Plus-Fixed Fee cortract with the Atomic Energy Commission. However, special projects are sometimes awarded by competitive bidding. An assortment of construction equipment including trucks, tractors, cranes, etc., is available on the island, but all construction materials, with the exception of coral aggregate and salt water, must be imported. i . Terrestrial and Marine F1ora_ and Fauna NOTE: The following sections were extracted from a document entitled "Preliminary Biological Survey of Sand Island - Johnston Atoll" (PCBSP, 1964). The work was accomplished under DoD Contract No. DA-18-064-AMC-56-A. For a more detailed discussion of Johnston Atoll, its history, terrestrial and aquatic flora and fauna, see Appendix A. (1) Vegetation; The low-lying coral islands of the central Pacific are characterized by flora that contain few species. Plants are dominantly wide-ranging tropical species along with a few endemics (Fosberg, 1949). Only three plant species occurred on the original Johnston and Sand Islands. One hundred and twenty-four terrestrial plants have been introduced by man. In general, the indigenous flora of the atolls increases in number of species as one proceeds westward in the Pacific. This would be expected from the closer proximity of western islands to larger islands and land masses with their complex floras. Rainfall plays a particularly decisive role in the plant life of the coral atolls. Those with little rainfall, such as Sand - Johnston Atoll, have a very low, sparse vegetation consisting of a few grasses, herbs, and dwarf shrubs. This contrasts strikingly with the luxuriant growth and many trees to be found on atolls with high rainfall. General Animal Life; The animals of the Pac-fic show an increase in number of species from east to west as is true of plants. Central Pacific Atolls, like Johnston-Sand, with their small size., sparse and relatively uniform vegetation, and dry climates cannot support a large variety of species. With increasing size, diversity of habitat, and increased rainfall the number of species increases. Proximity to large land areas is a factor that is of great importance in causing an "increase in the number o~ species. Many species, however, that reach the islands cannot find habitat suited to their survival. • (a) Mammals; The first men to visit the north central Pacific islands probably found only one mammal present, the Hawaiian Monk seal. Ths various tribes, however, probably brought along semi-domestic dogs and unintentionally the Polynesian rat (Rattus exulans). With the arrival of whalers, guano diggers, and traders, almost every i l and received by accident or intention l H-41 �one or npre mammals. Most of these either brought about their own 'destruction, rabbits (Oryctolagus) on Laysan Island ate all available food (Bailey! 1956), or were destroyed by other introduced species, e.g., rats usually were exterminated by cats. Domestic animals, such as dogs, horses, sheep, goats, pigs, etc., generally cannot survive without human care. In so=ne areas, cats and Polynesian rats occur on many uninhabited islands, and rabbits (Oryctolagus) occur on Phoenix Island, while Rattus, rattus, Rattus. norvegicus, and Mus musculus occur only on islands Inhabited by man. These TasttKree always occur in fairly close proximity to human activities and are probably dependent upon man for their large populations if not their existence. Several dogs are kept as pets on various islands and a monkey has existed for several years in a wild state on Kure Island. (b) Bjrds: The bird population with few exceptions is composed entirely of oceanic birds" or transient shorebirds. "he total number of breeding sea birds in the central Pacific is twenty-four with the maximum number occurring at the present time on any one island is seventeen. The number of species which breed on any one island is dependent primarily on mammals present and secondarily on suitable nesting sites. A few individuals will usually nest on an island even if good nesting sites are absent, but the presence of cats will prevent nesting by some three to seven species. Fifty-six bird species have been recorded on the atoll. Twelve seabird species nest on the islands and six migratory shorebirds have been regularly observed in recent years. Endemic land birds (excluding the main Hawaiian forms) are represented on.ly by the Laysan Finch of Laysan Island, a finch on Nihoa, and a parakeete and warbler in the Line Islands. An endemic duck is present on Laysan Island and a considerable variety of migrant ducks and small land birds have been recorded on the various islands. Finally wild populations of canaries and domestic pigeons occur on Midway. (c) Reptiles: The reptile fauna usually consists of one skink,. one gecko, and the Green turtle. Wetter islands support several species of geckos and skinks. (d) Amphibians: None are present in the Johnstcn Atoll area and no suitable habitat is present to permit their survival. (e) Fish: This group is still very poorly known and most authorities feel that the fish fauna of the various atolls will be very similar once complete collections have been made. Occasionally, sea turtles and porpoises are present in the lagoon. There are at least 94 species of inshore fish known and additional species probably exist. (f) Insects and Other Arthropods: This is another group that has been incompletely studied. In general, the"terrestr1al invertebrate fauna consists of 68 species, many of them introduced. This is to be expected in view of small land areas, little variety of habitat, and long distances from land masses. Man has been instrumental in introducing many new species to inhabited atolls, however, where this has happened insect faunas can be expected to be more varied. H-42 �(q) Land Crustaceans and Mollusks: Several types of crabs are found on most Pacific coral atoll Islands; land crabs, coconut crabs, and hermit crabs. Their occurrence In the central pacific varies. Herniit crabs are not presently found north of the Line Islands. Terrestrial mollusks are not; common on central Pacific atolls. Some, hov/ever, are ^ound in close association with the sea. These are called "shore-zone" mollusks (Wiens, 1962), H-43 �(This page intentionally left blank) �APPENDIX I TRANSPORTATION REQUIREMENT �(This page intentionally left blank) �1. INTRODUCTION: Transportation of the Orange herbicide presently stocked at the NCBC, Gulfport, Mississippi to Johnston Island, Central Pacific Ocean will be dependent on whether the proposed action, incineration at sea, or the principal alternative,incineration on Johnston Island,is selected. For incineration at sea,approximately 860',000 gallons would be removed from the drums and transferred by rail to the incinerator ship. For incineration on Johnston Island the drums of Orange will be transported to Johnston Island by ship from Gulfport. Shipment overland to a West Coast Port and then by vessel to Johnston Island or shipment via air flight only were also considered. Both of these alternatives are considered impractical because of higher cost, increased risk of product loss traversing the country overland, and the huge consumption of fuel connected with an air delivery of this magnitude. 2. CLASSIFICATION: Under the "Hazardous Materials Regulations" of the Department of Transportation (DOT), Code of Federal Regulations 49, Parts 100-199, Orange herbicide is not hazardous. Extensive experience over a number of years in the mid-1960's substantiates the adequacy of the shipping procedures which were then employed. a. Flamrnable C'lassificati.on; The DOT Transportation Regulation Section 173.115 defines a flammable Ifquio as one which gives off flammable vapors (as determined by flash point from Tagliabue's open-cup tester as used for test of burning oils, ASTM Test D1310) at or below a temperature of 80°F. Orange herbicide has a flash point of 295°F and vapor pressure less than 1 mm of mercury at 35 C. Therefore, it is not a flammable liquid. b. Poisons-B-Classification: Code of Federal Regulations Title 49 Transpprtation, Chapter 1 - HazardiDus jlateria"ls RegTHations Board»J1J3.343. L~ess• dangerous "poisons, Class 3, liquid or solidT poison label are described below: (1) For the purposes of Parts 170-189 of this chapter and except as otherwise provided in this part. Class B ooisons are those substances, liquid or solid (including pastes and semisolids)., other than Class A or Class C poisons, which are known to be so toxic to man as to afford a hazard to health during transDortation; or which in the absence of adequate data on human toxicity, are presumed to be toxic to man because they fall within any one of the following categories when tested on laboratory animals. (a) Oral Toxicity: Those which produce death within 48 hours in half or more than half of a group of ten or more white laboratory rats weighing 200 to 300 grams at a single dose of 50 milligrams or less per kilogram of body weight, when administered orally. (b) Toxicity on Inhalation: Those which produce death within 48 hours in half or more than half of a group of ten or more white laboratory rats weighing 200 to 300 grams, when inhaled continuously for a period of one hour or less at a concentration of two milligrams or less per liter of vapor, mist, or dust, provided such concentration is likely to be encountered by man when the chemical product is used in any reasonable foreseeable manner. �(c) Toxicity by Skin Absorption; Those which produce death within 48 hours in half .or more than half of a group of ten or more rabbits tested at a dosage of 200 milligrams or less per kilogram body weight, when administered by continuous contact with the bare skin for 24 hours or less. ( 2 The foregoing categories shall not apply if the physical .) characteristics or the probable hazards to humans as shown by experience indicate that the substances will not cause serious sickness or death. Neither the display of danger or warning labels pertaining to use nor the toxicity tests set forth above shall prejudice or prohibit the exemption of any substances from the provisions of Parts 170-189 of this chapter. c. For Truck .Shipment: National Motor Freight Classification (NMFC) 50320 compounds, tree or weed killing (herbicides), IVot othYrwi'se Indexed (NOI) or 2,4-0 (dichlorophenoxyacetic acid) or 2,4-D formulations. d. For Rail Shipment; Uniform Freight Classification (UFC) 96465 weed killing compounds, not otherwise "indexed' By name (NOIBN). 3. PROPOSED METHODS OF SHIPMENT: a. General: Overland shipment frorr NCBC, Gulfport, Mississippi to the Port of GulfporFwTTT move by rail, a distance of 2 1/2 to 3 miles. While not classified as hazardous under Hazardous Materials Regulations, the uncontrolled release of Orange herbicide can have a harmful effect on crops and aquatic life. For these reasons the precautions listed below will be enforced. These precautions are deemed reasonable and adequate for the situation. Some of these actions are routinely accomplished regardless of the product being shipped. In addition to the basic precautions discussed in the following paragraphs, an Operations Plan will be written to describe the transportation aspects with an emphasis on personnel and environmental safety. All parties who come into possession of the product will be instructed in writing of actions to be taken in the event of an accident. b. Bulk Shipment: For incineration at sea as the disposal method, the Orange stored at NCBC, Gulfport, Mississippi would be transferred from drums to tank cars for rail shipment to the Port of Gulfport. The Orange would then be loaded aboard the incinerator ship for transport to the incineration location. Necessary precautions will be taken during all phases of this operation. c. Shipment in Drums: For incineration on Johnston Island as the disposal method it would be transported to Johnston Island in drums. The product will be packaged in drums of 16 gauge steel or 18 gauge steel. This action satisfies Department of Transportation (DOT) requirements for Class B poison container,- as defined in Code of Federal Regulations, Title 49 - Transportation, Chapter 1 - Hazardous Materials Regulation Board, 173.346(a)(2). Drums will be inspected prior-to shipment to determine that no leakage exists. Any leaks detected during inspection will be positively corrected by tightening of closures, replacement of gaskets, or by drum replacement. Product in drums of questionable condition for safe and leak free transit will be redrummed. Shipment will be made in gondola cars with steel floors. These are open top cars 1-2 �. V with sides of 5 1/2 to 6 feet high. Use of this type car will permit overhead loading and unloading of drums with cranes, thus reducing time and cost in the loading and unloading operation. Lading will be blocked and braced in accorcance with rules of the Association of American Railroads (AAR rules). Prior to loading rail cars, the floor of the cars will be covered with plastic sheeting of sufficient width and length to allow sheeting to be folded up 10 to 12 inches along sides and ends of each car. This lining would serve to contain any product leakage while cars are loaded. Lifting of product from port will be scheduled aboard one vessel. Consideration will be given to lining the floor of the cargo holds with plastic sheeting prior to herbicide loading. Also to be considered will be the shipment of absorbent material in sufficient quantity to absorb minor product leakage. This absorbent material would be discharged with the product at Johnston Island either for use or disposal. 1-3 �(This page intentionally left blank) �APPENDIX 0 ANALYTICAL METHODS �(This page intentionally left blank) �I THE DETERMINATION OF 2,4-D AND 2,4,5-T HERBICIDES IN WATER A. REAGENTS 1. Benzene distilled in glass, pesticide e.nalysis grade 2. Ether distilled in glass, pesticide analysis grade 3. Concentrated ^504 4. Concentrated H3P04 5. Acid washed anhydrous Na2SOd or (5% solution of anhydrous Na?S04 pH <5) anhydrous Ha2S04 6. Anhydrous Na£ 7. Florisil activated at 650°C and kept at 130°C 8. N-methyl -N ' -rii tro-N-ni trosoquanidi ne •. 9. Potassium Hydroxide 10. Sodium Bicarbonate B. MATERIALS 1. Pyrex glass tubing, 1/8 inch O.D. 2. Glass wool 3. Gas-chrom1 Q 60/80 mesh 4. 9" Disposable pipet C. EQUIPMENT AND GLASSWARE 1. Varian Aerograph HY-FI III Model 1200 with a proportional temperature programmer, or sinilar instrument with electron capture detector. 2. Varian Aerograph Model 30 Recorder, 0-1 MV, half inch per minute or equivalent. 3. Dohrmann Microcoulometric Halide Titrating System/G.C. 4. A small oven, maximum temperature 150°C. 1 Aoplied Science Laboratories, Inc., State College, Pa. J-l �5. Prepurified nitrogen with pressure regulator 6. Fluidized sand aath 7. Kuderna-Dantsh evaporator, 125 ml with various size concentrator 8. One-liter separatory flask 9. Two-liter separatory flask tubes 10. 125 ml and 250 rnl Erlenmeyer flask 11. Various size volumetric flasks 12. Quart mason jars with teflon lined covers 13. Ultra pure oxygen with pressure regulator D. COLUMN PREPARATION 1. DC-200 silicone grease is coated 2.5 percent by weight on 60/80 mesh Gas-chrom Q. The material is also coated with 0.25 percent carbowax 20M, and packed into 1.5 mm - ID, 3 mm - OD heat resistant glass column 6 feet long. 2. OV-17 1.5 percent by weight, QF1 - fluorinated silicone 1.95 percent by weight, carbowax 20M 0.25 percent by weight are coated on 60/80 mesh Gas-chrom Q and packed into 1.5 mm - ID, 3 mm - OD heat resistant glass column, 6 feet long. 3. EGSS-X is coated 3 percent by weight on 100/120 mesh Gas-chrome Q and packed into a 2 mm - ID, 4 .mm - OD, glass column, 6 feet long. E. PREPARATION OF STANDARDS Herbicide standards are prepared from their methyl esters to contain from 2 x 10"9 g to 5 x 10"12g per y'l (microliter) in hexane or benzene in a volumetric flask. F. PROCEDURE 1. Sample Collection of Herbicides: The water sample is collected, using a precleaned quart mason jar with a'teflcn lined cover. The jar is submerged directly into water source to collect, sample. One-inch air space is left on top in the container. 2. Cleaning of glassware a. All glassware, except volumetric glassware, is heated to 300°C for sight hours to eliminate organic contamination after detergent washing and rinsing in acid water pH <2 and rinsing clean of the acid with organic free water. J-2 �b. Volumetric glassware is cleaned with sodium dichromate in concertrated sulfuric acid cleaning solution, rinsed clean of sodium dichromate with organic free water and final rinse with acetone nanograde distilled in gle.ss and dried in oven. 3 . Operating Parameters of the Gas Chroma tograph a. Oven temperature: 170°C b. Electron-capture detector, concentric tube design, D.C. mode, 90 volts temperature: 210°C. c. d. Nitrogen (prepurified) carrier gas: 40 ml per minute. e. 4. Injection port temperature: 210°C. Injection volume: 5 ul (microliter). Herbicide in Mater a. Total phenoxy acid herbicides and its esters, (1) Acidify (pH 2.0) the one-liter water sample with concentrated sulfuric acid. (2) Pour the sample irto a two-liter separatory funnel. Add 50 ml diethyl ether to the sample bcttle, rinsing the sides, and pour the solvent into the separatory funnel. Shake the mixture vigorously for one minute. Repeat three times. Since ether is highly soluble in water, the sample must be saturated with ether before extraction. Dissolve 5 grams of N a $ 0 to water before extraction. (3) Pour ether extract into a J joint 250 ml Erlenmeyer flask containing 2 ml of 37 percent aqueous potassium hydroxide. Add 15 ml H20 and insert a one-ball Snyder column.. Evaporate the ether on a steam bath; reflux for approximately 90 minutes. (4) Transfer the concentrate to a 60 ml separatory funnel. Extract the basic solution three times with 20 ml ether and discard the ether layer. Acidify the aqueous layer with 2 ml of cold 4:1 aqueous sulfuric acid to pH 2 and extract the herbicides with 20 ml ether three times. Transfer the ether layer to a 125 ml Erlenmeyer flask containing about 0.5 gram acid washed anhydrous Na2S04 in an explosion proof refrigerator for two hours or overnight. (5) Transfer the ether solution into a evaporator-concentrator apparatus with a 5 ml volumetric benzene. Concentrate the extract to about 0.5 ml, using bath at 7QOC or lower. During the ether transfer, it is the caked ^ 0 to obtain a quantitative transfer. $4 Kuderna-Danish flask and add 0.5 ml a fluidized sand necessary to crush (6) When the concentrated extract is cool, add 0.5 ml of 14 percent BFa-methanol reagent. Heat the contents at 500C for 30 minutes in a sand bath or water bath. J-3 �(7) Cool and add 4.5 ml of 5 percent aqueous Na2S04 solution to the reaction mixture, shake for one minute, allow to stand for approximately three minutes for phase separation. j (8) The benzene layer is pipetted from the receiver and passed through a micro cleanup column of florisil with more benzene to a volume of 5 ml. Then concentrate down to 0.5 ml for analysis. (9) Gas chromatograph the methyl ester of chlorinated phenoxy acid through the same chromatographlc columns as chlorinated pesticides. (10) Compare with known quantities of prepared herbicide standards. approximately 0.5 cm anhycrous sodium sulfate approximately 3.0 cm (florisil) approximately 0.5 cm anhydrous sodium sulfate packed with glass wool made from disposable pipe-;. b. Butyl and Isooctyl Esters of 2,4-D and 2.4V5-T (1) To a 1-liter water sample, add 1 N.NaOH to bring the pH to 8 or higher. (Caution: immediately start extraction; hydrolysis of the ester will take place if left standing). J-4 �(2) Pour the water sample into a two-liter separatory funnel. Add approximately 50 ml diethyl ether to the sample bottle, rinsing the sides, and pour the solvent into the separatory funnel. Shake the mixture vigorously for one minute. Repeat three times. Since ether is quite soluble in water, the sample must be saturated with ether before extraction. Total extracted ether volume is 150 mis. Dissolve 5 grams of Na2$04 in water before extraction. Save the water sample for extraction of the chlorinated phenoxyacids and chlorinated phenols. (3) Pour the ether extract into a J joint 250 ml Erlenmeyer flask containing sufficient anhydrous acidified Na2S04 to remove the water and store in an explosion proof refrigerator for two hours or overnight. (4) Transfer the ether solution into a Kuderna-Danish evaporator-concentrator apparatus with a 1 ml volumetric flask and add 0,5 ml benzene. Concentrate the extract to 0.5 ml, using a fluidized sand bath at 70° C or lower. During the ether transfer, it is necessary to crush the caked Na2$04 to obtain a quantitative transfer. (5) Cool the concentrate overnight. (6) The benzene layer is pipetted from the receiver and passed through a micro cleanup column of florisil with more benzene to a volume of 5 ml. Concentrate to 0.5 rnl for analysis using the columns normally used for chlorinated herbicides. (7) Gas chromatograph the esters of chlorinated phenoxyacid. The 3 percent EGSS-X coated column has a better ester separation for e-c detection. (8) Compare with known quantities of prepared herbicide standards. (9) Proceed with the extraction of the chlorinated phenoxyacid and chlorinated phenols from step "(2)" by acidifying the water to pH 2 with concentrated sulfuric acid. (10) Pour the sample into a two-liter separatory funnel. Saturate the sample with ether. Add 50 ml diethyl ether to the sample bottle, rinsing the sides and pour the ether into the separatory funnel. Shake the mixture vigorously for one minute. Repeat three times. Total extracted volume: 150 mis. (11) Pour the ether extract into a J joint 250 ml Erlenmeyer flask containing anhydrous acidified NaoS04 in an explosion proof refrigerator. Allow to stand for two hours or overnight. (12) Transfer the ether solutions into a Kuderna-Danish evaporator-concentration apparatus with a 5 ml volumetric flask and add 0.5 ml benzene. Concentrate the extract to about 0.5 ml, using a fluidized sand bath at 70 C or lower. During the ether transfer, it is necessary to crush the caked Na2S04 to obtain a quantitative transfer. J-5 �(13) When the concentrated extract is cool, add 0.5 ml of 14 percent BF3-methanol reagent. Heat the contents at 500C for 30 minutes in a sand bath or water bath. When chlorinated phenols are determined with the chlorinated phenoxyacids, add diazomethane dropwise until a yellow color persists. (14) After methyl ation witn the BF3-methanol reagent sample, cool and add 4.5 ml of 5 percent aqueous Na?S04 solution to the reaction mixture, shake for one minute, allow to s-;aiid for approximately three minutes for phase separation. After rcethylation with diazomethane, slowly warm the sample in a sand bath or water bath to 50°C for one-half hour; then use filtered air to evaporate the diazomethane. (15) The benzene layer is pipetted from the receiver and passed th rough a mi cro cleanup column of f'lorisil with more benzene to a volume of 5 ml. Then concentrate down to 0.5 ml for analysis. (16) Gas chromatograph the methyl ether of chlorinated phenoxyacid and the methyl ethers of chlorinated phenols through the gas chromatocraphic columns. (17) Compare with known quantities of prepared chlorinated herbicide and phenol standards. (18) Confirmation of the chlorinated herbicides and the chlorinated phenols by Dohrmann Microcoulometric Titrating System. (a) The left over sample from the electron capture detection analysis is further concentrated down to approximately 0.100 ml, and the whole sample is injected into the gas chromatograph and detected by the microcoulometric system for halogens, c • Extraction or ..... Partition of ~~ jhlorinated Phenpxy Acids and ~ (1) Pour the ether extract from Step b. of the total phenoxyacid herbicides and its esters into another 250 ml separatory funnel with 50 ml of 5 percent NaHCOs solution. Shake and wait for a few minutes for the two layers to separate. Repeat twice. Save both layers. The aqueous layer will contain the chlorinated phenoxy acid and chlorinated phenols. The ether layer will contain the esters. (2) Dry the ether layer over anhydrous Na2S04 and add 0.5 ml benzene. Transfer to a Kuderna-Danish evaporator-concentrator apparatus with 1 ml volumetric flask. Concentrate the extract to about 0.5 ml, using a fluidized sand bath at 70°C or. lower. During the ether transfer, it is necessary to crush the caked NaS04 to obtain a quantitative transfer. (3) The benzene layer is pipetted from the receiver and passed through a micro cleanup column of florisil with more benzene to a volume of 5 nil, then concentrated down to 0.5 ml for gas chromatography. J-6 �(4) Transfer the ac.ueous layer containing the chlorinated phenoxy acid and chlorinated phenols from Step a. to a separatory funnel and acidify with H2S04 acid. Saturate the aqueous layer with ether and extract with 50 mis diethyl ether three times. Dry the ether layer over anhydrous acidic Na2$04. Discard aqueous layer. Allow the extract to remain in contact with Na2S04 in an explosion-proof refrigerator for two hours or overnight. (5) Transfer the ether solution into a Kuderna-Danish evaporator-concentrator apparatus wi~h a 5 ml volumetric flask and add 0.5 ml benzene. Concentrate the extract to about 0.5 ml, using a fluidized sand bath at 70°C or lower. During the ether transfer, it is necessary co crush the caked Na2S04 to obtain a quantitative transfer. (6) When the concentrated extract is cool, add 0.5 ml of 14 percent BFs-methanol reagent for pheroxy acid. When chlorinated phenols are analyzed together with phenoxy acid, then use diazomethane (dropwise until yellow color persists). Heat the contents at 50°C for 30 minutes in a sand bath or water bath). (7) -Cool the methylated sample and add 4.5 ml of 5 percent aqueous Na2S04 solution to the reaction mixture, shake for one minute, allow to stand for approximately three minutes for phase separation. Cool the sample which has been methylated with diazomethane and completely destroy the diazomethane. (8) The benzene layer is pipetted from the receiver and passed through a micro cleanup column of florisil with more benzene to a volume of 5 ml. It is then concentrated down to 0.5 ml for analysis. (9) Gas chromatograph the methyl ester of chlorinated phenoxy acid through the same gas chromatographic columns as chlorinated pesticides. (10) Compare with known quantities of prepared herbicide standards. G. ACCURACY AND COMFOTS t 1. Minimum Measureable Concentration of Herbicide in the Water Sample 2,4-D 2,4,5-T 200 ppt 20 ppt 2. Discussion of the above minimum measurable concentration of herbicide: a. Using the procedure, accurate analysis of most water samples can be routinely accomplished. Amounts less than the above detectable limits can be detected by analyzing a larger sample volume or reducing the volume of extract to less than 5 ml. Not all extracts, however, can be reduced to such a low volume without an accompanying buildup of excessive interferences. J-7 �-i "l b. Ultramicro analytical techniques must be used to determine nanogram concentrations of pesticides found in the environment. For analytical results to be meaningful, glassware should be properly washed and heat treated at 300°C. Extensive cleanup is required because interfering impurities are greater than pesticide found,. Recovery of pesticides from the environment averages from 85 percent to 114 percent. c. All glassware and reagents used should be free of interfering compounds. A blank and standard should be analyzed with the samples until the analyst becomes proficient. "It was found that prompt handling of samples is necessary if the results of the analysis are to be representative of the condition of the water at the time of sampling. A water sample was selected from an area which had been sprayed for about 1-1/2 years with 2,4-D. Added 2,4-D almost completely disappeared after the spiked sample was allowed to stand at 72° - 74op. in a stoppered bottle for 10 days. Apparently, in water courses and soils which are regularly exposed to 2,4-D, certain organisms may develop the capability to degrado the chemical. Shipping samples from the collection point to the laboratory may take too long and means for resolving this problem must be found. Perhaps 'icing 1 or chemical fixing 1 and air shipment may be required." 1 'Determination of Phenoxy Acid Herbicides in Water by Electron Capture and Microcoulometric Gas-Chrpinatography, by D.F. Goelitz and W.L. Lamar, U.S.G.S. WSP-1817-C. Draft copy from authors. REFERENCES 1. C. Brown and Y.A. Nishioka, "Pesticides in Water. Pesticides in Selected Western Streams—A Contribution to the National Program," PCS tic ides %Oltpr1_njLjpu_rnaJ_ (Sept 1967) Vol 1, No. 2, 38-46. 2. C . W . Stanley, "Derivatization of Pesti:ide-Related Acids and Phenols for Gas Chromatographic Determination," Journal o_f_Agrijcu]tune and^Food Chemistry, Vol. 14, No. 3, May-June TT9667. " " 3. P.L. Punsley and E.D. Schall, "Gas Chromatographic Determination of 2,4-D and 2,4,5-T and Their Derivatives in Commercial Formulations," J. of the AOAC. Vol. 48, No. 2, (1965). ~™~ 4. K.W. Cheng and Wendell W. Kilgore, "Gas Chromatographic Determination of Pentachlorophenol and Sodium Pentachlorophenate Residue in Fruits." 5. Manual of Analytical Methods, Pesticide Community Studies Laboratories, prepared by Primate Research Laboratories, EPA, Perrine, Florida. J-8 i �r" II. ' GENERAL METHOD FOR CHLOROPHENOXY ACIDS FOR BIOLOGICAL "MATERIAL -,- A. REAGENTS 1. Benzene, Pesticide Grade Quality 2. H.exane, Pesticide Grade Quality 3. Ethyl Ether, Pesticide Grade Quality 4. Petroleum Ether, Pesticide Grade Quality 5. Concentrated Sulfuric Acid 6. Anhydrous Sodium Sulfate 7. Florisil, Calcined at 650°C and stored at 130°C 8. BF3~Methanol Reagent 9. Acetonitrite, Pesticide Grade Quality 10. Methanol, Pesticide Grade Quality B. GLASSWARE 1. Liquid Chromatography Column, 22 mm ID 2. Separatory Funnels 3. Kuderna-Danish Evaporator 4. Erlenmeyer flasks 5. Beakers C. EQUIPMENT 1. Gas Chromatograph, Tracer, Model 220, Dual Column, with two Ni63 Electron capture detectors and a digital integrator, VIDAR 6300, Autolab, with teletype attachment. a. A 6 ft U-tube, glass column packed with 1.5'» OV-17/1.9555 QF-1 on 80/100 mesh Gas Chrom Q was connected to detector No. 1. b. A 6 ft U-tube, glass column packed with 4% SL-30/6% QF-1 on 80/100 mesh Gas Chrom Q connected to detector No. 2. c. Oven Temperature - 190°C. d. Detector Temperature - 350°C. e. Injector Temperature - 225°C. f. Carrier Gas - Nitrogen (prepurified) 80 ml per ruin. J-9 �2. Gas Chroma tograph/Mass Spectrometer, Finnigan Model 3000D interfaced with a system/150 data handling system. a. Gas Chromatoc|raph (1) Column - 5 ft U-Tube, glass, packed with 3 'A OV-1 on 80/100 mesh Gas Chrorn Q. (2) Column Oven Temp. - 160°C. (3) Injector Temperature - 225°C. (4) (5) - Sample injection - 5 ill. (6) b Carrier Gas - Helium 25 nil per rnin. Transfer line - 18QQC. Mas^ Spjecjbronieter (1) Electron Energy - 70 eV (2) Mass Range - 50-300 anu (3) Pressure - 3 X 10'3 Terr. (4) Sensitivity - 10" amp per volt D. PREPARATION OF STANDARDS: Herbicide standards were prepared from the methyl esters, of 2,4-D and 2,4,5-T. Concentration of the standard solution for Gas Chrornatography was 10 picograms (10 X 10-" 2g) per microliter (yl) of each ester, in hexane. Concentration of standard for GC/MS was 0.1 nanograms (0.1 X 10~9g) per microliter (yl) of each ester, in benzene. E. PROCEDURE 1 . Extraction of Acids a. Biojogical Matenal (1) One third of total sanple material is placed in a blender and homogenized with anhydrous Na£S04 until a uniform mixture is obtained. (2) Transfer mixture to a beaker, add 25 ml of 1Q« HgSO^ in methanol and then enough ethanol to cove;" entire sample by 1 inch. Stir for 20 mi n . (3) Pour into Erlenmeyer flask and evaporate on stearn bath with a jet of air until about 35 ml ethanol remains. (4) Transfer to 500 rnl separatory funnel with 200 ml 50/i ethyl ether in petroleum ether, add 50 ml 4/u NallCOs anc^ shake carefully. (5) Extract by isolation of acids procedure. J-10 �b. ( 1 ) Sedi men t flate rial I (a) Weigh 2g of dry sample material into a screw cap tube about 15 cm in length. (b) Add 10 ml of 1:3 benzene-propanol mixture and rotate on a Fisher "Roto-Rack" at 40 rpm for 2 hours,. (c) Filter suspension thru a hexane washed Whatman #2 filter paper and collect the filtrate ir a clean test tube. * (d) Evaporate to about 0.5 ml. (e) Sample ready for methyl ati on. (2) Coral Materiaj (a) 100 g of coral are broken up into small pieces and placed in a 400 ml beaker. (b) Add sufficient slightly acidified benzene to cover the coral. (c) Stir mixture for about 30 minutes using a magnetic stirrer. Decant benzene and save. Repeat extraction two additional times. Collect benzene in same container. (d) Evaporate benzene to almost dryness using gentle heat with a slow air current. (e) Sample ready for methylation. 2 . I sol ati on of Aci ds^JjHol ogi cal Ma ten a! ) a. After releasing pressure in the separatory funnel several times, shake vigorously for 1 minute. Let layers separate. b. Drain bottom aqueous layer into another 500 ml separatory funnel. Repeat extraction twice using 15 ml ethanol and 40 ml NaHCOs solution each time. c. Combine the aqueous phases and discard the organic phase. Extract the combined aqueous phase twice using 25 ml CHCL-3 each time. Drain off the CHCL.3 and discard. d. Carefully acidify the aqueous solution with 25 ml 10% aq. H2S04. Extract acidified solution three times, using 30 ml benzene each time. Drain each benzene extract through a plug of cotton into a beaker,, e. Rinse cotton plug with benzene after the third benzene extract has filtered through. Remove cotton and replace funnel in beaker. J-ll �f. g. 3. Evaporate sample just to dryness on a steam bath. Sample ready for methylation. Methylation of Acids a. Make sample to a volume of 0.5 ml with benzene. BF3/methanol reagent and mix. b. Add 1 ml of Place on steam bath and boil for approximately two minutes. c. Cool and add about 4.5 ml of 5% aqueous 1^504 solution, shake and allow to stand for phase separation. d. 4. Benzene layer is ready for clean-up. Clean-up of Methylated Adds a. Acetonitrite Partitioning; Only fatty samples were partitioned with petroleum ether - acetonitrite prioT tD florisil clean-up. The non-fatty samples were passed through florisil column for clean-up without partition. (1) Add petroleum ether to the sample extract so that total volume in a 125 ml separatory funnel is 15 ml. (2) Add 30 ml of acetonitrite saturated with petroleum ether. Shake vigorously 1 m'n. and let layers separate. (3) Drain acetonitrite into a 1 liter separatory funnel containing 650 ml HgO, 40 ml saturated NaC-] solution and 100 ml petroleum ether. (4) Extract petroleum ether solution in the 125 ml separator with three additional 30 ml portions of acetonitrite saturated with petroleum ether, shaking vigorously for 1 min each time. Combine all extracts in the 1-liter separator. (5) Mix 1 liter separator thoroughly 30-45 seconds. separate and drain aqueous layer into second 1-liter separator. Let layers (6) Add 100 ml petroleum ether to second separator, shake vigorously 15 seconds, and let layers separate. (7) Discard aqueous layer, combine petroleum ether with the petroleum ether in original separator and wash with two, 100 ml portions H20. (8) Discard washings and drain petroleum ether layer through column of anhydrous Na2S04. Rinse column with three (about 10 ml) portions of petroleun ether. (9) Evaporate combined extract and rinses to 5-10 ml in KudernaDanish concentrator for transfer to florisil column. J-12 �b. Flon'sil Column (1) Prepare 22 mm ID column that contains approximately four inches of activated florisil topped with about 1/2 in. anhydrous NagSO/j. (2) Pre-wet column with 40-50 ml petroleum ether. Place Erlenmeyer flask under column to receive eluate. (3) Transfer sample through at about 5 ml/min. extract to column letting it pass - (4) Rinse extract, container and transfer rinses to column, and rinse walls of chromatographic column with additional small portions of petroleum ether. (5) Elute column at about 5 ml/min. with 200 ml 10$ ethyl ether/petroleum ether eluant. . (6) Concentrate eluate to appropriate volume for analysis. c. Gas Chromatography - Electron Capture Detector (EC): 5 microliters of the eluate are injected into eactf'oT the two columns.Chromatograms are analyzed for peaks which have the same retention time as that of the methyl ester standards of 2,4-D and 2,4,5-T. The practical sensitivity of the Electron Capture to standard solutions of methyl esters of 2,4-D and 2,4,5-T is 50 picograms (50 X 10-12 grams) of each. d. Gas Chromatography/Mass Spectrometry (GC/MS): Samples which have peaks of the same retention times as the methyl esters of 2,4-D and 2,4,5-T are analyzed by GC/MS. 5 yl of sample are injected into the injector part of the GC/MS systems. The methyl esters of 2,4-D and 2,4,5-T can be confined by using the data handling system of the GC/MS by comparing the fragmentation patterns of the suspected compounds with those of the standards. The practical sensitivity of the GC/MS to standard solutions of the methyl esters of 2,4-D and 2,4,5-T is 0.5 nanograms (0.5 X 10- grams) of each. III. TCDD ANALYSIS: The TCDD analyses reported in the Environmental Statement Part III were accomplished by the EPA Pesticide Laboratory at Bay St Louis MS and the Perrine Laboratory, Perrine FL;,therefore, the analytical procedures are not included in this appendix. J-13 �(This page Intentionally left blank) �' APPENDIX K DISPERSION MODEL STUDY PAGE 1. GENE RAT, ' K-l 2. DIFFUSION MODEL AND INPUT PARAMETERS K-l 3. RESULTS K-2 4. E N V I R O N M E N T A L IMPLICATIONS K-6 5. REFERENCES K-l 4 . �(This page intentionally left blank) �1. GENERAL: The main effort, in attempting to define the effects of burning Orange herbicide on the air quality at and around Johnston Island, was directed toward the use of diffusion equations to predict the ground level concentrations. 2. DIFFUSION MODEL AND 'INPUT PARAMETERS: a. The concentration, C, of gas or aerosols (particles less than about ZO microns diameter) at the coordinate points x, y, ?., from a continuous source with an effective emission height, H, is given by equation (\). The notation used to dcpicb this concentration is C (x, y, 7,) H). TI is the height of the plume center line when it becomes essentially level, and is the sum of the physical stack height, h, and the plume rise, A 1I. The following assumptions arc made: the plume spread has a Gaussian distribution in both the horizontal and vertical planes, with standard deviations of plume concentration distribution ip the horizontal and vertical of Cry and <rz, respectively; the rrican wind speed affecting the plume is u; the uniform emission rate of pollutants is Q; and total reflection of the plume takes place at the earth's surface, i.e. , there is no deposition or reaction at the surface. C ( x , y , z ; I I ) =-=— - exp : -\ 2 TT a 7. u V rry { exp [-V^IL2 ] -I- exp [ - l _ a ± l a ] } (1) Icrz ' Vcrz ' For concentrations calculated at ground level (z=o), the equation simplifies to: C ( x , y , o ; H ) = - - cxp T -| _5L_ Tcry az u V ay / 1 e x p r -| _ \ ay / _ ] Where the concentration is to be calculated along the center line of the plume (y=o): C (x, 0,0; I I ) = -Q- exp [-1 (—Ii)3l 1 aya7' U (3) \ (JZ / -t At distance equal to or greater than 2 x •[__: C (x,o,o;H) = -Q" (4) • ^ 2 n-1' ay L u X J i is the distance downwind where the , vertical diffusion starts being affected by the inversion. K-l (2) �The Holland Plume Rise equations was used to determine H: lm 5.,. 2 _ 68xlo --n /Ts-Ta] S Ts / This is modified for atmospheric stability so the result is: IT = h I- ^h ( 1 . 4 - . I P ) (6) The mixing depth, I.: I, = (6 - P) (121) ( T - Td) / 6 -i j^. (7) 12 f ,>;( 7.1 zo) The mixing depth of the atmosphere (thickness of the boundary layer) can be defined as that layer where vigorous mixing takes place due to thermal and mechanical turbulence. A TABLE K - 1 INPUT PARAMETERS J. I. 15.24 1.5 1600 18. 17 76. 5 1024 719 Stack height (m) Stack diameter (m) Stack temperature (°F) Stack velocity ( m / s e c ) Air temperature (°F) Air pressure (mbs) Mixing depth (m) 3. Ship 12 3 1625 20 76. 5 1024 719 RESULTS: a. In order to determine a conservative estimate of the ground level concentration, the following parameters and considerations were used: the highest ground level concentration wilLoccur with high winds and an unstable atmosphere; no deposition or reaction at the s u r f a c e ; no rain-out of the plume; the ship standing still in the water; and using the Holland Plume Rise Eq. b. Figure K-l shows the center line ground level concentration for a IICL plume at Johnston Island. The emission rate is 37, 000 Ibs/day. The maximum (1. 85 ppm) concentration occurcs at 0. 2 km downwind and decreases to 0. 007 ppm at 10 km downwind. Figure K-2 K-2 �H = 38.3 U = 7 *n F i g u r e K - l . C e n t e r line g r o u n d level f l C L concentration, J o h n s t o n Island. �Id" tr> ID- I j -3,00 I J +10O I +100 Figure K-2, EIori^ontal'ITCl c o n c e n t r a t i o n at 0. 2 km downwind, Johnston Island. 'K-4 �XT. Q-:=/<?*/., 5 H=3 U= 7 Figure K-3. Vertical HC1 concentration at 0. 2 km downwind, Johnston Island. �shows the horizontal extent of the concentration at 0. 2 km downwind. Figure K-3 shows the vertical extent of the plume. Figure K-4 shows the ground level isopleths and area, A, enclosed by the isopleths. Figures K-5 through K-10 are for a ship operating west of Johnston Island. Emission rates of 170 tons /day of Orange herbicide were used. Figure K-5 and K-8 show the center Line ground level concentrations. The maximum 2. 28 ppm (HC1) and 0. 81 ppb (Orange) occur at 0. 47 km downwind. At 10 km downwind the concentrations arc 50. 0 ppb (IIC1) and 19. 4 ppt (Orange). Figures K-6 and K-9 show the horizontal concentration, while figure K-7 and K-10 show the vertical. 4. ENVIRONMENTAL IMPLICATIONS: a. ft is very difficult to extrapolate ;hese results to the actual situation at and around Johnston Island. The parameters used for the study are not necessarily those which will exist when the incineration takes place. These parameters were used in order to provide a conservative estimate (worst case) and these conditions are never expected to be reached. b. Factors that will decrease the ground level concentration shown in this study for the ship are: the ship will be moving during incineration; the atmosphere is more towards neutral or stable, than unstable: the mixing depth will be higher; and there wi]l be a certain amount of deposition and reaction with the surface and rain-out of the plume. For Johnstor. Island incineration, all of these factors, except movement of incinerator, also apply. c. Another fact evident is that under all conditions studied, a majority of the time, the concentrations of interest will exist over the ocean, due to the prevailing wind direction at Johnston Island. K-6 �LFVEL. T. T. Q- 1*14 5 Sec.-' /^ SS.3 SOURCf 0.1 /.3L i.o 0.8 F i g u r e K-4. 0.4 o.V 0.0. Ground level isoplethes, Johnston Island. �5H/P Secr HU= Sec ''1 Dow/v/wiWD F i g u r e K-5, Center l i n e ground level IIC1 concentration, ship i n c i n e r a t o r . K-8 �CRoss'WMD Figure K-f>. Horizontal TTC1 concentration 0.47 kin downwind, ship i n c i n e r a t o r . K-9 �SHIP Q-/78S g 500- u= 300 w? 3« loo to- -3 Figure K-7. Vertical HC1 concentration at 0. 47 km downwind, ship incinerator. �,-l /o" DOWA/W/A/D F i g u r e K-8. Center line ground Lever Orange herbicide concentration, ship i n c i n e r a t o r . K-L1 �SHIP ID'5 - C ROSSVfi N D Figures K-9. tlorizontul O r a n » o h e r b i c i d e c o n c e n t r a t i o n at 0. 47 km downwind, ship incinerator. K-.12 �SHIP -i 5oo H- / / V ' (j = 9 -»*t .x i yc -^ fOO Figure K-10. \"erticai Orange herbicide concentration at 0. 47 km downwind, ship incinerator. �5. REFERENCES: R e a l s , G. A. , "Guide lo Local D i f f u s i o n of Air Pollutants, " Air Weather Service Technical Report 214, (197 IK Lydon, D. , Plume Rise, USAF E n v i r o n m e n t a l Technical Applications Center Report No 6611. (1973). Nozaki, K. Y. , .Mixing Depth Model Using Hourly Surface Observations, USAF Environmental Technical Applications Center Report No 7053 (1973). T u r n e r , D. B. "Workbook for Atmospheric Dispersion E s t i m a t e s , " US Department of Health, Education and Welfare, C i n c i n n a t i , Oil, Revised 1969. ''Meteorology and A t o m i c E n e r g y 1968" 1,'nited States Atomic E n e r g y Commission. K-14 �APPENDIX L COMMENTS TO: DRAFT ENVIRONMENTAL STATEMENT DISPOSITION OF GRANGE HERBICIDE BY INCINERATION January 1972-AF-ES-72-2D (This Appendix consists of comments received from 9 agencies resulting from their review Df the above Draft Statement) �(This page intentionally left blank) �STATE OF M S S I S S I P P I EXECUTIVE, CHAMBER J A C K ' S ON W I L L I A M LOWE WALLEn eovtiRNon February 11, 1972 Honorable. Aaron J. Racusin Acting Assistant Se.crc.tary o.C the Air Force Installation and Logistics Office of the Secretary Department of the Mr Force Washington, D. C. 20330 Re: Draft Environmental Statement-Disposition of Orange Herbicide by Incineration January" 197 ?.- -A? -E S -7 2 -2D Dear, Mr. Racusin: In compliance with applicable regulations, the above captioned environmental s t;}.L::r.'.cn t has been reviewed by appropriate State agencies concerned wit. \ various aspects of the disposition. Comments from State agencies are summarized in the latter prepared by itbc Air and Water Pollution Control Commission, and are enclosed- herewith. It is my opinion tha'; the attached environmental statement is satisfactory. I recommend that full consideration be given to the comments of our agencies in the final review. Sincerely, BILL WALLER ' GOVERNOR L-1 �IF Pollution Control Commission STATE OF M I S S I S S I P P I COMMISSIONERS OMMISS1ONERS GAME ft FISH COMMISSION DILLY JOE CROSS AMES W. CARRAWAY. CHAIRMAN BOARD OF WATER COMMISSIONERS JACK PEPPER A53FIELD TATE PLANT BOARD . i. T. GUICE. JR., VICE CHAIRMAN CHARLES W. ELSE YAZOO CITY ilL ft GAS BOARD . F. DOKTIIWICK CARD OF HEALTH OE D. DROWN IARINE CONSERVATION OMMISSION /. J. DEMORAN ASSOCIATE MEMBERS Glen Wood, Jr. STATE PARK SYSTEM SITNCER E. MEDLIN EXECUTIVE DIRECTOR POST OFFICE DOX 8?.7 TELEPHONE 334-6703 A a I BOARD PAUL DURT SIXTH FLOOR ROBERT E. LEE OUILDING /. E. GUPTON ACK.SON GEOLOGICAL SURVEY W. H. MOORE JACKSON, MISSISSIPPI 30209 •ERMIT A. JONES ANTON February 8, 1972 Mr. Edward A. May, Jr. Assistant to Ir.liG Coordinator Federal-State Programs Office of the Governor 510 Lamar Life. Building Jackson, Mississippi •; i '• '• .:,' •• .-. '• • :.'.•-: , r. •;-'••-"• ..'.; V.',''--.. J ;.,'A'•' ••'''••''' "" ' '' •'' Dear Mr. May: This letter is in reference to yours of January 26, concerning the draft environmental impact statement entitled "Disposition of Orange Herbicide by Incineration". A meeting was held in our office with concerned agencies of the State on February 3, to conduct a technical review of this statement and to coordinate the state's position in this matter. Copies of the impact stateir.cnt had previously been forwarded to these agencies. The consensus of this meeting, is enumerated below: 1. Department of the Air Force should explore further possibilities for use of the material under adequate control measures, preferably by the federal government, as in national and state forests or by returning to commercial use through some acceptable channel. Apparently the alternative of giving this nicitcrial away was not explored. It is felt that destruction of the material would be a needless waste and would create further expense. It is recognized that such action as suggested might require some emergency authority from Environmental Protection Agency but this should pose no great difficulty since a similar material is in everyday use. 1-2 �Mr. Edward A. May, Jr. February 8, 1972 Page 2 2. In the event incineration is taken as the alternative, it is requested that the federal government assume the responsibility for all trarisportion of the material to the point of incineration and provide all necessary safety measures, such as, but not limited to, shipping materials in small quantities and providing the necessary absorbents at the convenient locations if shipped by rail. 3. It is requested that the material be removed from its present location at Kecsler Air Force Base beginning immediately and without regard to the final disposition cf the material. It is felt -his is absolutely essential because of the proximity of the material to recreational and shellfish waters, as well as large densely populated areas, and further because of the history of hurricanes and tornadoes in that particular section of the country. It is our feeling there are many other -areas in the continental United States which would provide a much safer depository for this material. 4. The Mississippi Air and Water Pollution Control Commission should be notified in advance of any proposed movement of the material, of the routes to be taken, and of the safety precautions. * Copies of this statement are being forwarded to all of the involved agencies, as noted on the attached sheet. Yours very truly, Glen Wood, Executive Director GWjr:js L-3 �Mr. Kdv.'ard A. May, Jr. February 8, 3972 Page 3 Copies furnished: Mr. Billy Joe Cross, Director Mississippi Game & Fish Commission Post Office Box 45.1 Jackson, Mississippi Mr. Joe D. Brov:n, Director Divisicn of Sanitary F.ng ineeriny State Board of Health Post Office Box- 1700 Jackson, Mississippi. 39205 ' v, •Mr. Jack W. Pepper, Water ringinear Mississippi Board of Water Commissioners 416 Nortli State Street Jackson, Mississippi 39201 Mr. .V7.illiara J. Dcmoran Marine Biologist Gulf Coast Hescarch Lab Post Office Box AG Ocean Springs, Mi.ss. 3965'] Mr. Bobby R. Tramel Bureau of Sport Fislieri.es and Wildlife Post Office Drawer FV7 State College, Miss. 397G2 Dr. R. A. McLemore, Director Mississippi. Department of Archives and History Post Office Box 571 Jackson, Mississippi 39205 Attention: Mr. Elbcrt Hilliard * Colonel Wendell D. Lack, State Forester Missir.sippi Fores try Commi ssion 1106 Woolfolk State Office Building Jackson, Mississippi 39205 # Mr, 0. T. Guice, Jr.', Director Division of Plant Industry P. 0. Box 5207 State College, Mississippi 39762 Mr. V7i.ll.iam II. Moore Director and State Geologist Mississippi Geological Survey Post Office Box 4915 Jackson, Mississippi 39216 Mr. Spencer li. Medlin, Comptroller Mis s i s s i ppi Park Sy s t cm 717 Robert K. Lee Building Jackson, Mississippi L-4 �THE ASSISYANT SECRETARY OP COMMERCE Washington, D C. 2GP3C) February 18, 1972 Department of the Air Force IIQ USAF/PREV Washington, D. C. 20330 Dear Sir: The draft -environmental statement titled "Disposition of Orange Herbicide by incineration,." was received by the Department of Commerce for review and comment. The Department .of Commerce has reviewed the draft environmental statement and has the following comments to offer for consideration. The key question is the completeness of combustion - i.e., the fraction not exidized but carried up the stack. Once J ! ^ - 3 ? ^ . , 9 - . J A ? t . JrJ-LSD.. there is the atmospheric transilLJ....^-95r™.^' port, and diffusion problem to E point at the nearest hab_ita..tion^jpr jam: ej^tri.cted. '^99 arour.d the disposal plant. There "-.. is « 100 foot stack. Combustion temperature is 2500°F (1400°C) for 3 second dwell (p. 11). Tentative data show orange decomposes at 900° C. (but how long does it take at this temperature? e.g., water boils at 100° C, but a large pot of water must rc'.nain at this temperature for sometime before it boils away). See page 15 - the Illinois plant would release 5% of the HCl as a stack effluent. The combustion of gasoline in an auto engine is only partially complete - and hydrocarbons are emitted as wastes; i.e. unburnt cjas^qli^nc. The combustion temperature of an auto is undetermined and the dwell time is about 4 nillisoc, so the analogy may be poor. The safety of this operation will also depend on how continuously reliable and constant -arc thb actual temperature/prossure/dwell L-5 �- 2conditions inside the burner - because it will take more than a year of continuous burning to complebc the job. The constancy, uniformity and reliability of the contractors' facility arc therefore important questions which probably should be treated in the statement. We hope these comments will bo of assistance to you in the preparation of the final impact statement. Sincerely yours, t /ft ' Sidney R. Caller7 Deputy Assistant Secretary for Environmental Affairs L-6 �•.. l|,i\ > •/.-,-'•' DEPARTMENT OF AGRICULTURE omrr or THC stcr<s;TAHY •"•_./ W A S H I N G T O N . 0. C. 20250 FEE 2 2 ?372 Mr. Aaron J. Racusin Acting Assistant Secretary of the Air Force Washington, D.C. 20330 Dear Mr. Racusin: We have reviewed the Draft Environmental Statement on "Disposition of Orange Herbicide by Incineration". Several questions have arisen that you may wish to consider. The environmental statement does not contain data to show that effluent omissions would not contain biologically active dioxins. Data to show that dioxins are not emitted into the atmosphere must be provided. The statement does not provide for monitoring stack flume emissions from either o? the proposed-incinerators. Information should be provided to assure that the orange herbicide remaining in the emptied containers does not have a higher concentration of dioxin than was present in the lot as a whole. Such a situation would arise if the dioxin settles to the bottom of a drum. If that happens, much of the dioxin would go into the soil instead of being combusted. Damage to vegetation can occur -rom 2,4-D and 2,4,5-T in the vapor phase. Shipment of orange to the incineration site should be geared to incineration capacity so thai; large stocks are not kept in storage at the incineration site. We believe the environmental impact statement must contain data on temperatures required for total combustion. The statement must also identify the effluent gases, and intermediate breakdown products. For example, incomplete combustion may occur when the incinerator is shut down. IntgrjiiQdjja.te-combustion products may be potentially hazardous. 1-7 �The biological activity of the effluent gases must be documented and a scrubbing system specified that will assure safety. i The volume of water into which the sodium chloride is discharged and the rate and volume of fresh water inflow should be specified so that the increased salt content of the water can be determined. We hope these comments are helpful to you. A, Sincerely, T. C. BYERLY Assistant Director Science & Education Enclosure: 1 copy of Environmental Statement L.-8 �EXECUTIVE DEPARTMENT DIVISION OF PLANNING COORDINATION ! IESTON SMITH GOVERNOR BOX 12428, CAPITOL STATION AUSTIN. T E X A S 7871 1 PHONE S12 4 7 5 - 2 4 2 7 February 25, 1972 Mr. Aaron T. Racusin Acting Assistant Secretary of the Air Force Headquarters USAF/PREV Washington, D.C. 20330 Dear Mr. Racusin: The efface of the. Governor, Division of Planning Coordination. (State Planning and Development Clearinghouse), and affected Te.xas State agencies have reviewed Lhe draft environmental impact statement for the disposition of Orange herbicide by incineration in Deer Park, Texas, The Texas Air Control Board presently objects to the proposed project for several reasons which include insufficient technical information in the draft environmental statement .md the possible harmful effects to the area by adding additional air pollutants to the atmosphere . The Texas Air Control Board (TACB) ha.:; statutory responsibility and authority in mat tern of air contamination. The comments received from State agenr.ies are enclosed. Thank you for the opportunity to review this draft environmental impact statement. Sincerely, Ed Grishnm Director KGiCtt End. (4) ..• cc: Mr. Charles R. Barden, TACB Mr. James U. Cross, TP&WD Mr. Hugh C. Yantis, Jr., TWQB 1 •Dr1. James V.. Peavy, TSDIl Mr. A.. T. Traynor, USAF L-9 ED GRISHAM DIRECTOR �i; AND WILDLIFE DEPARTMCNT ;M.V«I •_• . " • • • » • . - . . • . C" '," "'-, .-• I ill' '.'. ,.Y-. 001. ni i, K*:.-,_F MAI,I"< .'-i. ,ir, "I "L-l.l i l.-s \ VJ ,,..'.'// tS'f.'P \JV~-J;--. joi. •< / r ji - C - ; Ml V L ' •! J A V C - . U CROC-:Ex: Ci.l 'h lime. TO , JOHN H R [TAG AN IJL'ILLliNG A U S T I N , T L X A S 7.-V/OL February 14, 1972 Mr. Ed Cokcr Division oT Planning Coordination KxecuLivo DtiparLaient Capitol Station Austin, Texas 78711 j Dear Mr. Cokcr: We have reviewed the draft environmental impact statement for the disposal of Orange Herbicide by incineration, anc. urc in general agreement with thn method of disposal, and the draft statement. Wo would rcconraencl that stack gases be monitored dicxin to prevent: any escape to the atmosphere. taken to prevent loss or spillage of the barrels arc disposed of properly, the Parks and Wildlife to the incineration of Orange Herbicide. for 2,4-U; 2,4,5-T and If other precautions are and if the empty barrels Department would net object We appreciate having had the opportunity to comment on this draft statement. Sincerely, MKS U. CROSS Executive Director RECEIVED L-10 FEB 15 '972 Div. Of Plan. Cnnrri I �CORDON FULCHER CHAIRMAN TEXAS WATER QUALITY BOARD J A M E S U. CROSS J. E. PEAVY. MD LESTtfi CLARX VlCE-CHAI r ."A'l BYRON T U N N E L L HUGH C. YANTIS. JR. Extcurivi DiHtcron J. DOUC TOOLE HARRY P BURLtl(?H --..:•. .-•• P.O. PH. 4 7 5 - 2 0 5 1 A.C. 512 314 WEST IITH .STREET 70701 BOX 1 3 ? 4 C CAPI-OL STATION 70711 AUSTIN. TEXAS February 1, 1972 Mr. Ed Griuham, Director Division of Planning Coordination Of.'lce of tlic Governor Capitol Station Austin, Texas 78711 • Dear Mr. Grisham: Jn response to your memorandum of January 2G, 1P72, 1 would like to restate the: comments of our letter of November 10, 1971, a copy of which in included in the Draft Environmental. Statement for the Disposition of Orange Herbicide by Incineration by J;he .Department of the Air Force. In restating our previous opinion, I would like to suggest that insofar as water quality is concerned, no environmental, statement or special permission is required so long as the disposal, by HollLns Purle is carried out •within the conditions of waste control order No. 01429 and so long as the solid waste disposal of decontaminated drums is curried out pursuant to stc.te statute. It should be understood that if the disposal of either the Orange herbicide or the drums \vas proposed to be carried out contra cy to state statutes, then this office would decline to authorize the disposal. Very ccs: All Board Members - Texas \Y;>l:ev Quality Board Mr. Josiah Wheat, Legal Counsel, T\VQB -. L-1T ECEIVED TED 3 197;; f)iV. nf Pk 1 Ton,-. �^Department of IAMF.S E. P E A V Y . M.C1.. M.P.H. rOMMISSIONEP OF H E A L T H BOARD OF H E A L T H AUSTIN, TEXAS I, B. C O P C L A N O . M.D. ' E P U T Y COMMISSIONER February 15, 1972 H A M P T O N C . R O L ' I N S O N , M.D.. C M A I f . ' ^ A N R O n E R T D. M C M - - O N . M.D.. V I C E - C ' i A i n . M H N W. K E N N E T H T l . U R M C N O . D.O.5.. S CC F> i- ~ A fi / N. L. B A R K T - l t J R . , W . D . C H A K L . E 5 MAX C O L F , M. D . MICK It C. IIOLCO'.ID, [>. O. JOHN M. SMI T V , jn., M. r>. J f SS W A Y N E V . E O T , R. PH. R O Y C E E. Y i l S C N C - A K r . R . M. S. ENG. Honorable PrcuLon SurLl'h Governor of T'JX.-IH State: Capi Lol * Auiitin, Texas. 78701 ATXF'.NTION: Mr. Ed Grishom Dear Governor Smith: The Draft I'livironiticntal Statement for the "Dispo;-;ition of Orange Hurbit-ide by Iiicineration," prepared by the Dr-partment of the Air Force has been reviewed by this Department. In considering the proposal with regards to possible pollution of 11 ic waters of the State, 'wo are .in accord with the viewpoints expressed by Mr. Hu^h C. Yanti.s, Jr., Executive Director of the Texas Water Quality Board, in his. letter of February 1, 1972, to Mr. Ed Grlsham, Director of your Division of PLinnincr Coordination. Mr. YantiH stated that if t'.ie project js carried out in such a manner as to ctmtrol the discharge so that the limitations set forth in Waste Control Order Number 01M29 are not exceeded, no conditions will exist which will require special or extra permission. However, when disposal by inei.nera tion is viewed from the standpoint of potential adverse air pollution conditions, wo concur with the statements and recommendations of Cored by Mr. Charley R. Dardon, Deputy Commissioner of the Air Control Section of this Department, who also serves as Executive Secretary of the Texas Air Control Board. J. E. Peavy, Commissioner' Health RECEIVED FEB 18 1972 L-12 Div. of Plan. Coord. �TEXAS Alll CONTROL BOARD 1100V/CST 49th STREET CHARLES R. DAEDEN, P. E. AUSTIN, T E X A S - 78756 EXECUTIVE S E C R E T A R Y WENOELL H. HAJ'RICK, M.D. E. W. ROBINSON • CHARLLS R. J A Y N E S JOHN 111.AIR JAMES 0. ADR/.,'.,1; FRED H-'Rfw.AN WILLIE L. ULICII, Ph.D.,P.E. HERBERT C. M..KEE, Pl.D.. P.E. Cliairman HERRERT W. WHITNEY, P.E. Vico-Cliaiiman February 14, 1972 Mr. Ed Grinhnm, Director Division of Planning Coordination Office of tho Governor Capitol Station Austin, Texcis 78711 Dear Ed: Following am our comments on the Draft Environmental. Impact Statement for Deposition of Or_anoc LV'^i-^A-^il k7 ^PC^-JJiEilti&J prepared by the Department of the Air Force i-n January, 1972: "Information received since the dra:It environmental statement on the incineration of Orange herbicide fror.i Kelly Air Force Base was written in October of 1971 makes it inadvisable to allow this operation to be conducted in 1ihe State of Texas at this time. The following factors were considered in evaluating tho proposal to incinerate, tho Orange herbicide in the Rollirirf Purle incinerator in Deer Park, Texas: 1. •j 2. The information submitted in the impact statement does not indicate that alternate methods of disposing of the herbicide have been thoroughly explored, or that these methods will be more harmful to the environment than burning the herbicide would be. Technical information submitted with the impact statement is insufficient to determine the feasibility of •destroying great quantities cf Orange herbicide by incineration. Although the impact statement indicates RECEIVED FED 10 1972 L-13 Div. of Plan. Coord. �that Rollins Purlc, Incorporated will comply with air pollution control regulations, methods of compliance and technical data are leicking; and no mention is made of - laboratory facilities or the analytical capability of the Rollins Purlc facility. On page twelve of the impact statement, the gravity of the problem is indicated by reference to the need for complete destruction of the Orange material in order to avoid contamination of the environment with hazardous combustion materials or unburned herbicide chemicals. The next sentence reveals that combustion stack emissions and liquid effluent monitoring systems and test methods have not yet been developed. The ultiir.a-e responsibility for technical errors and accidents is not clear. 3. The area around the proposed site of incineration, Air Quality Region VII, is a highly industrialized area which has relatively high concentration of air pollutants. The addition of combustion products from the incineration. of over two million gallons of Orange herbicide into the atmosphere of this area over a prolonged period could compound an existing problem and. might very well prove harmful. It might be desirable to explore the possibility of incinerating the Orange in a federally-owned facility located in a relatively unpopulated area. In view of the factors enumerated above, we feel that the destruction of Orange herbicide in the State of Texas, as outlined in the Air Force impact statement, would be imprudent at this time." We appreciate the opportunity to comment on this project. be of further service to you, please let me know. If I may Since rely/yqu/rs, /(/(4i/yisi Bardon, P7E. (j{ww\ .,.. liarles R. Executive Secretary Texas Air Control Board cc: Mr. Jim Mcnke, Regional Supervisor, Baytown Regional Office L-14 �karch 1972 '^AR hohprt Snanana 3ocretary of the Air Force D.C. Deiir Mr Searr.ans: Subject: DISPOSITION OF ORANGE 3Y INCINERATION A letter from John J Shau^hnesay, Colonel, U3AF, Chief Finns Group, Office of Legislative Liaison, to the US Con'rross:r.an Jarr.ea '.7 Sy.-ington on 11 February 1972, did invite consents from the citizens regarding the above subject aa outlined -flithin AF-ES-72-2D January 1972. I take the following exceptions to the basic stud/: 1. The basic "SUI.l'.vARY SiEST", na,?c i, rarae;raph 3, in part; thfi description of the size and location of one incineration nlant, located on a 200 aero site Just Southeast of Houston, in a city called Deer Park, Texas, and then describes a oeoond incineration Riant located at Sau<*ab, Illinois, (a) This would infer .that tha ]>!«.: it described at Deer Park, Texas is Just Southeast of Houston, Texas, a well known «ity, and it a H ^ o infers the second plant is located at Samlet, Illinois and where is Sau^et, Illinois? (b) If you d U r b searching for thin city of Sauget, Illlhnis, you will not find it on any road nap of thn s-:a te of Illinois, but if you should find a blofl-up rrar> of the St Louis, Xissonil and itg n.etropolihan area., you ui^ht notice a grrall city located across the l-isaissippi River from the Corps of Engineers, whooe ir.oorin^ and base denot is located at the foot of Arsenal Street and only one block further, the Headquarters of one of the rrajor USA? Agencies, The Aeronautical Chart and Information Center, located at Second and Arserul Street, St Louis, Lissourio (c) I invite you to read through tne baaie report, on pa^ea 10, 11 and 12, you notice the Deor Park, Texas incinerator staatlcs: ( i j A COUERCIAL INCINERATION P];xnt, carabln of burning ORANGK HerbicUe« (2) Locfttsd Near Houston, Texas, in a city called Deer Ptrk. (3) Presently burning Liquid waste froir. the surrounding industrial complex consisting of oil refineries arid chemical plants 8 The INCIKERATOtt is located on a 200 acre site, 15 ndles from the center of Houston and 4 n-.iles fro:i. tho n«arer>t oopulfition center of Deer Park ( that lies to t'r:e Southwest of the incinerator. (5) There is a Wfivailln" v/incl froa the Southfaat. (6) There ;u-e 35 peonle -,vorkin?» j.t thia incin«rator« (7) Natural f^aa is available for fuel, ho-iever, the natural ooi.'ibustion properties of the herbicide .vill provide the fuel required 0 (8) ORANG2 would normally be rr'.i.x2d with other waste co"ibustib le liquids during the incineration otore. Mon B * (9) The im-incirsitor is equipped 'vith ca.uatic scrubbers which convert tho hvdroiTPn chloride into aodiiui chloride (Balt)» (10) Thf incineration of the 2.3 I'i'llion -yallonn of herbicide will produce apr>roxin-.atoly A^.6 Trillion munds of carbon dioxide and 12. 1, million mounds of salt to bo dtsrshar^od into the surroimrin^ enviro'in-'nto (11) The daily rate of dlscharw -vould be for about /to.n. r s y a , banod on the inclnerflition of 5000 gallons of OHAXGE per every 2^ hour day. L-15 �•'Subject: DISPOSITION1 0? OilAITGS 3Y INCINERATION, AF-E5-72-2D January 1972 (d) I invite .vou to read further through -the btsic rfiDort, on pa?es 13, 14 and 15 you will notice ihe Sau^et, Illinois ilonnaito Coirrany Che-ica! Plant's incinerator stastico, the description of the before undescribed facility located within an unknown city! (1) A Corr.prcio.l FACTORY that hag an incinerator canablft of burning ORANGE anc1 its ingredient naterials* (2) Located Just across the r. ieflisainpl River from St Louis, Missouri, within the city of Saufft, Illinois.. (3) Presently is U3(-\1 to burn in-house arid custoxer-re turned contaminated polycliorinsited 'tynhenols. The Factory is located on a 13A Acre site, lo^J irllen :"rom the downtown center of St Louis, 1. isaouri, the company has approximately 10 acres cf stor afjn area available. (5) There is a prevailing win^ from the Southeast « (6) There are 1303 eirployeo.s working at this nanufacturin* factory, (7) The basic report ir.a^es no irerition of natural p;aa availability for incineration 0 (Kd 0 coT"ient: Natural £aa in excosa qua ni ties is available to the local eras company for underground storage only during the non cold ironths, fo? recycling into their ayste'n for cold month residential heating nefirs). (?) ORANGS would not be nixed with other waste cor.buatibl^ liquids, during the incineration operation. (9) The incinerator is lot/pqui-n^'d \vith a caustic scrubber which would convert the hydrogen chloricfl into sodium chloride (salt), but It has only a system f or rTOcflsai.Tj the incinerated products stack, exhaust £'.'*s through a water wash systei" including a vrnturi scrubber w>ilch diffuses the Races with water, to wash out 9f5*i of the hydrogen chloride as a liquid effluent and discharges this into a r.unicipal waste nlant, then into the f/.isaisninni River about 1 ir.ile award (10) The incineratioT of the 2.3 -nilllon gallons of ORANGE will Produce anproxiir.?.telv the jsan* 4-'Uo ndlLLon pounds of carbon diojd.de, but viith'out .caustic scrubbRra and processfd only through a. water wash Bystem, follov;ed by thf. USR of a venturi Bcrubter, this will relftaaj the unrecovered 5S> of t'lo hydrogen shlorice alon» with a voluminous amount of -water vanor to condense into varied conce.itraticna of Hydrochloric Acid i/.ist fallout. The amounts to bo considered is not referenced in the report, but ir. disr.iisooci by: "This liquid effluent and stack discharcre is within the existing permit limits'^ (11) The daily rate of discharge would de^ond unon the industrial factory need to dispose "of tha_ir orfri wasto n.a4;.oris.l in, an incinerator whose capicity ia onlv 2f?cO pallona every 24. hour neriod, and if this capicity Ls used only to incinerate ORANGE, it would take over ?00 days,, . !? 1 '• ' (e') I.'y excention to this basic nara^raoh Is, why d i d n ' t the SU'l'.'ARY SEKT state this, instead of trying to leavp the Insinuation that Sauret, Illinois is yust oom<? arwll nlaco, where no one hus ever hoard of, and probably would assure it is located out in the b-'ick country. If you '.vould considpr a 15 ii-ilc radiui circle dra^n about Sau^et, Illinois, you woiiild discover % metropolitan area with a nojiulatlon of much more than 1 ir.i-llon People,, At Depr Park you would discover thl. san.e 15 r.lle circle encloses a much srall^r copulation due to the loc.it^on of Deer Park 10 1/ilea froir, Houston, and the incinerator plant falls within thft a*'»a of the "Tidcland Cil Area", where a larc;e concentration of oil wells E r o r he fo\md. aa well as the surrounding area is somi-salt narah flat, tint i a ' populated . ": 1-16 .. '"'"' ' ' �Subject: DISPOSITION <V OKANGjS BY INCINERATION. AF-ES-72-2D_January 1972. ' ' '' _j 2. The basic study 1 a request for cogent from the Governmental Agencies: '.Vhy was not the State of kiss our i,| Th" County of St louis and/cr The CItv'of St Louis requested to ccn.rent on the effect of this incineration' of the ORA1CGS would have on their environ.ent, especially since they have a pollution code snore restrictive that that of the State of Illinois or the U.S. Government. ! • 3. "ho question of water dilution of the 90o of the Hydrogen Chloride into the waste trentnent plant in the forrr of Hydrochloric Acid, and then passed on into the Mississippi River? '"hat effect would this h.we on the fish, the -water fowl, the peonlc downstreaa. who depend on the -.voter fron, 'the Ii.ississiopl River for the water they drink? ".That effect would this have.' on the National Goal of ^reuchinn; the secondary sewa re treatment systeir' by 1975 o 4.. If the Sau^et, Illinois I.-.onsanto Cor.Ds.ny Plant's incinerator would be selectee' to dispose of this CHANGS, what security could be <»iven that a 100£ destruction or." this herbicide could be accomplished'' If an. alrr.ont impossible 995 destruction was obtained, .this would releane 23 ^f 9 pallons of pure ORA1JG3 in a vaporous state beinpr discharge into the ats^osph?^, alon=>; .vith the 5'- of tho Hydrogen Chloride reported volur.e that coulS not be recovered which \vpuld also be air diach<ir:~ed alon" with a tremendous quanity of water v^-oor to be disnersed over tho n.ctronolitan area of St Louia, where this 1 million plus hu;r.an persons reside and are er,;plo;ci One of try concerns la: .That, would ha one n if a nalfuntion of equipment would r«sult In less than total destruction of this ORATT'j3, how 1on» of a ti-ne span before tho reaction in operations to brin^ to a halt tho cliso.Ss.rge and remedy would be trade to undo the dairae;e created by such a iralfuntion? 5» The alternate methods au-7 nested to dispose of this dangerous c.aterisl. offer tho follo7;ing additional methods be considered: I (a) Burial in abindoned ealt or sulchur -nines, in the same fashion and method. used to dispose of hot radioactive v;aste iruterialo (b) Burial at sea, in an obsolete ship within an subnarlne trench, the sar.ie method the U.S. Army used to dispose of the unwanted Nerve Gas« (c) Atonic incineration within an underground cavern with a snail aton.ic energy device, that -voulf; produce the necessary destructiva heat for the incineration instananeously. 9 (d) Puminf into plb'ier an abandoned or dry oil well drilled to a dnpth of bflow 10,00") foet. In a It-rral scnr,o '(.oleums to the Govcrn.'i.fnt ulnce eithor donlfttion of oil resr-rvo or dry hole ctatue ruyir.onts have boon allcxved for tax purposes to the drillin?; company. /' IT Sesrrif;no, to quote the U.S. Government's stand on envloron.ental PolD.utico, that pollution ie a condition that knows no boundaries, either National, State,. or comnunity 0 (a) A rocpnt rrwetln^ of the MATO Country ropretrsntitivea at Scott.AJ-'R, Il'.in"-ij within 15 ".lie ft of the Dovmtown'st T,oiji.s, did' riscuss, world envioro;i.(>ntaj. pollution wobleii.s. It w.-±3 inr'icatod at ^hat ti rr? that tiie r.-etropollta1; :>\.. Louis was the taird dirtpst, foulest c.nci/or polluted city within the MAID Countries, exceeded only by a city in Tur'<u»y and by a city in Northern Euro ;>:,-. L-17 �Subject: DISPOSITION 0? ORANGE .BY I KG iKE RATION, AF-ES-72-2D January 1972 (b) A recent envirorr.en^al study of St Louis /etronolltan area indicated that Sauf»fit, Illinois was located within one of the two heaviest chemically polluted areas within ihe region under study. Have you reixf' the recent uafjazina article: A tree prows in Sau^eb'/ Where it cleacribes the last lone survinc; tree within the city, how the shrubs if they r.cnvi at all, enter a early c'ornant period with leaves turning yeliov» by early auiMier, how the p;:.'aas has died coinnletely or 5 e a sick yellow brown denenoin^ on how far they rt,ay be located fron: the source of the airbourne Dollution, a disaster at i£a very l-test, the Wonsanto Chemical Coii.pany and its incineratoro (c) For the location of the second polluted ;irea \vithin thfi St. To"is ft.etrqaolita; area, I refer you to the U3A? ^VIRC^.r^TAT, iiZALTII LABORATORY, hcClellan A'r'B, California, Report No. 69:.r-lC (n-olject No. E6P-£9) July 1969 entitled: Air Pollution Study Aeronautlc.il Chart anr1 Inforn.aticn Conter, South Annex, located at P900 South Broadway, St Louis, Ivliasouri. In conclusion, I innlore you to reconsider sorr.e other method of destroying this r.onstor other than by incineration and releasing the contaminating chendcala into the environn.ent. Sincerrly yours, r D Thornb^rry • Douplaa 104.14 Kfilvich Drive St Louis, Missouri 63137 L-18 �CITY COUNCILMEN LARRY McKAbKLi: JUDSON ROICNSON, JR. ii i V' iji -n "I ] i ij r* ~\ T i HOUSTON h i ! •^,;.-"'\l,!..^. ,L;.--,: LOUIE WELCH, MAYOR HOUSTON. TEXAS 77001 jAMrs J. M( CONNHOMER L. FORD FRANK O. MANCUSO DK.K Coi-ii.ini THANK L. MANN JOHNNY GOYIN CONTKOLLf-R LLONEL J. CA&-HI.IO Di PARiMI M or Jji inir Hi M.-III 1 1 1 1 ) N M.\((li(u,()R I I O I ' S I O N , Tl XAS ' "O.'S March 8, 1972 Cl.l.r.r K. Whltehoad, Colonel, USAI' Chief, H'.n v 1 r o n ,T o n t a I Pro t c c t i o n G r o u p Director-ale of Civil r,:a,';;incorini;; Dopai"tr:,rMit of the Air .Force? Headquarters 1'iilted States A.i c .Force Washington, D. C. Dear Colonel Whitehead: Tho environmental impact statement "Disposition of Orange HerbicldG by Inninei'ation, January, 1972" ho::, boon carefully revj'cv/od by nonbcrs of tha City oT Tfou:;ton PolluLion Control Dlvision. However, V.TO do wish to point oui; th;it tiiir; facility is not v.'ithin our jurisdiction. Accord:!. 113 to the infoi'T.otion in this Jinpact utaUonent, the Oranf.c liurblcido can be ."incinerated at 1908° i'1 resulting in tho for'nulation of "'iydrop;op. chloride and carbon dioxide. Ilov/ovcr, thi;; in rorr.ifi.olcn I c> ba:;cd on tentative combur,tion data av/aitlri;;, dct.nilnd i'c:jult™ of a combustion analyult; prop;rav. to bo completed by the Department of Agriculture by July., 1972. In addition the impact statement listed the normal stack discharp.ea for the Rollins Pur.le plant ao carbon ciio^ids and steam. Accordinp; to visual, oocorvations by our agency r.nioko dlncharpes from the Incinerator indicated that complete combustion in not always attained. Considering; thetic- factors, it is the opirion of this agency that the final combustion data is needed ncfore a decision is made to incinei'O.to t'r.c Grange herbicide. Also a co:riplet.c efficiency ::tudy i.; needed for the !?ollins Purl.e incinerator plant before a decision i.s inadc 'on vrhcther or not it can be .1 n c i n e r a t e d at t h 1 s fa c i. 111 y , L-19 �Cliff M. Whltchead, Colonel, USAP March 8, 1972 Pae;e 2 We appreciate the opportunity to comment on tblt; project. If additional information is needed from this agency, please contact our office. Sincerely, Victor N. Hov.-ard, P. E. Director Pollution Control Division VNH/fh Read and Approved: Albert G. Randall, ?•!. D. Director of Public Health L-20 �. •i . . - ENVIRONMENTAL PROTECTION AGENCY -.' • WASHINGTON. D.C. 20460 - /iSit DCS Mr. Aaron J. Racusin , Acting Assistant Secretary • o f ' t h e A i r !•' o r c c Office of the Secretary Headquarters USAP/PREV' Washington, D.C. 20330 ]£; « •'//*''' • Dear Mr. Racusin: We have reviewed the U.S. Air Force draft environmental impact statement on the disposal of Orange herbicide by incineration. The proposed action calls for the incineration of 2,338,900 gallons of Orange (including Orange TT) herbicide over a -16 8 -day period at c i t h e r Deer Park, Texas or Saugct, Illinois. We concur that the process of incineration if properly carried out under the .appropriate conditions can effectively reduce the components of Orange to carbon dioxide and hydrochloric acid. However, these two gaseous effluents must bo disposed of in such a way that they pose essentially no hazard to the environment. The final impact statement must provide additional information if -we arc to determine whether or not this project will be carried out' in a way which is protective of public health and the environment. We offer the following specific comments to assist you in the preparation of the final statement: 1. Special precautions should be taken to assure that efficient combustion conditions (product intake, temperature, and retention time) arc m a i n t a i n e d throughout the operation. These precautions ore necessary to insure that the original material plus any intermediate pyrolysis products arc burned completely and arc not present in the stack effluent. Since the natural combustion properties of the herbicide will provide the fuel required, there should be no mixing of this h e r b i cide with other combustible wastes as suggested for the incinerator j n Deer Park', Texas. L-21 �-2- 2. The estimate of 468 days for the complete incineration is based on a feed rate of 5,000 gallons a day. If incineration is carried out at Saugct, Illinois, this time period must be increased to over 810 days since the incinerator capacity is only 2,880 gallons per day. No calculations were presented for the total volume of the wash from 42,483 barrels and the time for incineration of that wash. 3. Proper disposition of the hydrochloric acid is necessary if there is to be no adverse effect on the environment. At the Saugct, Illinois, incinerator, the daily volume of hydrochloric acid discharge is not given. Consequently we cannot calculate the concentration of the acid and the pll of the wj.stc water. To assess the ability of the municipal sewer system to handle such a discharge over a long period of time, consideration should be given to the disposal of this waste dilute acid by s a l e , or free of charge, to companies who have need for such acid rather than disposing of it by sewer system discharge. On the basis of the d o c u m e n t e d calculation of 12.4 x 106 Ibs. of sodium chloride produced in Texas, it was calculated for these comments that there will be 7.7 x 10" Ibs. of hydrogen chloride carried off in the liquid effluent at Saugct. For each of the 810 days of operation, this is approximately 9500 Ibs. of hydrogen chloride. The document indicates that approximately 95% of the total hydrogen chloride evolve:! in the incineration will be scrubbed from the effluent gas, the remaining 5% being exhausted to the atmosphere. Based on the same calculations as v;crc IJTCC: Jr. the preceding paragraph, this is approximately 500 Ibs. per day hydrogen c h l o r i d e emission. Since the Saugct source is slightly cast of a line drawn directly south from downtown St. Louis, and because the document indicates a p r e v a i l i n g southeast wind, it appears likely that this daily emission of 500 Ibs. would fall into the area of d o w n t o w n St. Louis most of the time. Because the draft environmental impact statement has not provided enough o p e r a t i n g data on the incinerator at the I l l i n o i s site to calculate the concentrations of the hydrogen chloride emissions, it is i m p o s s i b l e to accurately determine the effect of t h i s amount o l: emissions on the surrounding community. It is safe to. say however, that such an amount of e m i s s i o n s over such a long icriod of t i m e could present a p o t e n t i a l l y serious c o n d i t i o n . 1-22 �— 3It. is felt that a c o r r e c t l y sized and operated sodium h y d r o x i d e scrubber a d d e d to the Sauget system would eliminate the hydrogen c h l o r i d e problem c o m p l e t e l y . The sodium chloride and sodium carbonate produced by the scrubber c o u l d be disposed of by controlled d i s c h a r g e into the sanitary sower system or d i r e c t l y jnto the river. In Deer Park, Texas, the a b s o r p t i o n s o l u t i o n w i l l bo discharged into Tucker Kayou. There .is not enough Information to compute the expected p l a n t effluent concentration of salt or s o d i u m carbonate produced by the reaction of sodium h y d r o x i d e and carbon d i o x i d e . This i s important because salt equilibrium can affect the biota of cstuarinc systems and especially that of Tucker Bayou which has a variable rate of. flow. The release of carbon d i o x i d e into the .atmosphere should pose no danger to the environment. We e m p h a s i z e the necessity and the importance of compliance with Federal, S t a t e , and local air and water pollution control regulations.. 4. Proper monitoring of the i n c i n e r a t i o n process must be put Into effect by both the contractor and the U.S. Air l ; orcc . Frequent periodic analyses of the stack gases and liquid effluent for unburned Orange pyrolyscs products, hydrogen chloride, carbon d i o x i d e , and ash (if any) must be made to assure that c o m p l e t e combustion is taking p l a c e . A technical r e p r e s c n t a t i v o should be present at the i n c i n e r a t o r facility throughout the operation to assure that all combustion controls and scrubbers are functioning properly and to check on the monitoring operation and proper operational practices. Any breakdown in control measures or devices must be cause for stoppage of the operation until the problem is corrected. 5. The empty drums should be decontaminated with kerosene and,an alkaline detergent and should be allowed to dry before being h a n d l e d further. The preferred treatment of the drums should be cither salvaging for further shipping uses or for smelting as "scrap metal. Their d i s p o s a l in landfi.ll is the least acceptable alternative. Tf, however, this method of disposal must be used, the l a n d f i l l site should be located on property so that the-L-c is no chance of runoff into streams, lakes, or groundwater systems. L-23 �-4- '* 6. The physical movement of 2,338,900 gallons of Orange from its present locations to the ultimate site of disposal is potentially a serious threat to the environment arid we feel the draft statement does not give sufficient information on movement details, such as mode of .transportation, off-loading, storage at disposal site, s p i l l containment, decontamination, etc. We recommend the following: (1) careful observance of Department of Transportation safety requirements in the transport of hazardous m a t e r i a l s ; (2) spelling out of specific modes and routes of transportation so as to p l a n for any contingency that m i g h t occur; (3) separate and individual contingency p l a n s covering such items as i m m e d i a t e f i e l d detoxification, health and safety considerations of personnel who m i g h t be involved in cleanup; (4) a firm written commitment from the transportation contractor that containment equipment is located and a v a i l a b l e l;o the contractor during transportation; and (5) p r c - d c s i g n a t L o n of the on-sccne coordinator prior to any shipment. Off-loading areas should bo equipped with materials and equipment necessary for rapid cleanup, and off-loading equipment should be checked thoroughly before the commencement of each loading or unloading in order to assure safe and d e p e n d a b l e operation. Furthermore, responsible persons engaged in off-loading should be given complete instructions in cleanup techniques along with instructions on how to proceed in case of a spill. j v * . , While shipment by water is cheaper than land and there lias never been a spill during water transport, it might be recognized that material s p i l l e d in a waterway would be distributed by the current. A land spill could be much more easily contained. If shipment is made by rail or truck, cleanup teams and equipment should accompany : the transport vehicles. ' *7. If the drums arc deteriorating, consideration should be given to cither rcdrumming or transfer to tankcars. As some of the Orange will be held for up to 2 1/2 years at the disposal site, there is question as to the advisability of storing the Orange in drums at all. If the site lias suitable bulk storage tanks available, these should be used. Shipping in bulk and.building several storage tanks at the site might prove cheaper and safer than rcdruniming, shipping pnd storing drums. L-24 �-5Becausc of. the extensive precautions which should be taken during transportation and the p o s s i b i l i t y of contamination o'f other cargo in the event of leakage, we feel the use of Orange d r u m s as filler cargo is inadvisable. 8. In the matter of s t o r a g e , whether in bulk or in drums, only those areas e s p e c i a l l y designed for storage of hazardous m a t e r i a l s should be used. Such areas should provide (1) structures to prevent surface water runoff from entering the area, (2) pavement and gutters to collect surface vat or runoff within the area, (3) drains to channel contaminated runoff to a holding facility, (4) materials and e q u i p m e n t necessary for rapid cleanup of spills, and (5) fencing to control admission to the areas. In a d d i t i o n , storage areas should be located remotely from occupied d w e l l i n g s . 9. The alternative of b u i l d i n g a new incinerator in a remote region should bo examined in detail. We appreciate the opportunity to review 'this draft environmental impact statement. Sincerely yours, Sheldon Meyers Director Office of Federal Activities L-25 �(This page intentionally left blank) �DEPARTMENT OF HEALTH. EDUCATION. AND WELFARE WASHINGTON, D.C. 20201 OFFICE OF THC SECRETARY MAR 1 3 "1972 Mr. Aaron J. Racusin Acting Assistant Secretary of the Air Force (Installations & Logistics) Washington, D. C. 20330 Dear Mr. Racusin: The Department of the Air Force draft Environmental Statement for the Disposition of Orange Herbicide by Incineration dated January 1972 has been reviewed. The following comments are offered. 1. The proposal is to destroy 2,338,900 gallons of Orange I and II herbicides by incineration. Orange I is 50/50 (by vol.) butyl 2,4-D and butyl 2,4,5-T. Orange T.I is 50/50 (by vol.) butyl 2,4-D and Iso-octyl J>,4,5-T. Incinerators to be used are at Houston, Texas and Sauget, Illinois. 2. The project description implies that the herbicide orange must be considered a very hazardous chemical which it actually is not. On the other hand, the polychlorinatcd dibenzo-p-dioxins which are highly toxic are not given that much attention. 3. On page 6 of the project description a contradiction secins to exist: One sentence suggests that impurities in 2,4,5-T could account for the tcratogenicity of that product. The next sentence suggests that both compounds are tcratogenic or fetotoxic to experimental animals of various species. This discussion, of course, is very important and should have been clarified, particularly regarding the dose/response data which arc available in the literature. It is necessciry to have this information on t-.ie teratogenicity of the nearly pure 2,4,5-T in mice strains, hamsters and chicks and lack of such effects in rats and rabbits available for comparison with the fctotoxicity of the "dioxin" compound in all species in which it lias been tested. The difference in the order of magnitude of toxicity of these chemicals is impressive. ' L-27 s Ares �Page 2 — Mr. Aaron J. Racusin 4. The major reason for concern exists' in the first sentence on page 7 regarding the possible formation of dioxins during Incineration. This is considered unlikely based on the acidic conditions and would in any case not lead to any emission into the environment because of the nigh incineration temperature. This judgment is unwarranted, because data exist on Hormacion of dloxin from precursors (equivalent, to breakdown products) during pyrolysis (Iligginbothuin, et al. Chemical and toxicologlcal evaluations of isolated and synthetic rhloro derivatives of dibenzo-p-dioxin. Na_ture 22Q\ 702-703, 1968) which make it clear that the. safety of the process depends entirely on the adequacy of the temperature control. The better known dioxins are stable up to a temperature of 7000C, but will break down at 900°C, Whether that is also true of more highly chlorinated dioxins is unknown. However, the chosen temperature of incineration is to be much higher to assure decomposition. Mo question is raised about the formation of other compounds, as, for instance, hc-xachlorobenzcnc during pyrolysis which may withstand the high temperature for some time. There is knowledge about the existence and persistence of other polychlorinated polycyclic compounds formed on combustion of hydrocarbon in the presence of chl'orine. Their toxicity has not been investigated. 5. A combustion analysis program to be carried out in collaboration with the USDA is expected to have results on pyrolysis available by July 1972 to assure complete destruction of the herbicide. Considering the difficulties encountered in determining trace amounts of the dioxins, it seems hard to believe that this program will be able to assure anyone of "complete" destruction of all pyrolysis products. This research activity will also not pay adequate attention to formation and destruction of othe>,r so far undescribed polymerization products since the time for completion of the study is too .short. As these studies will undoubtedly not utilize the large scale facilities Tor their research, no information on the function ol~ the actual combust ion facility will be available wher. the program gets started. 6. Free 1IC1 (hydrochloric acid) should not go into the air and water as occurs at the Sauget, Illinois incinerator but should be converted to a salt such as sodium chloride before disposal. L-2S �Page 3 — Mr. Aaron J. Racusin 7. The concern wiLh the disposal of the drums is excessive. They need to be cleaned out as proposed and thereafter could be handled like other drums which contained pesticides and need not be crushed and buried. Their contents never were that toxic. ,• 8. The alternatives to the proposed action are dealt with too quickly. Because a committee of experts has made its recommendations to EPA, alternative 2 and 3 should be reevaluated. Alternative 8 is not an alternative to the problem since it considers only the disposal of the drums. Alternative 7 Ln conjunction with 2 and 3 appears to be the safest procedure. Use in the proper manner and degradation in soil, admittedly over an extended period of time, seems to be the best solution, based on the possible hazard of dioxin or other polychlorinated hydrocarbon production during pyrolysis compared to the known hazard of the herbicide which is relatively small. The opportunity to review this draft environmental impact statement is appreciated. Sincerely yours, •Merlin K. DuVal, M.D. 'Assistant Secretary for ' Health and Scientific Affairs L-29 �(This page intentionally left blank) �Dffi -V- United States Department of the Interior^ D;^CTOH,yjA OFFICE OF THE SLCRKTAKY WASHINGTON, D.C. 20210 / >-.-'0 ft W2 19J2... 7 _'C , -N3T, Dear Mr. Racusini ... ^.Jv-vT F'.C ./. :., (fTUj-"*) YT P/^t In response to your letter of January 20, 197?» wo have reviewed the draft environmental stater-ient for tho proponed disposition of Orango Herbicide at Deer Park, Texas, and Saugct, Illinois. On page 10, it is stated that the incineration plant is capable of "burning Orange Herbicide, However, on pc.gss 11 and 12, we find that a combustion analysis program is underway ar.d that the results of the prograr. will not be available until July 1972. Since r.unicipil incinerators are generally incr.p-T.blo cf properly handling materials such as Orange Herbicide, the results of those studies should be made available for cor.ment prior to co:?.nicnce;n.ent of this program. Only tvro incineration sites were provenl^d in *the statement. So^.s comiiientary and explanation are required, Of the two incineration plants, the cnc at Ec-jr Park, TOJP.F., h-.'.r.; the advantages cf dist'.ncc from a mnjor population center, 1'irger capacity, end a caustic scrubber. The st'ick should be taller to porr.it greater rr.ixing of effluent gases, which will include corrosive hydro~en chloride. Abo'ut 800 pounds cf hydrogen chloride will bo crr.ittcd caily in stack g^ses. When combined with noicture of the atrcsphcre, the renultant hydrochloric ncid will attacfc i,-,otals and r.otr.'JL finishes and. increaseacidity of surrounding v.-atcrs, This could create a shift of aquatic organisms to more acid-tolerant but less attractive recreational species. Disposal of the drur.s by sale a.~ scrap or for reconditioning is not an alternative to the total proposed action; however, it is clearly one of several possible alternative:--- for disposal of the drur.s after they are c:.n.pt: od. We feel thr.t every effort should be np.de to recycle as nany drills, or tho scrap r.-vVT.!, ar, possible. Disposal of over ^2,000 steel cru".s in a land fil.l hardly CCCT'.G acceptable in today's clirr.ate, Guidelines for prcpc.rc.tien of drins for recycling or for scrc-'.p have been developed. Toxic wci.te dispc^/il syston.s have also been develcpid. InTornati.cn con'':e:rn.i.ng tliOv^e systems is available through tho National A5-r:.cultur<r-.l Chc~.icals Association. L-31 �< • Finally, we must express concern in regard to the large amounts of sodium chloride (13 tons) and C02 ( 5 tons) which will be discharged ^ daily. These discharges vrill place e. considerable additional burden on the air and '.ji'atic environment, and thosr potential impacts should be fully evaluated prior to issuance of discharge permits. The best available techniques for control of air and water pollution should be used. The discharge of large amounts of sodium chloride may adversely affect the aquatic environment . "At tines of low water (drought), this discharge might increase "tho 'salinity so as to favor those aquatic species most tolerant to this change and so cause a' shift of aquatic or^anis^s, It is also possible that salinity vrill increase in parts of Galvcston Bay so much that parasitis.M and probation in oyster bads vrill increase, These effects would be minimized with high dilution and discharge at a timo of high water. Applicable State and Sectoral air -and water quality standards should bo included in the statenwnt, and the methods used to meet these standards should be described, The feasibility of processing the sodiurr. chloride for chlorine, sodium, or alkali in a nearby chlor-alkali plant should bo discussed., as well as the irretrievable lo^s of the herbicide, if burned. We appreciate the opportunity to review this statement. Sincerely yours, \r Deputy Assistant Mr, Aaron J« Racusin Acting Assistant Secretary (installations and Logistics) Department of the Air Force Washington, D. C. 20330 L-32 t -% f •» -v-1 I Secretary of the Interior \/ �JJSA.j; ENVIRONMENTAL HEALTH 'LABORATORY . "^ KELLY AFB, TEXAS 78241 APPENDIX M BIOLOGICAL MONITQRING AMD TOXICITY STUDIES , IN SUPPORT QF "ORANGE" HERBICIDE INCINERATIO'N TESTS AT THE MARQUARDT COMPANY VAN NUYS, CALIFORNIA June 1974 �(This page intentionally left blank) �TABLE OF CONTENTS Section I. Page M-l INTRODUCTION M-2 A. SCOPE OF INVESTIGATION ] I. SUMMARY M-2 1. Description of Incineration Tests 2. Scope of Ecological Studies M-2 M-3 B. METHODS OF SPENT SCRUBBER WATER TREATMENT FOR AQUATIC BIOASSAYS USING STICKLEBACKS AND BRINE SHRIMP M-4 1. Art ificial Spent Scrubber Water 2. Spent Scrubber Water Collection and Treatment M-4 M-5 C. METHODS AND MATERIALS FOR ON-SITE ANIMAL BIOASSAYS M-5 1. 2. 3. 4. 5. Aquatic Test Animals Animal Bioassay Exposure Procedures Dilution Water Chemical and Physical Monitoring Techniques Treatment of Data D. METHODS AND MATERIALS FOR ON-SITE ECOLOGICAL OBSERVATIONS 1. Ecological Biomoniboring 2. Meteorological Moni toring III. M-5 M-6 M-7 M-8 M-8 M-9 M-9 M-9 RESULTS AND DISCUSSION M-10 A. RESULTS OF SPENT SCRUBBER WATER STUDIES M-10 1. General Characteristics of the Spent Scrubber Waters 2. Sensitivity of Aquatic Bioassays 3. Effect of Available Chlorine on Toxicity 4. Toxicity of Scrubber Waters (chlorine Removed) 5. Results of Brine Snrimp Studies B. RESULTS OF BIOMONITORIMG STUDIES 1. Results of Local Flora and Fauna Observations 2. Results of Tomato Plant Biomonitoring Studies M-i M-10 M-10 M-ll M-ll M-l3 M-14 M-14 M-14 �i i- TABLE OF CONTENTS (cont'd) Section .Page IV. CONCLUSIONS V. M-17 BIBLIOGRAPHY . 'M-18 Appendix A B Data Appendix Herbicide Toxicity Discussion M(A-1 M(B-1 " Tables 1. Effect of Available Chlorine Removal on Toxicity of SSW Used in Bioassays with Stickleback M-ll 2. Results of Toxicity Studies M-12 3. Wind Conditions During Test Burns... M-16 A-l. Fish Statistics M(A-l) A-2. Serial Dilutions Produced by Proportional Dlluters M(A-2) A-3. Results of Analyses of Dilution Water M(A-3) A-4. M(A-4) A-5. Results of Toxicity Studies Range of SSW Parameters for All 8 Burns B-l Acute Effects of 2,4-D Derivatives Upon Aquatic Animals... M(B-5) B-2 Non-Lethal Effects of 2,4-D Derivatives Upon Aquatic Animals B-3 . M(A-5) • M(B-6) Sensitivity of Selected Plants to 2,4-dichlorophenoxyacetic acid < M(B-8) Figures 1 A-l Relation of Tomato Plants to Incinerator Burn I Spent Scrubber Water M-ii • .. M-15 • M(A-6) �TABLE OF CONTENTS (cont'd) » Figures Page A-2 Burn II Spent Scrubber Water M(A-7) A-3 Burn III Spent Scrubber Water M(A-8) A-4 Burn IV Spent Scrubber Water M(A-9) A-5 Burn V Spent Scrubber Water M(A-10) A-6 Burn VI Spent Scrubber M(A-11) :, ' A-7 Burn VII Spent Scrubber Water M(A-12) A-8 Burn VIII Spent Scrubber Water M(A-13) A-9 Artificial Spent Scrubber Water A-10 Osmotic Toxicity Study with Artificial Sea Salts M-111 w M(A-14) M(A-15) �(This page intentionally left blank) �I. SUMMARY A. This report describes ecological and toxicological studies performed in support of incineration tests conducted jointly by the United States Air Force and the Marquardt Company. The incineration tests consisted of technical evaluations of a series of eight burns designed to investigate the destruction of "Orange" herbicide by combustion in a full scale, commercial incineration system. This system provided for the scrubbing of effluent combustion gases with a sodium hydroxide or "caustic" solution. No auxiliary fuel was used to incinerate the herbicide. Each of the test burns lasted from 2.27 to 5.93 hours. The ecological and toxicological studies described in this report provided real-time biomonitoring to rapidly detect biologically detrimental effects of the test burns in the area surrounding the incinerator, and to compliment the chemical analyses of spent scrubber water as regards toxicity. B. Atmospheric biomonitoring nethods utilized plants in the area surrounding the incinerator. Observations were made of the local flora in the area in addition to test plants placed in sixteen locations around the incinerator. The 160 test plants used were young tomato plants. Tomato plants are known to be especially sensitive to chlorophenoxy herbicides. Meteorological data was recorded throughout each test burn. The biomonitoring studies revealed no herbicide or other chemical damage to the plants in areas downwind from the incinerator. C. Biomonitoring of the eight spent scrubber waters consisted of bioassays performed on a representative sample of each test burn. Each sample was composed of numerous portions of spent scrubber water collected throughout the entire length of a tast burn. Test animals used in the bioassays were 3-spine sticklebacks (Gasterosteus aculeatus) and brine shrimp (A'"temia salina). No unexpected toxic effects were observed. The chlorine produced by incinerating the herbicide (a chlorinated hydrocarbon) was collected as free, available chlorine in the scrubber waters. As expected, free chlorine in the spent scrubber waters produced lethal effects on sticklebacks at 20-35 times the toxicity seen in scrubber waters in which the chlorine had been removed. The bioassays with the spent scrubber waters were compared to similar toxicity studies with arti-ficial spent scrubber water. The "artificial" spent scrubber water was used to establish the toxicity to be expected when aquatic organisms are exposed to such a . solution. Also, toxicity studies were performed to determine the effects of osmotic gradients on the test animals. The toxicities seen with the spent scrubber waters in which free chlorine had been removed were not significantly different from the toxicity found with artificial spent scrubber water. Osmotic toxicity studies indicated that unavoidable osmotic effects contributed largely to the toxic effects seen in the spent scrubber waters. M-l �II. INTRODUCTION A. SCOPE OF INVESTIGATION 1. Description of Incineration, Tests a. The ecological studies described in this report were in support of a testing program conducted jointly by the United States Air Force and the Marquardt Company to investigate the destruction of "Orange" herbicide by combustion in a commercial incineration system. Results of the incineration tests, were reported separately from the ecological studies. A brief description of the incineration tests is presented in the following paragraphs as background information to clarify the objectives of the ecological studies. b. Incineration tests were conducted at the Air Fprce-Marquardt Jet Laboratory at Van Nuys, California between 8 October 1973 and 21 December 1973. A ful.l scale, commercial (Marquardt) incineration.system was used. This system contained a combustion gas scrubber which used a sodium hydroxide solution to remove potential air pollutants from the incinerator exhaust. Since "Orange" herbicide is composed of chlorinated hydrocarbons, efficient combustion was expected to produce mainly HC1, C02, H20, Clg, CO, and particulate carbon in the effluent gases. These materials were removed in varying proportions by the scrubber system. The spent scrubber water was stored in holding tanks until chemical analyses and bioassays could determine that release of the material would not result in a water pollution problem. No auxiliary fuel was used to incinerate the "Orange" herbicide. A small amount of natural gas was used to preheat the incinerator before the herbicide was injected intorthe combustion chamber. c. The following two paragraphs are direct quotes from the summary of the published report of the incineration study entitled, "Report On The Destruction Of "Orange" Herbicide by Incineration," (April 1974). (Hereafter referred to as the "Incineration Report"). The report was written by the Marquardt Company and the USAF Environmental Health Laboratories at Kelly AFB and McClellan AFB. The two quoted paragraphs summarize the chemical analyses performed during the incineration tests and the final results of the tests. ' • [ . ' t d. "Extensive sampling and analyses were conducted to quantitate the constituents of the unscrubbed combustion gases, the liquid used to cool and scrub the combustion gases, scrubbed effluent gases, drum cleaning samples, and any solid residues deposited in the system. Samples were analyzed by mass spectroscopy, flame ionization, gas chromatography, and atomic absorption. Process system parameters and noise data were observed and recorded. s e. Test data demonstrated that the "Orange" herbicide was effectively and safely destroyed by incineration; no herbicide feed compounds were found (within the limits of detectability) in any combustion gas, M-2 �scrubbed effluent gas, spent scrubber water or combustion chamber deposit sample resulting from incinerator operation (four test burns) while using slot type fuel injection nozzles. Likewise, no herbicide feed compounds were found in samples resulting from incineration operations (four test burns) while using a central poppet type fuel nozzle except for one combustion chamber deposit sample and one spent scrubber water sample. This anomaly was attributed to the characteristics of poppet nozzle fuel injection. From sample analyses data, conclusions were made regarding possible undetectable discharge mass rates of herbicide constituents, effluent biological impact, formation of pyrolyzates and hydrolyzates, and possible criteria for drum.cleaning operations. Criteria were also established regarding incinerator ncise generation and incinerator process system functions." 2• Scope of Ecologj.cal_ Studjjis. The purpose of the ecological studies was to determine if the incineration of "Orange" herbicide could be accomplished without untoward effects on the plant and animal life in the vicinity of the incinerator. In addition, the ecological studies were designed to detect early symptoms of improper incinerator operation by real-time biomonitoring and to detect biologically harmful combustion byproducts should any escape detection in the chemical analyses of incinerator effluents. Environmental protection was provided by biomonitoring the two possible routes of contamination: a) spent scrubber water effluent, and b) air contamination downwind from the incinerator stack. a • Biomonitoring for Contamination of the Spent Scrubber Waters from Each of the IT Test Burn? The sodium hydroxide solution used in the incinerator's scrubber was expected to efficiently trap the acid gas products of combustion and any uhdestroyed herbicides or their incomplete combustion products. Bioassays were performed on spent scrubber water from each burn to insure that there was no unusual toxicity caused by the presence of unexpected chemicals in the SSW that might prove harmful to aquatic biota. The spent scrubber water from each individual burn was stored in a holding tank until completed bioassays with fish and brine shrimp together with chemical analyses indicated that it could be safely released into the Marquardt Company's 1.4 million gallon waste water holding reservoir. b. Ecological Studies to Determine if Biologically Active Emissions Were Produced ' . . ~ Biota in the area of the incinerator was closely observed to provide early detection of downwind air contamination with corrosive chemicals or unoxidized herbicides should the scrubber system not remove M-3 �all toxic materials. Records of wind speed and direction were kept for the time period of each burn. The oresence of animal life on the Marquardt property was observed and recorded. Condition of native and decorative plants on the Marquardt property and its perimeter was observed and recorded. Also, the condition of 150 tomato plants positioned in 16 stations surrounding the incinerator was closely observed for any damage. These plants were placed in their stations prior to the first burn and then observed for changes in the days following each burn. After the completion of the eight burns, plants selected from areas of highest potential exposure were observed for an additional two week period. B. METHODS OF SPENT SCRUBBER WATER TREATMENT FOR AQUATIC BIOASSAYS USING STICKLEBACKS AND BRINE SHRIMP 1. Artificial Spent Scrubber Mater a. Aquatic bioassays were utilized as a means of screening for unusually toxic factors that might possibly contaminate the used or "spent" scrubber waters of the 8 test burns. Unexpected toxicity of the scrubber waters could have been caused by a single toxic chemical or by combinations that are synergistic or contain potentiating factors. The results of the aquatic bioassays were reported as an "LC50."* b. To determine the relative toxicity that would normally be expected with a spent scrubber solution, an artificially "spent" scrubber solution (Art. SSW) was used for comparison or "control" bioassays. This artificial spent scrubber water was formulated by using the calculated quantity of hydrochloric acid that would be produced by Orange incineration in relation to other scrubber and incinerator parameters. These parameters were predicted by computer systems analysis for the Marquardt burner when incinerating "Orange" herbicide. Hydrochloric acid, in quantities representing the chlorine disposition from "Orange" herbicide, was added to fresh scrubber water. Then, the pH was adjusted to 7.0 using commercial grade sulfuric acid before this Art SSW was used in bioassays. *LC5p, or Lethal Concentration 50%, is a concentration value statistically derived from the establishment of a dose-related response of experimental organisms to a toxicant. The LC$Q represents the best estimation of the dose required to produce death in 50% of the organisms. Note that a more toxic chemical has a smaller LCsQ. The time period for which the 50% response was derived must also be indicated. In these tests with SSW, 48 hours was the time of exposure except as noted. M-4 �2. Spent Scrubber Water Collection and Treatment Spent scrubber water from each burn was proportionally sampled and collected in a 55 gallon drum throughout the entire period of each burn. At the end of a burn, c. forklift transported the drum to the toxicity testing laboratory. Enough SSW for the bioassays was immediately drawn from the drum and acidified to a pH of 3.5. The SSW was acidified to minimize the potential for alkaline hydrolysis of the relatively toxic herbicide esters should unoxidized herbicides have been present as contaminants. In addition., the acid pH promoted the escape of Cl2 and COg as gases. (See Appendix B for discussion of relative toxicity and hydrolysis.) Nitrogen was bubbled through the acidified SSW until tests indicated that available chion'ne* was less than 0.2 ppm. Just before use in the bioassays the SSW was adjusted back to pH 7 with unused scrubber water. C. METHODS AND MATERIALS FOR ON-SITE ANIMAL BIOASSAYS 1. Aquatic Test Animals a. Fish and crustaceans were used as indicator species in the bioassays of the scrubber waters from the eight test burns. The 3-spine stickleback (Gasterosteus aculjsatusj was used as the major bioassay test animal. This species of fish is "classed as "moderately sensitive" to pollutants.(5) However, sticklebacks can survive in a remarkable range of salinity extremes.(3) This characteristic made the stickleback an ideal species for use in assaying for toxic materials in the high specific gravity scrubber water. Thus, toxic action due to osmotic effects was de-emphasized, allowing a more concentrated solution of SSW to be used. Further, the sticklebacks were good mon'tors for "Orange" herbicide components since they were found to be very sensitive to the N-butyl ester of 2,4-D. In toxicity studies at the Environmental Health Laboratory at Kelly AFB, Texas (EHL/K), the 48 Hr, LCgo was found to be 0.54 ppm. *Free available chlorine. The LCgg of the first bioassay using spent scrubber water from burn I (SSW l) was compared with the LC5Q from the artificial SSW. The material from the actual burn was 20 times more toxic thar the reference bioassay using Art. SSW. (Art. SSW 48 Hr, LC50 = 10.4% vs. SSW I 48 Hr, LCso = 0.53%). This unexpected toxicity was found to be due to free chlorine dissolved in the SSW. Since toxicity of the chlorine could conceal the toxic effects of more pertinent contaminants, the above method was utilized to remove it. V-S �b. The sticklebacks were collected from San Antonio Creek at Vandenberg AFB CA. San Antonio Creek is a pristine stream originating by the base and emptying into the Pacific Ocean. It has clear, cold water with a specific gravity of 1.001. The sticklebacks were collected by seining. Only the smaller, sexually immature fish were retained for use so as~ to eliminate possible sexually-related metabolic differences that could produce added variations in response to toxicants. Mean fish weight was 245 mg. Mean fish length was 3.1 cm. (See Fish Statistics, Table A-l) c. The fish were acclimated to the laboratory environment a minimum of 5 days before being used. They were held in 30 gallon all-glass tanks equipped with charcoal and dacron-fluff filters. The fish adapted to captivity very rapidly and in two days were reacting with anticipation whenever anyone approached the tanks with food.' The fish were fed Tetramin^ flakes twice a day. d. Brine shrimp (Artemia sal ina) were hatched at EHL/(K) and transported to Van Nuys in Insulated containers oxygenated with batteryoperated air pumps. They were fed brewers yeast. Brine shrimp were 15-20 days old when used in the bioassays. The culture medium used for the shrimp was made by adding artificial sea salts* to the conditioned tap water to adjust the specific gravity to 1.022. The resulting brine solution was aerated at least 24 hours before it was used. 2. Animal Bioassay Exposure Procedures a. Dynamic Bioassays (1) "Dynamic" or continual-flow bioassays were performed on all the assays which used fish to detect toxicants in the spent scrubber water. A proportional diluter (8),(9) was used to provide five logarithmicallyspaced concentrations of each sperit scrubber solution. A sixth exposure chamber received 100% diluent water as the control. Two proportional diluters were used for these studies. Appendix Table A-2 shows the resultant dilutions of each.. • (2) Bioassays were performed in accordance with principles described in Standard Methods (12) and Sprague (10). Test animals were not fasted prior to testing. However, food was withheld during the actual assay period. Ten fish were used in each of the five concentrations and in the control (60 fish total for each assay). Exposure chambers were plastic rat cages modified to contain 4 liters of diluted toxicant. This provided a ratio of 0.6 gm of fish per liter of water. This is a more favorable ratio *Marine Land Sea Salts , Aquatic Systems Inc., East Lake, Ohio M-6 �than recommended in Standard Methods (12). The flow of diluted toxicant into each chamber was adjusted to a retention time of 2 hours which was equivalent to a 6 hour, 95% replacement time. This provided a better flow rate than the 8 to 12 hours, 90% replacement time recommendations of Sprague (10) and insured 'adequate maintenance of the dissolved oxygen concentrations. (3) Response of test: animals was recorded throughout a 48 hour test period except for selected runs in which a 96 hour exposure period was used to confirm the absence of cumulative effects. The quantal response measured was death. A fish was counted as dead when all gill movement ceased. Dissolved oxygen and pH were monitored to insure that the cause of death was not lack of oxygen or changes in pH. Water temperature was maintained at 20°C. Probit analysis was performed on the data recorded at 1, 2, 24 and 48 hours of exposure to evaluate quantal response to graded doses. Replicates were not performed due to time limitations and other material considerations. b. Static Bioassays Bioassays with brine shrimp were "static" types in which the experimental concentrations were not replenished during the exposure period. Five brine shrimp were placed in 200 ml of each concentration of spent scrubber water. The SSW was diluted with the same artificial sea water that was used to culture the shrimp. Two replicates of each concentration were used. Graded concentrations ranged frpm 40% to 100% spent, scrubber water. 3. Dilution Water a. Conditioned tap water was used as the diluent in all of the assays using fish. The water was conditioned in a plastic-lined 55 gallon drum. Initially the drum was filled with hot tap water. Water in the drum was aerated continuously to drive off chlorine gas and maintain a high dissolved oxygen level. Temperature was adjusted to 20CC by pumping the water through a stainless steel coil immersed in a refrigerated water bath. The water was then passed through a charcoal filter before it was pumped to the proportional diluters. The dilution water was repeatedly checked to insure that no chlorine residual remained. The resulting conditioned tap water was a fairly soft water (hardness = 56 mg/1) with a pH of 8.1. Comprehensive analytical characterization of the conditioned water is listed in Table A-3 of the Data Appendix. b. Dilution water for the brine shrimp static assays was prepared in the same manner as "the culture medium used for the shrimp. Artificial sea salts were added, to the conditioned tap water to adjust the specific gravity to 1.022. The.resulting brine solution was aerated at least: 24 hours before it was used. M-7 �4. Chemical and Physical Monitoring Techniques for several measured to temperature insure that gravity and chambers. a. Each concentration in each exposure chamber was monitored parameters throughout the exposure period. Temperature was insure that it remained at 20°C as dictated by the waterbath control system. pH and dissolved oxygen were monitored to these parameters played no part, in the fish mortality. Specific free available chlorine were also measured in all exposure b. The methodology used to measure these parameters is described as follows: (1) pH; An indicating, recording type pH meter (Analytical Measurements, Model 30WP) was used throughout the study. pH standards of 4.7 and 10 were prepared in the laboratory at EHL/K and used for calibration prior to each period of use. (2) Temperature : Large scale, laboratory thermometers were placed in the water bath and in each bioassay for a continuous monitoring of the desired 20°C. Readings were taken at least 6 times per day to insure proper operation of the bath and bioassay systems. •». (3) Dissolved Oxygen: A Yellow Springs Instrument Company, Model 51 A Dissolved Oxygen Meter was used in the survey. Calibration was accomplished prior to each use. Measurements of each concentration were taken at 0 time, 24 and 48 hours, during each bioassay. Dissolved oxygen measurements were taken of holding and acclimation aquaria repeatedly throughout the study. (4) Chlorine; A Prism Viewing,, Color Comparator, Federal Stock #6630-087-1838 (O.T. Kit)was used throughout the survey. This test uses a color reaction produced with Orthotolidine to measure the presence of free available chlorine in concentrations larger than 0.2 ppm. Concentrations smaller than 0.2 ppm were detectable as a slight color change. (5) Specific Gravity; A UrinaTysis Hydrometer was used to measure specific gravity of each dilution in the test chambers. The highest value measurable with this hydrometer is 1.060. The more dense, undiluted solutions of spent scrubber water were weighed to determine specific gravity. 5. Treatment of Data were determined by the probit analysis method of Litchfield and Wilcoxon. (6) Confidence limits for the LCso were not calculated because each assay for each individual spent scrubber water was not replicated, nor was it possible to repeat each assay for more balanced M-8 �and statistically satisfying partial responses on each side of the LCcg point. Each of the dynamic assays resulted in definitive dose-related responses. With the dynamic assays, no deaths occurred in the control fish so that no weighted correction factors J v/ere used. 1X50's and the slopes of the dose response curves are listed n Table A-4 in the Data Appendix. Other statistical treatments such as variance and standard error of the mean used standard formulas. (4) D. METHODS AND MATERIALS FOR ON-SilTE ECOLOGICAL OBSERVATIONS 1. Ecological Biomonitoring a. The species of each animal sighted on Marquardt property was rioted in the logbook used to maintain all observations. Plant life on the Marquardt property and the surrounding perimeter was monitored before, during and after the burns. The plant life was observed in order to detect any symptoms of auxin-like changes should chlorophenoxy herbicides contaminate the incinerator exhaust. Damage that could result from air contamination with corrosive chemicals such as chlorine or hydrochloric acid was also closely looked for during the observation per'od. b. In addition to native and decorative plants, young tomato plants (which are sensitive to highly chlorophenoxy herbicides) were used as bioassay organisms during the monitoring period. One hundred and sixty young plants (2 months old) were divided into groups of 10 and placed at 16 different stations around the test incinerator. The condition of the indicator plants was carefully recorded. Special care was taken to look for auxin-like and corrosive chemical damage. The height of each plant was periodically measured. During each of the eight burns the area around the incinerator was observed to determine which tomato plants were most exposed to the exhaust of the incinerator. On some occasions the steam from the incinerator exhaust was observed to be condensing and the droplets of moisture were falling out onto the tomato plants. After completion of the entire study, plants from six of the stations that received the most exposure were transported back to EHL/K. These plants were observed for two weeks to allow time for any latent damage to appear. 2. Meteorological Monitoring Wind speed, wind direction, and temperature readings were obtained every half hour during the incineration periods by calling Van Nuys Airport Weather Information. 'M-9 �III. RESULTS AND DISCUSSION A. RESULTS OF SPENT SCRUBBER WATER STUDIES . 1. General Characteristics of the Spent Scrubber Maters a. The spent scrubber waters (SSW) from the eight burns had a temperature of 164°F at the scrubber outlet collection point. Their pH values ranged from 10.5 to 11.8.and the average specific gravity was 1.057. Available chlorine concentrations ranged from 250-500 mg/1. Available chlorine existed completely as the "free" chlorine moity and none as "combined" available chlorine (12) Table A-5 in the Data Appendix lists other parameter ranges. Sample collection procedures and detailed analytical results are described in the incineration report. b. The major characteristics described above could reasonably account for severe detrimental effects on aquatic organisms should the scrubber effluent empty directly into a natural body of water. In actual industrial operations some form of treatment is usually used to reduce or eliminate the effects of thermal pollution and acid-base shifts. Free available chlorine can also be removed. However, chlorine is so reactive that its effects are transitory and, in a limited "mixing zone", are often considered acceptable. In most of the bioassays in this study, chlorine was physically removed. The chlorine removal process and pH adjustment increased the average specific gravity of the SSWs from 1.057 to 1.068. 2. Sensitivity of Aquatic Bioassays a. The general characteristics of SSW mentioned above produced inherent toxic effects on the aquatic test animals that, in effect, reduced the sensitivity of the assays for unknown toxicants. Therefore, the assays could only be expected to reveal the presence of acute, relatively highly toxic contaminants or combinations of contaminants. Based on previous aquatic studies with 2,4-D 2,4,5-T and their esters, the realistic assumption was that toxic effects of significantly toxic contaminants would be additive with the toxic effects normally expected from the high specific gravity scrubber waters. Therefore, the presence of a relatively highly toxic contaminant was expected to result in an obviously smaller [£50 (increased toxicity) when compared to uncontaminated scrubber waters. The pessimistic assumption would be that np_ additive effects occurred so that the presence of low concentrations of toxicants such as the N-butyl ester of 2,4-D would not be detected by an obviously lower LC5Q. b. Assuming no additional effects (the pessimistic assumption) the low level of detectability for the N-butyl ester of 2,4-D was calculated to be 3 ppm in the scrubber waters (available chlorine removed). This detection limit was calculated using the dilution range of 5% to 50% for each assay, M-10 �the high toxicity of the ester to Sticklebacks (48 Hr. LC5o=0.54 ppm), and a mean 48 Hr. LC50 of 17.9% for all 8 SSWs. / 3• Effect of Available Chlorine on Toxicity a. In the bioassays of the SSW, temperature and pH were held constant. Available chlorine was removed as described in Part II B^of this report. However, a few assays were run without chlorine removal. The comparison of toxicities.resulting from the absence or presence of chlorine is striking as shown in Table 1 below. TABLE I: EFFECT OF AVAILABLE CHLORINE REMOVAL ON TOXICITY OF SSW USE0 IN BIOASSAYS WITH STICKLEBACK. *. CHLORINE REMOVAL 24 Hr. 48. Hr. BURN I SSW BURN I SSW Yes No 12.8% 0.53% 12.8% 0.535 BURN III SSW BURN III SSW Yes No 28.8% 0.84% 28.8% 0.84% BURN VI SSW BURN VI SSW Yes No 29.5% 0.75% 20.5% 0.63% b. Scrubber waters not bubbled with nitrogen were 20-35 times more toxic. The conclusion that this toxicity was .due to available chlorine and not some other factor was based or chlorine measurements of SSW dilutions taken from the exposure chambers. Measurements of 0.4 ppm or greater available chlorine coincided with death in 100% of the fish in those exposure chambers. The 0.4 ppm value for toxic effects is in general accord with chlorine effects observed by other workers. (3),(7) 4. Toxicity of Scrubber Waters (Chlorine Removed) a. In each bioassay, sticklebacks were exposed to serial dilutions of each scrubber water that ranged from 5% to 50% SSW. The dose-related response of the fish to those concentrations were in the range expected from toxicity due mostly to osmotic effects. To demonstrate the relationship of specific gravity of the scrubber waters to toxiqity, new LC$Q values were calculated based on the specific gravity of the serial dilutions rather than the concentration of SSW. Therefore, the toxicity of SSW from each burn could be considered jointly for dose-response relationships established on the basis of specific gravity and concentration expressed as percent SSW. M-ll �TABLE 2 R E S U L T S O F T O X I C I T Y S T U D I E S SP. GRAVITY JU MATERIAL TESTED SP. GRAVITY OF TREATED SS1J 48 HR LC50 Art. SSW 1.1270 10.4% 1.017 SEA SALTS 1.011-1.032 NA 1.019 BURN I 1.075 12.8% 1.014 BURN II 1.079 16.0% 1.016 BURN III 1.061 28.8% 1.019 . BURN IV 1.063 16.5% 1.016 BURN V 1.076 15.5% 1.013 BURN VI 1.060 24.4% 1.017 BURN VII 1.076 12.5% 1.014 BURN VIII 1.050 16.7% 1.011 M-12 48 Mrs �b. A completely separate toxicity study was accomplished which established the dose-related response of the sticklebacks to pure differences in specific gravity. This study used a commercial marine salt mixture to compose saline concentrations that produced serial specific gravities ranging from 1.011 to 1.032. c. The results of all of these studies are summarized in Table 2, "RESULTS OF TOXICITY STUDIES". Comparing the 48 Hr. 1X50 values shown on Table 2, all 8 SSWs had higher concentrations than the reference "artificial SSW" (Art. SSW). However, the fact that the actual SSWs are less toxic than the Art. SSW is because the Art. SSW has a higher specific gravity than the 8 SSWs. The computer-predicted Art. SSW contained more solutes than the actual SSWs. Had the prediction been more accurate, less dilution would have been required, and the Art. SSW LCso value would probably have fallen somewhere in the range of the LC$Q of the actual burns. d. The specific gravity "LCso" (S.G. LCso) in Table 2 shows that the specific gravity expected to kill 50% of the sticklebacks in 48 hours is 1.019 when the solutes are sea salts. When the solutes are more similar to those found in actual scrubber water, as in Art. SSW, the specific gravity LCso drops to 1.017. Therefore, it is reasonable to assume that the toxicity of the SSWs with S.G. LCsos around 1.017 are primarily due to their osmotic: effects. BURNS II, III, IV and VI had SSW S.G. LC50.5 ranging from 1..016 and 1.019. v e. The specific gravity does-response curve of Art. SSW indicates that a 10% death rate would be expected in sticklebacks exposed to a specific gravity of 1.014 (S.G. LCio). BURNS I, V, VII and VIII have S.G. LC50 that range from 1.011 to 1.014. Compared to the Art. SSW, these 4 SSWs would be suspected to containing chemicals that contribute an additive effect to the expected osmotic toxjcity. However, these studies were not sensitive enough to positively detect such mild effects. f. The slopes* of the 48 Hr. dose-response curves are similar to the slopes of the dose-response curves for Art. SSW and sea salts. The mean 48 Hr. slope = 1.16 (a= 0.04) for all 8 SSWs plotted on a percent SSW to percent response curve. The slope value for Art, SSW = 1.14. When the responses were replotted against specific gravity, the 48 Hr. slopes of the SSW were still indistinguishable from those of Art. SSW and sea salts. (See Table A-4 Data Appendix) 5. Results of Brine Shrimp Studies Brine shrimp survived in 100% SSW and all serial dilutions of all 8 SSWs for 24 hours. Beyond 24 hours of exposure, death was sporadic and not relative to concentration so that an I.CSQ could not be calculated. *Slope of the dose-response function. (6) (Litchfield and Wilcoxon, 1949). M-13 �B. RESULTS OF BIOMONITORING. STUDIES T 1. Results of.Local Flora and Fauna Observations a. The Marquardt Company property is a very large industrial site surrounded by other industrial and aircraft industry operations. A large Air National Guard Base lies on the northwest perimeter of the Marquardt property (See Figure 1). The northern property line is bordered by aircraft hangars. The eastern perimeter is bordered by the Van Nuys Airport runways. • • b. All of these industries had sparse or no vegetation on their property. There were a few conifers in front of a hangar just outside the northeast corner of the Marquardt property. The company's unused strip of land on the northern border had little vegetation. The plants present were mainly tumbleweeds and bermuda grass which were mostly dormant. The tumbleweeds had matured and their seeds were apparently the food source for the blackbirds, house finch and mourning doves that fed in the area. The only other animals sighted were numerous domestic cats which had become feral. Other vegetation that was observed during the test burns included a few shrubs on the east perimeter and a variety of decorative plants and trees buildings on the southwest quarter of the Marquardt property. Trees and some shrubbery in a trailer park outside the southwest corner were also observed. Almost all deciduous plants were dormant or becoming dormant because of the late fall season. No effects of chemical damage were observed throughout the period of the test burns on the few slants that were still green. 2. Results^ of Tomato Plant B'omom'toring Studies Figure 1 shows the relationship of each station to the incinerator. There were 16 stations; each with 10 tomato plants. Table 3 is a. compilation of weather data taken during each burn. During the periods of low wind velocity the wind direction varied considerably. On these occasions the steam plume from the incinerator drifted from one direction to another and would disappear about 200 feed from the stack. An observer standing underneath the plume could feel droplets of moisture falling from the plume. The condensed moisture sometimes fell directly onto the tomato plants of Station 5. On the two days that the wind velocity was 19 mph, the wind remained constant in speed and direction throughout the burns. None of the tomato plants in the downwind areas exhibited symptons of auxin-like effects as would be expected from chlorophenoxy herbicide contamination. Also, no corrosive chemical damage occurred as would be expected had chlorine or hydrochloric acid been an air contaminant (Appendix B). All the plants from Station 5 and five other stations were shipped to EHL/K after the study. No deleterious effects were noted during the two weeks these plants were held for observation. M-14 �FIGURE 1: RELATION OF TOMATO PLANTS TO INCINERATOR Van Nuys Airport _______ I • . ., __ • __ u"1---F-AST^. . —=^S2"psvs=== ,i~=T;*"1' • " . -;4 j--3 'l.4 mg HOLDING i , INCINERATOR TEST, 2 HAINTENATC I 1 TEST tIA o.mt i*" i ' NORTH OFFICES I en (HEH.raocru| orFicn 1 BIT | I V -V k'^ST RH LOV BAT HIGH B*r f«i»r v MACttfNC SHOP MACHINE SHOP 1 jn t=3 it" LO . L L HACHmr 3 9A MGH B*r HACHIHC tHOP | ^ fllCiSION •ff LMBAf HACHIHC SHOP ^^--AIPI COMPRCiSOtt j. TQXICITY STUDIES ]. I REPBQOUCTU 10<B« WUHIItl IMW 21 •r't «INK<I«. HILlf JK HKt ., i •-;. Y �TABLE 3 W I N D C O N D I T I O N S D U R I N G T E S T B U R N S RANGE OF WIND DIRECTION AVERAGE WIND VELOCITY TEMPERATURE RANGE F 13 Nov 130°-155° 7 MPH 55-64 II 16 Nov 120°-180° 5 MPH 55-56 III 19 Nov 340°-NC° 19 MPH 58-NC IV 20 Nov 120°-160° 9 MPH 62-NC V 27 Nov 310°-350° 6 MPH 63-69 VI 28 Nov 350°-NC 19 MPH 60-NC VII 29 Nov Calm-varied 0 62-NC VIII 30 Nov Calm-1500 0-12 60-62 BURN NUMBER DATE I i-1' . �IV. CONCLUSIONS a. Sticklebacks, when exposed to graded dilutions of spent scrubber waters from each of the eight test burns, sustained mortalities that were directly related to concentration or dose. Acute mortality was maximal at 12 to 24 hours of exposure so that there was little change in LCcg values at times beyond 24 hours. In cases where exposure was extended to 96 hours., there was no increase in mortality with the increase in time of exposure. • b. The acute toxicity studies with sticklebacks indicated that when free available chlorine was removed, the toxicities of the spent scrubber waters were not higher than toxicities expected for solutions with similar osmolality. Therefore, no significant concentrations of acutely toxic contaminants were detected in the spent scrubber waters from the 8 test burns. Also, no effects from synergistic or potentiating combinations of chemicals were observed. c. Osmotic toxicity studies indicated that unavoidable osmotic effects contributed largely to the toxic effects exhibited by the spent scrubber wa ters. d. Free chlorine in the spent scrubber waters produced lethal effects on sticklebacks at 20-35 times the toxicities seen in scrubber waters in which the chlorine had been removed. Free available chlorine in the spent scrubber waters is a highly toxic factor that can be removed by proper treatment of such an industrial waste. e. Observations of local plant life and sensitive biomonitor tomato plants demonstrated that the 8 test burns produced no herbicide or chemical damage to plant life surrounding the incinerator. M-17 �V. BIBLIOGRAPHY 1. Brungs, W.A., "Effects of Residual Chlorine on Aquatic Life", J.WPCF, Vol 45, No 10, Oct 1573, pp 2J80 - 2193. 2. Cairns, J., Jr., "Fish Bioassays - Reproducibility and Rating", Revista de Biologia, Vol 7, No., 21 & 2, (1969), pp 1-12.. 3. Carlander, K.D., "Handbpok of Freshwater Fishery Biology", (1969) Iowa State University Press, Ames, Iowa. 4. Dixon, W.J., F. J. Mass.ey, Introduction of Statistical Analysis. 3rd ed., McGraw-Hill, New YorkTT9697 5. Jones, J. R., "Fish and River Pollution^, 1st ed., Butterworth & Co. Ltd./Toncfon England, (1964). 6. Litchfield, J.T. and F. Wilcoxon, :IA Simplified Method of Evaluating Dose Effect Experiments", J. Pharmacology & Experimental Therapeutics. Vol 96, (1949), pp 99-lT-T 7. McKee, J. E. and H. W. Wolf, Ed Water Quality Criteria. California State Water Quality Control BocirdT Publication No. 3-A, 1963. 8. Mount, D. I. and W. A. Brungs, "A device for Continuous Treatment of Fish in Holding Chambers", Transactions of the American Fisheries Society, Vol 96, No. 1, 20 Jan~T967, pp 55-57. 9. Mount, D.I. and W. A. Brungs, "A Simplified Dosing Apparatus for Fish Toxicology Studies", WaterJteSj. (1967), Vol 1, pp 21-29. 10. Sprague, J. B., "Bioassay Methods of Acute Toxicity", Water Res. Vol 3, (1969), pp 793-821. 11. Sprague, J. B., "Utilizing and Appling Bioassay Results", Water Research. Vol 4 (1970). pp 3-31 -v 12. Standard Methods of the Examination of Water and Waste Water, 13 ed., American Public Health Assoc., New York, (1971). 13. Water quality Criteria, Federal Water Pollution Control Administration, Quality Criteria. Fe Washington DC, April 1968. M-18 �- APPENDIX A (TO APPENDIX M) DATA APPENDIX �(This page intentionally left blank) �TABLE A-l FISH STATISTICS Weight in Gms Length* in Cm Arithmetic Mean 0.246 3.1 Standard Deviation 0.1013 0.442 i Variance Standard Error of Mean 0.01026 0.196 0.0320 0.140 (95%) Upper Confidence Limit 0.31816 3.42 (95%) Lower Confidence Limit 0.17326 2.80 Maximum Value . 0.433 3.9 Minimum Value 0.115 2.5 Range 0,318 1.4 Number of Values 10 10 *Fork Length as reported by Carlander^ ' indicates a size typical of Sticklebacks 3-4 months old. M(A-l) �TABLE A-2 SERIAL DILUTIONS PRODUCED BY PROPORTIONAL DILUTERS {Mount & Brungs(8),(9)} DILUTER NO. 4 CONCENTRATION EXPRESSED AS PERCENT OF THE STOCK SOLUTION* 0% Control 1 2 14% 3 19% 4 32% 5 58% 6 100% DILUTER NO. 5 1 0% Control 2 11% 3 19% 4 32% 5 58% 6 100% *Stock Solution for SSI/is with ChloHne removed consisted of 50% SSW. H(A-2) �TABLE A - 3 RESULTS OF ANALYSES OF DILUTION WATER (units in mq/L unless noted) LAB ANALYSIS (mg/1 unless noted) ITEM '•?M 1. COLOR 2. TURBIDITY 0 -0 4. DISSOLVED SOLIDS ,Q. .-. '.' J.JOTAL SUSPENDED^ MATTER 6. VOLATILE & FIXED SUSP MATTER :•:•.' ' •' • • w^iuft. 1 a 12. NITRATES Q_ 14. SULFATES 15. CADMIUM MU.vk.tu 4 Q _1 ,..,p- V::^' 2 1 • "'.•' .. .-.• . SSS'.^X^ 17. CHROMIUM (TOTAL) ^i L i; AM. XO.h>. i.jXf.'-ss* ;\.i li^;'^. -W^rt-W-s VS-.-.-.S- •,* 18. COPPER --_ — • • .' '•'• 19. CYANIDES S^SN-X^V 20. IRON '• ". " .' " 21. LEAD 22. MANGANESE wMvKv •Nv:^ • ;••;;. i-* . rt'^Vi^-i-!^ •• in . . • 23. SILVER 1 rri "• • • \p- 24. ZINC ' XvX-.1. 11" i-i;i; ,"!• ' ' '•'.•'•'• \ 25. Mercury 26. Total Organic Carbon I' I z/. Hardness ^EDTA as Mg/L c!aC03)=64 28. pH=8.3 29. Specific Gravity=1.005 M(A-3) < 1 •"r J'-.^. >Ak.SI 1 «.' I. 0 0 0 •"• i '".' .LI. -'-'.... «. •.'.k • 1 14. CHROMIUM (HEXAVALENT) ' ' HSVSViVS 1 6 0 :'•:;:';.;•:•;• _ ITT V l l I l.T o. : :V' ' ' ' :.;/i^Hi • roitfK :,.,.. .x^;. MSN iNS.A 5 1.. .?._ 'jL, ... : : .-, . :;.., :• •: ^j, 13. PHOSPHATES tf^sw** .*:.;.-• •vrwss-tv 0 O.. 10. CHLORIDES !:;••'; V" SSVS'tSVSV • 11 11. FLUORIDES t •! . •:- >•.••' .•/. ^»*SJivnv Ur its • _Z.-_°AS._* GREASES (Infrared_Metl L&& ^.X- . * s.juRFACTANTs (As mg/L LAj> ) .!.<A<~&^ 9. PHENOLS Units 5 1 .1 8_ . 8 0 3. CHEMICAL OXYGEN DEMAND •,:,$• • 5 1 -4 J... 5 -0 2 ,i... _n. 1 CvX"lwi rj .f'ffftfl 0 5 0 5 1 ^ 0 0 " ••g-, 0 • "•:^ 0 T" �TABLE A-4 RESULTS OF TOXICITY STUDIES SP. GRAVITY LC5n AT MATERIAL TESTED SP. GRAVITY OF CL2RxED SSW 24 HR LC5Q 48 HR LC50 SLOPE of 48 HR 24 HRS 48 HRS SLOPE OF 48 HR SP. GRAVITY OF SOL THAT 100% DEATHS IN 48 HRS NO DEATHS IN 48 HRS Art. SSW 1 .1270 11.5% 10.4% 1.14 1.018 1.017 1.0018 1.023 1 .012 SEA SALTS 1 .011-1.032 NA NA - 1.019 1.019 1.0018 1.025 1 .015 BURN I 1 .075 17.5% 12.8% 1.15 1.014 1.014 1.0016 1.019 1.009 BURN II 1 .079 17.4% 16.0% 1.21 1.017 1.016 1 .0027 1.027 1 .010 BURN 1.061 28.8% 28.8% 1.16 1.019 1.019 1.0014 1.024 1.015 BURN IV 1 .063 26.5% 16.5% 1.15 1.016 1.016 1.0018 1.021 1 .011 BURN V 1 .076 15.5% 15.5% 1.18 1.013 1.013 1.0023 1.023 1 .008 BURN VI 1 .060 29.5% 24.4% 1.14 1.021 1.017 1 .0020 1.024 1 .008 BURN VII 1 .076 12.5% 12.5% 1.10 1.014 1.014 1.0022 1.016 1 .009 BURN VIII 1 .050 24.3% 16.7% 1.22 1.013 1.011 1.0023 1.016 1 .005 III X=1.16 X=1.0020 6 = 0.04 6 = 0.004 �TABLE A-5: RANGE OF SSW PARAMETERS FOR ALL 8 BURNS Parameter (mg/1 unless noted) • Range of Quality Temperature (8F) when collected 164 10.5 - 11.8 pH *r Speci"ic Gravity 1.044 - 1.073 Specific Conductances (pmho/cm) 11.3 -15.8 Total Solids or Total Dissolved Solids (x 103) 61-87 Suspended Solids 56-97 Chlof des (xlO3) 16.5 Free and Total Chlorine Residuals -28.0 250-500 Sodium (x 103) 32-38 Iron, Total 3.0 - 5.0 Total Alkalinity (x 103 as CaCOs) 32.0 - 52.5 Carbonate Alkalinity (x 103 as CaCOs) Hydroxyl Alkalinity (x 103 as CaCOa) . 22.4 - 36.4 9.6 - 16.1 Bicarbonate Alkalinity (x 103 as CaCOs) M(A-5) 0 �s_ <u BURN I SPENT SCRUBBER WATER -!-> OrtJ o II -1- 4-> TOXICITY CHANGES (LCsO) WITH INCREASE IN TIME CD =3 40% -- OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS (0 <D 0) -I-1 O (O O i- ir> <u — .a -Q c => 30% -- O i•i- O cr. -i-> c: c a> O) Q. (.> '.O E O -M <_> c 20% •- a> •— o <r> sj= <u 4-> Q- (O O> 10% t i— Q. 10 X O LU 12 24 Hours of Exposure to Test Concentrations FIGURE A-l 36 48 �sO) BURN II SPENT SCRUBBER WATER O LT> O II O ••- TOXICITY CHANGES (LC50) WITH I-NCREASE IN TIME CD OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS 40% .. -!-> S- fO O> o s- <u +* o to LT> CD O I <J d> o c o. oo 20% .. O OJ (J SO) Qd) (O 0> fO (A i— 3 <V i— i (O 10% - - in Q. X o s- 2 24 Hours of Exposure to Test Concentrations FIGURE A-2 36 48 �o * cj03 BURN III TOXICITY CHANGES (LC 50 ) WITH INCREASE IN TIME o •«- n - 1 1 fO •*-> <O QJ OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS - \ SCU -l-> 0 40g -«- \ O ~ - SPENT SCRUBBER WATER 50% -, S- S5 m ' a; J2 _Q C O ••- 3 S0 4-> 00 S- 4J to 1^ 00 SOifc f— ' • <=. a.cu a. u oo c 8 = <u 20% - • i— <J as i^ (1) <U 1 VI fO cu -o •<-> a; (O 10 's 10% t) - CD u "J' s- •— Q. ' O X t-J ' • ' « 0 •. y 12 24 Hours of Exposure to Test Concentrations FIGURE A-3 36 4 �SO! O Lf) BURN IV SPENT SCRUBBER WATER 50% ^ II TOXICITY CHANGES (LCso) WITH INCREASE IN TIME (!) O OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS C +-> s_ fO O) o 40% -r s- LO O) ~— •• -Q .a §s •1- (J 30% ' ' -|J OO ni O) r». l/l O C_> +-> E 20% - - 10 i.= 0) -)-> Q. O) _J l/> TJ Qi "O +-> fO <U (/I 3 O .— 3 0) SQ. X 1— O 10% .. (/) LU —i12 24 Hours of Exposure to Test Concentrations FIGURE A-4 36 48 �s_ s BURN V SPENT SCRUBBER WATER 50%-r II • ! 0> tO O ^"""^ »^" TOXICITY CHANGES (LC50) WITH INCREASE IN TIME OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS 3 C. 40% " -M < S(U -!-> o s. o to LD 0) •—' -Q § •r- i o I 30% •• O £ Ol O O) QOO O -!-> c c_> i— c 20* O ra £- f 4-* O) O) O_ n3 3 O <U S- (O X i— a. 12 Hours of 24 to Test Concentrations FIGURE A-5 36 48- �cu -t-> O <O LD3 O _1 C O II •!- BURM VI SPENT SCRUBBER bO%-r TOXICITY CHANGES (LC50) WITH INCREASE IN TIME OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS ID O C 4J 40%-- S- <L> -!-> O to o s- ••- f O LO' O) ' vt fO c o> OJ CL O CO O C 0) O S— 0) Q_ 20%- - i— iQ J= +-> <U _l 01 Ol "O 3 0> o s- r— (O Q. X 12 24 Hours of Exposure to Test Concentrations FIGURE A-6 36 48 �SO) (""^ -l-> fO un -^ o _i BURN VII SPENT SCRUBBER WATER 50%^. c o II -1+J O) 3 TOXICITY CHANGES (LC5Q) WITH INCREASE IN TIME OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS 40%-- ro O) O' O if) o •i- SO) (O s- Ol s- 30% O ro ro c 1) O) § -!-' \ Q. LO i— O (O 20%-i- S- d) 01 -o ro 0) 3 0> •— (0 Q. X o uj 12 24 Hours of Exposure'to Test Concentrations FIGURE A-7 36 48 �sa; +J O(O LTCS BURN VIII SPENT SCRUBBER WATER o II O) T- TOXICITY CHANGES (LC5Q) WITH INCREASE IN TIME OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS 3 3 i— ro O C T ro CD O> +•> O rO \ O SLO OJ .—, o J2 O S_ ••- o -!-> 00 (O S_ +J "c oi QJ U . CO O •!-> O E 0) 20%- - i— O ro &. -E CL) +-> OL. 0) _i to ro -l_> O) ro in i— <si 10%-- 3 JU O 1i— Q. ro X CJ 1 1 1 12 24 Hours of Exposure to Test Concentrations FIGURE A-8 36 48 �s- O) ARTIFICIAL SPENT SCRUBBER WATER on o ii i^ TOXICITY CHANGES (LC50) WITH INCREASE IN TIME O) 3 40% .. OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS i (O O d) 4-> Q n o s- 1 30% 4. o s-.- •i- O' (O S- -l-> d) Q. 20% - - O 4J o c >T5% i— O ro S- 10% - (0 in r— I/) (O X U LU T-l- 12 - 24 Hours of Exposure to Test Concentrations FIGURE A-9 36 �OSMOTIC TOXICITY STUDY WITH ARTIFICIAL SEA SALTS 1.045 -• TOXICITY CHANGES (LC50) WITH INCREASE IN TIME OF EXPOSURE OF THE FISH TO THE TEST CONCENTRATIONS 2' o o «£ ' o 1.035 -• Q. • (O I tn a •o o> 1.025 4- (A £ o. X o LO 1.015 -• 1.005 •• -4- 12 24 Hours of Exposure to Test Concentrations FIGURE A-10, 36 �(This page intentionally loft blank) �APPENDIX B (TO APPENDIX M) HERBICIDE TOXICITY DISCUSSION This Appendix consists of information pertinent to this report which describes the effects of chlorophenoxy herbicides on plants and aquatic animals. The material quoted was written by Major Inman for the "Candidate Environmental Statement for Disposition of Orange Herbicide by Incineration", March 1974, USAF Environmental Health Laboratory, Kelly AFB, Texas. (1) Metabolism and Distrjbutigr^ (a) General Comparisons: The behavior of the chlorophenoxy herbicides in non-mammalian aquatic ariTnals is quite different than the behavior described for terrestrial mammals and birds; The herbicides have a greater toxic potential for aquatic animals. First, the route of entry is different in most instances. The aquatic animal absorbs the herbicide which is distributed throughout his total environment (absorption is mainly via gills in fish). Then, the differences in renal function must be considered. Generally, non-mammalian aquatic animals do not have highly developed kidneys. Thus, once the herbicide is in the aquatic animal's body, some metabolic changes must occur in the molecule to make it more polar if it is to be excreted. Toxicity testing is also necessarily different with aquatic animals. Usually, aquatic animals are placed in a concentration of the toxicant to gradually absorb the material at a rate depending on the aninal's physiology and the behavior of the toxicant in the particular water conditions. Therefore, the actual dose to each animal is not known in most studies with aquatic animals. In contrast, toxicity studies with terrestrial animals usually allow calculation of a known dose per unit weight of each animal. Thus, toxicities are often reported as "LDXx" (Lethal Dose) for terrestrial animals and "LCXX" (Lethal Concentration) for aquatic animals. (b) Metabolism in Fish: Donald P. Schultz (Fish-Pesticide Research Laboratory, Bureau of Sport Fisheries and Wildlife, 1973) studied the uptake, distribution, and dissipation of '^C-labled dimethyl amine salt of 2,4-D (DMA-2,4-0). Three species of fish were exposed to 0.5, 1.0 or 2.0 mg/1 concentrations of herbicide for up to 84 days exposure period. No mortalities occurred, nor were adverse biological effects observed at these exposure levels. The highest radioactive residue found in muscle tissue occurred in Bluegills exposed to 2.0 mg/1 for 84 days (1.065 mg/kg). However, gasliquid chromatography indicated that over 90% of the radioactive residues consisted of metabolites of 2,4-D. The major metabolite in the fish was found to be 2,4-D glucuronic acid conjugate. Current investigations have found at least six metabolites of 2,4-D in fish. Thus, in contrast to many of the organochlorine pesticides which undergo biomagnification through the food chain, DMA-2,4-D is metabolized in fish without accumulation of the parent compound. M(B-l) �(2) Behavior in Aquatic Systems (a) Solubility Limits and Rates Vs. Hydrolysis Rates: The esters of 2,4-D or 2,4,5-T found In Orange fierBTclde have a very limited solubility in water. Because of this very low solubility, the actual concentrations of esters produced in-a body of water by accidental contamination would likely be much less than the "expected value" calculated from the volumes Involved. The USAF EHL(K) is in the process of studying the behavior of Orange herbicide in aquatic systems especially sea water. In one study using artificial sea water*, Orange herbicide was mixed into the water in an amount equal to 150 mg/1. Had all components gone right into solution, by computation, ester concentrations would have been 64 mg/1 (2,4-D NBE) and 61 mg/1 (2,4,5-T NBE). The actual, measured concentrations were 2 mg/1 (2,4-D NBE) and 1.8 mg/1 (2,4,5-T NBE) immediately after mixing. These increased to 18 and 22 mg/1 of 2,4-D NBE and 2,4,5-T NBE, respectively, at 24 hours and then started a rapid decline to 7.5 and 9.5 mg/1 at 48 hours after mixing. The rate of disappearance of the ester of 2,4-D was fairly rapid and was assumed to be mainly a result of hydrolysis. The half-life of the ester was 15 hours. The addition of natural biota such as bacteria, algae and fish would be expected to produce an even faster disappearance of 2,4-D NBE. Evidence that this occurs was observed in studies EHL(K) is conducting with marine animals at the National Marine Fisheries Laboratory in Port Aransas, Texas. In one of these studies, shrimp were exposed in five different concentrations of 2,4-D NBE and natural sea water. The average half-life of the ester in the five concentrations was 5 hours. This was 1/3 of the half-life observed in the situation where no biological systems existed. (b) Circulation of Water in_Re1ation to Avai1abi1ity of Herbicide for Absorption": Some of the toxicTty"studies compl eted sofar Indicate the complexity of trying to predict the ecological results of a planned or accidental contamination of a body of water with phenoxy herbicides. At EHL(K), Orange herbicide was mixed in a fish tank at a concentration that would theoretically produce a 200 ppm (v/v) concentration 1f such a high concentration were'possible. Most of the herbicide rapidly sank to the bottom of the tank after mixing. Fathead minnows placed in the tank showed no ill effects during two weeks of exposure. Yet in a toxicity study under the same conditions but with continuous agitation of the water by aeration, all of the fish died in a "20 ppm concentration" of Orange herbicide water in 24 hours. Subsequent studies revealed that some circulation of the water was essential if a dose-related response was to be established in toxicity studies with the N-butyl esters of 2,4-D and 2,4,5-T. Thus, the actual effect seen in nature.might well depend on a factor such as the degree of mixing in the affected body of water. M(B-2) �(c) Importance of Hydrolysis: It is important that when the esters of 2,4-D and 2,4,5-T hydrolyze, their foxicity to aquatic animals is decreased by almost a factor of 10 (paragraph (3)(b) below). In the static situation described in the paragraph above (no aeration), the rate of hydrolysis was probably faster than the rate that the ester went into solution so that lethal concentrations were never attained. Toxicity studies with freshwater and saltwater animals at EHL(K) have been the so-called "Static Bioassay" in which no attempt is made to maintain a constant concentration of the herbicide ester in each test chamber. "Concentrations" are theoretical and based on volumes of herbicide and water mixed together rather than from analysis of water to quantitate the herbicide. Most studies reported from literature are of the same type. The toxicity tests at EHL(K) revealed that in both freshwater and saltwater, most of the test organisms had responded at twelve hours of exposure. There was rarely any increase in mortality past 24 hours. • i , (d) Other Factors Affecting Actual Concentration: Many other factors can inf1uence. the"concentration of N-butyl esters of 2,4-D and 2,4,5-T in a body of water. In studies where large amounts of Orange herbicide were placed in water, the globules of the herbicide appeared to become coated with an opaque material that may have inhibited the ester from going into solution. Cope (1970) treated ponds with 0.5 ppm to 10 ppm propylene glycol butyl ether ester (PGBE) of 2,4-D. He was able to measure residues of herbicide absorbed or adsorbed in vegetation and bottom sediment for 6 weeks after treatment in the 10 ppm treated pond. Crosby (1966) reported that 2,4-D decomposes rapidly in the presence of water and ultraviolet light. (3) Toxicity (a) Factors Affecting Toxicity: The toxicity of the chlorophenoxy herbicides to aquatic animals vanes considerably with many factors such as water chemistry variables, temperature, and the particular salt, ester or amine form of the herbicide considered. Species susceptibility varies greatly. For example, the 96-hour TL5Q* for fathead minnows exposed to DMA2,4-D was found to be 335 mg/1. Yet, for bluegills and channel catfish the TLgQ values were 177 and 193 respectively. A temperature increase from 17°C •to 20°C increased the'relative toxicity to the catfish from a TL50 of 193 mg/1 to 125 mg/1 (Schultz, 1973). (b) Toxicity Comparisons by EHL(K): The USAF EHL(K) (1974), performed static toxicity studies with Orange herbicide. Also, toxicity studies were performed using each individual N-butyl ester of 2,4-D and 2,4,5-T. Freshwater bioassays using the fathead minnow (Pimephales promelas) resulted in a 48 hr LC$Q of 3.4 ppm for Orange herbicide containing 14 ppm TCDD. The 48 hr LC50s for esters of 2,4-D and 2,4,5-T were 2.8 ppm and 5 ppm respectively. The 48 hr LC5o for 2,4-D in the minnows was 270 ppm. The 2,4,5-T 48 hr LCso concentration was 333 ppm. Note that the toxicity of ester formulations were considerably more toxic than the respective acid. Also, EHL(K) found the N-butyl ester of 2,4-D to be more toxic than the N-butyl ester of 2,4,5-T. M(B-3) �In salt water studies by EHL(K), the 48 hr LC$Q values in the shrimp (Penaeus sp.) were 5.6 ppm for 2,4-D NBE and 33 ppm for 2,4,5-T NBE. Oysters (Crassostrea virgim'ca) were exposed to "potential concentrations" of 2,4-D NBE ranging from 0.5 ppm to 85 ppm. The only acute effect observed was the death of one of the oyster (10%) in the highest concentration at 48 hours. (c) Other Animals and Other Effects: Many other aquatic animals besides fish can be affected by phenoxy herbicides. Saunders (1971) studied the effects of the propylene glycol butyl ether (PGBE) form of 2,4-D on six freshwater crustaceans. He found the following 48 hr TL50 values: Daphnia magna = 0.10 ppm, seed shrimp = 0.32 ppm, scud = 2.6 ppm, sowbug = 2.2 ppm, glass shrimp = 2.7 ppm, and crayfish had an unknown value larger than 100 ppm. Cope (1970) studied the chronic effects of PGBE ester of 2,4-D on the bluegills. Survivors of ponds treated with high concentrations (10 and 5 ppm) had a 2 week delay in spawning. For pathologic lesions, hightreatment fish had earlier and more severe effects than did low-treatment fish. The pathology involved the liver, vascular system and brain. Remarkably, growth of the fish was faster in the ponds receiving the high-treatment than in the lower-treatment ponds. Tables B-l and B-2 were extracted from a U.S. Forest Service Environmental Impact Statement (EIS-OR, 1973). The tables indicate the effects of herbicides on other aquatic species and point out some toxic effects that can be measured other than death of the organisms. d. Behavior in Plants (1) Distribution and Metabolism: Orange herbicide is a systematic herbicide that affects plants by a hormonal type of action usually described as "auxin-like" or "auxin-type". Auxins are any of a group of substances which promote plant growth by cell elongation, bring about root formation, or cause bud inhibition or other effects. 2>4-D and 2,4,5-T are compounds of this type. When applied to leaves of a plant, chlorophenoxy herbicides are absorbed through the cuticle into the plant system. The N-butyl ester forms of 2,4-D and 2,4,5-T found in Orange herbicide are usually more effective than more polar forms because of better absorption into the plant. This is also demonstrated in Yamaguchi's work (1965) in which he found that 2,4-D moves into plant leaves better from acidic solutions than from alkaline solutions. Approximately ten times as much 2,4-D was abosorbed from a medium having pH 3 than one with pH 11. 2,4-D has a pKa of 2.8 and would be highly disassociated at pH 11. Once the herbicide is in the plant it is translocated to areas where food is being stored as in rapidly growing new roots and shoots. The chlorophenoxy herbicides can be stored in certain cells of the plant. Also, metabolism occurs through degradation of the acetic acid side chain, hydroxylationof the aromatic ring, or conjugation. (2) Tpxicity: Once in the plant, herbicides act by interfering with the photosynthetic, respiratory, and other plant processes causing the plant to lose its leaves and ultimately die. Plant susceptability to sublethal exposures of 2,4-D is markedly influenced by the growth condition of the plant and by environmental factors. Since most of the injury is expressed by growth response, the plant must be growing in order to show injury. In M(B-4) �TABLE B-l ACUTE EFFECTS OF 2.4-D DERIVATIVES UPON AQUATIC ANIMALS utKivAiivt ANIMAL rnNr-NTRATrnN EFFECT Isooctyl esters (From 3 manufacturers) Bluegill 10-31 ppm 48 TLm Hughes & Davis (1963) PGBE ester Bluegill 17 ppm 48 TLm Hughes & Davis (1963) Butoxyethanol ester Bluegill 1 . 4 ppm 48 TLm Hughes & Davis (1963) PGBE ester Shrimp 1 ppm (48 hrs) 20% mortality Butler (1965) or paralysis PGBE ester Fish (salt water) 0.32 ppm 48 hr TLm Butler (1965) Alkanolamine Salt Bluegill 435-840 ppm 48 hr LC50 Lawrence (1966) Dime thy 1 ami ne Salt Bluegill 166-458 ppm 48 hr LC50 Lawrence (1966) Isooctyl ester Bluegill 8.8-59.7 ppm 48 hr LC50 Lawrence (1966) REFERENCE Dime tliyl ami ne Salt Fathead Minnow 10 ppm 96 hr LC50 Lawrence (1966) Acetami.de Fathead Minnow 5 ppm 96 hr LC50 Lawrence (1966) Oil soluble amine salt Bluegill, Fathead Minnow 2 ppm 4 mo. LC,g Lawrence (1966) PGBE Ester* Blucgill , Fathead Minnow 2 ppm 4 mo. LC,Q Lawrence (1966) Butoxyethyl ester Bluegill & Fathead 2 ppm 72 hr LCgg Lawrence (1966) Butyl and isopropyl esters, mixed Bluegill 1.5 - 1.7 ppm 48 hr LC5Q Lawrence (1966) N,N -Dimethyl cocoamine salt Bluegill 1 .5 ppm 48 hr LC5Q Lawrence (1966) Ethyl ester Bluegill 1 .4 ppm 48 hr LC5Q Lawrence (1966) Butyl Ester Bluegill 1 . 3 ppm 48 hr LC5£) Lawrence (1966) Isopropyl ester Bluegill 1.1 ppm 48 hr LC™ Lawrence (1966) *Propylene Glycol Butyl Ether M(B-5) �- F TABLE B-2 NOM-LETHAL EFFECTS OF 2,4-D DERIVATIVES UPON AQUATIC ANIMALS DERIVATIVE ANIMAL DOSE EFFECT REFERENCE Butoxyethanol ester Oyster 3.75 ppm (96 hrs) 50% decrease in shell growth Butler (1965) Butoxyethanol •ester Shrimp 1 ppm (48 hrs) No effect Butler (1965) Butoxyethanol ester Fish (salt water) 5 ppm 48 hr. TLm Butler (1965) butoxyethanol ester Phytoplankton 1 ppm 16% decrease in C02 fixation •Butler (1965) Dimethyl ami ne Oyster 2 ppm (96 hrs) No effect on shell growth Butler (1965) Dime thy 1 ami ne Shrimp 2 ppm (48 hrs) 10% mortality or paralysis Butler (1965) Dimethyl ami ne Fish (salt water) 15 pprn (48 hrs) No effect Butler (1965) Dime thy 1 ami ne Phyto. plankton 1 ppm (4 hrs) No effect on COg fixation Butler (1965) Ethyl hexyl ester Oyster 5 ppm (96 hrs) 38% decrease in shell growth Butler (1965) Ethyl hexyl ester Shrimp 2 ppm (48 hrs) 10% mortality or paralysis Butler (1965) Ethyl hexyl ester _Fish 10 ppm (salt water) (48 hrs ) No effect Butler (1965) Ethyl hexyl ester Phytoplankton 1 ppm (4 hrs) 49% decrease in C02 fixation Butler (1965) PGBE ] ester / Oyster 1 ppm (96 hrs) 39% decrease in shell growth Butler" (1965) PGBE !_/ ester Shrimp 1 ppm (48 hrs ) No Effect Butler (1965) Fish 4.5 ppm 48 hr TLm Butler (1965) PGBE I/ estsr I/ (salt water) PGBE is propylene glycol butyl ether. M(B-6) �TABLE B-3 Sensitivity of selected plants to 2,4-dicbJoroplienoxyacetIc acid* Sensitive AppMe Mains, sp. Birch Bctufa, sp. Boxdder Acer in, Dogwood Curniis, sp. Elderberry Sambiictis, sp. Fors> thia Fonylhia. sp. Grajxs Vitif, sp. Hickory Carya, sp. Lambs-quarters Clienopodium album, L. Linden TI/IU, sp. London plans tree Platanus acerijolia (Ait.) Willd. Maple, Norway Acer platanoides, L. Oak. black Quercus velulina, Lam. Sorrell Rumex, sp. Aster, wild Ajter, sp. Cedar Cherry 1'runus, sp. Cherry, choke Primus virginiana, L. Corn Zna mays, L. Gladiolus Gladiolus, sp. Henilock a, sp. Mulberry Moras, sp. Oak, pin Quercus paiusiris, L. Oak, red Quercus paiusiris, L. Peach fruaux ptrsica, Sieb. & 7.ucc. Potato Solarium tubeioaum, L. Privet Ligustrum, sp. Sumac /?/IMJ, sp. Tobacco Nicotiana, sp. Tomato Lycopersicon escultr.tum, Mill. Tree'ofheaven Ailanthiis cltissima, Mill. Wiilcria Wisteria, sp. Yellow wood Cladrastis lulea, Koirh Ziani.t Zinnia, sp. ]n(«;rnie<]i;ife Ragweed, giant Ambrosia Irifida, L. Rhododendron Rhododendron, sp. Rose .Roja, sp. Spruce, Colorado blue P/ccfl punger.s, Liquidambar styracifl.ua, L. Yew Tar us, sp. Resistant Ash Fraxinns, sp. Bcari, bush f'haseolus vulgaris, L. Ilra.tsica oleracca, L. * Eggplant Sulanum meloitgena, L. Pear Pyrus comrnunis, !„ Peony Paconia, sp. Rhubarb Rheum rhaponticum, L. Sorghum Sorghum vulgarc, Pcrs. FROM AIR POLLUTION CONTROL ASSOCIATION REPORT MO. 1 M(B-8) �addition, plants in shaded areas respond more slowly than those exposed to direct sunlight. Because of these various factors which affect plant response to tie 2,4-D type herbicide, differences in lists showing plant susceptability should be expected. Orange herbicide is effective on a wide variety of woody and Droadleaf plant species. Other lower plant forms can also be affected by auxin-type herbicides. Even unicellular algae exhibit toxic effects or die when exposed to 2,4-D or 2,4,5"-T (Walsh, 1972). However, much higher doses of tie herbicides are required than for plants with a more complex structure. V £ (3) Herbicides as Air Pollutants: Although herbicides have long been accepted as environmental pollutants'which affect sensitive vegetation, the air pollution aspects of volatile herbicides have not been widely explored. However, there is growing evidence that some 2,4-D compounds may be present in the ambient atmosphere in some parts of the United States at levels sufficient to cause adverse growth effects on sensitive vegetation. During 1962 through 1964, Vernetti and Freed measured 2,4-D concentrations in air samples taken in an agricultural area of eastern Oregon. Concurrently, they surveyed for auxin-like plant damage in the areas where the air samples were taken. In the spring of 1962, measured concentrations of the isopropyl ester of 2,4-D in the air ranged from 0.015 ppm to 0.64 ppm. This was during the time of year when the huge wheat fields of the area were being treated for weeds by aerial application of the isopropyl ester. Plant damage to tomato crops appeared to coincide with periods of highest measured concentrations of the isopropyl ester. Other plants, especially locust trees, also showed growth regulator symptoms. Legislation in the state curtailed the use of the isopropyl ester and decidely reduced the contamination and .resulting plant damage. Laboratory studies by Vernetti and Freed indicated that 0..015 ppm would be the threshold concentration of isopropyl ester that tomato plants could be exposed to and still survive under the conditions of the experiment. Volatility studies by the same workers demonstrated that the isppropyl ester was three times more volatile than the butyl ester. In fact, complex analyses of the air samples ruled out butyl and other esters of 2,4-D as principal contaminants. -. (4) Relative Species Sensitivity: Different researchers vary in their results of relative plant sensitivity to phenoxy herbicides. From field observations, grapevines and box elder appear to be among the most sensitive since they respond to 2,4-D air pollution when other plants showed no evidence of injury. Injury to grapevines may result from exposure to levels in the ppb range. Other workers report tomato plant damage in the ppt range. Walsh (1972) reports a 50% reduction in growth of unicellular marine algae exposed to phenoxy herbicide concentrations of 50 to 300 ppm. Other relative sensitivities are indicated in Table B-3. M(B-7) �APPENDIX N INFORMATION ON INCINERATOR SHIPS Documents included in this appendix are listed in the order of appearance. *1. Extract from Prof. Dr. Klaus Grasshoff of Kiel University's report on: Possible effects of burning chlorinated hydrocarbons at sea. *2. Burning of chlorine containing liquids on the incineration ship Matthias. Investigations on combustion gases: 26 August 1971. *3. Effect on the Marine Environment of the Combustion at Sea of Some Industrial Waste. **4. L'Incineration in Haute Mer de Residus Industriels Chlores. **5. Incineration on the High Seas of Chlorinated Industrial Wastes. 6. Testimony by Mr. H. Compaan at the Ocean Incineration Hearing, Houston TX, 4 Oct 74 (Data on Vulcanus incinerator efficiency) * From a number of documents submitted by Antillian Incinerating Company N.V. ** Original French document provided by Ocean Combustion Services. �(This page intentionally left blank) �Extract from Prof.Dr.KLAUS G&ASHOF of Kiel University1s report out PoBS.ible effects oj^burning^ chlorinated hydro carbon^ at sea*.' Page 2, line 27: By means of extensive controlled measurements, the BAYER Company of Leverkusen, Germany, has established that if the burning of chlorinated hydrocarbons is carried out at temperatures higher than 1,000° C, more than 9 . 0 & of the materials are completely 9./ burnt. A combustion of 12 ts per hour of material containing an average of 30/& of chlorine will result in 3*6 ts hydrochloric aci<*. and about 19 ts carbon dioxide. (Part of the carbon will also be transformed into carbon monoxide) About 12 kg per hour of chlorinated hydrocarbon will be destroyed only partially or not i * at all. The hydrochloric acid condenses quiclcly with the water vapour contained in the air. In moderate wind conditions, the smoke plume will spread over a sea area of at least 250rOOO c£ .1 before the hydrochloric acid falls into the water. This means that ttbcu'j 15 i hydrochloric acid would fall on a square rcetre per hour. The sea water has a considerable capacity to neutralize acids, J irhich can be expressed as its total alkalinity, i^e#, the sum of all i" the weak alkalies contained in sea water. p . . "•* * Of these, the most imp— -crtarit ar: the acid carbonates (about 7 ^ , the carbonates ( 0 £ 6) 2|) and the borates ( $ » 4) Other alkalies, due to their small voltuaei play only a minor role and are therefore not discussed here. ** N-l �* 2 CCOg« ' *CB(OH)4" Vith a salt content of about 34/0 (dependent om conditions at the place of combustion:) the total alkalinity of the surface sea water A will average 2.3 milli equivalents' per litre. In other words:, 1 m sea crater can neutralize about 80 g hydrochloric acid.. This neutralis-ation reaction will result in carbon dioxide, boric acid and chlorine ions, as shown below:: CO,,, +2HC1 = C02 + H20 + 2 Cl~ B(OH)4, + HC1 = B(OH)3 + H20 + Cl" The water of the North Sea contains an average of 19 g chlorine _ '3 2 ions (Cl~) per litre, or 19 kg per m' . The 15 g chlorine ions per mresulting from the coobustion mentioned aboTO?, represents an increase in thfr chlorine ions content of 0.08 %+ In fact, in tbe Nortlf Sea there is a turbulent mixing which produces- vertical water exchanges, vhich expend evem to very deep water., In additioa, there are fast horizontal movements due to the tides* Consequently, the quantities of hydrochoric acid which fall each, hour on the surface of the sea spread in at least 100 times nore water. As a result, the increase' in chlorine ions content is smaller than 0.001/i, and thus too small to be determined by the normal measuring methods.. This is also valid for the temporary decrease in total alaalinity, which is probably about 0.4 milli equivalents aa&cMzarataacaAaaaiataxHiJ^tjje per litre* After the mixing mentioned above has taken* place, this decrease- will be about 0.004 milli equivalents, which is not measurable either* 2 . N-2 �addition, a new equilibrium is restored, as the resulting carbon dioxide escapes into the aimosphore, and the calcium carbonate, from the particles of materials contained in the sea water, is dissolved. The disturbance of the carbonic acid system through the neutralization of the falling hydrochloric acid appears, in realistic terms, much less than the disturbance brought about by the assimilation (intake of carbon dioxide) or the respiration (output of carbon dioxide) through the natural biological processes. The possibility of ecological disturbance caused by the snail increase of the chlorine ions content can be discarded. As mentioned earlier, 12 Kg/hour of chlorinated hydrocarbon are not completely burnt. However, these products do not condense immediately with the water vapours, but are spread by atmospheric movement over considerably larger areas. In this ; iray, the quantities of chlorinated hydrocarbons which reach the sea are negligeable compared with those re ching it through the rivers or in othar ways, ae veil as through evaporation of insecticides in the atmosphere. date: June 22nd.73 N-3 �•(This page intentionally left blank) �CORPORATION ?iant : Leverkusen Management Office fiivision: AHALO-Airlaboratory fittejjeot: Burning of chlorine containing liquids on the incineration ship Matthias* Investigations on combustion gases : 26 august 1971* IB drier to establish the combustion efficiency, analyses vere made of the @£gahio components and the hydrochloric acid contained in the combustion gases P8§tilting from the burning of three different mixtures: a mixture of solvents, Bildhjjing to the category of inflamable fluids classified as K 1 (3100 Kg/h); ftffliXtureof liquids classification K 2 (3450 Kg/h) containing Diehlorpropane ; §fii a mixture of liquids classification X 3 (3750 Kg/n) containing Chloronitrife§n3ene as the main component. combustion teaperature was kept between 1400 and IJOO'C. The combustion length was 3-6 hours for each product. eaoh combustion, the following camples were taken: 5 instant samples 3 adsorb t ion samples on silica-gel 2 concentration samples in n-Butanol the combustion gas samples were taken by using a 2 m long cuartz glass tube,, Penetrating in the furnace about 0.4m below and at 1 meter distance from the edge* From this cuartz glass tube, the gases first had to go through ndensate separator* following methods were used for the Identification and the quantitative of the organic components: SV analyses, gaschromatoeraphy combined with mass spectrography, gaschromatography @@meined with selective detectors, especially flame ionization and electrons 6ap%ure detection, the silica gel process for establishing the organic linked of results The gas chromatogram of the instant samples, which were taken in 0.5 1 evacuated gas sampling pipes, retained in the zone of higher boiling hydrocarbons, between £ and 6 components. Their concentration of about 1 vol ppm for each sample, was lee low for their identification, even when making full use of the .highly resilience ability of the mass spectro,£r.iphy. �-2- UV-analyaes of the 100 1 samples of coabustion gases concentrated in v-Butanol, did not permit either the identification of the only slightly •ttggested absorbtion strips. Volumes between 30 and 100 1 of combustion gases absorbed on silica*gel, were taken, to determine the organically linked carbon; the total carbon -content of 10 to 25 rag/m that was found, corresponds to the concentration established in the gaschromatograms. For a combustion gas volume of 43,000 m /h,, the unburnt percentage, calculated from the total content in carbon, respectively from the sum of the higher boiling components, is between 0.02 and 0.08 w %. Consequently, the combustion efficiency is for all 3 burned mixtures higher than 99-9$» The condsnsates caught for each of the three mixtures (2-10 ml/100 1 combustion gas) were neutralized with HaOH and diluted to 1:50 with aired town water. The toxieity of this liquid was tested in laboratory by using golden orfe (Idus joelanotus). Two golden orfe were kept in this liquid for each condensate. After 4 days exposure in these liquids, no harmfull effect whatsoever on the golden orfe could be established. N-6 �CENTER OF BIOLOGICAL STUDIES AND RESEARCH AND OF OCEANOGRAPHIC MEDICINE (C.E R.B.O.M.) The nal:ional institute for health and medical research Pare de la Cote Avenue Jean Lorrain NICE (A.M.) Telephone 89.32.92 I NCI ME R R O T T E R D A M (The Netherlands) EFFECT ON THE MARINE ENVIRONMENT OF THE COMBUSTION AT SEA OF SOME INDUSTRIAL WASTE GENERAL REPORT Project leader : Dr. M. Aubert Collaborators : A. Fruchart; J. Ph. Breittmayer, G. Flatau; D. Puel; F. Laumond; M. Perrin; B. Chabanne; M. Collet-Planas N-7 Foundation of the town of NICE �INDEX 1. INTRODUCTION AND THE OBJECTIVE OF THE STUDY 2. MEASUREMENTS AND SAMPLING "Iri SITU" 2 3. BIOLOGICAL TESTS 5 4. CHEMICAL ANALYSES 8 • A. 8 B. Investigation of the chlorinated waste 8 C. 5. Nature and composition of gases Investigation of heavy tnetals CONCLUSIONS 10 13 N-8 �1. INTRODUCTION AND THE OBJECTIVE OF THE STUDY G.E.R.B.O.M. was requested by the Company INCIMER to study the consequences that a method of incinerating various liquid chlorinated waste at sea, has on the marine environment. This technique is used at present in the North Sea, with the agreement of the Dutch official authorities. Consequently, based on the measurements performed in. the North Sea and the samples taken, which were submitted to various laboratory tests, we tried to predict the effect of this incineration in the Mediterranean Sea, where the Company intends to extend its activities. The studies which we show, had to be performed at short notice, which explains why they are not completed. Nevertheless, they make possible a good approach of the problem and especially, it allows a comparison between the incineration method and the straight throwing-into the sea, which is the more frequently used method. N-9 �2. MEASUREMENTS AND SAMPLING "IN SITU" During two days we attended the burning of chlorinated waste, supplied from various sources, in the North Sea,, in the zone assigned for this operation by the Dutch official authorities. After a preheating with fuel, the waste is injected into the furnace, where it burns by itself at a temperature of about 1300°C. The resulting smoke, .although immediatelybeatendownby the wind blowing at 25 to 40 knots, is very rapidly diluted: it is possible to move in the smoke plume as near as ten meters from the furnace, without feeling any discomfort, so much the more, there is no danger whatsoever for the ships that we saw crossing the plume at a distance of few cable lengths. The measurement of the pH of the sea. water under the plume, showed that the increase in acidity is measxirable only on a distance of about 50m from the furnace: we took advantage of a moment when the ship faced head wind, for taking measurements along its side, which gave the following results. Distance to the Furnace p.H. SaltnessO/00 10 m 30_m 50 m Control samples 7.6 7.8 8 8.1 to 8.2 34.31 34.33 34,47 34 to 34.20 Moreover, this minimal acidification is only temporary, because all measurements made during the ship's sailing, before and after the burning within as well as outside the incineration zone, gave pH's of 8.1 to 8.2. Moreover, this acidification has a bearing only on the superficial layer. However, it could be somewhat more pronounced when the sea is totally calm, because then, less diffusion takes place. Anyway, in the Mediterranean Sea, where the pH is 8 to 8.2, one can expect that figures below 7, would be rare. Consequently, these* conditions are acceptable. One notes also a slight increase of the saltness, without important consequences. N-1'0 �However we were interested in the smoke falling out in the sea and in its possible toxicity: for this, we took suction in the plume and let the combustion mixture bubble-up in a container filled with sea-water. This container has a very small opening and it is high enough to make the contact between the smoke and the'water last as long as possible (see illustration here below). direction Furnace Suction pump 0 « 1• Conlalner (60 liters) In the experiment, the capacity of the suction pump was 1 litre/m. The suction took place during thirty-four hours, i.e.: 2040 litres gas at about 40°C, i.e. about 1800 litres at 0°C. During this handling, the pH of the jL sea water contained in the 60/container,, went down with one unit, which corresponds more or less to a contribution of 0.16 mole of hydrochloric acid. If the sucked gas would not have been diluted, one would have recuperated about 20 acid moles. Consequently, one must admit that the smoke is diluted 100 times at 5m distance from the furnace. Of course, this dilution was enhanced by the very strong wind. However, it is thinkable that with a.slight wind, the smoke is not blown down immediately on the sea's surface, and in this way it will be similarly diluted (with air) by the time it reaches the water. N-ll �4. Jt Any way, the concentration we obtained in the 60^ container, is higher •• i. than what one can actually find in the sea. This is important, because this concentrate was used for establishing a laboratory nutrition chain. Further,we took samples of the plancton, the sea water and of the fish, . -i within and outside the incineration area. Unfortunately we did not find the same kind of fish in both places, which makes the comparisons difficult. The counting of the phytoplanctonic populations, does not show significant differences between the burning area (samples 1 to 4) and the neighbouring areas (samples 5 and 6). The content in diatomae in all the samples is low, but one could not say that this is caused by the incineration. Plancton Sampling Place : Incineration Area Samples 1 to 4 Other flagellates, among which also Nanoplancton ' (per ml) Diatomae (per ml) Dinoflagellates (per ml) 1 14 ' 1 570 2 70, - 240 3 4 rare' 360 4 8 - 2850 Sampling Numb er Plancton Sampling Place : Off Rotterdam Samples 5 and 6 Other flagellates, among which also Nanoplancton (per ml) Sampling Number Diatomae (per ml) Dinoflagellates (per ml) 5 31 rare 630 6 21 rare* 5760 N-12 �5. 3. BIOLOGICAL TESTS ! 1) Unburnt liquid effluent We investigated the toxicity of the unburnt effluent, with respect to ' -T various marine and estuary species: cyprinides crabs nereids mussels For all these organisms, death resulted within less than ten hours, for dillutions up to 1/10,000. L As for the phytoplancton. even for a dillution of 1/10,000 one notices a stop in the growth and the mortality of Asterionella japonlca and Diogenes sp. The zooplancton Artemia salina did not live more than one day in a dillution of 1/10,000. We did not push further these tests,, which were made only for t allowing some comparisons, arid which show that throwing of chlorinated hydrocarbons into the sea, can be catastrophical for the marine environment. » 2 ! ;' The concentrate of smoke in sea water The same toxicity investigations were carried out during thirty four hours, with the sea water in which the smoke had bubbled--up. Concentrations of 1; £; £; 1/8; 1/16; 1/32; 1/64; 1/128; 1/256; 1/500 were used, for the following marine or estuary species: N-13 �6. cyprinldes rascassides crabs nereides mussels No mortality or any physical disturbance was experienced, even •when the undilluted "bubbled-up" water was used. The length of the observation periods was seven days. For the zooplancton Artemia salina no differences were found between the control samples and those living in the bubbled-up water, whatever its concentration was. The observation period was 15 days. For the phytoplancton, the undiluted bubbled-up water causes to the Diogenes sp. a facing of the colour, indicating a change of the chloroplasts, thus a loss of the photo-synthesis function. Diluted bubbled-up water have no effect within 12 days. With Asterionella Japonlca a delay of the growth was noticed after the 5th day, whereas normally this takes place only the 8th day, this phenomenon being sensitive mainly for dilutions up to 1/8. Beyond the llth day, one notices for all the cases a higher mortality than the normal. This smoke concentrate was then used in a 1/4 dilution to investigate the inducted toxicity. This dilution was chosen in order to avoid disturbances with the Diogenes sp. and because the Cyprinides used, cannot put up with the strong saltnesses (for this species, fresh water must be added to the sea water). The tested nutrition chain, has the following components: phytoplancton -Zooplancton (Diogenes sp.) (Artemic salina) fish mamals (Cyprinides) (Mus musculns) M4 �This chain was chosen because, being of the pelagique type, it fits well to the given problem and because we did not have time for other tests. The poisoning periods were 8 days for the marine species and 12 days for the mice. Neither mortality, nor physical disturbance, nor abnormal i behaviour was observed at any level. N-15 �8. 4. CHEMICAL ANALYSES A. Nature and composition of the p;ases: released by the combustion atl.300°C. These measurements were performed at the analytical laboratory of C.N.R.S. (National Company of Scientific Research). The samples were taken in a pan made of silicon, placed in a silicon tube, fixed in the upper part of a tubular electrical furnace and heated to 1300°C. i The tube is moved very slowly, in order to have as much as possible a complete combustion. Despite this precaution, the combustion has an explosive characteristic which results in the formation of very fine particles of soot (little quantitative importance). Under these conditions, the gases are composed of carbon dioxyde and monoxyde, steam, undefined traces of hydrocarbons, and of hydrochloric acid released at a rate of 123 litres per kilogram of chlorinated waste. As explained here above, these gases are very much diluted before falling into the sea and do not represent a danger for the marine •* environment. Work is being carried out for trying to determine the composition of the soot. B. Investigation of the chlorinated waste: This investigation was performed: on two samples of sea water from the incineration area on two samples of sea water from outside the incineration area on four samples of mackerel caught in the incineration area on two herrings, caught outside this area .• on one poisoned mouse from the nutrition chain on one control mouse N-16 �1) Water samples After extractions are performed on a 250 ml sample, with three times 100 ml petrol-ether, the solvent is dried up by evaporation, retaken in 10 ml hexane, and analyzed by chromatography in vapour phase (Carlo Erba 2200 - column OV101 2m, temperature: 150°C - flow (N200)-30 ml/mn,, injected amount 2 y l - detection by capture of the Ni electron). A solution of the straight effluent at various concentrations is used as standard solution. 2) Fish and mice samples After pounding a known amount of the sample (muscle for fish, lever, kidney, hart, lungs, muscle for mice) this is purified by being passed through a column of 40g of florisil (200 ml of an * extracting solution made of 65% petrol-ether and 35% methylene chloride). The solution containing the extract is concentrated until it is dry and retaken with 10 ml hexane. A solution of the straight effluent • ' is passed through a similar florisil column and used as standard Solution. Results We were unable to determine the presence of chlorinated waste in the. samples provided for analysis. The solutions standard used for the water analyses being 1.62 ppb, one can estimated in a first approximation that the concentration in effluent is lower than 1.62 ppb, which, when repprted to 1 g water sample, it corresponds to a concentration lower than 0.023 mg/g. We did not find any noticeable difference in the pace of the chromatograms of the control mouse and the poisoned mouse. The chromatograms of the caught fish, show peaks, but these peaks could not be identified with those of the chromatogram of the straight effluent solution. N-17 �10. C. Investigation of heavy metals This investigation was made for mercury and lead: In the fish and plancton caught in the North Sea in the waste before the combustion in the bubbled-up water in the different links of the nutrition chain ^ The following table gives a summary of the results of these analyses: Hg ppm (humid weight) 0.69 0.33 3.52 0.66 0.64 (4) 0.80 0.36 (1) 3.54 64.3 (2) Plancton 1.03 (3) Incineration area (1) (2) Mackerel Pb ppm (humid weight) 1.58 10.5 Effluent before burning Herring 0.114mg/l 0.35 0.50 0.34 0.24 (3) Plancton (I) (2) North Sea outside the incineration area 0.14 0.62 (3) 1.47 13.2 (4) 5.27 52.7 N-18 �11. Hg (ppm) Pb (ppm) (humid weight) (h. wt. ) * Bubbled-up water 0.72g/l micro-seaweed + control specimen 0.14 0.81 micro-seaweed + poisoned zooplancton 0.22 4.09 (1) 0.04 0.71 <2) 0.04 0.63 (3) 0.05 0.27 Poisoned cyprinides (1) 0.04 0.50 (2) 0.07 0.44. (3) 0.10 0.65 (4) 0.10 0.92 (1) 0.09 1.- (2) 0.05 1.- (3) 0.04 • 1.- (1) 0.09 1.- (2) 0.09 1.- (3) 0.08 1.- Control cyprinides Laboratory Nutrition Chain Control mouse Poisoned mouse From these figures it appears: 1) That the waters receiving the fall out of the incineration, show no difference with the rest of the sea. It is evident that in such changeable environment, the pollutions come from many places and can be found everywhere. The contribution of the burned waste appears negligible, any way short term. It is impossible to follow "in situ" the long term consequences. N-19 �12. 2) That no mercury or lead accumulation takes place in the organisms of the nutrition chain living in an environment clearly more concentrated in burned gas than the sea surface during the incineration. 3) That despite all, there are traces of mercury In the effluent. This mercury seems not to be in the form of methyl-mercury, because It is not accumulated in the nutrition chain. However one should make sure that a longer period of exposure to poisoning has no other consequences and that the receiving environment does not contain micro-organisms capable of methylating the mercury. The measurements concerning cadmium, another dangerous metal, *^e being carried out. N-20 �5. CONCLUSIONS The purpose of our experiments was to give an answer on the biological and sanitary aspect of the process of incineration at sea of chlorinated liquid waste. These experiments are by no means exhaustive, but they are sufficiently significant for guiding and allowing the taking of immediate decisions, based on the knowledge one has on the short term consequences. Thus, it appears to us: v 1) that the process does not seem to bring about changes in the biological mass 2) that smoke entering the marine environment does not seem to have an effect on the productivity. However, if this smoke comes into the sea in large volumes, there are some indications, such as the i discolouration of the Diogenes sp_., showing that the neutrality is not perfect. 3) , that no phenomenon of accumulation through the nutrition chain takes place, neither for the mercury, nor for the lead, nor for the chlorinated hydrocarbons. We did not yet investigate the possible \ presence of other toxic materials such as cadmium or benzopyrenes, which could exist in the soots, but anyway, they have not caused any disturbance in the various links of the nutrition chain we have studied. In the present state of our knowledge, it seems that the process of incineration does not cause, certainly not short term, any special harm to the oceanic environment. . It appears anyhow very superior to ths method of straight throwing these industrial (waste) into the waters, as it is practiced usually. This straight throwing, causes a complete and immediate destruction of the seal if e, even in very low concentrations, much inferior to 1/10,000. ! Moreover, even lower concentrations than these, will have results with •N-21 .. ' . . �14. dangerous consequences for the consumer of marine products. Naturally, this favourable advice for the burning, must be confirmed by the long term continuation of the measurements, as a certain number of points have still to be determined. It is evident that this advice concerns only the tested products and that any change in the nature of the burned waste would reopen the question. Exact measurements would be necessary to evaluate the possible harrofulness of these products. January N-22 �L'lWUlUEEATIO.J EH HAUTE HER DE RESIDUS INDUSTRIALS CHLCRES Le Minist-irc charge de 1' Environnement (Directior: de la Prevention des Pollutions ct Nuisances) a etc, courafit 1973, saisi de deux dema.ndes d'autorisation d 1 ir.cineration for.-nulees, par deux societes etr.angircs spticialisees dans la destruction en mer, a partir de navires special ement equipiis, des residus chlores (hydrocarbures et sol van ts clores) produits par 1'in-Justrie Les Societes IncJner j ^ r i c c g et leurs La premiere demande a etc fcmulee par le canal de la Dire-:tio.i generale des services ^.ariti-es de la Ccn?,ign.Le M a r i t i m e et Charbonnicre WORMS par la Scciete :i OCEAN CCMBO'STION EESVICIi" de Rotterdam. La S.A.R.L. " INCIMER " dc Marseille _a ete a 1'origine de la seconds. Chacune des societes concernees dispose d'un ou ds plusieurs navires incinerateurs special eT.ent equipes : les Mattliias I et Mathias II pour I3CIKER, le VULCAN-J3 pour 1'O.C.S. dont le tableau ci~apres (TableaM I) resume les caractcristiques essentielles. Ces navires ont, sur le plan de la conception, en common : - unc capacity de stockage de volume variable. - un ou deux fours circulaires £ ciel ouvert, revetus int6rieurement de briques refractaires. - un ensemble de bruleurs special ement adaptes au type de produits A incinerer et fonctiormant avec atomisation d'air comprime. - un systerce d 1 alimentation du Four en air assurant un execs d'air ne'cessaire a la combustion complete des produits. Cette alimentation est assuree par un ou plusieurs ventilateurs. Produits Incir.eres - Mature et Volvjne... Les produits pour lesquels les deux societes "INC.IMES" et "O.C.S." ont sollicite ur.e autorisation d 1 incineration sont des produits residuaires de 1'industrie chimique en grande p'artie constitues d' hydrocarbures chlores, ayant pour formule chinique generale la for.r.ule : C x H y Cl 2 (o). dans laquelle x peut etre egal a 1,2,3 ou 4, y A 0,1,2,3, ou A, z a 2 , 3 , 4 , 5 ou 6. N-23 �TAHLEAU N° 1 X N C X M 8 R MATHIAS I - MATIIIAS II Sec Ieies NavJres o.c.s. VULCANUS Cnrnct p ilos nnviro3 'Jypc kO m Longueur hors tout Largcur Tirnnt d'oau en charge Jnugc bruto Vitesse i8 m Cargo transforms 72,80 m 10,05 m 5.20 m 11 noeuds Rqu jpuge C n p a c i t u de stockago * 12 ho times 550 t cargo trans for me 1C1,95 m m 7, ; tO m 3.089 tx 13 noeuds l6 homines M.V 1350 t 3.505 m3 ', *» | itonblo fond (hauteur) j Noinbre de citernos Hal lost 6 0,80 m environ 1 2 + 2 cuves on pontee Ne se leste jamais 0, 90 m minimum 15 4 capa cites a 1'avant + coffcrdans et double fond Installation d H ncincration 1 5 Incinoratours - Noinbre 0 exti'rieur 0 intt'ricur ^5,50 m ^,80 m 6 m hauteur Alimentation air UrGleurs - N" ombre Debit unitaire Clapacitn d 'incineration totale ou 6 8 O t 8 t/h 1 t/h 3,6 t/h 8 a 10 t/h 5 t/h 1000*C C • 10,'15 m 9O.OOO m3/h 3/incinerateur (type Saack 20 a 22 t/h d * inc I ncration T" minima 1c T° n i a x i m a l n " 1000fl'C 1500° C l-'iOO°C -1650°C '.i I �Ces produits dorjt la composition n ' e s t pas stable ct qui no dormer lieu a aucutnc r e u t i l i a a t i o n emaricsit ccsentiellement des c h a i s e s fabrication de nratieres p l a s t i q u e s , ds chlorure de vinyl monornerc ^ p a r t i r d'fethylene, de nombreux produits pharmaccutiques, d' insecticides, dc pesticicl utilisant toutcs tes hydrpcarbures chlores comme produit de base. Conune la formule 1'indique, la teneur en chlore de ces residue peut varier dans de notables proportions, ce que traduisent les chiffres . avances par les industriels et spcialistes qui oht ete confrontes aux problemes d'incinerati'on. .•• Dans urn article cpnsacr6 a 1 "Incineration de rejets liquides et recuperation de produits chimiques" et paru dans "Informations Chinie" (*} M. Hidemasa Tsuruta evalue a 65-70 % la quantite de chlore contenue nornjtle.ment dans les residus chlorcs rejetes par les installations de VCM a partir d'ethylene. •T Le Pro£esseur Dr Klaus Grasshof, chef du Departement "Chimie des Mers" 2. 1'Institut d1 Etudes Maritimes" de 1'Universite de Kiel, estime, quant It lui, a 30^ le pourcentage nioyen de chlore contenu dans les rejets brulis er. mer a, partir du port de Rotterdam. • D'autres documents enfin font 6tat de teneurs variant de 20 a 80 Jt, la ntoyenne se situant aux environs de 50%. On poss&de peut de donriees sur le volume global de ces rejets. Selon le Professeur Docteur Klaus Grasshoff , cite pr^ccdcn^-ant, 1<quantite1 de tels produits residuaires atteindrait 100 a 130.000 tonnss/an en Europe Occidentale (dont 50 a 70.000 tonnes en Allemagne Federale). La Society SOLVAY evaLue, quant a elle, Ik 200 000 tonnes la quantite d'hydrocarbures et de solvaats chlores rejetes par 1'industrie chimique de I 1 Europe de 1'Ouest. '> En ce qui concerne la Prance, les estimations font p^iuve de la me*me incertitude et varient selon Les sources d' information de 25 h 60 000 tonnes/an, quantites essentiellenent en provenance des industries chimiques SOLVAY/PECHIHEY - OGINE KUHLMAN/RHOKE P30G1L. Traitement actuel digs .re jets, en F_rance_. Ces produits residuaires sont actuellement 4limin^s de facons tree diverses legal es ou il!6gales. Au nombre de ces dernieres, le re jet de quantitesgeneralement peu importantes tra;isportees en fdts ou par citernes J.iiis les cours d'eau, d*anciennes carrieres desaffect^es oa decharges d' ordures non surveillees doit etre raisonnableiTient retenu. * Information Chimie, n°i24,0ct.l973,pp. 179-186 • t •/ • « • N-25 �Sur le plan legal, il existe actuellercent deux stations priv'v de destruction de liquidcs organiques chlores, appartenant respectivemertt aux societes UGINE XUHLMANH et RHCNE-PROGIL. Ainsi cettc dcrniere society dispose-t-clle i Saint de Haute Provence) en fonctionnement avec Chlo£ 1 et les ateliers de trichlorethylene et de divers solvants chlores d'une unite experimental^ de 0,7 t/h en usage depuis 4 ans et d'une unite industrielle de 1,4 t/h en fonction depuis 3 ans selon le procede brevete RHONE PR03IL. La Societe Solvay dispose egalement d'une unite de traitement mai*hors de France au nive.iu du Group e. Leur capacite reduite est. sans doutc le reproche majeur^.ue 1'on peut leurs faire. Dans ces installations il est procede a la destruction, des residus chlores par pyrolyse ou combustion en atmosphere oxydante avec recuperation d'acide chlorydrique par lavage a eau vive. En general les liquides residuaires, a la difference des carburant brfllent mal. Leur incineration pose done de nombreux problemes, en particulier ceux lies a la faible chaleur de co.tibustion, a leur viscosite elev3e,ti 13 presence de particulcs solides et dans certains cas a la poliTiierisation ou a la decomposition des produits. D'une faccn cenerale une augmentation de la teneur en chlore rend plus difficile leur incineration. De mcme agissent les fortes teneurs en eau et en cendres. Cependant I 1 utilisation de bruleurs a haute efficacite permit de brfller, sans carburant auxiliaire, des rejets ayant des pouvoirs calorifiques relativement faibles se situant entre 2.500 et 3.500 K cal/kg. Cependant pour des teneurs en chlore superi cures a 70 % (pouvoir calorifique inferieur a 3. 000 K cal/kg) il s'avere necessaire pour assurer une bonne combustion, soit d'utiliser un carburant auxiliaire, soit d'ajouter aux produits incineres un carburant de pouvoir calorifique plus eleve. Ceci etant et de facon theorique, dans des conditions de combustion optimales, les gaz sortant du four contiennent essentiellement de I'Azote du gaz carbonique, du chlore et de 1'acide chlorydrique. Ces co:istituants obeissent & plusieurs reactions dont notammsnt : H20 -t- C12 ____ > 2 HC1 + £ 02 • • •/ • • • N-26 �Cettc reaction d'd-quilibre est deplacic. vers la droite temperature croit - Ainsi la quantite de chlore libre diminue : - si on 2iic7n»p.te la temperature (les Hautes tcmn^raturoo " ^-". l '.• ment utiles pour realiscr une combustion complete des composes organiques, cependant la rcsitance des materiaux refractaires limite cette temperature a environ 1.500° c). - si on augmente la quantite de vapeur d'eau. - si on -iiminue autant que possible la quantity d'oxygene. Principe de 1 'Incineration en Mer. L'incineration en haute mer a partir de navires specialement equipes fait appel au proced£ de pyroJiyse "evoque precedemment mais s'en distingue par I 1 absence d 1 installations de lavage et de recuperation d'acide chlory dri que . Techni que de 1 ' incin£rati on . Le four est tout d'abord prechauffe au fuel jusqu'a une temperature de 1000 degres environ dans le cas des MATHIAS I et II et de 1403 -IjOO0 C dans le cas du VULCANUS avant que les residus a incinerer ne soient introduits. .Lorsque ces temperatures sent atteintes,' I"1 inject ion "des' il'^ dans la ou les chambres de combustion est entreprise par le moyen de por.pes d'injection pouvant etre branchees soit sur une seule citerne de stockage, soit simultanement sur plusieurs ou la totalite des citernes. L'utilisation de brQleurs doubles permet d'introduire directe.7.ent dans la .flamme produite par la combustion du fuel des quantites croissar).tes de liquides residuaires et de moduler les apports en fonction de la temperatu qui doit toujours se mainteriir au dessus d'un certain seuil conditionnant la complete pyrolyse des produits traites. L 1 afflux de fuel peut etre.ain-si reduit , sinon arrete totalement. Dans le cas ou la temperature tombe en dessou: du seuil de complete pyrolyse, un syteme automatique retablit I 1 injection de fuel. * Dans le cas de produits dotes d'un pouvoir calorifique inferieur i 3000 K cal/h, une injection continue de fuel peut s'averer nccessaire et etre r endue effective . Dans les cas extremes, I 1 incineration de residus aqueux est ainsi possible, moyennant une consommatLon evidemment tres accrue de fuel. En I1 absence d 1 installations de lavage et de recuperation d'aci^c chlorydrique, la totalite des gaz de ctunbustion se repand dans I 1 atmosphere puts apres condensation par la vapeur d'eau contenue dans I 1 air esc prccipitee sur la surface de la mer. • • •/ . . • N-27 �Cette precipitation" a 6te presentee par les industriel-, co-••.• -n'-i conunc sons inconvenient pour la fa-me et la florc marines. En par', if n :. i : a 6te considers quo 1'acidc chlorydriquc produit serait tr.L>s r op id erne.-u: :\^utralise du fait des teneurs elevees en elements basiques que presenters les caux marines. . Lors de la neutralisation il y aurait production de gaz carboniqut d'acide borique et de chlorure. . / II s'6tablirait en outre apres un laps de temps tres court un nouvel dquilibre du fait que le gaz carbonique degage s'echappe dans I 1 atmosphere, et que le carbonate de calcium present dans 1'eau passe & 1'et^t A* solution. Ces reactions auraient ainsi pour effet de retablir le degre d'ciicalinite cinterieur. '. '• En fait la complexity des phenomenes qui se deroulerit dans le milieu ffiarin dont 1'equilibre est souvent: precaire ont incite 1'Admini strati or. a une approche prudente du probleme et a dcmander aux industriel$ qu'avant: tout excjnen de leur demande, un dossier scientifique et technique aussi complet que pos'sible soit constitue sur les precedes d 1 incineration en mer et: sur les risques de nuisances qui leur sont associes. A cet effet le. Ministere charge de 1'Environnement a propose aux industriels qu'independ?_-ninent de 1'etude des docanents ayant trait aux observations et analyses faites par des laboratoires etrangers ou fran9ais a I1occasion de campagnes d1incineration au large de la Hollande , une experimentation grandeur nature portant sur des produits chlorcs rejettis par 1' ir.dur.trie chimique francaise soit rdalisee sous le controle des Adininistratiors et Organismes concernes par la protection et la defense du milieu marin. N-28 �L1EXPERIMENTATION PORTANT SUR L1INCINERATION ' ' EN HER ET SES RESULTATS •. . But. sur : . L 1 experimentation se proposait de recueillir routes informations . - la qualite des effluents a la sortie des incinerateurs (gaz de combustion et imbrules). - la dispersion et la qualite des effluents gazeux dans I 1 atmosphere. * . m ~ . ~ - les phenomenes associes & la retonbee des effluents gazeux sur la surface de la mer (mesures de pH...) - 1* incidence de. ces re jets sur le milieu marin au point de vue ecologie. en partant de produits incineres ay ant, sur le plan des. caracteristiques physico-chimiques, valeur de reference pour toute eventuelle autorisation d'incinerer que pourrait ulterieurement delivrer 1 'Administ ration. Moyen mis en oeuvre. '.' On participe & l^xpermentation qui s'est deroulee du I9.au 22 Avril 1974 au large de ROTTERDAM, a l"interieur du permis octrbye par- les autorites neerlandaises aux navires incinerateurs : * le navire incinerateur Vulcanus de 1' "Ocean Combustion Service" pour le compte de la Societe Maritime et Charbonnidre WORMS * le navire incinerateur MATTHIAS II, de la society allemande . Stahl-Und-Hech-Bau, Bochum pour le compte de la society INCIMER. N--29 �Etude des charges - Mer.ures phy si cochimi qiics Charge du Vulcanus Charge du Matthias II 1• - . • • • • . ~ . -• • ';. 1,267 Jesures jshysioues ••' i,,o5i • Jensit^ £ 20° C 1..035 cs • Iscosite a 20° C fctervalles ds distillation fitrc 52 et 190 ° • • .7^^- .'.'-. '.":.;;. :' '.r'. ^/K:-:.-W,.; :;;;.; •.'•••; ' •.•". <ir . " -'-".. : "-. - ^tJ .•-. . £/ . .*• •' •' '. . -.- „ _ - ! — — - 97 % ". •* • . - ." -* f .-. ; •'•••'-• ••'•••-" ' •'"•- 47 0,3 •3. ' '-.:££•„..• ..i._'' ....::_: j'-'. «£<-- . • :- - • • ' _- - - • •--'•- . o . :; •; 7 . -" . ; - •• •• *- . • ' 3,4 ' 3 .•-••.. ' .'.'_' • • 0,3 N-30 . - . • •'. . ~ : Kon detects Hon dfitcct^ ' ''• '••-•' ' - 71 ,. ; -'. •• 4 - •' . • K 2 l.> ' * « " " '; " ; - ". . >'• . - - . . - ' ' "•- '.-"0,3 " ' ' . ; -:'. • ' "• . • ....' .- Von d£tecte '• • - . . Bon dfitectfe ...ty'::^-.'^:...' 'V " 0 0,787 cs . - • . OL -'.' ' ' -^ ' • ' . - - - . •'..•/? •..••*:- -• . ' - 7-.15 •- ' - - ' - . : " : '. - . -:'_ "' 43,, 2 ttaux lourds -(o.D.m.) ~ /L&—~* • 97,5 I - . ^ . _• • :; r - " - • . . - • nalysc 61ementaire f « pondo • ral J ;: "•• •:'-""- .*. . ' ' '•„..:•; '" ' ' ! .- 7 -' ? •-•.-''"•'' 0,4 0,5 ' -' ' 6,5' .r 0 ' . -• . •' -•'•• ./^ 2 . <0,3 0,9 - •.- " •':•• • * . . . _ 1,2 - ' . . ...... �ETUDE DBS CHARGES - MESURES SPECrRQCRAPHIQUES Charge du MATTHIAS II ( en 'I. poids ) Hexeries Propanal Cfi H J2 C H. - C H. - C = 0 H 2,47 14,16 Acetone 2,92 1-2 Dichloropropane C H - C - C H j 0 C HZ 01 - CH Cl - C H3 Epichlorhydrine C H2 - C H - C H Cl 28,17 4,24 \f 2-3 dichloroprcpene C HZ = C Cl - C H2 Cl 3,02 di (chloroisopropyl)ether ( C H2 - Cl - C H \ Q 28,54 3 chloropropylether C H3 ) 2 ( CH2 Cl -• CH- - C1I2 )2 0 2 chloropropylether ( CH. - C H Cl - CH2 >2 0 •autres corps % • ••• _.-._^M__^, ,-..,,—. 5,49 6,47 -_, 4,52 - Charge du VULCANUS ( en 'U poids ) . Ch 1 or o forme CH C1 t| 2 3 Cl - CH2 Cl + 1-1 dichloroethane C Tetrachlorure de C. C Cl4 CH2 Cl - CH2 Cl C Cl 2 := c ci2 CH C 1 2 ' Cl H2 Cl 1-2 dichloroethane Tetrachlorethylene 1-1-2 trichlorethane autres corps N-3T ' 01 1, • 2,35 73,03 6,60 11,05 6,96 �II convient de noter les differences de composition qui separent ces deux produits provenant rcspectivement de I 1 Industrie chimique t ilJf "'.•'• et anglaise et consideres par les industriels comme reprcsentatifs de In production francaise en matiere de rejets industriels chlores. '. ./. Analyse des efriucnts A Ic^sortie dc_s_ir.c_in^rateMrs._ Deux dosages, celui du chlore et du phosgene, ont et£ effectu6s & bord des navires incinerateurs. Leurs resultats figurent ci-apres (en p.p.m.) Matthias II • t • • Vulcanus * s Chlore t • • • • • 250 i 2 Phosgene • • 2000 ' • 1100 O - ••?:;-- **" • *, 2 mesures. . • Ces mesures ont et£ completees de recherches sur les imbrOlds . li qui des, solides ou gazeux pouvant prover.ir d'une combustion incomplete des '.. charges. Les recherches effectuees sur les produits" pieges lors de la combustion des residus chlores charges S bord du Vulcanus ne mettent en evidence dans le gaz de combustion que des quantitcs negligeables (0,5 p.p.m.) de composes correspondent aux produits les plus lourds de la charge. .*'On peut done estimer^que lra_p_yroly_s_e est pratiquement complete[jtex_z le^cas d u Vulcanus. • . - . . . Des recherches identiques effectuees sur les produits pieges lors de la combustion des residus charges a bord du Matthias II donnent des rcsultat's pratiquement identiques quant aux quantites d'imbrules (de 1'ordre de 0,5 p.p.:*.). . Cependant il faut noter que parmi ces imbru!6s figurent : - des composes legers type acetone - egalement presents dans la Charge. " , • • - . ' . -' - des"goudrons" insolubles d,ans 1'eau, de nature encore indeterminee (recherche d'eventuels cancerigenes en cours). Lc premier point implique que dans le cas du Matthias II la tempferature de combustion n'est pas unifonnement maintenue aux environs de 1000/ 1100° - comme pa~aissaient 1'indiquer les enregistreraents de t^ effectues N-32 �.* le Ministere charg£ de I1 Environnement (Direction de la Pr-jven* tion dcs^Pollutions et Nuisances - Service dcs Probl£mes de la Her et des Oceans) represente par Monsieur Jean Marie MACSJN, Chef de .rfission. . • • * 1'Institut Scientifique et Technique des Pechcs Maritimes (l.S.T.P.M. ) represente p a r : . . - le navire oceanographique Thalassa. . ' i .• * - Messieurs ALZIEU et HAGGI . . * le Centre National'pour I 1 Exploitation des Oceans (C.H.E.X.O.) represent^ par Monsieur MO'JRLON, coodinateur des actions en mer et Mademoiselle JULLIEN. . . * 1'Institut francais du petrole (l.F.P.) represente -. ar Kessieur - ROUSSEL et BUZON (Branche Chimie Eaffinage - Division physico. chimie appliquee). . ••,.*-"• .* le Connnissariat a 1'Energie Atoaiiquc (c.E.A.) represent^ .par : •" • • "" . .• " ." - Monsieur PLATZER, Coordination de 1'Analyse, C.E.A. Fontenay aU: Roses. - '''"••' Monsieur'VAVASSEUR et Monsieur LE E50NEG, Dspartenent de protection, Service Technique c1Etudes de protection et de pollution atmospheriques C.E.A. Saclay. .: Monsieur HAULET, Departe^ient de protection, Service technique d1Etudes de protection et de pollution atmospheriques C.E.A. Fontenay aux Roses. ..•".-• .• Monsieur'BLAIN, Departemtaitide Recherches et d'Analyses - Servic "Etude des Analyses, C..E.A. Fontenay aux tfoses. .Analyse des charges. ' . . - • . .' . > v• -• "". ' • \Jn seul type de produit a donne lieu a incineration,' sur checun des navires concernes. Les analyses effec'tuees sur les prelevements'realises & bord des navires ont donne les re suit a ts suivants (Tableaux II et III).. .' •»'«/ • • • Nr3-3".. . �i'partir^des thermo-couples months sur te- parois du four - mais tombe en'dessous du scuil de dissociation des composes Idgers (400"j. • dans la noter a (de 100 rejetes ' La presence de goudrons pourrait ctre quant a elle prioecupante mesure ou des Elements cancerigenes seraient mis en £videncp. I1 rn<- * ce propos que compte tenu dcs debits de gaz de combustion mis eu jeu a 140 000 m /h), 50 a 70 kg de residus solides ou goudronneux sent par heure par le Matthias II. jtude du panache. II a et6 proced^ au dosage de 1'acide chlorydrique au voisinags et dans le panache £mis par les deux navires incinerateurs. A 1'issue de ces dosages, il convient de retenir que les concentrations maximales d'acide chlorydrique dans les panaches, a quelques metres au dessus du niveau cc la mer sont du mene.ordre'de grandeur (quelques v.p.m.) pour le Matthias et le Vulcanus. Etude de j.'eau de mer. - Les mesures de pH effectuees de facon continue & la surface de la ner au cours de I 1 experimentation n'ont pu mettre en Evidence aucune variatio sensible de la qualite du milieu superficiel marin. Par ailleurs les analyses effectuees sur les prelevements d'eau de mer realises au point d 1 impact maximum des rejcts gazeux sur le milieu marin n'ont decele aucur.e trace d'hydrocarbures. N-34 �CONCLUSIONS ET ODJECTIFS. 'Des premiers resuitats obtenus & 1'issue ae I1experimentation il resulte que : . - . • ' - .. . '. 1) En ce gui concerne les charges A incinerer. - les caracteristiques physico-chimiques des rejets de I1Industrie chimiques susceptibles d'etre elimines par incineration sent compte tenu des premiers resuitats essentiellcment variables. La notion de produit (s) test£ (s) lors de I1experimentation et ayant valeur de reference pour toute eventuelle. autorisation H incinerer que poarrait delivrer I1Administration doit done Stre 6cartee jusqu'a plus ample information. . Ceci implique, que si le principe de I1incineration en mer eat admis par I1Administration, toute autorisation sera subordonnee & un controle rigoureux de la qualite des chargements. . Ce.controle pourrait comporter : - une analyse relative:nent sommaire du produit embarque (en vue de deceler, le cas echeant, la presence de metaux lours en quanc.iL6s prohibit.!ves). - un essai d1incineration a 1'echelle reduite afin de deter miner la qualite des effluents de combustion. 2) En ce qui concerne. la pyj'plyse des charges. - si la pyrolyse parait ccmplete dans le cas du Vulcanus, quelques reserves peuvent etre felites sur la combustion qui s 1 opera a bord du Matthias II (presence d'imbrules lagers et goudronneux). Le facteur temperature de combustion doit etre en consequence considere comme primordial. Ceci implique que le coritrSle des temperatures au cours de la combustion doit faire 1'objet de dispositions speciales et que toutes les parties du ou des fours puissent etre controlees en service pour verifier leur temperature. • • •/ • • • N-35 . �3) En co qMi ccnrorne 1' jnc-ricncc r dc-r> rctomb/ios i des .gar. j de_ . combustion. . ; - exception f a i t e des inbruleo solides ou goudronneux/cn p a r t i c u l j des i.Vibruli-s non iiiisciblcy j 1'eau clor.t la r.ocivito r<_;;t.<. • '.montrer (etude en cours)^ 1'emission de chlore ct d ' a c i d e chior. drique ne parait avoir aucune action sur le. milieu .marin. Compte tenu de ce qui precede le Ministere charge de 1'Environnemcnt propose que : . -. . . . - une legislation approprice pour I 1 incineration en mer -;oit- il;:;boree et que des decrets d 1 application tienncnt compte sur le plan technique, en particulier : * de la.necessifce de controler la nature de chaque chargement ayant incineration en TC rcferant, le cas echcant, aux indications fournies par un "incinerateur de controle" reproduisant en la'ooratoire les conditions reelles de I 1 incineration en mer. " • • * de la necessite de disposer de fours et de brflleurs assurant une pyrolyse complete des produits traites. * de la neccssite de controler de facon continue et en tous points la temperature du ou des fours de combustion. - dans I'imiriediat un certain nombre de dispositions seront prises pour que les navires incine-reteurs puissent exercer leur activity .& partir de ports francais et a 1'interieur. de zones.mari.times ; qui leurs seront specialerient affectees, moyennant toutes precautions relatives a la protection du nilieu marin. , N-36 �. PTD-HC-23-1^-75 FOREIGN TECHNOLOGY DIVISION INCINERATION ON THE HIGH SEAS OF CHLORINATED INDUSTRIAL WASTES by Author Unknown N-37 �FTD-HC -23-11-75 EDITED TRANSLATION 10 September 1974 PTD-HC-23-14-75 INCINERATION ON THE HIGH SEAS OP CHLORINATED INDUSTRIAL WASTES By: Author Unknown English pages: 13 Source: Unknown, pp. 1-14 (SEE FSL 15702) Country of Origin: France Translated under: F33657-72-D-0853 Requester: AFLC/SGB ' THIS TRANSLATION IS A RENDITION OF THE ORIGINAL FOREIGN TEXT WITHOUT ANY ANALYTICAL OR EDITORIAL COMMENT. STATEMENTS OR THEORIES ADVOCATEDOR IMPLIED ARE THOSE OF THE SOURCE AND DO NOT NECESSARILY REFLECT THE POSITION OR OPINION OF THE FOREIGN TECHNOLOGY DtVISION. PREPARED BY. TRANSLATION DIVISION FOREIGN TECHNOLOGY DIVISION WP.AFB, OHIO. Date 10 sep 19 74 FTD-HC -23-14-75 N-38 �U. S. BOARD ON GEOGRAPHIC I^AMES TRANSLITERATION SYSTEM Block Italic A a A a B 6 6 • i B B B B r r r A E e n A Hi m 3 3 E M d t 3K 3 1 U Transliteration Ai a Bi b V> V G> g D> d Ye , ye; E, e* Zh , zh Zi z Ii i Block P P C c T T Italic P C T P c m y y ** y y 0 t X X X X U U u V H H V V HI LU w 14 b bl b U| m M H H fl M a a Y> H H K K K> k ;i n n A M M M M Lt i M, m H H H M N> n 3 3 0 0 0 0 0) 0 !0 tO n n 77 n P> P fl fl y b bl b ui W L i hi b 3 K> 8 Transliteration R, r S, s T, t U, u F, f ' Kh, kh Ts, ts Ch, ch Sh, sh Shch, shch " u Y, y k 1 t E, e n x Yu, yu Ya, ya *ye initially, after vowels, and after t, B; e elsewhere. When written as e in Russian, transliterate as ye or e. The use of diacritical marks is preferred, but such marks may be omitted when expediency dictates. GRAPHICS D I S C L A I M E R All figures, graphics, tables, equations, etc merged into this translation were extracted from the best quality copy available. N-39 �RUSSIAN AND ENGLISH TRIGONOMETRIC FUNCTIONS Russian English _ sin cos sin cos Kfr tg ctg tan cot sec cosec sec CSC sh ch sinh cosh tanh coth sech csch th cth sch csch arc arc arc arc arc arc sin"1 -1 cos sin cos tg ctg sec cosec tan"1 cot"1 -1 sec esc""1" sinh"1 arc sh arc ch arc th arc "cth arc sch arc csch cosh" „! tarih _l ' coth sech" csch" curl log rot lg N-40 �tNClNF.RATiON ON'THE HIGH' SEAS Or CHLORINATED INDUSTRIAL WASTES During 1973, two requests authorizing the incineration of chlorine wastes (hydrocarbons and chlorinated solvents) in specially equipped vessels, were presented by two foreign Companies specialized in the destruction of wastes on the open sea, to the (ministry in charge of Environnement (Pollution and Nuisance Prevention). i Companies of incineration and thej.r equipment s The first request was presented through the Channel of the Gennral Direction of Naval Services of tne " Compagnie maritime et Charbonniere WORMS", by the Society " Ocean Combustion Service" of Rotterdam. The 5.A.R.L. INCIWER of Marseille originated the secondVequest • Both of these Companies own one or several incinerator-ships specially equipped : Mathias I and Mathias II for INCIItiER, and the Vulcanus for Q.C.S, ; the following table (Table I) will give a summary of their main characteristics. From a basic point of view, those ships have in common : - a storage capacity of expandable volume. - one or two circular furnaces open to the atmosphere, lined with firebricks. - a set of burners adapted specially for. the type of product to incinerate, and functionning by atomisation of compressed air. - an air-feeding system to the furnace providing air in excess so that the combustion of the products is complete. This air supply is provided by one or several fans. s Incinerated products - Nature and \/ol_um e. s' The products for which both Companies INClMER and O.C.S. have applied for a permit to incinerate are the residual products FTD-HC-23-00.14-75 .. : N-41 �TABLE No. 1 I N C I N E R COMPANIES SHIPS HIATHIAS I - NATHIAS II O.C.S. UULCANUS I Carasteristics of ° •f the ships S Type Overall length Transformed freighter 72,8O m 40 m i8 m. ilidth ' 10,85 m transformed freighter 101,95 m 14, 40 m » 7,40 m 5,2O m Draught 3.089 tx Cross gauge Speed 11 knots 13 knots Creui 12 men 16 men •Storage capacity 550 t i350. t 3.505 m'j 0 9 0 m minimum .. 22 0.80 w f?nprox. -^Double bottom (height) 6 Number .of tanks 15 12 + 2 tanks on deck 4 spaces at the front + cofferdams & double bottom No ballast Ballast Incineration Equipment Incinerators - Number Exterior ( Interior i Height Air input Burners - Number 1 5 2 5,50 m 4,80 m 6 m 10,45 m 9.0 0 0 0 m3/h 8 0,8 t/h 1 t/h Delivery ;>-.:• un i. 3,6 t/h 8 Q 10 t/h Total incineration capacity or 5 t/h Technique of incineration 1000 »C 1000* *C T*minimum 1500° C T0 Maximum 3/incinerators (Saack type) 2O a 22 t/h l4008C •1650-C �of chemical industries, mostly chlorinated hydrocarbons having for their general formula the following : C x Hy C12 (0) where x can be equal to 1,2,3 or 4; y to 0, 1, 2, 3 or 4; z to 2,3,4 5 or 6. These products of unstable composition and which cannot be re-utilized come essentially from the manufacture of plastics and monomers of vinyl chloride (\/Cffl) from ethylene, and numerous pharmaceutical products, insecticides, pesticides, all using chlorinated hydrocarbons as a basic product. As indicated in the formula, the chlorine contents of these . wastes can vary a great deal, and this is reflected by the figures mentioned by manufacturers and specialists for the: incineration problems, In an article about the "Incineration of liquid wastes and regeneration of chemical products" oublished in "Information Chimie"* (Chemical Information), Mr Hidemasa Tsuruta estimates that the quantity of chlorine normally present in the chlorinated wastes as a reject from the plants producing V/CN from ethylene is about 65-701?. Professor Klaus Grasshof, head of the Department of "Chemistry of the OceanS" at the Institute fo marine Studies at Hiel University gives an estimate of 3CK, as an average percentage of chlorine content in the wastes burnt at sea off the Harbor of Rotterdam. Other documents mention amounts varying from 20 to 80$, with an average of about 50?S. Few actual data are given on the total volume of these wastes For Dr Klaus Grasshof (-nentioned above), the quantity of these resicus would be 100 to 130,PHO tons (metric tons) per year in Western Europe ( 50 to 70,000 for West Germany). The Company SHLVAY approximates as.200,000 tons the quantity of hydrocarbons and chlorinated solvents rejected by the Chemical industry olp Western Europe. For France, the estimates present the same inaccuracy and vary with different sources of information from 25 to 60,oOO tons per year, amounts produced mainly by the Chemical Industries of 50LVAY-PECHINEY, UGINE-KUHimAN, RHONE-PROGIL. * Information Chimie 124. October 1973; 179-186. FTD-HC-23-0014-75 N-43 �Actual treatment of the wastes in France^ These residues are actually disposed of by various means, legal or illegal. Among the latter group, the rejects of generally negligible amounts carried by barrels or tanks to. streams* disaffected quarries., or un-patrolled dumps, must be reasonably accounted for. '. ' i , • Legally, there are now two privately owned stations of destruction of chlorinated organic liquids, belonging to, respectively, UGINE-KUHLMAN and RHONE-PROGIL. In St Auban (Alpes of Haute-Provence), the Company RHONE-PROGIL disposes, functionning with Chloe* 1 and the Plants of trichloroethylene and various chlorinated solvents , of an experimental unit of 0,7 tons /hour now in use for 4 years; and of an industrial unit of 1.4 t/h using for 3 years a procedure patented .by RHONE-PROGIL. The Company SOLVAY owns also an unit of treatment at the Group level, but outside of France. The major fault which can be formulated is their reduced capacity. " ^ In those Plants, the chlorinated wastes are destroyed by pyrolysis or combustion by oxidation with recovery of hydrochloric acid by running water washing. ^ In general, the liquid-waste, unlike the carburants, burns very poorly. Their incineration is bound to many problems, due in particular to their low temperature of combustion, their high viscosity, the presence of .solid, particles, and in certain cases to the polymerization or decomposition of the products. •'I Generally speaking, the higher the chlorine contents, the more difficult the incineration. The high water or ash content behave similarly .'However, high efficiency burners can consume, without auxiliary carburant, some residue with the low calorific power of 2500 to 3500 Kcal/kg When the chlorine content is higher than 70^ (calorific power less than 3,000 K cal/Kg) it becomes necessary, in order to have a complete combustion, either to use an auxiliary carburant, or to add to the products to be incinerated a carburant with higher calorific 'power. , In those conditions of ootimum combustion, theorically the gasses released by the furnace contain essentially: nitrogen > carbon dioxide, chlorine and hydrochloric acid. N-44 FTD-HC-23-0014-75 �These components follow several reactions such as: H20 4 Cl2 -- t "* 2 HC1 + 02 This equilibrium is displaced towards the right when the temperature increases, so that the amount of free chlorine decreases: - if the temperature is raised (high temperatures are also useful to realize a complete combustion of organic compounds; however the resistance of the firebricks limits this temperature to 1500 C) . - if the amount of water vapor is increased. - if the amount of oxygen is lowered as much as possible Principle of Incineration at sea * The incineration on the high sea by specially equipped ships is based on the f orementionned pyrolysis technique, but it does not include the equipment for washing and recovery of hydrochloric acid. Technique of incineration The kiln is preheated by fuel to a temperature of approximately 1000° C. for the ships Nathias I and II, and of 1400 to 1500°C. for the ship Vulcanus, before the residues are brought in. 'jjhen the above temperatures are reached, the wastes are injected into the combustion chamber (or chambers) by means of injection pumps which can be plugged on one storage tank alone, or simultaneously on several or all of the tanks. The double burners make it possible to introduce, directly into the flame of the burning fuel, increasing quantities of liquid wastes and to modulate the input as a function of the te-nperature, which must be maintained above a certain threshold, as a necessary condition for the complete pyrolysis of the treated products. The flow of fuel can then be reduced, if not comoletely stopped. '.'Jhen the temperature falls beloli the threshold of complete pyrolysis, an automatic system reactivates the fuel injection. * In the case of the products having a calorific power inferior to 3000 K cal/h, a continuous fuel injection might be necessary, and be still efficient. In extreme cases, the incineration of aqueous wastes lis possible, of course with an increased fuel consumption. In the absence of equipment for washing and recuperation of hydrochloric acid, all the gas of combustion is released to the atmosphere, then after condensation by water-vapor of the air, is precipitated onto the surface of the sea, N-45 �This harmless that the the high precipitate has been described by the manufacturers as being to the marine fauna and flora. In particular, it is considered hydrochloric arid produced would be rapidly neutralized by contents of alkaline elements of sea water. During the neutralisation process, carbon dioxide, boric acid and chlorides would be produced. After a short time lapse, a neui equilibrium would be established because the released carbon 'dioxide escapes to the atmosphere promptly, and the calcium carbonate present in the water is solubilized. The effect of these reactions would be to re-establish the previous degree of alkalinity. In fact, the complexity of the impact on the precariously balanced marine media has incited a prudent approach to the problem by the Administration who requires from the manufacturers, before examination of their application, a scientific and technical documentation as complete as possible concerning the procedures for incineration at sea, and the risks of nuisances associated with them. As a result, the ministry in charge of Environment has proposed to the manufacturers that, independently of the study of documentations concerning the analysis performed by foreign or french laboratories on the incineration experiments off the coast of Holland, a full scale experiment,directed towards the chlorinated wastes rejected by the French Industry, be realized under control of the Administration and Commission for the protection and defense of marine life. N-46 �EXPERINENT ON I N C I N E R A T I O N AT SEA, AND RESULTS Purpose This experiment proposed to collect data on: the quality of effluents released from incinerators (combustion gas and unburnt) the dispersion and quality of gaseous output to the atmosphere. the facts associated u.i'oh the gaseous fall-outs on the surface of the sea ( aH measurements etc..) the effect of these juastes upon the marine life from the point of view of the ecology. beginning with incinerated wastes having standard physico-chemical characteristics which could be used as reference for an eventual permit of incineration to be granted by the adminsitration. Means of experiment employed In the experiment carried out between the 19 and 22nd of April. 1974, off Rotterdam, under a permit granted by the Dutch authorities to the incinerator ships: * incinerator ship Vulcanus from "Ocean Combustion Service" representing the Sociffte' maritime and Charbonniere WORMS * incinerator ship MATTHIAS II, of the German Company Stahl-Und-Blech-Bau, Bochum for the Company INCIWER * The ministry in charge of Environment (Division of Prevention of Pollution and Nuisances - Department of the Problems of Sea and Oceans) represented by Mr Jean Marie MASSIN, Head of the expedition. * the Scientific and Technical Institute of the Sea Fisheries (l.S.T.P.ff. ) represented by - the ocean going vessel Thalassa. Messrs ALZIEU and flAGGI N-47 �* the National Center for Ins exploitation of the Oceans (C.N.E.X.O.) represented by fflr. WIOURlQN, coordinator of the experiments at sea and miss JULLIEN. * The French Institute of Petroleum (l.F.P.) represented ^ Messrs ROUSSEL and. BUZON (Section Chemical Refinery Division applied physico chemistry) • f * the Atomic Energy Commission (C.E.A.) represented by Mr PLATZER, Coordinator of the Analysis, C.E.A., Fontenay aix Roses. fflr VAVASSEUR and Wr LE 8RCNEC, Department of Prevention, Technical Services for the study- of protection and air pollution C.E.A. Saclay. Mr HAULET, Department of Prevention, Technical Services for the study of protection and air pollution, C.E.A. Fontenay aux Roses. Wr B L A I N , Department of Research and Analysis, Section: Study of Analysis, C.E.A., Fontenay aux Roses. Analysis of Loads Only one type of product mass incinerated on each ship concerned, Analysis of the samples collected on the ship gave the following results: (Tables II and III). The difference in composition of the two products coming, respectively,from the german and the english chemical industry and considered by the manufacturers as representative of the french production of chlorinated industrial wastes should be noted. Analysis of the effluent of the incinerators Two quantitative analysis were performed aboard ships: the chlorine and carbonyl chloride (phosgene), Results in p.p.m. • : Iflatthias II : • Chlorine 1 : Phosgene : : » Uulcanus * • i t '250 2 : : : 2 measurements N-43 '2000 1100 < 1 �TABLE: ii Study of the loads Physicochemical data :Load of the Matthias II Load of the Vulcanus 5 Physical measurements Density at 20° C. ; * Intervals of distillation between 52 and 190° riementary analysis ( * by weight) c \^ g Q Cl Heavy Mstals-(p.p.m, ) y Cu Fe Hg Na P Pb Si Zn 1.267 •t. « t : 1.085 cs 0.787 cs 97,5 < 97 ^ t t t • t i t : Viscosity at 20° C. Cr '..Ofil 43 ..2 7.15 Not detected Not detected 47 . 25 4 Not detected Not detected 71 i i 0.3 t ; 0.3 * j J ; j : i I ' 0.4 .0.5 3 6.5 0 0 2,5 7 ,2 <0.3 . 3.. 4 0.9 3 2 0.3 1.2 N-49 �TABLE STUDY OF THE LOAD III - SPECTOGRAPHIC ME A SURE HIE NTS Load of the MATTHIAS II ( in < Height) Hexanes Propanal Acetone 1-2 Dichloropropane 2,47 C 6 "12 CH--CH -C =0 H ' C H, - C - C H , 3 u 3 0 C IL 01 - C1I Cl - C H 2 C 11, - C H - C H4 Cl 14,16 2,92 28,17 4,24 Epichlorhydrine 2-3 Dichloropropane di (chloroisopropyl) ether 3 chloropropylether 2 chloropropylether ^ / o C H, = C Cl - C H0 Cl 2 2 ( C H2 - Cl - C U )Q f\ * • 3,02 4 28,54 • A • . .' « H. ) 2 ( -f*li f*l pit pu N f\ \jH,j bl - "Ho ~ 9 ' ? 5,49 i 6,47 ( cn3 - c H ci - cn2 )2 o Other 4,52 Load of the Vulcanus ( in < weight) Chloroform +1-1 dichloroethane Carbon Tet. 1-2 dichloroethane Tetrachlorethylene 1-1-2 trichlorethane : 3 . ' C H. CL - CH Cl 2 2 1,01 .4 . CH0 Cl - CH, Cl * 2 2i35 C Cl, = C Cl. 6,60 C H C1 ^ ^ CH Cl - Cl H, Cl * * 11.05 6,96 other N-50 �These measurements were completed by research on the un-burnt fluids, solids, or cases coming Prom incomplete combustion of the loads. The study of the products trapped during the combustion of the chlorinated wastes loaded on the Uulcanus shows only negligible amounts (C.5 p.p.m.) of the compounds corresponding to the heaviest products of the loads in the gas of combustion. The pyrolysis is then practically complete in the case of the Vulcanus. Similar studies performed on the products trapped during the combustion of the wastes on the Matthias II gave almost identical results for the unburnt quantities (about 0.5 p.p.m.) However, one must remark that among those unburnt are: i - light compounds of the type acetone, also present in the load. - "tars", insoluble in water, of indetermined nature (under study for eventual carcinogens) of by of of The first point implies that in the Matthias II the temperature combustion is not maintained uniformly at 1000 to 1100°C. as indicated the temperature recording of the thermo-couples installed on the wall the furnace, but locally falls below the threshold of dissociation light compounds (400°C.) The presence of tars could be worrysome to the extent where carcinogenic elements would be demonstrated. It must be mentioned that te.king into consideration the output of gas of combustion (100 140,000 nr/h), 50 to 70 kg of solid wastes or tar are emitted by (tlatthias II per hour. Study of the mixture of gas Hydrochloric acid titration was performed next and in the gas mixture emitted by the two incinerator ships. It must be noted that the maximal concentrationsof hydrochloric acid in the air mixture a few meters above the sea water surface are in the same range ( a few v.p.m.) for the Matthias and the Vulcanus. Study of the sea juater The pH measurements performed continuously at the surface of the sea during the experiment could not reveal any variation in the superficial marine media quality. Analysis of the samples of sea water obtained at the maximal impact point of the gaseous rejects on the marine surface showsno trace of hydrocarbons. N-51 FTD-HC-23-0014-75 �= J. -•t CONCLUSIONS AND AIMS 1 From the first results obtained from the experiment, it is concluded that: 1 ) For the loads to incinerate - the physico-chemical characteristics of the chemical •industry wastes susqeptible to be destroyed by incineration are taken into consideration in the first and essentially variable results. A simple notion of product (s) tested by the experiment and Usable as a reference for any eventual permit of incineration released by the Administration must be set aside till more information is provided. : - This implies that, at sea is accepted will be subject to This control could though the principle of incineration by the Administration, all authorizations a strict control of the quality of the loads. imply: - a brief analysis of the loaded products (in order to detect, if necessary, the presence of heavy metals in prohibitive amounts) . • a test of incineration on a small scale in order to determine the quality of the combustion effluents. 2) For the pyrolysis ,of rthe loads t - if the pyrolysis seems to be complete in the case of the Vulcanus, a few reservations could be made on the combustion aboard the Matthias II (light unburnt products and tars). Consequently, the factor " te mpe r at _urs of c omb us 1 1 on " must be considered as primordial. * ~~ This implirs that the control of the temperature during the combustion must be the object of a special attention, and that all the parts of the furnace (s) should be controlled during use to check the temperature. FTD-HC-23-0014-75 - N-52 �3) For the incidence of gas of combustion fall-outs * < - with the exception of the unburnt solids or tars (in particular of the unburnt not miscible with water of which toxicity still has to be demonstrated [under study]), the release of chlorine and hydrochloric acid seemsto have no impact on the marine life. In consideration of the facts above, the ministry in charge of the Environment propdses that . - an appropriate legislation for the incineration at sea be enacted and that the decrees of application consider the technical point of view, in particular: •fe * The necessity of checking the nature of each load before incinsration, referring, if necessary, to the indications provided by a test incineration, duplicating in laboratory the actual conditions of the incineration at sea. * The necessity of using furnaces and burners performing a complete pyrolysis of the treated products. * The necessity of checking continuously and at all points the temperature of the furnace (s) of combustion. s - very soon a number of arrangements will be made so that the incinerator-ships can operate from french ports, and inside a marine zone which will be specially designated for this use, with all precautions concerning the protection of the sea life. FTD-HC-23-0014-75 N-53 �Unclassified Security DOCUMENT CONTROL DATA - R & D (Stcurlty flmitlllctllon el Hilt, body ol tbllrtct tnd IntHflng tnnoltllon mull bo tnltrfd wh*n ih» onrtll npetl It ctmnllltd) 2*. REPORT S E C U R I T Y CL Atll FIC» TION I O R I G I N A T I N G A C T I V I T Y (Cotfonlt tulhot) Unclassified Foreign Technology Division Air Force Systems.Command U. S. Air Force 1 lb. G R O U P REPORT TITLE INCINERATION OF THE HIGH SEAS OF CHLORINATED INDUSTRIAL WASTES t D E S C R I P T I V E N O T E S (Typt ol report tnd Inelunlvt dmitt) Translatlon > AUTHOR!!!) (T/r«l n»m*. mlddlt Inliltl, Imtl nmmt) Author Unknown REPORT D A T E 7b. NO. OF ».l. Y O T A L NO. OF P A C E * 13 M. C O N T R A C T OR O R A N T NO. 0.1. ORIOlNATOR'l R E P O R T NUMBERID FTD-HC-23-1^-75 fc. PROJECT NO. OTHER REPORT NO(S» (Any olfiM number* thrnt mmy b* IM* nport) . 1UPPLEMENTARV NOTES 1 1 . (PONIORING M I L I T A R Y A C T I V I T Y , Foreign Technology Division Wright-Patterson AFB, Ohio Ta.. , 11 DD ,FN°o"vM.,1473 N-54 Unclassified Security Classification �WITNESS NO. : 4 NAME : H. COMPAAN . OCEAN INCINERATION HEARING OCTOBER 4,. 1974 I am H. Compaan of the central laboratory TNO. TNO is the National Research Council of the Netherlands. It is a nonprofit, semi -governmental research organization, employing about 4,000 distributed over many laboratories, committees, and working-groups. The Central Laboratory TNO has the special task to carry out multi -disciplinary research. I am heading a research group of 11 , working mainly on problems of marine pollution and partly on air pollution. The department of the Dutch government that is responsible for the environmental control of the Dutch Continental Shelf in the North Sea, gave TNO orders to search fcr uncombusted organic chlorine compounds in the exhaust gases of the Vulcanus during normal practice. The investigations. on the Vulcanus were carried out on May 29, 1974, on the North Sea, 20 miles northwest of the Hague. During the incineration of VCM - production waste containing approximately 70% combined chlorine, we took a number of stack samples in different ways. The samples were taken by myself and o:ie assistant. The samples were obtained from the top center of the left incinerator by suction through a cooled quartz tube. The exhaust gases were led through: a) an impinger filled with water (organic free), b) an impinger filled with 1 N sodium hydroxide (organic free) c) an absorption tube filled with chromosorb 102. During the sampling, two colleagues from the Central Technological Institute, TNO were measuring the flame temperatures of the incinerator and the carbon monoxide, carbon dioxide and oxygen contents of the exhaust gases. The organic chlorine compounds were obtained by extraction of the scrubber liquids with cyclohexane and by thermal desorption from the absorption tubes., The samples were analyzed by gas chromatography with 4 different detection methods: a) flame ionization detection b) electron capture detection c) helium plasma detection d) mass spectroscopy Helium plasma detection and mass spectroscopy gave the most conclusive results. The helium plasma detector showed clearly the presence of small amounts of organic chlorine compounds. With the mass spectrometer evidence was obtained for the presence of some organic bromine compounds as well. The total amount of organic chlorine thus found corresponds to a concentration of about 3-5 ppm in the exhaust gases, or not more than 40 ppm on the basis of the feed. This corresponds to a combustion efficiency of 99.996 percent. During the incineration a sample of the waste was taken at a point N-55 �near the burners. Gas chromatographic - nass spectroscopic analysis showed that the waste had the usual composition. The samples were taken from 10 A.M. to 2:40 P.M. At 12:30 P.M. the flame temperature Was 1200 - 1300°C. At 2:00 P.M. the flame temperature was 1300 - 1400°C. 'a The final report will be ready in October 1974. [The above complete testimony is retyped from material available during the public hearing conducted by the Environmental Protection Agency in Houston TX on 4 Oct 1974. The hearing was relative to a permit application (No. 730D008C) from Shell Chemical Company"to discharge to ocean waters off the coast of Texas] N-56 �- APPENDIX 0 COMMENTS TO: REVISED DRAFT ENVIRONMENTAL'STATEMENT DISPOSITION OF ORANGE HERBICIDE -BY INCINERATION April 1974-AF-ES-72-2D(l) A. This section presents the letters of comments which were forwarded to the Air Force on the revised Draft Environmental Statement. All comments received are included and the Air Force reply follows each comment. B. Comments were received from the following: * ? United States Government Agencies/Departments i Atomic Energy Commission Department of Agriculture $, Department of Commerce Department of Defense (Health and Environment) Department of Health, Education and Welfare (2 letters of comment.) Department of Interior Department of Transportation Environmental Protection Agency State Governments Hawaii (3 letters of comment) Mississippi Other interested Groups American Eagle Foundation Center for Law and Social Policy (Representing Friends of the Earth and the National Audubon Society) The Marquardt Company V "J L • �(This page intentionally left blank) �UNITED STATES ATOMIC ENE:RGY COMMISSION WASHINGTON, O.C. 20545 JUL 5 1974 Dr. Billy E. Welch Special Assistant for Environmental Quality Office of the Assistant Secretary Department of the Air Force Washington, D. C. 20330 Dear Dr. Welch: [1] This is in response to your letter dated May 9, 1974, inviting the U. S. Atomic Energy Commission to review and comment on the revised Draft Environmental Statement entitled, "Disposition of Orange Herbicide by Incineration." [2] We feel that the United States Air Force environmental statement is well prepared in almost all areas. Of particular concern is Johnston Atoll wildlife; however, the statement does elucidate the lack of hazards and adverse effects the proposed action will have on the wildlife. The statement also demonstrates that there should be no adverse environmental effects from incineration either on the special ship or Johnston Island, given proper equipment operation within specified safety constraints. [3] We do have some concern in areas of the statement which do not seem to be covered with sufficient detail. These are: 1. Transfer of the herbicide to the incinerator, including "de-drumming," bulk storage, control of spills, etc. 2. Clean-up of emptied drums. 3. Disposal of emptied drums. [4] With respect to item 1, our prime concern is for the health and safety of all involved in or in proximity to the Island operation. This should be the primary consideration in the planning, scheduling, funding, and execution of whatever method is employed. Sufficient advance notice of the method of choice should be provided to field agencies to allow for coordinated and orderly design and construction of the "de-drumming" and transfer facilities. If the schedule for emptying the drums is anticipated to exceed a year, early construction of a bulk storage facility should be considered to minimize re-drumming and expedite the ultimate transfer operation. 0-1 �Dr.. Billy E. Welch - 2- [5] As for drum clean-up, the statement documents that even with repeated rinsing of the emptied drum, which is not only expensive and timeconsuming, all the residue cannot be removed and that the difference between rinsed and unrinsed drums probably may not be worth the effort. [6] We presume that the problem of drum disposal is still under study and feel that more consideration should be given to salvaging the drums so they ultimately become ingots. In any event, the crushed drums should be shipped in a sealed container in order to prevent release of any residual herbicide during shipment. [7] Another area in the statement which we feel has been given marginal consideration is the alternatives to incineration. The alternatives such as "use," "return to industry" are briefly covered and have not been costed out. We should like to suggest that additional review be made of the possibility to return this chemical to the economy, if such can be. done. Possibly the chemical processing industry could use this chemical as a raw material in another process. If this alternative is not economically sound nor technically feasible, we feel that such fact should be documented and that incineration is truly the only alternative. j In summary, we feel that this draft statement adequately shows that there will be no adverse environmental impact from proper incineration, if in fact this is the only alternative. We would prefer that the incineration be done at sea since" this will minimize exposure of the chemical to the Island personnel and request that as the methods are selected and procedures written, the health and safety of this personnel be of primary concern. [9] We do object to incineration on Johnston Island for several reasons, but primarily because of the excessive length of time required for construction of a facility for disposal and for the actual disposal. Additionally, Incineration on the Island is certain to cause an obstruction to our readiness program that now exists. Our final objection "is the high cost of construction and the continuing excessive environmental pollution which could occur by having leaking levels of herbicide around for a much longer period of time. 0-2 �Dr. Billy E. Welch - 3- [10] Since facilities for incineration at sea are in existence (e.g., the ship Vulcanus) and total disposal could be accomplished in less than two months, we prefer this method of incineration. This mode will also eliminate the obstruction to our readiness effort at a minimized cost to the Government. [11] We have appreciated the opportunity to review and comment on the statement. Sincerely, Liverman General Manager for iiomedical and Environmental Research and Safety Programs cc: Council on Environmental Quality (5) 0-3 �RESPONSE TO COMMENTS FROM THE ATOMIC ENERGY COMMISSION LETTER (5 Jul 74) 1. (Paragraph 2,3,4 AEC Ltr) A complete dedrumming and transfer operation has been planned and engineered for Johnston Island (Part IKE.) The health and safety of personnel and the maintenance of the environment are prime considerations in this plan. Sufficient notification will be provided for the orderly implementation of the "dedrumming/transfer" project. 2. (Paragraph 3,4,5,6 AEC Ltr) See Part II.E. for drum disposal information. * 3. (Paragraph 7 AEC Ltr) See Part I for Air Force action toward EPA registration of Orange herbicide. 4. (Paragraph 7 AEC Ltr) See Part V.C for Air Force action on the return of Orange herbicide to manufacturers. 5. (Paragraph 9,10 AEC Ltr) The proposed disposal action is incineration at sea with incineration on Johnston Island as the principal alternative. 0-4 �DEPARTMENT O- A G R I C U L T U R E O I - n C E O r THE 5ECRETMJY WASHINGTON. D. C. 2O250 June 19, 1974 Dr. Billy E. Welch Special Assistant for Environmental Quality Department of the Air Force Washington, D. C. 20330 Dear Dr. Welch: We have reviewed the revised draft environmental statement on "Disposition of Orange Herbicide by Incineration"—AFES-72-2D ( ) April 1974. The statement is well organized, 1, well written, and significant research data are presented to support the effective and safe disposal of orange herbicide by incineration. We concur in the proposal to dispose of orange herbicide by incineration in a remote area near or on Johnson Island in the Pacific Ocean. With proper concern for the environment as outlined in the revised draft environmental statement, we concur that incineration is the most environmentally safe and most effective method of the alternative procedures that could be considered for the disposal of orange herbicide. Sincerely, F. H. Tschirley Coordinator Environmental Quality Activities 0-5 �RESPONSE TO COMMENTS FROM THE DEPARTMENT OF AGRICULTURE LETTER (9 JUN 74) No reply required. 0-6 �UNITED STATES DEPARTMENT OF COMMERCE The Assistant Secretary for Science and Technology Washington. D C. 20230 July 10, 1974 Dr. Billy E. Welch Special Assistant for Environmental Quality Office of the Assistant Secretary Department of the Air Force Washington, D. C. 20330 Dear Dr. Welch; The draft environmental impact statement for the proposed "Revised - Disposition of Orange Herbicide by Incineration," which accompanied your letter of May 9, 1974, has been received by the Department of Commerce for review and comment. The statement has been reviewed and the following comments are offered for your consideration. The accidental discharge of Orange Herbicide into the air, ground or under "worst case" conditions is discussed under various conditions in the environmental statement. Two "worst case" conditions, that are not discussed, however, are the fate and effect of Orange Herbicide under the "worst case" conditions of either (1) jettisoning of the cargo of the vessel Vulcanus or (2) accidental sinking of the Vulcanus, Consideration should be given to these possibilities, even though they may be remote. Thank you for giving us an opportunity to provide these comments which we hope will.be of assistance to you. We would appreciate receiving a copy of the final statement. Sincerely, 1 X ,^-^^ j{ •f~''L' "ViV. •/«...< Sidney'R. Caller Deputy Assistant Secretary for Environmental Affairs 0-7 ,ei*> �RESPONSE TO COMMENTS FROM THE DEPARTMENT OF COMMERCE LETTER (10 Jul 74) Information on possible environmental impact resulting from the jettisoning of the Orange cargo or sinkage of the incinerator ship has been included in Part III.C.5.a. 0-8 �ASSISTANT SEICRETARY OF DEFENSE WASHINGTON, D. C. 2O3O1 •i 1 HEALTH AND ENVIFJONMENT JUL 1974 MEMORANDUM FOR Special Assistant for Environmental Quality... 3AFILE SUBJECT: Revised Draft Environmental Statement "Disposition of Orange Herbicide by Incineration" [1] The following comments on the Draft Environmental Impact Stjitement, "Disposition of Orange Herbicide by Incineration, " are provided in response to your memorandum of May 9, 1974. [2] In view of EPA withdrawal of its legal motion seeking a ban on the use of 2-4-5-T, further consideration should be given to disposition of that portion of the material which corresponds to c u r r e n t commercial formulation through controlled use by DoD or other governmental agencies. * [3"] With respect to disposal via ship incineration, we would suggest that the possibility of accidental release of the material as a result of uncontrolled shipboard fire or nEitural causes be discussed.. [4"| The discussion on incinerating the herbicide on Johnson Island should include the possible effect of the HC1 from the exhaust on space tracking equipmen t and on the aluminum housing of certain of the stored chemical munitions. [5] The Office of the ASD(I&L) also noted that no fully satisfactory method of disposal of the drained drums is proposed in the statement. Incineration of the drums to remove herbicide residues should be considered. This could be included as a requirement in the service contract. After incineration, disposal of the drums by any number of environmentally acceptable methods is possible including salvageJor reuse of the metal.. H. R. Smith -• Acting Deputy Asst Secretary of Defense (Environmental Quality) 0-9 �RESPONSE TO COMMENTS FROM THE ASSISTANT SECRETARY OF DEFENSE FOR HEALTH; AND ENVIRONMENT LETTER (1 Jul 74) 1. (Paragraph 2 SoD for H&E Ltr) See Part I for Air Force action toward EPA registration of Orange herbicide. 2. (Paragraph 3 SoD for H&E Ltr) Information on possible environmental impact resulting from the jettisoning of the Orange cargo or sinkage of the incinerator ship has been included in Part III.C.5.a. 3. (Paragraph 4 SoD for H&E Ltr) If the principal alternative of incineration on Johnston Island were used, meteorological constraints and ambient air monitoring would be utilized to insure that hydrogen chloride does not represent a health hazard to personnel. These precautions would also insure that structures and space tracking equipment are not affected. Additional information on the effects of hydrogen chloride has been included in Part III.B.2.C. 4. (Paragraph 5 SoD for H&E Ltr) See Part II.E. for drum disposal information. 0-10 �DEPARTMENT OF HEALTH. EDUCATION. AND WELFARE OFFICE OF T-IE SECRETARY WASHINGTON. D.C. 20201 .AUG 23 1974 D-:. Billy E. VJelch Special Assistant for Environmental Quality Department of the Air Force Washington, D. C. 20330 Dear Dr. ;.relch: [1] Uo have reviewed the revised draft Environmental Impact Statement concerning the "Disposition of Orange Herbicide by Incineration." [2] OF vital concern to this Department from the proposed action ic the impact to the physical environment and subsequent potential contaminextion of food for man and animal. A related problem involves the transportation of the phenoxy compounds, the transfer of the chemical to the ship, rind one of increasing magnitude is the handling and disposal of wastewater and used containers. The potential seriousness of health and environmental hazards due to accidental causes-, improper disposal and handling of the chemical and containers must be treated in the final impact statement, if we are to determine whether or not this project will be fully protective of public health and the environment. [3] I'hysical movement of 0.86 million gallons of Orange from its present location in Gulfport, Mississippi, to the ultimate cite of disposal is a potentially serious threat to the environment and contributing factor to contamination of food for man arid animal use. The draft statement, in our opinion, does not give sufficient information on movement and handling procedures, j'.nother problem exists in the disposal of the empty 55-gallon stool drums. We feel the impacts resulting from container disposal should be discussed in the final statement. Land fill of these drums is questioned since the material can be recycled thereby eliminating any potential hazard once and forever. 0-11 �Page 2 - Dr. Welch [4] The other proposed disposal options are not discussed in the type of detail which would allow conclusions to be drawn about their viabil-iby. [5] We note that incinerating Orange Herbicide at the specified temperature, pressure, dwell-time, combined with high efficiency scrubbing, will provide safeguards against the release of highly toxic dioxins. However, the problem of pyrolytic synthesis of dioxins received minor discussion in this revised statement, depending .solely on the use of sufficiently high temperatures to complete the destruction. As seated in the draft statement, the formation of dioxins on pyrolysis can occur at lower temperatures; however, the possibility of cold spots in the furnace- or its break-down have been inadequately considered. ? [6] We do not dispute the completeness of the Marquardt Company's land-based incinerator study. The analyses of the exhaust gases are adequate and. well discussed. However, it is questionable that under actual operational conditions, sustained combustion efficiencies of 99.999% can be maintained consistently, knowing that incinerator design is not a well defined process. [7] Vie could not adequately review the shipboard incinerator concept, since the pilot plant or operational data was not presented. Also, the destruction efficiency of 99.9% for this incinerator was not validated by adequate data; therefore, it can only be concluded that this efficiency was an extrapolation from the Marquardt Company study. In an operation of this magnitude with the potentially serious public health considerations, this type of information should be provided. [8] Unmonitorcd incineration on-board the ocean vessel as described in the statement does not provide the safety assurances considered necessary for the disposal of Orange herbicide. Lacking are the high-efficient scrubbing devices and monitoring instrumentation necessary to provide adequate health and environmental safeguards. The' statement is silent regarding the potential environmental impacts which would occur in the event an accident should occur on the vessel while loaded with Orange herbicide. [9] There are no complete comparative cost analyses for the two proposed alternatives presented. 0-12 �Page 3 - Dr. Welch [10] It is our opinion that the "worst case" analysis used in defense of minimal environmental impact can be improved. The dispersion model derived in Appendix K is not complete. This should include general mass transfer equations with supporting simplifying assumptions. Also, in a "worst case" analysis, conversions of less than 99.9% should be used especially since this incineration efficiency is not validated by hard data. For example, if 0.1% conversion corresponds to 0.576 Tons of herbicide/day discharge to the atmosphere, for a conversion of only 90%, this would correspond to about 57.6 Tons of herbicide/day discharged to the atmosphere. [11]The estimated 22-26 days required to incinerate 2.3 million gallons of Orange herbicide using the vessel does not include in the calculations the volume of drum and other wash water which will result from the disposal operation or the time required to load the chemical into the ship in preparation for incineration. Considering these factors, we estimate that the time required to dispose of 2.3 million gallons of Orange herbicide is underestimated. [12]In conclusion, it is our considered opinion that: 1. Incineration under tightly controlled parameters is an acceptable method of destroying the Orange herbicide; 2. Prior to use of any incinerator, except the one presently certified by actual pilot testing, the same type and quality of pilot tests with gaseous and liquid effluent analyses must be conducted on said incinerator. This will provide the necessary assurances that the selected disposal method protects the public health and safety, reduces to the maximum the potentially serious threat to the environment and is not a contributing factor to contamination of food for man and animal use; 3. Whatever incineration method is selected, adequate and continuous monitoring of the gaseous and liquid effluents therefrom are' required; 4. Transfer and transport of the chemical from Gulfport, Mississippi must be provided with proper safeguards and likewise the chemicals on Johnston Island, if th-ay are to bo destroyed by s'.ii/.board disposal; and 0-13 �Page 4 - Dr. Welch ; 5. Careful considercitio.i must be given the handling, cleaning and ultimate disposal of the contaminated drums. '[13] We feel that the only pos.lr.ivc; aspect of the oh-'board incinerator is that it alleviates tho problem in a short period of time. The land-based operation will require seven months oh a 24-hour/day operation and will rocui vo f-.ho 'Air Force to participate. The on-board incinerator cijpv ?.:\r.£; to trans'fer th?. disposal problem and the potential impacts, public health and environmental to ancthsr iiaedia. The possibility tliat i,. ;.\ay .itt a precedent Jor i.icincrr.tion of all hazardous matorinl at i?:i?o cannot be dismissed. ? [14] Thank you for the opportunity to comment on this statement. Sincerely, Charles Custard Director Office of Environmental Affairs 0-14 �RESPONSE TO THE COMMENTS FROM THE DEPARTMENT OF HEALTH, EDUCATION'AND WELFARE (23 Aug 74) 1. (Paragraph 2,3,11 HEW l.tr) See Part II.E. for drum cleaning/ disposal. "* "'. 2. (Paragraph 2,3 HEW Ltr) An operations plan will be prepared for all handling, transfer and shipments of Orange which are accomplished in support of the incineration project. This plan will stress personnel and environmental safety and include contingency planning for accidents. • 3. (Paragraph 4 HEW Ltr) See Part V, Return to Manufacturers, Fractionation, and Chlorinolysis for information on these alternatives. 4. (Paragraph 5 HEW Ltr) The Vulcanus incinerators utilize a vortex circulation to increase the path of combustibles through the incinerator and to minimize the potential for the creation of cold spots. In addition, temperature is measured at different locations in the incinerator. The Air Force will specify contractually for the minimum temperature within the incinerator. Temperature is very Important as regards dioxin destruction and is in fact the reason for the high temperature to be specified in the contract (minimum of 1400°C for the Vulcanus). The Orange herbicide combusted in the Marquardt test burn had a high dioxin concentration (-13 mg/kg) compared to the total Orange stock (Part II.F.). No evidence of pyrolytic synthesis was noted in the Marquardt test, see Appendix E. 5. (Paragraph 6,7,8,10 HEW Ltr) The Air Force position is that the environmental impact of the incineration of Orange herbicide can be adequately assessed without further test burns and without monitoring for the proposed action of incineration at sea, see the Air Force response to comments from the EPA, the Marquardt Company, and the Center for Law and Social Policy. 6. (Paragraph 13 HEW Ltr) The Air Force feels that for this project Incineration at sea is the more environmentally safe Orange destruction action. Although it is felt that the principal alternative of incineration on Johnston Island can be accomplished in an environmentally safe manner, the potential for damage to the reef and bird communities of the delicate ecosystem of Johnston Atoll warrants concern for any incineration operations on the island. This view is shared in some of the letters of comment to the RDES; see comments from the state of Hawaii and the Center for Law and Social Policy. It is noted that the comments from the State of Hawaii reveal that they are concerned with the negative aspects involved in establishing an incinerator system on Johnston Island; namely, that it could be used for other waste materials in the future. '. • • * NOTE: Paragraph 9, HEW Ltr is lot within the scope of this environmental statement and paragraph 12 is a restatement of previous paragraphs. 0-15 �(This page intentionally left blank) �DEPARTMENT OF HEALTH, EDUCATION. AND WELFARE OFFICE OF THE SECRETARY WASHINGTON, D.C. SEP 20ZOI . ' 4 1974 Dr. Billy E. Welch Special Assistant for Environmental Quality Department of the Air Force Washington, D. C. 20330 Dear Dr. Welch: This is an addendum to my letter of August 23, 1974 transmitting this Department's comments on the djraft Environmental Impact Statement for the "Disposition of Orange Herbicide by Incineration." We wish to point out the need for clarifying the fact that Orange, as the n-butyl ester (1:1) 2,4-D and 2,4,5-T is not the same chemically as the commercially available herbicide 2,4-D and 2,4,5-T. The environmental impact statement refers to the later and does not indicate the distinction between the physical properties of this chemical and those of Orange. The anticipated toxicity, stability and other characteristics of Orange are somewhat different, the esters arc harder to handle and it does not degrade as easy. Also, we note that, the draft statement fails to address the potential for water pollution and the effects of the impact on the marine physical and biological environment from hydrochloric acid and other by-product emissions resulting from the incineration process. Sincerely, Charles Custard Director Office of Environmental Affairs 0-17 �RESPONSE TO COMMENTS FROM THE DEPARTMENT CF HEALTH, EDUCATION AND WELFARE (4 Sep 74) 1. (Paragraph 2, HEW Ltr) Every effort was made to accurately portray the description and characteristics of Orange herbicide, see Part I.A.I, and Part II.F. Part II.F. includes the procurement, specifications, the results of analytical^analyses for TCDD, and a table citing the general physical/ chemical properties of the herbicide. The rather large number of individuals who have had inputs to the statement, may have inadvertently contributed to this situation, i.e., lack of distinction between "commercially available herbicide 2,4-D and 2,4,5-T" anc Orange herbicide. Any such lack of distinction between Orange herbicide ard any other pesticide formulations described/referenced in the statement is certainly unintentional. The statement, "Orange herbicide is not a registered herbicide and cannot be used or sold" appears in Part I.C.3. and Part V.C.I. It is noted that Transvall, Inc., Jacksonville, Arkansas advertises for sale a herbicde called Brush-Rhap® which is registered uder EPA Registration No. 11687-11 and which contains 29.0% butyl ester of 2,4-D, 28.2% butyl ester of 2,4,5-T, and 42.8% inert ingredients. In addition, the Pesticide Handbook Entoma, 24th Edition, College Science Publishers, State College, PA (1972) lists a compound called Woodkill manufactured by the Chemical Co,Division of Techne Corp. St. Joseph Mo, as containing 42.67% butyl ester of 2,4-D and 42.20% butyl ester of 2.,4,5-T and registered under EPA #449-28. Another product, Line Rider® 22 (EPA #677-95-AA) manufactured by the Diamond Shamrock Co. contains 28% butyl ester of 2,4-D and 27% butyl ester of 2,4,5-T. 2. (Paragraph 3, HEW Ltr) The environmental impact of hydrogen chloride and other by-product emissions resulting from the incineration process is addressed in Part III. C--8 �United States Department of the Interior OFFICE Or TIFE SECRETARY WASHINGTON*, E.G. 20210 In reply Refer To: FSF/EA <ER 74/648) - JUL Dear Dr. Welch: This is in response to your request of May 9, 1974, for review and comments on the proposed Disposition of Orange Herbicide by Incineration, Johnston Island, Pacific Ocean. Deep well disposal should be avoided. Development of fissures from seismic vibrations could permit migration of the herbicide to ground water. Th3 plan, as outlined, for the incineration of Orange Herbicide on Johnston Island or at sea in this general area appears to be an acceptable mode of disposal of this material. Maintenance of high performance by the incinerators and constant monitoring of effluents will be required to minimize environmental impacts. We are concerned also about disposal of the drums. We suggest that the final statement specify the landfill site to be used, if this is to be the method of disposal, and that there be a discussion of potential leaching of herbicide remnants and resulting environmental impacts. Sincerely yours, Ify—Si < £ep(lXf AaaiBtaut Secretary of the Interior Dr. Billy E. Welch Special Assistant for Environmental Quality Office of the Assistant Secretary Department of the Air Force Washington, D.C. 20330 0-19 �RESPONSE TO COMMENTS FROM THE DEPARTMENT OF THE INTERIOR LETTER (9 Jul 74) 1. (Paragraph 2 Dol Ltr) Deep well injection is not considered as a viable means of Orange disposal, Part V.D. i 2. (Paragraph 3 Dol Ltr) See the Air Force response to the letter of comment from the Center for Law and Social Policy relative to monitoring. 3. (Paragraph 4 Dol Ltr) Sse Part II.E. for drum disposal information. 0-20 �DEPARTMENT OF TRANSPORTATION MAILING ADDRESS. UNITED STATES COAST GUARD £%^™,^WS/73) WASHINGTON. D.C. 30590 PHONE /202) 426 _2262 JUN l 3 1974 •Dr. Billy E. Welch Special Assistant for Environmental Quality Office of the Assistant Secretary Department of the Air Force Washington, D. C. 20330 Dear Dr. Welch: This is in response to your letter of 9 May L974 addressed to the Coast Guard, Office of Marine Environment and Systems, concerning the revised draft environmental impact statement on the Disposition of Orange Herbicide by Incineration. .• The Department of Transportation has reviewed the draft statement. The Coast Guard commented as follows: "The VULCANUS has never demonstrated a 99.9% combustion efficiency for incineration of chlorinated hydrocarbons as indicated on page 16 of subject environmental impact statement. It appears that the agents for the VULCANUS have assumed that the 99.9% combustion efficiency achieved with chlorinated hydrocarbons on another incineration-vessel, the MATHIAS I, also applies to their vessel. "The Test Facility Schematic on E-7 of subject EIS is not legible even under high magnification. "It appears safe to conclude that there will be no adverse effect caused by the incineration of Orange Herbicide in a remote area of the Pacific. " The Department of Transportation has no further comments to offer nor do we have any objection to this statement. However, the concern of the Coast Guard should be addressed in the final environmental impact statement. The opportunity to review this draft statement is-appreciated. R.I. PRICE • . Clii ; , < " • • . . - - • •• 0-21 wd Systems �RESPONSE TO COMMENTS FROM T>E DEPARTMENT OF TRANSPORTATION (13 Jim 74) 1. (Paragraph 3 DoT Ltr) The comments on the incineration efficiencies of the Vulcanus are correct. However, information on the incineration of chlorinated hydrocarbons'aboard the Vulcanus has been received since the revised draft environmental statement was written. This information is summarized under "hydrocarbons" in Part II.B.2. and presented in Appendix M. 2. (Paragraph 4 DoT Ltr) Although the schematic used for the revised draft environmental statement was legible, clarity was lost, in the printing process. An effort was made to improve the clarity of the schematic in the final environmental statement. 0-22 �UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON. D.C. 20460 JUL 118/4 OFFICE 0- THE. ADMINISTRATOR Dr. Billy E. Welch Special Assistant for Environmental Quality Office of the Assistant Secretary (Installations and Logistics) Department of the Air Force Washington, D.C. 20330 Dear Dr. Welch: The Environmental Protection Agency has completed its review of the revised draft environmental impact statement (EIS) for the proposed Dispositioii^of Orange Herbicide by Incineration dated April 1974. The proposed action surfaces major concerns that need to be documented more fully in the environmental statement. t. Four important aspects of this proposed action were not discussed in sufficient detail in this draft EIS: incineration, drum disposal, handling safety, and other alternatives. They should be discussed thoroughly in the final EIS. EPA's concerns with these fours aspects of the proposed action are described in the attached comments. In light of our review of this revised dra::t statement and in accordance with EPA procedure, we classified the project as "LO" (Lack of Objections) a:nd rated ~he draft statement as "Category 2" (Insufficient Information) . We would be pleased to discuss our classification or comments with you or members of your staff. Sincerely yours, Sheldon Meyers Director Office of Federal Activities Enclosure 0-23 �Introduction The Environmental Protection Agency has reviewed the revised draft environmental impact statement prepared by the Department of the Air Force for the disposition of Orange herbicide by incineration. The proposed action is the incineration of approximately 2.3 million gallons of Orange herbicide in a remote area near or on Johnston Island in the Pacific Ocean. Our comments on this administrative action follow. Incineration f There is no test data on the Vulcanus incinerator. Extrapolation of the Marquardt data to the Vulcanus incinerator operation is not possible because burner design and destruction concepts differ appreciably from the Marquardt process. For example, the: high decree of turbulent mixing which allows short dwell times in the Marquardt process may not be achieved by the Vulcanus incinerator. Theoretically, the Vulcanus incinerator should be able to destruct Orange herbicide and dioxin based on temperatures and reported (but unconfirmed) dwell time. To prove this theory, testing should be conducted to determine concentrations o : breadown products, : unburned Orange herbicide esters, and dioxin. Sampling during a very extensive test for particulate was not done isokinetically, thus invalidating the emission data presented (Table D-3) on page E(D-21). Drum Cleaning (Part II.E.) U.S. Environmental Protection Agency, "Regulations for Acceptance and Recommended Procedures for Disposal and Storage of Pesticides and Pesticide Containers," (40 CFR Part 165, Federal Register, May 1, 1974) are mandatory to Federal agencies for purposes of 0-24 �2. implementing E.O. 11752. Part 165.9(b) specifies triple rinsing or 'incineration or specially designated land fill for containers which formerly contained organic pesticides. The environmental statement does not contain a firm commitment to this level of treatment. The implication (page 23) that unrinsed containers will be disposed of at sea is in violation of 40 CFR 165.7. The preferred disposal, in our opinion, would be smelting as scrap metal or salvaging for further shipping uses. Disposal by landfill is the least acceptable alternative. If disposal by landfill is the alternative selected, the landfill site should be located such that there is not a chance of runoff into surface or subsurface waterways. The ultimate disposal of container drums should be specified. Transportation and Handling Safety (Appendix I) Transfer operations to and from the rail car and to and from the ship are the most hazardous. Consideration might be given to "containerization" or drums with flat car shipment and, perhaps, containerized loading to avoid individual spill opportunities. The physical movement of 860,000 gallons of orange from its present location at the Naval Construction Battalion Center, Gulfport, Mississippi to Johnston Island is potentially a serious threat to the environment, and the draft statement does not give sufficient information on movement details, such as mode of transportation, off-loading, storage at disposal site, spill containment, decontamination,, etc. We recommend the following: (1) careful observance of Department of Transportation safety requirements in the transport of hazardous materials, (2) spelling out of specific modes and routes of transportation so as to plan for any contingency that might occur, (3) separate and individual contingency plans covering such items as immediate field detoxification, health and safety considerations of personnel who might be involved in cleanup, (4) a. firm written commitment from the transportation contractor that containment equipment is located and available to the contractor during transportation, and (5) predesignation of the onscene coordinator prior to any shipment. Off-loading areas should be equipped with materials and equipment which should be checked thoroughly before 0-25 �3, the commencement of each loading or unloading in order to assure safe and dependable operation. Furthermore, responsible persons engaged in off-loading should be given complete instructions in cleanup techniques along with instructions on how to proceed in case of a spill. While shipment by water is cheaper than land and there has never been a spill during water transport, it might be recognized that material spilled in a waterway would be distributed by the current. A land spill could be much more easily contained. If shipment is made by rail or truck, cleanup teams and equipment should accompany the transport vehicles. In the matter, of storage, whether in bulk or in drums, only those areas especially designed for storage of hazardous materials should be used. Such areas should provide (1) structures to prevent surface water runoff from entering the area, (2) pavesment "and gutters to collect surface water runoff within the area, (3) drains to channel contaminated runoff to a holding facility, (4) materials and equipment necessary for rapid cleanup of spills, and (5) fencing to control admission to the areas. In addition, storage areas should be located remotely from occupied dwellings. Alternatives We must take exception to ths statements (page 119) that technology is not currently sufficient to permit the disposal of Orange herbicide by either chlorinolysis or fractionation. Not only are both methods entirely feasible technologically, but they may also offer the most practical means of disposition from the standpoints of economics and resource recovery. These means of disposal deserve much greater .consideration than is evident in the EIS. 0-26 �RESPONSE TO COMMENTS FROM THE ENVIRONMENTAL PROTECTION AGENCY LETTER (11 JULY 1974) - ' : ' • ' : ' • • . ' 1. INCINERATION: The following is to provide information on the background and,,purpose of the Marquardt Company test burn of Orange herbicide, see also Part II.C.I. and the Air Force response to the Marquardt Company comments. a. The Air Force investigated the feasibility of conducting anOrange herbicide test burn at the Rollins Environmental Services industrial waste disposal facilities in New Jersey, Louisiana, and Texas. The Texas site was never considered feasible for a variety of reasons including regulatory agency approval and the potential environmental impact. In addition, the incinerator system was programmed for extensive modification which did not meet the time frame of the disposal project. The Louisiana site, although a candidate for the large scale disposal of Orange, was also programmed for modifications which prohibited it from meeting the test burn schedule. A detailed test burn protocol, including an operational and ecological monitoring program, was prepared for a test burn of Orange herbicide (230 drums) at the New Jersey site. The New Jersey site was undergoing modifications which were acceptable to the test burn schedule. The test burn protocol was presented to representatives of Region II EPA and representatives of the New Jersey Bureau of Air Pollution Control on 4 May 1973. The test burn was tentatively scheduled for Jul 73; however, the following situation developed: comments were not received from the EPA concerning the test burn protocol, the Rollins Environmental Services took longer than anticipated to accomplish the modifications and obtain regulatory agency approval, and the Chairman of the Louisiana Governor's Council on Environmental Quality advised the Air Force that the large scale incineration of Orange in Louisiana would not be welcomed. In addition, an ecological study including aerial infrared photography of the New Jersey site conducted by the Air Force revealed that crops in very close proximity to the incinerator were a species that are very sensitive to chlorophenoxy herbicides; thus, incinerator tests during the growing season involved a possibility for crop damage.- The plan for this test burn was, therefore, not concluded and the chance of accomplishing a large scale test burn and subsequent disposal of the entire Orange stock in a conventional commercial incinerator within the U.S.. was judged to be very remote. After careful consideration, the Marquardt Company was chosen to conduct a test burn with.the SUE** system, see Part II.C.I. for the rationale leading to this selection, the test burn was conducted under Los Angeles Air Pollution Control District Authority to Contract Number A77791. The Marquardt Company test burn was accomplished to obtain data concerning the incineration of Orange under specified incinerator operating conditions to determine contractural specifications to be levied upon any contractor - and not specifically to determine the suitability of the Marquardt system for the large scale disposal of Orange. b. The Air Force approach to the destruction of Orange via incineration has been to obtain, combustion data and incinerator operating conditions which may be applied to a contractor as contract specifications. In this sense, the extrapolation involves a judgment on combustion efficiency for a given incinerator at prescribed incinerator operating conditions rather than an extrapolation of data in a purely technical nature. It is the Air Force position that sufficient data is available on incineration of Orange so that a judgment can be made on the 0-27 �efficiency of treatment to be expected under specified incinerator operating conditions. This data includes five studies concerned with the combustion of Orange 'Appendix D and E) and the data on incineration by incinerator ships and at the Rocky Mountain Arsenal, see paragraph c. below. It is emphasized that while the relative pyrolysis efficiencies of the Marquardt test burn ranged from 98.98 percent to 99.999 percent, the efficiency of the Vulcanus for environmental impact analyses was selected at 99.9 percent in the RDES. In tiie final environmental statement, the analyses were also shown for 99.0 percent and 95.0 percent with the conclusion that even these efficiencies may be deemed environmentally acceptable for a 22-26 day period over the open tropical sea (Part III.B.2. and Part III.C.5.). The 95 percent destruction would not be acceptable to the Air Force; however, it is the Air Force position that an efficiency approaching 99.9 percent can be attained, see paragraph c. below. c. Since the RDES was published, the Air Force has received information concerning the efficiency of incineration of chlorinated hydrocarbons aboard the Mathias and Vulcanus incinerator ships and on the ecological aspects of incineration at sea (North Sea). This information is included in Appendix N and is summarized in Part III.B. and C. This information, while not on Orange herbicide incineration, attests to the high efficiency attained in chlorinated hydrocarbon incineration (99.9 psrcent) and to the rrinimal environmental impact of the incinerator emissions. In addition, essentially complete destruction (>99.9 percent) of mustard agent, a material with similar physical/chemical properties as Orange, is accomplished by incineration at RockyMountain Arsenal, see Part V.A.2. d. The stay time for the Vulcanus incinerator has been recalculated due to receipt of more detailed information from Ocean Combustion Service and is reported in Part II.C.2. as approximately 0.6 seconds instead of the original 0.25 seconds. e. In view of the above, it is the Air Force position that sufficient information is available to adequately assess the environmental impact of the Orange disposal via incineration and that further test programs are not required. f. The participate sampling was done according to established procedures for isokinetic sampling. The results showed that isokinetic conditions were rot always maintained. This problem is discussed in detail on page E(D-22). 2. DRUM CLEANING * a. See Part II.F. for drum cleaning information. b. This response below is in reference to the following quote from the EPA letter: "U.S. Environmental Protection Agency, 'Regulations for Acceptance and Recommended Procedures for Disposal and Storage of Pesticides and Pesticide Containers,1 (40 CFR Part 165, Federal Register, May 1, 1974) e.re mandatory to Federal agencies for purposes of implementing E.O. 11752." (Emphasis added). 0-28 �(1) Executive Order 11752, 38 FR 34793, dated 19 December 1973, states that it is the responsibility of heads of Federal agencies to "ensure that applicable standards specified in section 4 of the order are met on a continuing basis" (E.G. at Section 3). Section 4 (a) (7) states that "Heads of Federal Agencies shall insure that their facilities conform to requirements of Federal regulations and guidelines respecting manufacture, transportation, purchase, use, storage and disposal of pesticides promulgated pursuant to the provisions of the Federal Insecticide, Fungicide and Rodenticide Act, as amended by the Federal Environmental Pesticide Control Act of 1972." (FIFRA and FEPCA). EPA issued the above-cited "Regulations and Recommended Procedures" on May 1, 1974. The "Regulations" governing acceptance by EPA of compounds whose registration is cancelled are mandatory and minimize EPA's responsibilities. However, the recommended procedures, Title 40 FR §165 et. seq., are another matter. Note the language employed: - "recommended procedures" in Title 40 FR .!5165.2(c) and §165.8 and "procedures not recommended" in 165.7. Section 165.8 generally states as the standard for agencies to follow, that pesticides " . . . should be disposed of according to the following procedures ..." (Emphasis added). This language seems to present the procedures for disposal of pesticides as worthy of notice or to attract favorable attention to them. The only "mandatory" reference in the recommended procedures is found at Title 40 FR §165.2(c) which states "These disposal procedures are mandatory only for the Agency in carrying out its pesticide and container disposal operations."TEmphasis added). EPA has, under the Executive Order 11752, authority to establish mandatory guidelines for Federal agencies, but it has chosen not to exercise that authority at this time. The EPA administrator's comments in FR, Vol. 39, No. 85 - Wednesday, May 1, 1974, at page 15237 explains why this choice was made: " . . . adequate disposal sites and tie necessary facilities are not readily available nationwide, and significant information gaps exist which make it infeasible to write specific criteria for certain disposal methods and procedures. Further, information on the full extent of environmental damages and of the economic impact of such regulations is lacking. Therefore, the Agency has retained the recommended procedures approach. At such time as this information has been obtained and analyzed, consideration will be given to proposing comprehensive regulations relative to storage and disposal." (2) Since EPA, apparently for sound practical reasons, has not yet chosen to exercise its authority under E.O. 11752, it is our opinion that the recommendatory language of the recommended procedures do not, and were not intended to, establish a Federal regulation or guideline. (3) Without specific standards binding the agencies, they may use their sound discretion and judgment, within the scope of applicable statutes, in determining the best means of disposing of pesticides. 3. TRANSPORTATION AND HANDLING SAFETY: An Operations Plan will be prepared for handling, transfer, and shipments of Orange which are accomplished in support of the incineration project. This plan will include personnel and environmental safety procedures and describe the monitoring to be accomplished during these operations (see Appendix I. and Part I I.E.). 0-29 �4. ALTERNATIVES: See Part V.I. and V.J. for information on chlorinolysis and fractionation. 0-30 �.£/'. ' 0 7 » ,\',\ JOHN A BURNS RICHARD E. MARLAND. Pn.O ' VIVA'_•.•>!.-on TELEPHONE NO 5486915 STATE OF HAWAII ' " '' OFFICE OF ENVIRONMENTAL QUALITY CONTROL OFFICE OF THE GOVERNOR SOJ'-M LI-'. .•'../I 3F July 9, 1974 Billy E. Welch, Ph.b Special Assistant : o Environmental Quality :r Department of Air Force Office of the Assistant Secretary Washington, D.C. 20330 SUBJECT: Disposition of Orange Herbicide by Incineration Dear Dr. Welch, [] ] As of this date, this Office has received two comments on the subject project. An attached sheet lis'-s the responding agencies. We hope that these comments are helpf\il to you. We also thank you for giving this Office an opportunity to review the draft environmental statement, particularly in view of the deadline extension you granted. Although this Office finds the draft environmental statement adequate in most areas, we offer the following comments: [2] Option I (Incineration at sea) • 1. Although burning Orange Herbicide at sea away'from civilization and marine life may not have any harmful effect, air pollution still exists as an environmental problem. We should be concerned with limiting the problem of air pollution through the use of a scrubber system with constant monitoring of air emissions throughout the process of incineration instead of an uncontrolled burning operation. Thus, the conclusion in the draft environmental statement that monitoring is unnecessary (p. 64) should be reconsidered. One must not conclude that the environmental impact of air pollution in a populated area is in any way different from the impact in desolate surrounding. 2. A scrubber system in the gas effluent stack would minimize the pollutants in the air. A monitoring system would be able to keep an accurate account of the emissions and any unanticipated high level readings from the stack during the burning of Orange Herbicide. 0-31 �Page 2 3. There is little mention of the exhaust from the fuels for the burners. Would the exhaust react with the products emitted from the incineration? [3] Option II For incineration at Johnson Island (Option II), there is'one area of great concern. One of the waste effluents without the scrubber in the stack is HCl gas (about 18.5 tons daily or 25 ppmv/v). If HCl gas comes in contact with moisture, it converts into hydrochloric acid. Since the relative mean humidity is 75%,. the HCl gas could possibly convert to HCl acid. Thus, the offshore waters and the surrounding areas would be contaminated. Marine life may be harmed by the change in pH of the ocean or the acidic aerobic state. Any metal equipment nearby may be damaged by corrosion. Rain is another factor that must be considered since acid-rain may result. One feasible idea that was briefly mentioned but should be. considered in more detail is photodecomposition. Photodecomposition has the advantage of being economical, non-polluting to the air, and recyclable to useful chemicals. Although it is stated on page 84 that 2,3,7,8-tetrachlorodibenzo-p-dioxin is neglible in aqueous suspensions and wet and dry soil, another solvent can be used, like alcohol, where photodecomposition does occur. The Environmental Center at the University of Hawaii has a major criticism. It is felt that there is insufficient data on the ecology of terrestrial and aquatic biota of Johnson Atoll. Appendix A needs to be expanded to include data describing the species present, their geographical distribution and density, and behavioral characteristics. Although there are detailed data of physical and technological information, the biological aspects are almost ignored. Thus, on that basis the Environmental Center recommends the shipboard alternative for disposition of the Orange Herbicide. [4] We hope that the final statement will be available for our review, and that it will address the comments presented here. t [5] Thank you very much for the opportunity to review your environmental statement. lard E.. Mar land Interim Director Attachment 0-32 �LIST OF RESPONDING AGENCIES State •> 1. Department of Planning & Economical Development (June 19, 1974) 2. Environmental Center 0-33 (July 3, 1974) �j JOHN A BURNS Governor . • ,';,i DEPARTMENT OF PLANNING ' AND ECONOMIC DEVELOPMENT SHELLEY M. fVARK D 'cclor £ EDWARD J.GREANEY. JR. Dei" ' • Oi odor 250 South King St. / Honolulu, Hawaii 96813 / P. 0. Box 2359 / Honolulu. Hawaii 96804 June 19, 1974 Ref. No. 1057 I-IF.I-'QRANDUM TO: Dr. Richard E. Mariano, Interim Dirc/ctcr Office of Environmental Quality Control tfROM: SUUJECT: Review of Revised Draft Environmental Statement for Disposition of Orange Herbicide by Incineration We have reviewed the above subject draft. It appears to be a very detailed and conscientious appraisal of the environmental impacts which may be expected. However, since the subject matter is of a very scientific nature and may be of direct concern to the State of Hawaii due to our geographical position, it is recommended that detailed comments be sought from other State agencies that have the necessary expertise to adequately evaluate this proposal. 0-3* �University of Hawaii at Manoa \ Environmental Center Maile Bids. ™ • 2540 Maile Way Honolulu, Hawaii 96822 Telephone (80S) 948-7361 Office of the Director July 3, 1974 MEMORANDUM TO: ' ' . Richard Marland " FROM: • Jerry M. Johnson, Acting Director SUBJECT: Revised Draft Environmental Impact Statement for Disposition of Orange Herbicide by Incineration, April 1974 [1] I have reviewed the subject EIS and have the following comments to offer. [2] I find the statement to be adequate in most aspects. In fact I believe the Department of the Air Force, except for the one major exception delineated below, should be commended for the overall quality of the document. [3] My only major criticism is that insufficient data are provided on the ecology of terrestrial and aquatic biota of Johnston Atoll. Appendix A is a very brief and unsatisfactory summarization of what appears to be a comprehensive baseline ecological survey of the biota of concern. Without data describing the species present, their geographical distribution and density and their major behavioral, characteristics, the reviewer is able to neither assess the significance of the individual species and their communities nor the possible impact on them of the on- land incineration alternatives. I can understand the reluctance of the U.S.-, Department of the Air Force to reproduce the entire document summarized in Appendix A for each copy of the final draft EIS. -However, it is impossible for the reviewer to obtain a copy of the document from the Department of the Air Force, if at all, within the time constraints placed on the review process ." I boliovo the originating agency cou]cl hnvo 0-35 �Richard Marland 2 July 3, 1974 jt done a much better job of summarizing. The Department went to great detail and cost in presenting other cispects (Appendices D, E and K). Thus I find the almost complete lack of biological data somewhat of an enigma. This lack appears to be a cavalier disregard for the biological aspects and a somewhat enthusiastic and overriding concern for the physical and technological considerations . [4] On the basis of the data provided in the Final Draft, I can only recommend the shipboard alternative as a reasonable mode jcor orange herbicide disposal. I foresee the deleterious consequences of this alternative as being minimal. Furthermore, the ship could possibly be used for future disposal of chemicals as wc.M. If a permanent incineration structure were placed on the Island, a tremendous economic pressure would be created for disposal thereon of future military wastes and mistakes. It is not only the incinerator effluents that would be of concern on land. The stresses created on the biota by the logistical aspects alone could be serious. 0-36 �x°.v >.^ JOHNA BURNS ?S' "'"^\'\ RICHARD E MARLAND. Pll D TELEPHONE NO 548-6915 STATE OF HAWAII OFFICE OF ENVIRONMENTAL QUALITY CONTROL OFFICE OF THE GOVERNOR loCI'ALlK.-V .ML- yi noov3d -ONC- -Hi • f-fi" K"-1 July 11, 1974 Billy E. Welch, Ph.D. Special Assistant for Environmental Quality Department of the Air Force SAG/ILE Office of the Assistant Secretary Washington, D.C. 20330 SUBJECT: • Draft Environmental Statement on Disposition of Orange Herbicide By Incineration Dear Dr. Welch, This Office had received an additional comment from Dr. John L. T. Waugh, Chemistry Department at the University of Hawaii on the subject above. We are forwarding the comment to you in order for it to be reviewed. Please append it to our correspondence dated July 9, 1974. We hope that this has not been a great inconvenience to you. Thank you for your cooperation in this matter. Sincerely, Richard E. Marland Interim Director Attachment 0-37 �• To: • 1st July, 1974. Dr. Jerry M. Johnson, Environmental Center. Prom: " John L.T. Waugh, Chemistry Department. Air Force Proposal on p RANG 3 Herbicide Disposal ThJo is a iong-chy and annoying report, which illustrates in, many places, the •ir.i... Lculoua wjifj Lawfulness, C'.IQ enor.viou;j expense, the uncontrolled planning, the I ::ii~i v.ovi i.-.hii'.kv.ny, and the casual disregard for areas remote from Washington, u.-jt.:oci.atod with Defense Department operations. It io pointed out on the inoiiio i>,~ ,-.;,r cover of this sjevcraX-huncircd-fDaga report that it is economically prir..uod paper, although the subject matter involves the single-minded topic i.ig an accumulation of 2.3 million gallons of herbicide, on which i.jo.iror.tly millions of dollars have already been spont on shipping it back and i'o.'cli around the world, storing and re -drumming, apart from the initial iVianufacturing cost. It is most difficult to believe that one or more of the sever, manufacturers .of this . material could not devise a method of converting v_iio ORANGE herbicide into useful industrial chemicals such as carbon tetrachloride, ciiroor.yl chloride, hydrogen chloride, and chlorine, for a fraction of the cost already involved for shipping and storage, and in a fraction of the 3-year period which has now elapsed since the Department of Defense shopped using this r.-.c-cerial in Vietnam. Why should one or more of the original manufacturers nor pu-c soir.e research effort into developing the necessary technology at whatever capi.c«ii expense is necessary, rather than compounding the problem by erecting i.:ac:i.ii cics simply for the destruction of this massive amount o:: material, at ci site which is only 717 miles southwest of Hawaii? v.-,e above question is based on the assumption that the sea-going incineration .jl«n, even aboard a special ship such as the VULCANUS, will hopefully be abandoned; the lack of abilty of any person, technical department, or governmental ;.^o.-.cy of any country, to accurately forecast ocean and climatilc conditions c.«.'Lnc, die period of injecting many thousands of tons of hydrogen chloride, carbon monoxide and ..dioxide, particulate carbon, into the environment during 'che *.~.c iteration of such large amounts of material, especially under conditions w/iere access to technical advice, control, monitoring, is remote, would appear this mode of destruction a very risky and ill-advised venture.' At least, in a land-based operation, a reasonable degree of ccntrol can be excercised and vi.-.c /.umber of possibly indeterminate hazards greatly reduced. Since the herbicide i& apparently all contained in 55-gailon drums, the emptying, decontamination, and cisposal of these 40, OCO-odd drums alone is a major problem. Incidentally, •che XAROUARDT COMPANY report, appears to be the only part of this whole document wi-.j-oh gives some detailed consideration to this aspect of the overall disposal ^roblem. 1 c would seem reasoncbly sensible to suggest that instead of shipping the 0.86 ;.. . 1 . Ion gallons of herbicide from GulCport, Mississippi, to Johnson Island, ..i'. i.,ie estimated cost of $450,000, constructing incineration 'facilities tlvro, •LI.',,.OI.I> Jjroi.i the tcchi-iical and manufuccurin<) cc-nl-.re.'i in the country, that Dow, i, i venue;;, or one of the other 5 orj.yinui jiit«i,uJ"acturou OL: the OiiANGI1: hernicioo,, :-..,.o,,",^ be contracted to utilize, further develop if necessary, their present ccc/.nolgy, with a view to recovering the chlorine content of these 2,300,000 gallons v- ." .'ir. Loriul in soiVio industrially u:.<.'fal form. 0-38 �JOHN A. DURNS £/ !**>•&,_ niCHAnD E MARIANO, PH.D. TELEPHONE NO. 543-6915 STATE OF HAVVAII OFFICE OF ENVIRONMENTAL QUALITY CONTROL OFFICE OF fHE GOVERNOR 550 I I'M iVAUWILA ST HOOM 301 M/..V.MI %<ii.l July 15, 1974 Dr. Billy E. Welch Special Assistant for Environmental Quality Department of Air Force SAG/ILE Office of the Assistant Secretary Washington, D.C. 20330 SUBJECT: Draft Environmental Statement on Disposition of Orange Herbicide by Incineration Dear Dr. Welch, This Office has received an additional late comment from the Department of Agriculture (State of Hawaii) dated July 10, 1974 on the above subject. We are forwarding the comment in hopes that it may be reviewed even at this late date. Please append it to our correspondence dated July 9, 1974. We apologize for the inconvenience created by this comment We look forward to the final environmental statement. Thank you for your cooperation in this matter. Sincerely, Richard E. Marland Interim Director Attachment �\S\V JOHN A. BURNS GOVERNOR. 7/// X ^ i ^ ^ W FREDERICK C. ERSKINE CHAIRMAN. BOARD OF AGRICULTURE WILLIAM E. FERNANDES DEPUTY TO THE CHAIRMAN 8TATB OF HAWAII DEfaARTMENT OF AGRICULTURE i«ae so KINC 6TREE" HONOLULU. HAWAII July 10, 1974- MEMORANDUM TO: Dr. Richard E. Marland, Interim Director Office off Environmental Quality Control SUBJECT: Draft Environmental Impact Statement Incineration of Orange Herbicide Department of the Air Force - Johnston Island This draft environmental impact statement addresses concerns relating to disposal of Orange herbicide. Orange herbicide contains approximately equal parts by volume of the normal butyl ester of 2,4-dichlorophenoxyacetic (2,4-D) and the normal butylester of 2,4,5-trLchlorophenoxyacetic (2,4,5-T) acid. A small quantity, known as Orange H, contains the isooctyl ester of 2,4,5-T instead of the normal butylester. No direct agricultural impact is anticipated. llerbicidal formulations containing 2,4-D or 2,4,5-T are used for control oE plant pests in agricultural operations in Hawaii. In 1968 197,227 pounds oE 2,4-D arid 6,128 pounds of 2,4,5-T were used in sugar cane plant pest management. Other operations used about 1,400 pounds 2,4-D and 14,000 pounds 2,4,5-T. Control of plan;; pests in pastures depends upon the continued use of 2,4,5-T although this use is declining as better control is achieved. An impurity, 2,3,7,8-Tetrachlorodibonzo-p-dioxin (CGDD), in some lots of Orange Herbicide is teratogenic (malformed fetuses and living offspring) in experimental animals. For this reason military and certain other uses of 2,4,5-T ceased Ln 1970. There are approximately 860,000 gallons and 1,400,000 gallons in storage at Gulf Port, Mississippi and Johnston Island, Pacific Ocean, respectively. Controlled incineration at high temperature is recommended for disposal. Two alternative controlled incineration methods described are for either units mounted on a vessel designed specifically for disposal of toxic combustible wastes or located at a leeward site on Johnston Island. Regardless of the cliolro of ay A (:r>m, Johiinton Inland will bo tho si to Eor atom^o find hnncll. Ing .in |i/irt ol! the dl.upoiuil. uyHto.m. The environmental impact statement provides an adequate assessment of the technology of Orange herbicide incineration. Option 1, incineration at sea is 0-40 * �- 2prpferred. No significant detrimental environmental effects can be expecteru Crom this method of disposal. Analysis of risks from adoption of Option 2, incineration on Johnston Island, are less well defined. Use of coral rock or sea water scrubbers would create disposal problems. Direct atmospheric discharge of combustion products with due consideration of wind directions and velocities would be preferred. 15i.ologi.cnl monitoring was described. There arc seme concerns for the adequacy oE the monitoring protocol. Baseline sampling was limited to a few days in October 1973. Thfi choice of top predatory animals and the dominant plant (foral) spccips would appear to be adequate for monitoring. However, frequency of sampling, number of sample por site and species were inadequately described for evaluation. A detailed sampling protocol keyed to operational schedules is lacking. It is recommended that such a protocol be provided for review prior to any Johnston Island operations. Such a sampling protocol should be developed showing relation to shoreside handling and storage operations even though incineration at sea is practiced. Th.-mk you for the opportunity to review this document as it relates to our concerns. REDERICK C. ERSKINE Chairman, Board of Agriculture 0-41 / �RESPONSE TO COMMENTS FROM THE STATE OF HAWAII LETTERS (9,11 and 15 Jul 74) • .- * 1. (Paragraph 2-1 S of Hawaii 9 Jul 74 Ur) Installation of an acidic gas scrubber on the incinerator ship is not practical. Such a system would require considerable energy for operation. And unless a caustic scrubber was used (requires cargo space for alkaline chemical), the liquid discharge from the scrubber would result in focalized water pollution. The stack discharge of combustion gases into the atmosphere actually provides for dispersion of the material into the atmosphere rather than concentrating possible impurities into liquid scrubber discharges. The bulk of the incinerator discharges is non-persistent and non-reactive, or subject to photodecomposition and/or hydrolysis. The discharge of such material into a .desolate ecosystem for a short period of time should result in a negligible impact. The oosition that "air pollution" may occur during this period is appreciated; however, it is deemed acceptable since it has minimal impact on the ecosystem. 2. (Paragraph 2^-3 S of Hawaii 9 Jul 74 Ltr) No auxiliary fuel is used for the ''burners" during the incineration of Orange herbicide. However, auxiliary fuel is used to bring the incinerator to operating temoerature prior to injecting the herbicide which is capable of sustaining the necessary incineration temperature. 3. (Paragraph 2-2 S of Hawaii 9 Jul 74 Ltr) See the response to the letter of comment from the Center for Law and Social Policy relative to monitoring. 4. (Paragraph 3-1 S of Hawaii 9 Jul 74 Ltr) The Air Force does not presently plan to incinerate the Orange herbicide at Johnston Island. However, if the principal alternative of incineration on Johnston Island is initiated, the environmental impact upon the ocean adjacent to Johnston Island associated with the discharge of hydrogen chloride from an incinerator stack on Johnston Island is discussed in Part III.C.S.c., Reef Area. A "worst case" analyses revealed that any damage to the reef on an acute basi.s would be minimal and that the long term chronic effects can not be predicted. Metero'logical constraints and ambient air nonitoring would be utilized to insure that hydrogen chloride would not adversely affect personnel, structures, or the environment. Information or the reaction of hydrogen chloride in air and effects on structures is included in Part III B.2.c. 5. (Paragraph 3-2 S of Hawaii 9 Jul 74 Ltr) Sufficient data is not available to appraise the removal of TCDD from Orange via photodecomposition. 6. (Paragraph 3-3 S of Hawaii 9 Jul 74 Ltr) As stated on the initial page of Appendix A, the document "Ecological Baseline Survey of Johnston Atoll Central Pacific Ocean" was not included for the sake of space conservation but was availabe by request from the USAF EHL, Kelly AFB, TX. It is interesting to note that only one request for Appendix A was received, and they were provided a copy. 7. (Paragraph 4 U of Hawaii, Manoa 3 Jul 74 Ltr) There are no present interests for establishment of a permanent incinerator on Johnston Island. In fact, the Air Force intends to incinerate at sea. 0-42 �8. (Paragraph 1 & 3, Atch to S of Hawaii, 11 Jul 74) Efforts to return the Orange herbicide to manufacturers for reprocessing have been explored and they are described in Part V. 9. (Paragraph 2, Atch to S of Hawaii, .11 Jul 74) "Worst Case" analyses are presented for decomposition compounds resulting from incineration at sea and at Johnston Island (Part II.B. and II.C.). The destruction of Orange herbicide in "land based" incinerators was also considered, but they were not viable alternatives for reasons presented in Part II.A., II.B. and V.A. 10. (Paragraph 2, Atch to S of Hawaii, 11 Ju'l 74) The section on drum cleaning and disposal.in the Marquardt Co. report was written by Air Force personnel. However, a new section on the disposal of drums has been included in the final environmental statement (Part II.E.). 11. (Paragraph 7 D of Agriculture, Hawaii 10 Jul 74 Ltr) The comments on biological sampling and concern for the adequacy of sampling protocol are appreciated, it is realized that the data from samples collected in Oct 1973 is somewhat meager. This data has been updated and is presented in Part III. C.I. A detailed protocol of sanpling, including biological sampling, would be implemented if any Orange herbicide is incinerated on Johnston Island. 0-43 �(This page intentionally left blank) �STATE OF MISS5ISSIPPI O F F I C E OF THE G O V E R N O R WILLIAM L. WALLER WM, M. HEADRICK GOVERNOR COORDINATOR OF FEDERAL-STATE PROGRAMS STATE CLEARINGHOUSE FOR FEDERAL PROGRAMS TO: Dr. Billy E. Welch, Special Assistant for Environmental Quality Office of the Assistant Secretary Department of the Air Force Washington, D. C. 20330 State Clearinghouse Number 74051501 Date: May 15 1974 ' PROJECT DESCRIPTION: Draft Environmental Statement -- Disposition of Orange Herbicide by Incineration -- Revision of January 1972 Statement. (x ) 1. The State Clearinghouse has received notification of intent to apply for Federal assistance as described above. (x ) 2. The State Clearinghouse has reviewed the application(s) for Federal assistance described above. ( —) 3. After proper notification, no State agency has expressed an interest in conferring with the applicant(s) or commenting on the proposed project. 4. The proposed project is: ( ) consistent ( ) inconsistent with an applicable State plan for Mississippi. 5. Although there is no applicable State plan'for Mississippi, the proposed project appears to be: ( sistent ( ) inconsistent with present State goals and policies. ) con- COMMENTS: The attached comments represent the review of this project when disposition by incineration within the Continental United States was proposed. By conferring with all participants, these comments are validated for this statement. Each item in the summary letter of the Air and Water Pollution Control Commission applies whether incineration takes place' on this Continent or at sea. The urgency of moving this to a safer storage place is increased due to the passage of more than two years.. This notice constitutes FINAL STATE CLEARINGHOUSE REVIEW AND COMMENT. The requirements of Office of Management and Budget Circular No. A-95 have been met at the State level. Edward A? May, Jr. Assistant to the Coordj/dtor SUITE 4OO. WATKINS I3LDO. . SIO GEOROE STREET 0-45 « JACKSON 392OI • (OOI) 3B4-7S7O �STATE Of-' M I S S I S S I P P I iJTivt-! c i i A JACKSON W M LIAM LOWS WALLER February 11, 1972 Honorable Aaron J. Racusin Acting Assistant Secretary of the Air Force Installation and Logistics Office of the Secretary Department of tha Air Force Washington, D. C. 20330 Re: Draft Environmental Statement-Disposition of Orange Herbicide by Incineration January 1972--AF-US-72-2D Dear Mr. Racusin: In compliance with applicable regulations, the above captioned environmental statement has been reviewed by appropriate State agencies concerned with various aspects of the disposition. Co7.mier.ts from State agencies are summarized in the latter prepared by the Air aad Water Pollution Control Commission, and are enclosed herewith. It is my opinion that the attached environmental statement is satisfactory. I recommend that Eull consideration, be given to the comments of our -igcncics in the final, review. •?• Sincerely, BILL WALLER QOVERNOR 046 �S T A T E C L E A R I N G H O U S E \ ' 1 TOR F E D f. R ' A L * P R O G R A M S -T .• Federal-State Programs Office of the Governor 510 Lamar Life Bldg. 'Jackson, Mississippi 39201 Telephone 354-7570 State C].p.aringhou.--a No ' 72020901 Date: Fchr«ary 9, 1972 / Aaron J. Racuain Acting Assistant Secretary of the Air Force Installation and Logistics Office of the Secretary Department of the Air Force Washington, D. C. 2D330 PROJECT DESCRIPTION: Department of the Air Force Draft Environmental Statement -Disposition of Orange Herbicide by Incineration - January 1972 AF-ES-72-2D TO: (x ) 1. The State Clearinghouse has received notification of intent to apply for Federal assistance as described above. (—) 2. The State Clearinghouse has reviewed the application(s) for Federal assistance described above. ( -• ) 3. After proper notification, no State agency has expressed! an interest in conferring with, the applicant(s) or commenting on the. proposed project. ( " ) A. The proposed project is ( State Plan for Mississippi. (--) 5. ) consistent ( ) inconsistent with an applicable Although there is no applicable State Plan for Mississippi, the proposed projec' appears to be ( ) consistent ( ) inconsistent with present State goals and policies. COMMENTS: The summary of comments from all State agencies concerned is included in the attached letter from the Air and Water Pollution Control Commission. This completes the ; review. . '' This notice constitutes FINAL STATE CLEARINGHOUSE'REVIEW'AND COMMENT. The requirements of U.S. Office of Management and Budget Circular No. A-95 have been met at the State level. David R, Bowen Coordinator of Federal State Prcgrams 0-47 �Comaaasson Air & VV ttier Pollution S T A T E OF M I S S I S S I P P I COMMISSIONERS COMMISSIONERS GAME ft FISH COMMISSION DILLY JOE CROSS JAMcS W. CA'HKAWAY. CHAIRMAN BAS^FIELO BOARD OF WATER COMMISSIONERS JACK PEPPER STATE PLANT BOARD O. T. GUICE, JR.. VICE CHAIRMAN CHARLES W. ELSE YAZOO CITY OIL a CAS BOARD J. P. BOflTHWICK BOARD OF HEALTH JOE D. DROWN ASSOCIATE MEMBERS Glen Wood, Jr. MARINF. CONSERVATION COMMISSION W. J. DEMORAN STATE PARK SYSTEM SPENCER E. MEDLIM EXECUTIVE DIRECTOR POST OFFICE BOX 827 TELEPHONE 334-0783 A ft I BOARD PAUL BURT SIXTH FLOOR ROBERT E. LEE BUILDING W. E. GUPTO*J JACKSON GEOLOGICAL SURVEY W. H. MOORE JACKSON, MISSISSIPPI 30209 HERMIT A. JONES CANTON February 8, 1972 fir. Edward A. May, Jr. Assistant to the Coordinator Federal-State Programs Office of the Governor 510 Lamar Life Building Jackson, Mississippi v - * ii Vj '! : ^ -"• 'i •,.' iv1'"'... -v V ''•;'.-£ i'->.«-•" •''/A"''•-,„ 1 -• iv , 'j ';, v-*'''•'-'''-'*- ' ^ *!rt1' ' _. \ . — >"" •»,! -JT | I Dear Mr. May: This letter is in reference to yours of January 26, concerning the draft environmental impact statement entitled "Disposition of Orange Herbicide, by Incineration". A meeting was held in our office with concerned agencies of the State on February 3, to conduct a technical review of this statement and to coordinate the state's position in this matter. Copies of the impact statement had previously been forwarded to these agencies. The. consensus of this meeting is enumerated below: 1. Department of the A.J r Force should explore further possibilities for u ' ! of the material under adequate control s. measures, preferably by the federal government, as in national and state forests or by returning to commercial use through some acceptable channel. Apparently the alternative of giving this material away was not explored. It is felt th£.t destruction of the material would be a needless waste and would create further expense. It is recognized that such action as suggessted might require some emergency authority from Environmental Protection Agency but this should pose no great difficulty since a similar material is in everyday use. 0--48 t .. '* �[•lr. Edward A. May, Jr. February 8, 1972 Page 2 2. In the ovonl; incineration is taken as the alternative, it is requested that the federal, government nsuumc the responsibil i. ty for all trans poet: ion of the material to the point of incineration anJ. provide all necessary safety measures, such as, but not limited to, shipping materials in small quantities and providing the necessary absorbents at. the convenient locations it" shipped by rail. 3. It is requested that the material bo removed from its present location at Keesler Air Force Base beginning immediately and without regard to the Einal disposition of the material. It is felt this is absolutely essential because of the proximity of the material to recreational and shellfish waters, as well as large densely populated areas, and further because of the history of hurricanes and tornadoes in that particular section of the country. It is our feeling there are many other areas in the contine.nt.al United States which would provide a much safer depository for this material. 4. The Mississippi Air and Water Pollution Control Commission should be notified in advance off any proposed movement ef the material, of the routes to be taken, and of the safety precautions. Copies of this statement ace being forwarded to all of the involved agencies, as noted on the attached sheet. Yours very truly, Glen Wood, Jr Executive Director GWjr:js 0-49 �M r . Ko'v/ard A . M a y , J r . F e b r u a r y 8, .1972" Copies f urni.r.;hc:d: . . Mr. Bil.ly Joe Crocs, Director M.i ssi ssipp.i. Garr.o & Fish Coiruiiissiion Post Office Box 45,1 Jackson, Mississippi Mr. Joe D. Brown, Director Dlvis.ion of Sanitary Engineering State Board of IIcalLh Post Office Box 1700 Jackson, Mississippi 39205 •Mr. Jack W. Pepper, Water Engineer Mississippi Board of Water Commissioners 4.16 North State Street Jackson, Mississippi 39201 Mr. V7.il.11 am J. Dc[noran Mar.ine Biologist Gulf Coasl Research Lab Post Office Box AG Ooaan Springs, Miss. 39654 Mr. Bobby R. Tramel Bureau of Sport Fisheries and Wi.ldl.ifc Post Office Drawer FW "-tatc College, Miss. 39762 Dr. R. A. McLemore, Director Mississippi Department of Archives and Ilisvory Post Office Box 571 Jackson, Mississippi 39205 Attention: Mr. Elbcrt liilliard Colonel Wendell D. Iiack, State Forester Missis-sippi Forestry Conmiission 3106 V.'oolfolk State Office Building Jackson, Mississippi 39205 Mr. 0. T. Guice, Jr., Director Division of Plant Industry P. 0. Box 5207 State College, Mississippi 39762 Mr. Wi.1.1 i.am H. Moore Director and State Geologist. Mississippi. Geological Survey Post Offi.ce Box 4915 Jackson, Mississippi 39216 Mr . Sp enee r F,. Med 1 in, Comp t ro!i ] er Mississi.ppi Park System 717 Rcbot.-t E. Leo Building J a e k;; c n, Mis si s si pp i 0-50 : '• �RESPONSE TO COMMENTS FROM THE STATE OF MISSISSIPPI LETTER (15 May 74) 1. See Part I for Air Force action toward EPA registration of Orange herbicide. 2. The Mississippi Air and Water Pollution Control Commission will be notified of any proposed large scale movement of the herbicide in Mississippi. In addition, the Commission will be apprised of plans for dedrumming and transfer of the herbicide from the NCBC, Gulfport to the incineration ship. 0-51 �(This page intentionally left blank) �THE. AMERICAN EAGLE FOUNDATION SI'ITI-: JOO-I72!HI S'lRl.hT. NAV \V\SI IINXi'I ON. D < : J( X K )O • A •'() 2O2-2OK-(i,()r) DONALD D. CARRUTH W I L L I A M G. A L L E N P'iT'-IDLNT VICE PnC5ini:NT Dr. Billy E. Welch Special Assistant For Environmental Quality (SAFILE) Office of the Secretary U.S. Department of the Air Force Room 4D873, The Pentagon Washington, D.C. 20330 Dear Dr. Welch: [1] This office has reviewed with great interest the "Revised Draft Environmental Statement — Disposition of Orange Herbicide by Incineration, April 1974, AF-ES-2D(1)". [2] The February and March 1972 responses to the January 1972 draft environmental statement made available to the Council on Envirormental Quality and the public ^fives strong support to not allowing residual stocks of Orange Herbicide to be disposed of in any of the fifty states of the United States. Further research on the disposition of this herbicide by government, private and educational organizations/at the request of the Air Force, gives additional support to the need for destroying this chemical waste by high-temperature incineration through the use of the M/V Vulcanus — a specially equipped and designed vessel which has been used in North Sea waters ror destroying hazardous/toxic chemical wastes for the past 22 months. [3] Since the European generated industrial chemical waste is not of the same chemicalmix as that of Orange Herbicide, and since the February 15, 1974 letter of transrnittal by the President, National Academy of Sciences to the President of the Senate, Speaker of the House of Representatives, and the Secretary of Defense, of the report: "The Effects of Herbicides in South Vietnam, Part A — Summary and Conclusions", we feel that the national as well as the international interests surrounding the actual destruction of residual stores of Orange Herbicide would be be«t served by a monitoring of the vessel's incineration process. The monitoring project should include the taking of necessary samples of stac^ emissions and the product being incinerated, under varying burner and firing conditions, fljid 0-53 �-2- feed and air flow rates and combustion temperatures; and determine by methods to be prescribed, the parameters of fallout patterns and rates of salt water assimulation of such fallout to a depth of at least two meters below the water surface. '•? We appreciate your consideration in making available to our national environmental organization copies of the Air Force's revised draft EIS of April 1974. Sincerely yours, Donald D. Carruth President 0-54 �RESPONSE TO COMMENTS FROM THE AMERICAN EAGLE FOUNDATION LETTER (25 Jun 74) 1. (Paragraph 2 AEF Ltr) The Final Environmental Statement proposes the destrgction of Orange herbicide by incineration under a proposed action of incineration at sea on a specially equipped vessel or as the principal alternative of incineration on Johnston Island. In addition, it is also felt that the herbicide could be incinerated in an environmentally safe manner at. the U.S. Army Rocky Mountain Arsenal (RMA), CO, see Part V.A.2. 2. (Paragraph 3,4, AEF Ltr) The monitoring project described in the American Eagle letter as regards incineration on board a vessel at sea is very comprehensive and represents quite a formidable task. The disposal of Orange seems to become a vehicle by which extensive data would be obtained on the incineration process. The fact that the Vtlcanus has been "used in North Sea waters for destroying harardous/toxic chemical waste for the past 22 months" seems to refute the need for extensive monitoring of a one time (26 clay) incineration of Orange in the Pacific Ocean. The environmental assessment of the proposed action of incineration at sea (Part III) and the information available on the efficiency of incineration of chlorinated hydrocarbons at sea and their associated environmental impact (see Parts III.B.2. and III.C.5.) also minimize the need for stack and ecological monitoring. The Air Force position is that operational monitoring of the Vulcanus incinerators (temperature, fuel/air flow, pressure, etc.) is adequate for the proposed action of incineration at sea and that stack sampling and analyses is not required. See also the Air Force response to the comments from the Center for Law and Socia" Policy and the EPA. 0-55 �(This page intentionally left blank) 0-56 �CENTER FOR LAW AND SOCIAL POLICY June 126, 1974 Dr. Billy E. Welch Special Assistant for Environmental Quality The Pentagon Room 4 D 873. Washington, D.C. 20330 Dear Dr. Welch: Revised Draft Environmental Statement on Disposition of Orange Herbicide by Incineration [1] On May 13, 1974, the Department of the Air Force published a notice (39 Fed. Reg. 17120) soliciting comments on the Department's Revised Draft Environmental Impact Statement on Disposition of Orange Herbicide by Incineration [,AF-ES-72-2D(l) ] . The following comments on that impact statement are submitted on behalf of the Friends of the Earth and the National Audubon Society (hereafter "the environmental organizations"), two environmental organizations with a worldwide membership of more than 350,000 persons and an established history of concern about pollution of the marine environment. The environmental organizations have undertaken numerous efforts to improve the quality of the marine and coastal environment by means of testimony, policy analysis, educational programs and litigation. [2] The issue addressed in the impact statement is the disposition of 2.3 million gallons of Orange herbicide presently stored at Johnston Island and in Gulfport, Mississippi. The herbicide is highly toxic as are some of its components, e.g., dioxin. The impact statement thoroughly examines several alternative means of disposing of the Orange herbicide, including the possibility of returning the herbicide to the manufacturers, deep 0-57 �Dr. Billy E. Welch June 26, 1974 Page 2 (injection) well disposal, buria] in underground nuclear test cavities, sludge burial", microbial reduction, chlorinolysis, soil biodegradation, and incineration. The impact statement proposes the incineration method, rejecting the others as being either inadequate to destroy the dioxin, otherwise environmentally unsound, or only in the developmental stage and thus unavailable for present use. The impact statement recommends that incineration take place either on board a specially designed vessel in the open tropical ocean west of Johnston Island or in a facility constructed on Johnston Island. [3] The environmental organizations concur that the only reasonable method of disposal is incineration. We strongly urge the adoption of incineration at sea. Incineration at sea, as the impact statement clearly reveals, is the most environmentally sound of the two methods for the following reasons. [4] The most toxic and environmentally hazardous byproduct of incineration is hydrogen chloride. The best means of minimizing the potential hazards of hydrogen chloride is to disperse the gas over the widest passible surface area. To achieve this end, incineration aboard a moving vessel is clearly preferable to incineration on Johnston Island. If the incineration occurs on Johnston Island, the hydrogen chloride will drain off the land and will collect in the waters adjacent to the Island. Since the hydrogen chloride would disperse over a smaller surface area, concentration levels could be significantly higher and the environmental impact more severe. [5] Incineration at sea, west of Johnston Island is far preferable. These waters are generally poor in nutrients, and marine life is scarce when compared to that found in coastal areas or near island dwellings. Furthermore, if incineration occurs on Johnston Island, the human inhabitants and flora and fauna might be adversely affected by the combustion gases, as might the ecologically important bird community located on nearby Sand Island. By incinerating at sea, the Orange herbicide can be disposed .of at a down-wind location sufficiently distant from both Johnston and Sand Islands. 0-58 �Dr. Billy E. Welch June 26, 1974 Page 3 [6] Our support for incineration is based on several assumptions. First, the combustion temperatures must remain at least 1400°C'throughout the entire operation. This requirement must be met to destroy all of the toxic components of the herbicide. Second, the impact statement mentions that incineration operations are subject to mechanical malfunctions and outlines failsafe measures required to protect the environment and provide safety of personnel. These recommended safeguards range from procedures to preclude and contain any spillage of Orange herbicide during transportation to the incineration site to installation of mechanized devices which prevent the feedirvg of herbicide into the. incinerator's burners if combustion chamber temperatures fall below 14QO°C. We assume that these suggested failsafe procedures will be utilized. As an added precautionary measure, we recommend that stack samples be collected periodically and held for analysis, in order to demonstrate, if necessary, that the toxic components of the"Orange herbicide were, in fact, destroyed. [7] Finally, the impact statement does not indicate whether the 45,000 storage drums would be cleaned before disposal, nor does it propose a method of drum disposal. We suggest the drums be cleaned with a light petroleum in order to remove as much herbicide as possible. The cleaning fluid should then be incinerated in the same manner as the Orange herbicide. Although the iir.pact statement finds this process to be expensive, it appears to be the .only means of destroying substantially all of the Orange herbicide. After cleaning, the drums should be smelted. . ' [8] A major omission oE the impact statement is its failure to relate "the dispositipn to the Marine Protection, Research and Sanctuaries Act of .1972 (33 U.S.C. §1401), and the Convention on Marine Pollution by Dumping of Wastes and Other Matter (London, 1972). The Marine Protection, Research, and Sanctuaries Act prohibits "transporting from the United States...except as authorized by permit...any...material for dumping...into ocean waters" (33 U.S.C. §1411(a)). [9] The act defines dumping as the "disposition of matter of any kind or description" (33 U.S.C. §1422(c),(f)). While incineration is not a normal form of dumping, it does come under the purview of the Act and the safeguards of the Act should be applied. 0-59 �Dr. Billy E. Welch June 26, 1974 Page 4 [10] The Convention on Marine Pollution by Dumping of Wastes and Other Matter prohibits, "any deliberate disposal at sea of wastes and other matter from vessels" without obtaining a dumping permit (Articles III, IV). Although this Convention is not yet in force, the United States has deposited its instrument of ratification, as have others. Because of this and since the Convention may be in force at the time the Orange herbicide is incinerated, the U.S. should comply with at least the objectives and spirits of the Convention. Article VI of the Convention requires that records of the nature and quantities of all matter permitted to be dumped, the location, time, and method of dumping be reported to the new international organization which will be created under the Convenbion. We suggest that the United States report the required information to all countries who have ratified the Convention. The U.S. would satisfy the permit requirement by complying with the Marine Protection, Research and Sanctuaries Act. [11] If you have any questions concerning the above, we would be happy to amplify our comments or provide additional information. Sincerely, r^jT - \-i.l »Vr N Richard A. Frank RAF:cl 0-60 �RESPONSE TO COMMENTS FRCM THE CENTER FOR LAW AND SOCIAL POLICY LETTER (26 Jun 74) 1. (Paragraph 4 CL & SP Ltr) The environmental impact upon the ocean associated with the discharge of hydrogen chloride from an incinerator as a result of incineration of Orange on Johnston Island is discussed under "Reef Area," Part III.C.5.a. A worst case analyses reveals that any damage to the reef on an acute basis would be mirimal and that any long term chronic effects on the reef could not be predicted. A monitoring plan would be in operation should any Orange be incinerated on Johnston Island. Monitoring stations would be selected to include evaluation of water in the plume fallout area and around the reef. However, the Air Force does not presently plan to install a facility for the incineration of Orange at Johnston Island. 2. (Paragraph 5 CL & SP Ltr) If Orange herbicide is incinerated on Johnston Island meteorological constraints and an ambient air monitoring program will be in operation to insure that personnel, the bird community on Sand Island, and flora and fauna are not affected. 3. (Paragraph 6 CL & SP Ltr) The final contract for any incineration of Orange will include specifications on temperatjre requirements, operational monitoring and recording (temperature, fuel flow, air flow, operating pressures, etc.) and failsafe procedures. 4. (Paragraph 6 CL & SP Ltr) The desirability of collecting stack samples for subsequent analysis upon completion of the incineration phase of the project (non-real time monitoring) is appreciated. The feasibility and necessity of such action has been studied by the Air Force. The Air Force's position is that neither real time nor non-real time monitoring is required for this disposal project. This position is based on the evaluation of the environmental impact which would result from incineration of Orange at sea. The analysis based on an anticipated Orange destruction of 99.9% reveals that insignificant impact would occur. For perspective, the worst case analyses was also accomplished for Orange destruction efficiencies of 99.0 and 95,0% with the results indicating what is deemed as a minimal and acceptable environmental impact (see Parts III.B.2. and III.C.5.). Information received on incineration of chlorinated hydrocarbons at sea shows that the incinerators utilized by the vessels tested were capable of essentially complete destruction of the hydrocarbons with negligible environment impact. This information is contained in Appendix N and summarized in Part III.B. and 11I.e. The incineration of mustard agent at Rocky Mountain Arsenal is accomplished by incineration with essentially total destruction of the agent (see Part V.A.2.). In view of the above, it is the Air Force's position that the operational monitoring (temperature, fuel flow, etc.) will be sufficient for this relatively short project and that neither real time nor non-real time monitoring is required,. 5. (Paragraph 7 CL & SP Ltr) See Part II.E. f°r drum disposal information. 0-61 �(This page intentionally left blank) �l arquardt I COMPANY CCI Corporation \, . 16555 SATICOY STREET • VAN NUYS, CALIFORNIA 91409'TELEPHONE (213)781-2121'TWX 910-495-1710'CABLE MARQCOR . • ' " . •••: ' • June 21, 1974 Ref: 2000/115 • Department of the Air Force Office of the Assistant Secretary Billy E. Welch, Ph.D. Special Assistant for Environmental Quality Washington, DC 20330 • • ; ^ Dear Dr. Welch: ' " ' j / •' ' The following comments are provided in response to the USAF Revised Draft Environmental Impact Statement for the Disposition of Orange Herbicide by Incineration, April 1974, AF-ES-72-2DO). , ' '-. * . •- We are pleased that our unique SUdden Expansion (SUE®) burner was selected as the incinerator used to perform the only two full-scale test burns of Herbicide Orange and that a copy of our Final Draft Report on the Destruction of Orange Herbicide, February 1974, was included as Appendix E of the Revised Impact Statement. This report documents the 99.998% destruction efficiency of the SUE® incineration system. 1. The SUE incinerator (a commercial incinerator) system tested by the USAF in no way resembles the definitjon of a "conventional" liquid waste incinerator as defined in Part V.A.I .a. Appendix E of the Revised Draft Impact Statement contains a detailed description of the SUE incinerator system, pages E (B-l) through E (B-10). The combustion efficiency of 99.998% demonstrated in the test program is extremely high for an incineration process, and we know of no other commercial incinerator with documented efficiency approaching 99%. . * " . * Part II C.2.(c)(l) states that the incineration systems installed on the ship Vulcanus are conventional incinerators. 2. Part II C.2.(c)(3) and (4) states that information from Ocean Combustion Service B.V., Rotterdam, The Netherlands, indicated that 99.9% of chlorinated hydrocarbons feed is destroyed. No information, data, test reports, or references are provided to support this claim. Further, no mention of tests or data substantiating the ability to destroy the dioxin (TCDD) is made. . ~ '? '. 0-63 An Equal Opportunity Employer �To: .USAF Special Assistant for Environmental Quality 3. -2- June 21, 1974 Ref: 2000/115 Part II C.2.(c)(3) states that data presented in Appendices D and E indicate that incineration of Herbicide Orange can be successfully accomplished on board 1-he Vulcanus. All referenced test data representative of full-scale incineration of Herbicide Orange was obtained from the SUE® burner incinerator system. As recognized combustion experts, with 29 years of corporate combustion experience, we disagree with this statement for two reasons: (a) Data from one type of combustion system cannot be assumed to apply to a different type or size combustion system without extensive testing to validate the assumption. It is only conjecture that the incinerator OR the ship Vulcanus would destroy Herbicide Orange at an efficiency of 99.9% since no tests have been run on the ship incinerator. Los Angeles County, for instance, requires afterburners on solid and liquid waste incinerators as a result of testing units with a single chamber like the incinerator on the Vulcanus. Combustion efficiency is closely related to the efficiency of fuel * and air mixing in a unit, combustion frequency, combustion stability and stay time. Large-diameter combustion chambers often present mixing problems/ combustion frequency problems, and combustion stability problems that result in low combustion efficiency and products of partial combustion. Partial incineration results in destructive distillation and often produces more undesirable products than dumping the raw product into the atmosphere. (b) Experience has proven that mixing, burning rates, and efficiencies determined from one size burner cannot be applied to a different size burner of the same type (let alone a different type of burner). One incinerator chamber (three burners of unknown size) on the Vulcanus would incinerate Orange at a rate of 6-2/3 pounds per second (pps) versus .14 pps for a 12-inch-diameter SUE burner. Scaling is avoided in the Marquardt system by adding additional 12-inch-diameter SUE® burner modules to increase system capacity without changing combustion efficiency. Mixing of fuel (herbicide) and air is the single most critical parameter in the incineration process. This fact was proven by tests conducted at Marquardt (Appendix E) establishing that the poppet nozzle could not be used above 2/3 of the stoichiometric herbicide/air ratio/whereas the standard SUE slot nozzle injectors could be used with very high overall burning efficiencies. In fact, the poppet nozzle/SUE burner combination somewhat resembles the mixing process in most commercial incinerators. Thus, if an incinerator with burners other than the slot nozzleequipped SUE type is used to destroy the herbicide, it cannot be assumed that it will operate in the same fashion and with the same efficiency as the SUE system without thorough testing and data analysis. Viscosity of the fuel (Orange Herbicide) directly affects the efficiency of any nozzle. The herbicide had to be heated to a minimum of 90 F (best results at 180°F) to reach efficient destruction. Heating 20 to 24 tons per hour to 90*T+ may present a major problem on board the Vulcanus. 0-64 �To: USAF Special Assistant for Environmental Quality -3- June 21, 1974 Ref: 2000/115 A further complication arises'in very large-diameter incinerators because of the potential for stratifying of zones of burning gases which have different fuel/air ratios. It is impossible to detect this improper mixing by measuring the temperature of the gases at various points because the same temperature can be reached by lean (excess air) burning or by overstoichiometric (insufficient air) burning. The combustion products in the two cases are vastly different and in the case of the overstoichiometric mode probably will contain large quantities of raw or partially decomposed herbicide. Stay time is no cure or substitute for adequate mixing. The combustion process (more properly defined as oxidation) proceeds very slowly after the initial flame front and requires extremely highlevels of turbulence with very short mixing paths. None of these characteristics have been shown to exist in the Vulcanus units. Therefore, it is our opinion that if the mixing in the burners does not approach 100% efficiency, 99.9% destruction efficiency cannot be achieved. 4. The comparison of incineration times of the two proposed systems (22 - 26 days for the Vulcanus vs. 200 days For the land-sited system on Johnston Island) is technically accurate, but misleading from a total-time-required aspect. In order to realistically compare the two options for a time-and-facility cost, the following considerations must be incorporated into the analysis: (a) The land-based system can be fabricated at the contractor's plant and shipped in easily assembled modules. Fabrication and installation time of a SUE liquid incineration system on Johnston Island would be equivalent to availability of the Vulcanus,. (b) A SUE burner system consisting of 10 burner cans equivalent to the land-based Option 2 system would require a small portable 2500-gallon Feed tank which v/ould be continuously charged by the drum-emptying facility (1 drum/5 minutes = 12 drums/hour X 55 gallons = 600 gallons/hour). Such a 10-can SUE*^ burner system would consume the Orange Herbicide at a rate of 600 gallons/hour. System capacity can be increased by adding additional 12-inch-diameter SUE burner modules which incinerate the herbicide at a rate of 60 gallons/hour each. (c) Appendix I 4.a. and Part II E. indicate that all drum emptying will be conducted on Johnston Island. Drums would be shipped from Gulf port to Johnston Island via rail and ship. This implies that the Vulcanus would steam to Johnston Island, berth, load 925,493 gallons of Orange Herbicide, and then tteam to the burn area for incineration at sea. No time estimate for this operation is included. (d) No POL storage tanks approaching 1,000,000-gallons capacity are shown on Johnston Island. In order to obtain efficient utilization of the Vulcanus incineration capacity, 950,000 gallons of Orange Herbicide would have to be available for loading when the ship berthed. At the rate of 12 drums/hour (660 gallons) it would take 60 working days (24 hours per day)-to fill the 1,000,000-gallon tank to the required 950,000 gallons. 0-65 �t I ; To: USAF Special Assistant for Environmental Quality - -4• -June^l, 19>4 Ref: 2000/115 : ' ' . " -' : .-. •': I At the stated rate, the Vulcanus can incinerate its complete capacity of 925,493 gallons in 8.6 days. Allowing 3 days from its berth at Johnston Island to the incineration area and the same time to return to berth, the total voyage would take 15 days. Thus, the ship would either sit idle for 45 days or cycle to an alternate assignment. i. (e) The cost, time, and environmental impact of building a 1,000,000-gallon tank on Johnston Island has not been addressed. (f) If the drum-emptying operation is to be performed In Mississippi, a separate impact statement should be prepared or the subject impact statement expanded to include this additional operation. (g) Use of a portion of the existing POL storage tanks on Johnston Island would provide a tank capacity of approximately 50,000 gallons (the assumption is made that two 25,000-gallon diesel tanks would be made available; the remaining tanks would be required for normal operations). Therefore, the Vulcanus would have to stay in port 55 days to take on a complete load. Allowing 1/2 day to load each 50,000 gallons (9 X 1/2 = 4,5 days), the total cycle time per voyage would be 74 days (4.5 + 3 + 3+8,6 + 55). • : (925,493 gallons - 50,000 gallons available at start = 875,493 gallons 875,493 gal lore _ ,7 50,000 ga I Ions/tank ' , \ ', 50,000 q Ions/tank gal . . . . ,* 0>j/> II—-r\—= 3.16 days/tank 15,840 gallons/day '' 3.16 days/tank X 17.5 tanks = 55 working days @ 24 hours/day) In view of the above-mentioned facts, it appears that the time required for Option 1 and Option II is similar. If a 1,000,000-gallon tank were constructed, Option I would be approximately 180 days plus tank construction time plus tank flushing and flush fluid incineration time plus tank dismantling and removal. If .an existing 50,000gallon storage tank capacity is assumed, Option I becomes 220 days. 5. Part II D.I .C states that the cargo (Orange) can be discharged directly into the sea in the event that the safety of the Vulcanus and her crew is threatened. Discharge of 925,000 gallons of Herbicide Orange into the Johnston Island area, open tropical ocean, or longrange effects on the Hav/aiian Islands is not considered or included in the "worst case" evaluations. 0-66 �To: USAF Special Assistant for Environmental Quality -5- June21, 1974 Ref: 2000/115 We appreciate the opportunity to review and comment on this Draft Environmental Impact Statement. We respectfully request copies of other comments when received and a copy of the final Impact Statement when it is released. '4 Very truly yours, THE MARQUARDT COMPANY R. V, Haas, General Manager Environmental Systems Division 0-67 �RESPONSE TO COMMENTS FROM THE MARQUARDT COMPANY LETTER (21 Jim 74) 1. (Paragraph 1 TMC Ltr) The revised draft envjronmental statement did not state that the SUE incinerator is ^conventional incinerator. The flame and fuel/air characteristics of the SUE system are felt to be very important in the acquisition of data on Orange combustion from which judgments can be made concerning overall requirements for efficient conbustion. Undoubtedly such a judgment can be made with better validity than had another specialized incinerator system such as molten salt, fluidized bed., or a system which utilizes pure oxygen as the oxidizer been selected,for the test incineration. It is noted the Air Force initially intended to perform a test burn in a conventional incinerator but opted for the SUE - when plans for the conventional incinerator could not be concluded (see Part II C.I.). 2. (Paragraph 2 TMC Ltr) Neither the Vulcanus nor any other incinerator vessel has been used for the destruction of Orange and its TCDD contents. Some information on the incineration of chlorinated hydrocarbons on incinerator ships has been submitted to'the Air Force (see Appendix N). This information reports incinerator efficiencies greater than 99.9% and attest to the negligible short term environmental impact associated with incineration at sea. Information from Rocky Mojntain Arsenal also reports a high efficiency of destruction of mustard agent, 99.9% (see Part V.A.2.). 3. (Paragraph 3 TMC Ltr) The Marquardt Company has taken exception to the following statement on page 15 of the revised draft environmental statement: "A comparison of incineration characteristics of the 'Vulcanus1 versus those known to be acceptable based on the data presented in Appendices D and E Indicated that Orange herbicide can be successfully incinerated on board the 'Vulcanus1." The company's position 1s stated in the following quote from paragraph 3 of their letter: "Data from one type of combustion system cannot be assumed to apply to a different type or size combustion system without extensive testing to validate the assumption." There is no basic disagreement with this statement as regards the direct extrapolation of data. The question is — can a judgment be made on the probable destruction of Orange herbicide via incineration with the data that is presently available? Such data includes five studies concerned with the combustion of Orange and the data on the incinerator ships and Rocky Mountain Arsenal. The Air Force's position is that such a judgment can be made in fact, this position was the underlying reason for the course of action which resulted in the test burn at the Marquardt Company. That is, the Marquardt test burn was designed to obtain data on overall incinerator operation/efficiency which could be used for contractual purposes (see Part II.C.l.). 4. (Paragraph 3 TMC Ltr) The following comments are concerned with the need for an efficient injection system and mixing in the incinerator. The Marquardt system was proven to be extremely efficient for both the poppet nozzle and the slot nozzle and for all fuel feed temperatures(viscosity). Table 1-6, page E(I-13) and Table 2, page T-3ITshow that the relative pyrolysis efficiency 1s 99.99 percent for both Run I (poppet nozzle, Orange feed temperature 66-63°F, Wf/Wa 0.086) and Run III (poppet Nozzle, 0-68 �Orange feed temperature 92-90°F, Wf/Wa 0.106). Run II was conducted under the same conditions as Run I except that the feed temperature was 98/96°F and had a relative pyrolysis efficiency of 99.98 percent. The shift to the slot nozzle allowed a higher fuel flow rate and higher efficiencies of 99.998-99.999 percent were attained. The flow rate increase is attributed to the hydraulic characteristics of the nozzle; the higher combustion efficiercy is attributed to the greater efficiency of the slot nozzle as an injection system. The Marquardt system was extremely efficient for all test runs and the slot: injection system was responsible for the highest destruction rate and efficiency. It is emphasized that the effiencies with the poppet nozzle were quite high and that as the Marquardt Company letter states "...the poppet. nozzle/SUE!^ burner combination somewhat resembles the mixing process in most commercial incinerators." It is the Air Force's position that a properly engineered incinerator system which can operate under specified overall combustion conditions, and is equipped with a well designed injection system and a turbulent combustion space would be an acceptable incineration system. . i 5. (Paragraph 4 TMC Ltr) Both incineration at sea and on Johnston Island have been programmed to PERT Charts and the project times are not similar. The present plan for incineration at sea does not include the construction and use of large volume storage tanks. When the incinerator ship is loaded at Gulfport, railroad cars will be utilized to transfer the Orange (dedrummed) from NCBC to the dock. On Johnston Island aircraft refuelers will be utilized to transfer the Orange from a dedrumming facility to the ship. A dedrumming/loading rate of 1,000 drums per day is planned. These transfer systems are readily jittainable for scheduling purposes, easily managed and controlled, and very*satisfactory from an environmental impact standpoint. The activities conducted at both Mississippi and Johnston Island will be well planned and include complete environmental and industrial hygiene considerations. 6. (Paragraph 5 TMC Ltr) Information on possible environmental impact resulting from the jettisoning of the Orange cargs or sinkage of the incinerator ship has been included in Part III.C.5.a. 0-69 �(This page intentionally left blank) �LITERATURE CHED Abend, H.E. 1942. Ram£arts_of-the_P_ac1fij:_. j Doubleday, Garden City, N.Y." Advisory Committee on 2,4,5-T. 1971. Report of the Advisory Committee •on 2,4,5-T to the Administrator of the Environmental Protection Agency. AEC/DOD--Atomic Energy Commission/Dept of Defense. Facilities Brochure. 1971. Johnston Atoll AEC/DOD--Atomic Energy Commission/Dept of Defense, Plans, Johnston Atoll. n.d. Master Site AEC/DOD--Atomic Energy Commission/Dept of Defense., support requirements plan—Pacific Area. n.d. Facilities and ; Air pollution—Niagara County. "1964. Comprehensive Area Survey Report No. 3. New York State Air Pollution Control Board, Albany, New York. 5 Air Pollution Control Association. 1970. Recognition of air pollution injury to vegetation. APCA, Pittsburgh, Pa. Aly, O.M. and S.D. Faust. 1964. Studies on the fate of 2,4-D^and ester Derivatives in natural surface waters. J.Agr. Food Chem." 12:541. Amerson, A.B., Jr. 1973. Ecological baseline survey of Johnston Atoll, central Pacific Ocean. Smithsonian Institution, Washington, D.C. (USAF Contract F-44620-67-C-0063). Ashmore, S.A. 1973. The geomorphology of Johnston Atoll. Off., Tech. Rep. 237:1-27. Naval Ocean. Audus, L.G. I960. Microbiological breakdown of herbicides in soils. Herbicides and the soil. Blackwell, London. In Bamesberger, W.L. and D.F. Adams. 1966. An atmospheric survey for aerosol and gaseous 2,4-D compounds. In Organic pesticides in the environment, Advances in Chemistry No. 60. American Chemical Society, Washington, D.C. Baue1", L.R. Eight. 1965. Historical report of Johnston Atoll. Joint Task Force • s •i .' ^ Baughman, R. and M. Meselson, a. 1973. An analytical method for detecting TCDD (Dioxin): Levels of TCDD in samples from Vietnam. Environ. Health Perspect. No. 5:27. Baugiman, R.W. and M. Meselson. b. 1973. Memorandum on TCDD production by pyrolysis of sodium 2,4,5-T. Harvard Univ., Cambridge, Mass. �Berndt, W.O. and F. Koschier. In vi&w uptake of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) by renal cortical tissue and rabbits and rats. •Toxicol . Appl . Pharmacol . 26:559. Besselievre, E.B. 1969. New York, N.Y. The treatment of industrial wastes^. ~ ' McGraw-Hill, Bjorklund, N.E. and K. Erne. 1966. lexicological studies of p'nenoxyacetic acid in animals. Acta Vet. Scand. 7:364. Bleiberg, J.M. ejt al_. 89:: 793. 1964. Industrially acquired porphyria. Arch. Derm. Brock, V.E., W.V. Heukelem, and P. Helfrich. 1966. An ecological reconnaissance of Johnston Island and the effects of dredging. Brock, V.E., R.S. Jones, and P. Helfrich. 1965. An ecological reconnaissance of Johnston Island and the effects of dredging. Annual report. Hawaii Inst. Marine Biol., Tech. Rep. 5:1-90,. Brown, E. and Y.A. Nishioka. 1967. Pesticides in selected western streams-a contribution to the national program. Pestic.. Monit. J. 1(2):38. Brown, K.S., M.C. Johnston and J.D. Niswander. 1972.. Isolated cleft palate in mice after transportation during gestation. Teratology 5:119. Bryan, E.H., Jr. 1942. American Polynesia and jhe Hawaiian Chain. Pub. Co., Honolulu, HI. ....... "" Tongg Bureau of Sport Fisheries and Wildlife. 1972. Handbook of procedures for pesticide residue analysis. Govt. Printing OffTce, Washington, D C . ."~ Byerly, T.C. 1970. Letter to Sen. Hart and Magnuson. Cheng, K.W. and U.W. Kilgore. 1966. Gas chromatographic deterni nation of pentachlorophenol and sodium pentachlorophenate residue in fruits. 31:259. Christensen, H.E., ed. Washington, D.C. 1971 . Toxic substances. U.S. Govt Printing Office, Clark, C.E. et al . 1964. "he fate of 2,4-dichlorophenoxyacetic acid in sheep. J. Agr.TbocT Chem. 12:43. Collins, T.F.X. and C.H. Wi'lliams. 1971. Teratogenic studies with 2,4,5-T and 2,4-D in the hamster. Bull. Environ. Contam. Tcxicol. 6:559. Colmer, A.R. 1953. The action of 2,4-D upon Azobacter of some sugarcane soils. Appl . Microbiol. 1:184. Cope, O.B., E.M. Wood and G.H. Wall en. 1970. Some chronic effects of 2,4-D on the Bluegill (l.epom.-a macAocl'iAjwA ) . Trans. Amer. Fish. Soc. 99:1. �Courtney, K.D. and J.A. Moore. 1971. Iaratplpgy_ studies with 2,4,5-trichlorophenoxyacetic acid and 2,3,7,8-tetrachiorodibenzo-p-dioxin. Toxicol. Appl. Pharmacol. 20:396. Crosby, D.G. and Tutass, H.O. 1966. Photodecomposition of 2,4-dichlorophenoxyacetic acid. J. Agr. Food Chem. 14:596. Crosby, D.G. ejt al_. 1971. Photodecomposition of chlorinated dibenzo-p-dioxins. Science. 173(3998):748. DAF/DNA--Dept. of the Air Force/Defense Nuclear Agency. 1973. Memorandum of agreement concerning the transfer of host-manager responsibility at Johnston Atoll. (Effective 1 Jul 73). DeRose, H.R. and A.S. Newman. 1947. Persistence of growth regulators in the soil. Soil Sci. Soc. Amer. Proc. 12:222. / DNA--Defense Nuclear Agency. 1972. Summary report of conference on compatibility of RED HAT and Herbicide Orange with readiness activities on Johnston Island. Hq Field Command, DNA, Kirtland AFB N.M., 14-16 Nov 72. DNA/AEC--Defense Nuclear Agency/Atomic Energy Commission. 1973. Memorandum of agreement betweer Field Command DNA and AEC Nevada Operations Office regarding contractual arrangements at Johnston Atoll. (1 Jul 73). DNA/PACAF—Defense Nuclear Agency (CJTF-8)/15th Air Base Wing (PACAF). 1971. Support agreement concerning USAF/DNA responsibilities of Johnston Island Readiness Facilities. (1 Nov 1971). DNA/PACAF—Defense Nuclear Agency/Pacific Air Forces. 1973. Support agreement between Pacific Air Forces and Field Command, Defense Nuclear Agency. (Effective 1 Jul 73). DOD/AEC~Dept. of Defense/Atomic Energy Commission, a. 1965. Agreement on responsibilites for planning for the support of readiness and conduct of atomic test operations outside North American Continental limits and related budgeting and funding. (September, 1965). i DOD/AEC--Dept. of Defense/Atomic Energy Commission, b. 1965. Memorandum of agreement regarding contractual arrangements at Johnston Atoll. (18 Feb 65). Dow Chemical Co. 1970. Petition, Part IV, Item 3. EIS-OR~Forest Service. 1973. Environmental impact statement—The 1973 herbicide use on the Deschutes, Winema. Ochoco, and Fremont National Forest, Oregon. Forest Svc., USDA, Pacific Northwest Region, Portland, Oregon. [EIS-OR-124C-F]. Emerson, J.L. e_t al_. 1970. Teratogenic study of 2,4,5-trichlorophenoxyacetic acid in the rat. Toxicol. Appl. Pharmacol. 17:317. �. .i • Emery, K..O. 1956. Marine geology of shallows, central Pacific Ocean. • . ' . .. . '• Johnston Island and its surrounding Geol.~ "— — - - —<—• Amer.- _-Bull. 67:1505. ^ • • ^ •- Soc. ^"• "• -"- ™ ™ ^ Emery, K.O. 1955. Transportation of rocks by driftwood. Peterology. 25:51. J. Sediment. ; Environmental Protection Agency. 1972. Water Quality Standards. Digest (August), Washington, D.C. Criteria Environmental Protection Agency. 1973. Guidelines for preparation of en virpnmenta1 statements. EPA Region X, Seattle, Wash. "" """" *• Erne, K. 1966. Distribution and elimination of chlorinated phenoxyacetic acids in animals. Acta. Vet. $cand. 7:240. ;. Food and Drug Administration. 1972. Pesticide Analytical Manual, V-.I, Methods Which Detect Multiple Residues. FDA, U.S. Dept. of HEW, Washington, D.C. • Fosberg, F.R. 1949. 3:338. Flora of Johnston Island, central Pacific. . . -'' Pac. Sci. Fox, A.S. et al. 1970. Restricting the use of phenoxy herbicides U$DA Agricultural Economic Rept. Np. 194. . •, ' . ; \ Gehring, P.J. ' et. al_. 1973. the fate of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) following oral administration. Toxicol. Appl. Pharmacol. r 26:352. . ' • ' . : . . Gleason, M.N. et al. 1969. Clinical toxicology of commercial products. 3rd ed. WTTlTarns & Wilkins, Baltimore, Md. = r* Goelitz, D.F. and W.L. Lamar. n.d. Determination of phenoxy acid herbicides in water by electron capture and microcoulometric gas chromatography. USGS WSP-1817-C. Draft copy. U.S. Geological Survey, Washington, D.C. Goldberg, L. 1971. Trace chemical contaminants in food: harm. Food Cosmet. Toxicol. 9:65. Potential for Gosline, W.A. 1955. The inshore fish fauna of Johnston Island, a central Pacific atoll. Pac. Sci. 9:44V2. Goulding, R.L. 1973. Waste pesticide management. Final Narrative Report. Environmental Health Sciences Center. Oregon" State Univ., Corvallis. '" " Gratkowski, H., D. Hopkins, and P. Lauterbach. 1973. The Pacific Northwest region. J. Forestry. 71:318. t Henderson, R.S. and E.C. Evans, III.. 1973. Continuous flow marine organism holding tanks: A proposed joint NUC/HIMB project for marine biological and environmental studies. NUC TN 1123. Naval Undersea Center, Sari Diego, Calif. ' '. • HAC—Herbicide Assessment Commission. 197.2. Background Material Relevant to Presentations at the 1970 Annuaj .Meeting of the AAAS and Preliminary Report of the Herbicide Assessment Commission; both reprinted in Congressional Record 118(32): S3226-3233 March 3, 1972. �f . -.• Lauterback, P. 1967. Chemical weeding and release of conifers in western Cregon and Washington'. Symposium Proceedings: Herbicides and vegetation management, Oregon State Univ. Corvallis, Oreg. Leopcld, A.D., P. Van Schaik, and M. Neal. herbicide absorption.. Weeds. 8:48. 1960. Molecular structure and Lutz, J.F., G.E. Byers, and T.J. Sheets. 1973. The persistence and movement of picloram and 2,4,5-T in soils. J. Environ. Quality. 2:485. Manigold, D.B. and J.A. Schulze. 1969. Pesticides in selected western streams—a progress report. Pestic. Monit. J. 3:124. : ., Marshall, J. 1825. Royal Navy biography, V. IV. Gorman Pub. Co., London, England. . • Matsumura, F. and J.H. Behezet. 1973. Studies on the bioaccumulation and microbial degradation of 2,3,7,8-tetrach1orodibenzo-p-dioxin. Environ. Health Perspect. No. 5:253. Metcalf, L.D. and A.A. Schmitz. 1961. The rapid preparation of fatty acid esters for gas chromatographic analysis. Anal. Chem. 33:363. Miller, S.S. Techno!. 1974. 8:18. Emerging technology of chlorinolysis. Environ. Sci. " Mitchell, J.W. et al. 1946. Tolerance of farm animals to feed containing 2,4-D. J. Animal Sci. 5:226. Montgomery, M.L. and L.A. Norris. 1970. A prelininary evaluation of the hazards of 2,4,5-T in the forest environment. USDA Forest Service Research Note PNW-116. National Primary and Secondary Ambient Air Quality Standards for Carbon Monoxide. 40 CFR 50.8, 36 FR 22384, 25 Nov 71; as amended by 38 FR 25678, 14 Sep 73. Navy Hydrographic Office, a. '1959. Johnston Island and Reef. 5356. U.S. Navy, Washington, D.C. H.O. Chart b. 1959. Sailing directions for the Pacific islands, V.III, The southcentral groups. 6th ed. H.O. Publn. 80, Change 12. U.S. Navy, Washington, D.C. • Navy..Public Works Office. 1964. Long term land management plan, Johnston island. 14th Naval District, Pearl Harbor, Oahu, Hawaii. Nishimura, H. and S. Miyamoto. 1969. Teratogenic effects of sodium chloride in mice. Food Costnet. Toxicol. 7:415. Norris, L.A. 1970. Degradation of herbicides in the forest floor. P. 527, Tree growth and forest soils. Ed. by C.T. Youngberg and C.B. Davey, Oregon Univ. Press, Corvallis. O'Connor, G.A. and P.J. Wierenga. 1973. The persistence of 2,4,5-T in greenhouse lysimeter studies. Soil Sci. Soc. Amer. Proc. 37:398. Odum , E.P. 1971. Fundamentals of ecology. W.B. Saunders, Philadelphia, Pa. �House, k.B. e£ al_. 1967. Assessment of ecological effects of extensive or repeated use of herbicides: Final report. Midwest Research Inst., Kansas City, Mo. AD82*-.314. 1967. Phenoxy herbicide residues end their persistence. Institute, Kansas City. Mo. [AD 726367]. Midwest Research Innes, J.R.M. e_t a_^ 1969. Bioassay of pesticides and industrial chemicals for tumorigenTcity in mice: A preliminary note. J. Natl. Cancer Inst. 42:1101. " " " i Johnson, J.E. 1970. Symposium on possible public health implications of widespread use of pesticides. Amer. Inst. of Biological Sciences, Bloomington, Ind. Joint Hazards Evaluation Group. 1972. An evaluation of hazards to Island and transient personnel as associated with RED HAT stores and aircraft operations on Johnston Atoll. (Jil 72). Joint Task Force Seven. 19H9. A Johnston Island climatological study. Meteorological Center, Pearl Harbor, Hawaii. Kalter, H. and J. Warkaney. 1959. Experimental production of malformations in mammals by metabolic procedures. Physiol. Rev. 39:69. Kearney, P.C., E.A. Woolson, and C.P. Ellington, Jr. 1972. Persistence and metabolism of chlorodicxins in soils. Environ. Sci. Tecnnol. 6:1017. Khanna, S. and S.C. Fang. 1966. phenoxyacetic acid in rats. Metabolism of C 14 -labeled 2,4-dichloroJ. Agr. Fqod_Chej. 14:500. King, C.T.6. e_t aJL 1971. Screening of the herbicides 2,4,5-T and 2,4-D for cleft palate production. Teratology. 4:233. Kinne, 0. 1970. Mjrji_ne_ecolj)C(y_, V.I. Wiley-Interscience, New York, N.Y. Kirch, J.H. 1967. Special herbicide combination for rights-of-way brush control. Symposium Proceedings Herbicides and Vegetation Management, Oregon State Univ., Corvallis, Oreg. Klingman, D.L. and W.C. Shaw. 1967. Using phenoxy herbicides effectively. USDA Farmer's Bull. No. 2183, GPO, Washington, D.C. Klingman, D.L. et al_. 1966. Residues in the forage and in milk from cows grazing forage treated with esters of 2,4-D. Weeds. 14:164. Kopenski, R.P. and M.P. Wennekens. 1966. Circulation patterns Johnston Atoll, winter-summer 1965. Office of Naval Research, Spec. Pub. 93:1-240. Langer, H.G. 1973. The formation of dibenzodioxins and other condensation products from chlorinated phenols and derivatives. Environ. Health Perspect. No. 5:3. �Palm, C.E. et^ al_. Weed control. 1968. Natl. Principles of plant and animal pest; control, V.2 Academy of Sciences, Washington, D.C. Publn. 1597.. / Palmer, J.S. 1963. Chronic toxicity of 2,4-D alkanolamine salts to cattle.. J. Amer. Vet. Med. Ass. 143:398. * Palmer, J.S. and R.D. Radeleff. 1964. The toxicologic effects of certain fungicides and herbicides on sheep and cattle. Ann. N.Y.. Acad. Sci. '111:729. Penfound, W.T. and V. Minyard. 1947. Relation of light intensity to effects of 2,4-dichlorophenoxyacetic acid on water hyacinth and kidney bean plants. Bot. Gaz. 109:231. Petero, S.U. and M. Strassburg. Arzeim. Forsch. 19:1106. 1969. Stress als teratogener faktor. Pimentel, D. 1971. Ecological effects of pesticides on non-target species. Sovt. Printing Office, Washington, D.C, POBSP--Pacific Ocean Biological Survey Program, Sm'thsonian Institution, Washington, D.C. [unpublished report ] : 1964. Staff. Preliminary biological survey of Sand Island, Johnston Atoll. Prpgram/Budget Decision 282. 1969. Transfer of Johnston Atoll. (10 Dec 69). Pursely, P.L. and E.D. Schall. 1965. Gas chromatographic'determination of 2,4-D and 2,4,5-T and their derivatives in commercial formulations J. Ass. Offic. Anal. Chem. 48:327. Radeleff, R.D. p. 242. 1964. Veterinary toxicology. Lea & Febiger, Philadelphia, Pa., Redfield, A.C. and L.A. Walford. 1951. A study of chemical wastes at sea. Publ. No. 201, National Academy of Science, National Council. Rowe, V.K. et al. n.d. Toxicology of chlorinated dibenzo-p-dioxins. ResearcFTLab, Dow Chemical Co., Midland, Mich. Biochemical St. John, L.E., Jr., D.G. Wagner, and D.J. List. 1964. Fate of Atrazine, Kuron, Si 1 vex and 2,4,5-T in the dairy cow. J. Dairy Sci. 47:1267. Sanders, H.O. 1970. Toxicities of some herbicides to six species of freshwater crustaceans. J. Water Pollut. Coritr. Fed. 42:1544. Schultz, D.P. 1973. Dynamics of a salt of (2,4-dichlorophenoxy)acetic acid in fish, water and hydrosol. J. Agr. Food Chem. 21:186. Schwetz, B.A. et al. 1973. Toxicology of chlorinated dibenzo-p-dioxins. Environ. Health Perspec. No. 5:87. �Sec Def—Secretary of Defense. Nuclear Readiness to Test. 1969. Memorandum for Secreatry of Air Force: (30 Oct 1969). 1970. (27 Apr Memorandum for Director, Defense Nuclear Agency: Readiness to Test. 1970). " ' : : ' • ' ;i . ' .'• '• t ."1970. Memorandum for Secretary of the Air Force and Director, Defense Atomic Support Agency: Operation RED HAT, Phase II Johnston Island. (3 Dec 70). Seckel, G.R. 1962. Islands region. Atlas of the oceanographic climate of the Hawaiian Fishery Bulletin. 193:371. Shelton, P.C. ms., in prep. The natural history of Johnston Atoll, central Pacific Ocean. ( . ^ Res. Bull. Atoll w •w _ . .j Shennan, J.L. and W.W. Fletcher. 1965. The growth in vitiio of microorganisms in the presence of substituted phenoxyacetic and phenoxybutric acids. : Meed Res. 5:226. , • ~ ' • * . Smith, A.E. 1972* The hydrolysis of 2,4-dkhlorpphenoxyacetate esters to 2,4-dichlorophenoxyacetid-acid in Saskatchewan soils. Weed Res. 12:364-372. _——; .' " T. " Smith, D.D. and R.P. Brown. 1971 Ocean.disposal of barge-delivered liquid and solid wastes from U.S. coastal c i t i e s " P H S Publn. 2113. Govt. FrTnting Office, Washington", D.C. Sorg, T.J. and H.L. Hickman. 196$. Sanitary landfill facts. Public Health Svc. Publn. 1792. Govt. Printing Office, Washington, D.C. , ' •" " i Sparschj, G.L. et^ al_. 1970. Teratogenic study of 2,3,7,8-tetrachlprodibenzop-dioxin in the rat. Toxicol ---i ~r - Appl. Pharmacol. 17:317. _ Stahl, Q.R. 1969. Air pollution aspects of hydrochloric acid. Litton Systems, Inc., Bethesda, Maryland. Available from Clearinghouse for Federal Scientific and Technical Information, Springfield, Va, Publication PB188067. •. • . . - . ' • • • r rStanley, C.W. 1966. Derivatization of pesticide-related acids and phenols for gas chromatographic determination. J^Agr. Food Chem. 14:321. * . ' * Sterling, t.D. 1971. Difficulty of evaluating'the toxicity and teratogenicity of 2,4,5-T from existing animal experiments. Science 174:1358. . .. ., * "* ' • . • •" ^. ...... Stojanovic, B.J., M.V. Kennedy, and F.L. Shuman. 19'72. Edaphic aspects of the disposal of unused pesticides, pesticide wastes, and pesticide containers. J. Environ. Quality. 1:'54. ' ; •' Stojanovic, B.J., M.V. Kennedy, and W.C. Shaw. '197?. Technical report on thermal decomposition of Orange herbicides. Miss. Agricultural and Forestry Exp. Sta. and Plant Science Research Div. of USDA^ Miss.. State Univ., State College, Miss. ' ' . - [ �Suskind, Raymond. 1973. Chloroacne and associated problems. Paper presented at Natl. Inst.^ of Environ. Health Sciences Conf. on Chlorinated Dibenzodioxins and Dfbenzodlfurans, Research Triangle Park, N.C. Thiesen, P.A. 1967. Chemical weeding and release of conifers in southwestern Oregon. Symposium Proceedings: Herbicides and vegetation management, Oregon State Univ., Corvallis, Oreg. Thomas, T.C. and J.N. Seiber. In press. Evaluation of Chromosorb 102 as a medium'for trapping pesticides from air. Bull. Environ. Contam. Toxicol, accepted for publication August 1973. • • • • • * • " Thorp, T.E. 1960. Johnston Island, a library brochure. Prepared for the Pacific Missile Range. Dept. Geog., Univ. Calif., Riverside. U.S. Air Force. 1968. 'Durchase Description No. AFPID, 23 Feb 68. U.S. Air Force. 11 Apr 68. 1968. D • urchase Description No. AFPID 6840-;, Amend'. 1, - • r — U.S. Army. 1969. Herbicides used ii Southeast Asia. Rept. No. SAOQ-TR69-11078. Plant Scisnces Lab, Fort Detrick, Md. (Contract #FD-20509-11078). U.S. Army. 1973. Ocean dumping in the New York bight: an assessment of environmental studies (by George Pararas-Carayannis). Technical Manual No. 39. U.S. Army, Corps of Engineers, Coastal Engineering Research Ceite1'1. U.S. Dept. of Agr. 1964 and 1966. Div., USDA. 1970. Report and tables on domestic use of a 2,4,5-T, Production Resources Branch, Farm Production Economics '- 1972. Thermal decomposition of Orange herbicides. Mis's. Agricultural and Forestry Experimental Station and Plant Science Research Div, USDA. Cooperative Agreement No. 12-14-100-10, 673(34). U.S. Dept. of Commerce, Environmental Data Service. 19/2. Local ciimatological data, annual summary with comparative data, Johnston Island, Pacific. National Climatic Center, Asheville, N.C. USAF EHL(K)--USAF Environmental health Laboratory, Kelly AFB. a. ' 1973. Letter regarding ARL analyses for BTU content of Gulfport Orange herbicide stocks. (12 Oct 73). r b. 1973. Statistical presentation of the results of analysis for dioxin concentrations found in Orange herbicide analyses performed by Dow Chemical Co. Unpublished'data. USAF EHl.(K), Kelly AFB Texas. USAF Histories, Pacific Air Forces Base Command, 1959-1963. USAF RPL-USAF Rocket Propulsion Lab. 1972. Contract No. FO-4611-72-C-0087. �USDHEW—U.S. Dept. of Health, Education and Welfare. 1969. Reoort of the Secretary's Commission on Pesticides and Their Relationship to Environmental Health. Govt. Printing Office, Washington, D.C. Walker, C.M. 1973. Rehabilitation of forest lands. J. Forestry 71:136. Walsh, G.E. 1972. Effects of herbicides on photosynthesis and growth of marine unicellular algae. Hyacinth Cont. J. 10:45. Wennekens, M.P. 1969. Johnston Island regional oceanography, Section 6. Office of Naval Research, San Francisco, Calif. Wetmore., A. ms. a. Field notes, 1923. 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The ecological consequences of massive quantities of 2,4-D and 2,4,5-T herbicides—summary of a five year field study. Presentation to the Weed Science Society of America, Las Vegas, Nev. Young, A.L.,E.L. Arnold, anc A.M. Wachirski. 1974. Field studies on the soil persistence and movement of 2,4-D, 2.4,5-T and TCDD. Presentation to the Weed Science Society of America, Las Vegas, Nev. Zielinski, W.L., Jr. and L. Fishbein. 1967. Gas chromatographic measurement of disappearance rates of 2,4-D and 2,4,5-T acids and esters in mice. J. Agr. Food Chem. 15:841. Zinkl, J. e_t aJL 1973. Herratological and clinical chemistry effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin in laboratory animals. Environ. Health Perspect. No. 5:111. V �� Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 011 Folder The folder containing the original item. 0094 Series The series number of the original item. Series II Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Description An account of the resource <strong>Corporate Author: </strong>Department of the Air Force Date A point or period of time associated with an event in the lifecycle of the resource 1974-11-01 Title A name given to the resource Final Environmental Statement on Disposition of Orange Herbicide by Incineration Subject The topic of the resource herbicide disposal ecological impact biodegradation dioxin Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 051 Folder The folder containing the original item. 1346 Series The series number of the original item. Series III Subseries II Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Young, Alvin L. Description An account of the resource <strong>Corporate Author: </strong>Office of Environmental Medicine, Veterans Administration, Washington, D. C. Source A related resource from which the described resource is derived Human and Environmental Risk of Chlorinated Dioxins and Related Compounds Date A point or period of time associated with an event in the lifecycle of the resource 1982 Title A name given to the resource Long-Term Studies on the Persistence and Movement of TCDD in a Natural Ecosystem Subject The topic of the resource dioxin Eglin AFB ecological fate biodegradation ao_seriesIII https://www.nal.usda.gov/exhibits/speccoll/files/original/5c56b76a52235883573a7e79bc378e2f.pdf 2abd017e641043200a441dac5938a007 PDF Text Text Item ID Number °1165 Author Young, Alvin L. United States Air Force Occupational and Environmental Report/Article Title The Toxicology, Environmental Fate, and Human Risk of Herbicide Orange and its Associated Dioxin Journal/Book Title Year Month/Day Color Oct ber ° D Number of Images 263 DeSCrlptOU NOtBS A'v'n *-• Young filed this item under the category "Human Exposure to Phenoxy Herbicides and TCDD" Thursday, April 05, 2001 Page 1165 of 1180 �• 4 MTlftrO A-L. eVdL Report OEHLTR-78-92 r ^j-—-' j •••4>^ USAF OEHL TECHNICAL REPORT THE TOXICOLOGY, ENVIRONMENTAL FATE, AND HUMAN RISK OF HERBICIDE ORANGE AND ITS ASSOCIATED DIOXIN Alvin L. Young, Captain, USAF John A. Calcagni, Lieutenant Colonel, USAF, MC Charles E. Thalken, Lieutenant Colonel, USAF, VC James W. Tremblay, Major, USAF, BSC October 1978 Final Report I Approved for public release; distribution unlimited PREPARED FOR: The Surgeon General United States Air Force Washington, D.C. 20314 USAF Occupational and Environmental Health Laboratory Aerospace Medical Division (AFSC) Brooks Air Force Base, Texas 78235 �NOTICES This report has been released to the National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161, for sale to the general public. *** Qualified requestors may obtain copies of this report from Defense Documentation Center (DDC), Cameron Station, Alexandria, Virginia 22314. *** This technical report has been reviewed and is approved for publication. WILLIAM E. MABSON, Colonel, USAF, BSC Commander �UNCLASSIFIED S E C U R T t V ' t V A S S I F I C A T I O N OF T H I S P A G E (When Data Entered) READ INSTRUCTIONS BEFORE COMPLETING FORM REPORT DOCUMENTATION PAGE 2. GOVT ACCESSION NO 1. REPORT NUMBFR 3. RECIPIENT'S C A T A L O G NUMBER USAF OEHL - 7 8 - 9 2 i t " . ; ':" C-inrt Subtitle) 5. TYPE OF REPORT & PERIOD COVERED The Toxicology, Environmental Fate and Human Risk of. • i , Herbicide Orange and Its • Associated. Dioxin - • , Fin; I 6. PERFORMING ORG. REPORT NUMBER 3 ?. AUTHOR,,, /\yvin L. young, Captain, USAF John A. Calcagni, Lieutenant Colonel, USAF, MC Charles E. Thai ken, Lieutenant Colonel, USAF, VC : James U. Tremblay, Major. USAF, BSC 8. C O N T R A C T OR G R A N T NUMBERfa.) 9. P E R F O R M I N G O R G A N I Z A T I O N N A M E AND ADDRESS 10. PROGRAM ELEMENT, PROJECT, TASK A R c A & WORK UNIT NUMBERS US Air Force Occupational and Environmental Health Laboratpry Brooks AFB TX 78235 11. 12. CONTROLLING OFFICE NAME AND ADDRESS REPORT DATE October 1978 The Surgeon General US Air 'Force 13. NUMBER OF PAGES Washington, DC 20314 14 M O N I T O R I N G A G E N C Y N A M E 4 ADDRESS^/ different Iron Controlling Olficv) 15. S E C U R I T Y CLASS, (at this report) Unclassified 1Sa. DECLASSIFI CATION/ DOWN GRADING SCHEDULE 16. D I S T R I B U T I O N S T A T E M E N T (ol this Report) Approved for public release; distribution unlimited. 17. D I S T R I B U T I O N STATEMENT (ol the abstract entered In Block 30, It different 18. tram Report) S U P P L E M E N T A R Y NOTES Authors: A.L. Young, PhD J.A. CaVcagni, MD C.E. Thalken, DVM J.W. Tremblay, P.E. 19. KEY WORDS (Continue on reverse aide II nocessary and identity by block number) clorinated phenols 2,4-dichlorophenoxyacetic acid (2,4-D) dioxin environmental monitoring herbicides Herbicide Orange phenoxy herbicides Pacer HO Ranch Hand South Vietnam toxicity - animal toxicity - human 20. A B S T R A C T fContinue on reverse aide If necnssary and Identify by block number) The use of herbicides in South Vietnam between 1962 and 1971 was reviewed, including the nature and quantities of herbicides used, their handling and application.' Emphasis was placed on Herbicide Orange, a 50:50 mixture of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), with its associated contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The atrisK US military population in South Vietnam was defined to establish the potential for exposure in handling "and application of Herbicide Orange. The environmental fate of the phenoxy herbicides and TCDD was reviewed to evaluate E O . T I O M O F I - . ' 6 5 I S OBSOLETE U N C L A S S I F I FD SS.CURITY CLASSI f : » iT, r;) A G E (Wien Deta Entt-rr ' �UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAOBftWiwi £>•<« Entered) Item 19. Key Words (cont): 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) Item 20. Abstract (cont): the potential for human risk associated with exposure to areas previously treated with Herbicide Orange. The occupational and environmental aspects of the project to incinerate at sea 2.22 million gallons of Herbicide Orange durinc the summer of 1977 were summarized to assess the potential for human exposure in handling large quantities of the material. Scientific data were reviewed on incidents and episodes involving suspected poisoning of humans or animals by phenoxy herbicides or TCDD. Literature dealing with animal toxicology and the effects of human exposure to 2,4-D, 2,4,5-T and TCDD was reviewed to correlate exposures with symtomatology. iv UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGEfHTion Data Entered) �PREFACE The use of herbicides in support of tactical military operations in South Vietnam from 1961 to 1971 has had (and continues to have) a negative impact on the use of pesticides by numerous facets of our society. fjrior to the Vietnam conflict, herbicides were considered invaluable to agriculture, innocuous to human life and of little environmental concern. Today, seven years after the last herbicide mission in Vietnam, these same herbicides are the center of scientific debate involving not only ecological but also medical, legal and political issues. The United States Environmental Protection Agency (EPA) has recently issued a Notice of Rebuttable Presumption Against Registration (RPAR) of pesticides containing one of these "Vietnam" herbicides, while at the same time some Veterans of the Vietnam Conflict have reported medical problems they claimed were the result of herbicide exposure while assigned to military duties in Vietnam. In April 1978, the Surgeon General of the United States Air Force (USAF) tasked personnel'of the USAF Occupational and Environmental Health Laboratory, Brooks AFB, Texas with updating previous scientific assessments of possible adverse effects to human health resulting from exposure to the herbicides, especially Herbicide Orange used in South Vietnam during the Vietnam Conflict. The present report was assembled using the latest available published scientific information, previously unpublished data, and observations from medical and scientific personnel intimately associated with the herbicides in question. The report reviews the use of phenoxy herbicides in Vietnam, their environmental fate, and pertinent animal and human toxicological studies. In addition, a description is given of the 1977 military operation for the disposal of Herbicide Orange emphasizing the facets of environmental monitoring and industrial hygiene. The document concludes with an assessment of the risk to human health following exposures to the phenoxy herbicides. Special emphasis was placed upon the chemistry, environmental fate and toxicology of the trichlorophenoxy herbicide contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD or dioxin). The authors are indebted to Kenneth C. Back, PhD, Chief Toxicology Branch, Toxic Hazards Division, United States Air Force 6570th Aerospace Medical Research Laboratory, Wright-Patterson AFB Ohio for his critical review of-this document and the many recommendations he made to improve the qualify of the discussions on toxicology. Special thanks are expressed to Rodney W. Bovey, PhD, United States Department of Agriculture", Texas A&M University, College Station, Texas, for his assistance in providing copies of the foreign literature on the phenoxy herbicides. �The services of many staff members and consultants of the United States Air Force Occupational and Environmental Health Laboratory are acknowledged. Special acknowledgement is made to Mrs Joyce G. Kidd who served as the general editor, and to the following typists who willingly worked numerous overtime hours in preparing this manuscript: Ruth S. Bledsoe; Yolanda Carrisalez; Irma Ledesma; Lorraine M. Polonis; Nancy L. Ragan and Trina Roark. �CONTENTS Page PREFACE v CHAPTER I .THE USE OF HERBICIDES IN SOUTH VIETNAM I. INTRODUCTION 1-1 II. THE HERBICIDES USED IN SOUTH VIETNAM A. Historical B. Descriptions of the Herbicides Used in Operation RANCH HAND 1-1 1-1 1-3 C. Quantities of Herbicides Sprayed in South Vietnam D. Land Area Sprayed with Herbicides in South Vietnam III. THE AIRCRAFT, SPRAY SYSTEMS AND MISSION CONCEPT IN OPERATION RANCH HAND A. Historical B. Spray Systems and Characteristics of the RANCH HAND Aircraft C. Mission Concepts 1-8 1-11 I-11 1-11 1-14 1-15 IV. PERTINENT DEPLOYMENT AND BIOLOGICAL FACTORS OF THE HERBICIDES 1-18 A. Use Patterns of Individual Military Herbicides B. Canopy Penetration of Defoliants « V. 1-18 1-20 ESTIMATED QUANTITIES OF INDIVIDUAL CHEMICALS SPRAYED IN SOUTH VIETNAM A. Herbicide Orange and its Components 2,4-D, 2,4,5-T and TCDD B. Military Projects that Involved Handling Herbicides Orange, Purple, Pink or Green VI. SUMMARY 1-21 1-29 1-29 LITERATURE CITED 1-32 LIST OF TABLES 1. Selected physical, chemical and toxicological properties of the three major military herbicides used in South Vietnam, 1962 - 1971. VI 1 1-5 �2. Number of gallons of military herbicide procured by the U.S. Department of Defense and disseminated in South Vietnam during the period January 1962 - December 1964. 1-9 3. Estimated number of gal of military herbicide procured by the U.S. Department of Defense and disseminated in South Vietnam during the period January 1965 - February 1971. 1-10 4. Comparison of data from three sources of the estimated number of acres treated in South Vietnam during the period of January 1962 - February 1971. Data make noi allowance for multiple coverage. 1-12 5. The number of acres treated in South Vietnam, 1962 - 1971, with military herbicides within the three major vegetational categories. Data represent areas receiving single or multiple coverage and for 90 percent of all areas treated. 1-13 6. Concentration, ppm, of TCDD in samples of Herbicides Orange and Purple. 1-23 7. Composition, percent, of selected samples of Herbicide Orange in relation to military specifications. 1-27 8. Estimated quantities of herbicides and TCDD disseminated in South Vietnam from January 1962 - February 1971. 1-28 9. Data on the major military projects involved in the handling and/or spraying of Herbicides Orange, Purple, Pink or Green in support of military programs in South Vietnam. 1-30 LIST OF FIGURES 1. Chemical structure and nomenclature of the major herbicides used in South Vietnam, 1962-1971. Formulas A and B comprised Orange, C and D - White, and E was Blue. 1-6 2. Structure and physical/chemical characteristics of 2,3,7,8- tetrachlorodibenzo-p-dioxin, TCDD or dioxin. VII I 1-22 �CHAPTER II DISPOSAL OF HERBICIDE ORANGE Page I. INTRODUCTION 11-1 II. HISTORICAL BACKGROUND II-l III. DESCRIPTION OF LAND-BASED OPERATIONS A. NCBC, Gulfport MS B. Johnston Island I1-2 II-3 II-4 * IV.. LAND-BASED OPERATIONS MONITORING PROGRAMS A. Monitoring Equipment and Procedures B. Analytical Procedures and Methodologies V. LAND-BASED MONITORING RESULTS II-5 II-6 II-7 II-8 A. NCBC, Gulfport MS II-8 B. Johnston Island 11-10 VI. SUMMARY AND CONCLUSIONS 11-15 LITERATURE CITED , 11-19 LIST OF TABLES 1. Results of industrial hygiene air samples collected inside the dedrumming facility Project PACER HO NCBC, Gulfport MS, 24 May 10 June 1977. II-9 2. Results of ambient air samples collected at Gulfport MS, Project PACER HO, 24 May - 10 June 1977. 11-11 3. Results of industrial hygiene air samples collected inside the dedrumming facility, Project PACER HO Johnston Island, first loading 27 July - 5 August 1977 11-12 4. Results of industrial hyigiene air samples collected inside the dedrumming facility Project PACER HO, Johnston Island, second loading, 17-23 August 1977. 11-13 5. Results of industrial hygiene "breathing zone" samples collected inside the dedrumming facility Project PACER HO, Johnston Island. IX 11-14 �6. Results of downwind ambient air samples collected at Johnston Island, Project PACER HO, 27 July - 23 August 1977. 7. Results of upwind ambient air samples collected at Johnston Island, Project PACER HO, 27 July - 23 August 1977. 11-16 11-17 CHAPTER III ENVIRONMENTAL FATE OF 2,4-D, 2,4,5-T AND TCDD I. THE ENVIRONMENTAL FATE OF THE PHENOXY HERBICIDES III-l III-l IJ.I-4 III-6 THE ENVIRONMENTAL FATE OF TCDD 111-7 A. Analytical Limitations 111-7 B. Laboratory Studies of TCDD C. Field Studies of TCDD III-7 III-ll D. Environmental Production of TCDD E. Photodegradation of TCDD III. III-l A. Physical/Chemical Factors Influencing Disappearance of Herbicide B. Biological Degradation of the Phenoxy Herbicides C. Accumulation and Metabolism of Phenoxy Herbicides in Animals II. INTRODUCTION 111-20 111-21 IV. SUMMARY LITERATURE CITED II1-22 III-24 LIST OF TABLES 1. Concentrations of TCDD, parts per trillion, in the Herbicide Orange biodegradation plots, AFLC Test Range, Utah, four years after applications, 111-15 2. Concentration of TCDD in soil profile of Grid 1, Test Area C-52A, Eglin AFB, Florida. 111-17 LIST OF FIGURES 1. Semi-loaarithmic olot of soil concentrations (parts per million) of herbicide in Herbicide Orange biodegradation studies at Eqlin AFB, Florida, and Hill AFB, Utah. TIT-13 �2. Semi-logarithmic plot of soil concentrations (parts per trillion) of TCDD in Herbicide Orange biodegradation studies at Eglin AFB, Florida, and Hill AFB, Utah. 111-14 CHAPTER IV THE TOXICITY OF 2,4-D, 2,4,5-T AND TCDD IN ANIMALS I. II. INTRODUCTION IV-1 REVIEW OF 2,4-D TOXICITY IN ANIMALS . A. The Acute and Short-Term Toxicity Potentials of 2,4-D IV-3 IV-3 B. The Subacute and Chronic Toxicity Potentials of 2,4-D . . IV-5 C. Absorption, Distribution and Excretion of 2,4-D D. Embryotoxic, Fetotoxic and Teratogenic Potentials of 2,4-D IV-17 E. Carcinogenic and Tumorigenic Potentials of 2,4-D IV-20 F. Mutagenic and Cytogentic Potentials of 2,4-D in Animals IV-23 REVIEW OF 2,4,5-T TOXICITY IN ANIMALS IV-26 A. The Acute and Short-Term Toxicity Potentials of 2,4,5-T III. IV-16 IV-26 B. The Subacute and Chronic Toxicity Potentials of 2,4,5-T C. Absorption Distribution and Excretion of 2,4,5-T IV-26 IV-31 D. Embryotoxic, Fetoxic and Teratogenic Potentials of 2,4,5-T IV-36 E. Carcinogenic and Tumorigenic Potentials of 2,4,5-T IV-46 F. Mutagenic and Cytogenic Potentials of 2,4,5-T IV-47 IV. REVIEW OF TCDD TOXICITY IN ANIMALS A. The Acute and Short-Term Toxicity Potentials of TCDD IV-50 IV-50 �B. The Subacute and Chronic Toxicity Potentials of TCDD IV-52 C. Absorption Distribution and Excretion of TCDD IV-56 D. Embryotoxic, Fetoxic and Teratogenic Potentials of TCDD IV-61 E. Carcinogenic and Tumorigenic Potentials of TCDD F. Mutagenic and Cytogenic Potentials of TCDD IV-71 SUMMARY OF THE LITERATURE REVIEW OF THE TOXICITY OF 2,4-D, 2,4,5-T AND TCDD IN ANIMALS IV-72 A. 2,4-D IV-72 B. 2,4,5-T IV-73 C. TCDD IV. IV-63 IV-74 • LITERATURE CITED IV-76 LIST OF TABLES 1. Summary of literature data on the no-effect, LD^Q and LD-iuu levels of the acute toxicity of 2,4-D in nn animals IV-6 2. Summary of literature data on the subacute and chronic toxicity of 2,4-D in animals IV-13 3. Summary of literature data on the embryotoxic, fetotoxic and teratogenic potentials of 2,4-D in animals IV-21 4. Summary of literature data on the carcinogenic and tumorigenic potentials of 2,4-D in animals IV-24 5. Summary of literature data on the no-effect LD50 and LD-inn levels of the acute toxicity of 2,4,5-T in animals IV-27 6. Summary of literature data on the subacute and chronic toxicity of 2,4,5-T in animals IV-32 7. Summary of literature data on the embryotoxic, fetotoxic and teratogenic potentials of 2,4,5-T in animals IV-41 8. Summary of literature data on the carcinogenic and tumorigenic potentials of 2,4,5-T in animals XII IV-48 �9. Summary of literature data on the no-effect, 1050 'and levels of the acute toxicity of TCDD for animals IV-53 10. Summary of literature data on the subar.ute and chronic toxicity of TCDD in animals IV-57 11. Summary of literature data on the embryotoxic, fetoxic and teratogenic potentials of TCDD in animals IV-64 12. Summary of literature data on the carcinogenic and tumorigenic potentials of TCDD in animals IV-69 CHAPTER V 2,4,5-T/TCDD EPISODES I. II. INTRODUCTION V-l INDUSTRIAL EXPERIENCES V-2 A. Industrial Processes B. Industrial Episodes ' V-2 . V-5 III. VIETNAM EPISODE IV. , EASTERN MISSOURI HORSE ARENA EPISODE V. THE SEVESO, ITALY EPISODE VI. V-12 V-17 V-19 GLOBE, ARIZONA EPISODE V-21 VII. THE SWEDISH LAPLAND EPISODE V-24 VIII. THE AWAMUTU, NEW ZEALAND EPISODE IX. DISCUSSION OF LITERATURE AND CONCLUSIONS X. SUMMARY V-26 V-28 V-32 LITERATURE CITED V-33 LIST OF TABLES 1. Total United States production and use of 2,4,5-T herbicide for the period 1961 through 1969. V-3 2. Industrial incidents associated with the manufacture of chlorinated phenols. V-7 XTM �3. Some clinical features observed in cases of chloracne associated with production of 2,4,5-T and other chlorinated phenols. V-10 LIST OF FIGURES 1. Synthesis scheme for production of the n-butyl ester 2,4,5-T (NBE 2,4,5-T) and site where formation of TCDD may occur. V-4 CHAPTER VI HUMAN EFFECTS OF HERBICIDE ORANGE I. II. INTRODUCTION . VI-1 PHARMACODYNAMICS VI-1 A. B. C. D. VI-1 VI-1 VI-2 VI-4 Percutaneous Entry of Phenoxy Herbicides Ingestion of Phenoxy Herbicides Tissue Analyses for the Phenoxy Herbicides Pharmacodynamics "of TCDD III. ADVERSE EFFECTS VI-4 A. Limitations of Referenced Studies B. Phenoxy Herbicides That Do Not Contain TCDD C. Trichlorophenol (TCP), 2,4,5-T and TCDD D. Cancer VI-12 VI-27 CONCLUSIONS VI-28 A. Pharmacodynamics B. Effects of the Herbicides VI-28 VI-29 C. Effects of TCDD IV. VI-4 VI-6 VI-30 V. SUMMARY VI-30 LITERATURE CITED VI-31 LIST OF TABLES 1. Levels (part per million) of phenoxy herbicides in human tissue or body fluid following ingestion of fetal dose. VI-3 2. TCDD levels in a human body. VI-3 3. Distribution of symptoms in 292 workers employed in the production of the amine salt and the butyl ester of 2,4-D VI-7 xiv �4. Distribution of adverse effects in case reports following the ingestion of non-TCDD containing phenoxy herbicides. VI-9 5. Distribution of reported adverse effects following exposure of field workers and applicators to 2,4-D. VI-11 6. Organ systems reported affected after occupational exposure to PCP, TCP, 2,4,5-T or TCDD. VI-13 7. Signs, symptoms, and disorders reported after occupational exposure to TCP, 2,4,5-T or TCDD. VI-14 8. Special clinical studies following occupational exposure to TCP, 2,4,5-T or TCDD. VI-15 9. Organ systems reported affected after exposure to TCP and TCDD following an industrial accident. VI-17 10. Signs, symptoms and disorders reported after exposure to TCP and TCDD following an industrial accident. VI-18 11. Special clinical studies after exposure to TCP and TCDD following an industrial accident. xv VI-19 �CHAPTER I THE USE OF HERBICIDES IN SOUTH VIETNAM I. INTRODUCTION The introduction of herbicides in 1962 into the armed conflict in Vietnam represented an application of a new technique for modern warfare. Their use in a defensive role was for defoliation. Their use in offensive roles was for food crop denial. The herbicides most widely employed were the phenoxyacetic acids. They were extensively used for almost a decade throughout the forested, semi-populated, regions of South Vietnam. Assessments -of their ecological impact in South Vietnam have been published (see Chapter V). An assessment of the effects of herbicides on the human indigenous populations of South Vietnam has also been conducted (11). No assessment has been made of potential adverse human effects of the phenoxy herbicides or the toxic contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) on personnel of the U.S. Military forces. Adverse human effects in military personnel due to the herbicides or the contaminant would be predicated on the assumption that an exposure occurred. The presence of military spray aircraft or the observation that drums of herbicide were stored on a military installation, or even smelling the odor of "herbicides" in the air does not necessarily constitute an exposure to the herbicide per se. An exposure would have had to involve physical contact for a sufficient period of time to permit the chemical(s) to penetrate the body. This chapter examines those factors that would have influenced the likelihood of such exposures. They include: 1. the nature of the herbicides used in South Vietnam, 2. the nature of the herbicide applications, 3. the procedures employed in the handling of the herbi- cides, and 4. the quantities of individual chemicals sprayed in South Vietnam. Detailed examinations of these "parameters" are reported in the following sections. II. THE HERBICIDES USED IN SOUTH VIETNAM A. Historical The discovery and early history of the phenoxy herbicides 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) have been reviewed by Peterson (31). Peterson noted 1-1 �that the effectiveness of these plant growth regulators as "herbicides" was determined in mid-1944 field trails at Beltsville and Camp Detrick (now Fort Detrick), Maryland. The outstanding effectiveness of these two herbicides in controlling the growth of broad-leaved plants and weeds, coupled with their apparently low mammalian toxicity and low application rates, resulted in their rapid acceptance in world agriculture. Peterson (31) reported that the annual production of 2,4-D alone exceeded 14,000 pounds in 1950 and 36,000,000 pounds in 1960. Irish et al (26) and Darrow et al (14) have documented the early military use of the phenoxy herbicides. They reported that the earliest aerial spray trials (conducted in military aircraft) occurred in 1944 and 1945. Three different mixtures of 2,4-D were used in these early tests. Although herbicides were not used in tactical military operations in World War II, a small program for screening potential herbicides for military use continued after the War. By 1951, personnel at Fort Detrick had determined that the vegetationcontrol chemicals of choice were mixtures of the butyl esters of 2,4-D and 2,4,5-T. In 1959, the Crops Division, Fort Detrick, conducted the first large-scale military defoliation effort at Fort Drum, New York. This project involved the aerial application of the butyl esters of 2,4-D and 2,4,5-T to approximately four square miles of vegetation. Its success prompted the Office of the Secretary of Defense (OSD) in May 1961 to request that the Crops Division determine technical feasibility of defoliating jungle vegetation in the Republic of Vietnam. As part of a project to evaluate herbicides and defoliation techniques (Project AGILE) in Southeast Asia, Brown (7) conducted eighteen different aerial, spray tests (defoliation and anticrop) with various formulations of commercially .available herbicides. The choice of these herbicides was based "upon the chemicals that had had considerable research, proven performance, and practical background. Also, other factors had to be considered, such as availability in large quantity, costs and known or proven safety in regard to their toxicity to humans and animals" (7). The results of these tests were that significant defoliation and anticrop effects could be obtained with two different mixtures of herbicides. The first was a mixture of the n-butyl esters of 2,4-D and 2,4,5-T and the iso-butyl ester of 2,4,5-T. This mixture was code-named "Purple". The second "military" herbicide was code-named "Blue" and consisted of the acid and sodium salt of cacodylic acid. The colored bands which were painted around the center of the 55-gallon drums served as aid to the identification by support personnel. Brown (7) reported that the first shipment of Herbicides Purple and Blue was received at Tan Son Nhut Air Base, Republic of Vietnam, on 9 January 1962. These were the first military herbicides used in Operation RANCH HAND, the tactical military project for the aerial spraying of herbicides in South Vietnam. Two additional phenoxy herbicide formulations were received in limited quantities in South Vietnam and evaluated during the first two years of Operation 1-2 �RANCH HAND. These were code-named Pink and Green and will be described in the subsequent section. By January 1965, two additional military herbicides had been evaluated and brought into the spray program. These were code-named Orange and White, and are also described below. Herbicide Orange replaced all uses of Purple, Pink, or Green and eventually became the most widely used military herbicide in South Vietnam. In April 1970, the Secretaries of Agriculture; Health, Education and Welfare, and the Interior jointly announced the suspension of certain uses of 2,4,5-T. These suspensions resulted from published studies indicating that 2,4,5-T was a teratogen. Subsequent studies revealed that the teratogenic effects had resulted from a toxic contaminant in the 2,4,5-T, identified as 2,3,7,8-tetrachlorodibenzop-dioxin (TCDD). 'Subsequently, the Department of Defense suspended the use of Herbicide Orange (4). At the time of the suspension, the Air Force had an inventory of 1.37 million gallons of Herbicide Orange in South Vietnam and 0.85 million gallons at the Naval Construction Battalion Center (NCBC), Gulfport, Mississippi. In September 1971, the Department of Defense directed that the Herbicide Orange in South Vietnam be returned to the United States and that the entire 2.22 million gallons be disposed of in an environmentally safe and efficient manner. The 1.37 million gallons were moved from South Vietnam to Johnston Island, Pacific Ocean for storage in April 1972. B. Descriptions of the Herbicides Used in Operation RANCH HAND The following military herbicides were used in South Vietnam in Operation RANCH HAND. The first three were extensively used in both defoliation and anticrop programs. Only limited quantities of the herbicides Purple, Pink or Green were used in South Vietnam, and then primarily during the 1962-1964 time period. 1. Herbicide Orange Orange was a reddish-brown to tan colored liquid soluble in diesel fuel and organic solvents, but insoluble in water. One gallon (gal) of Orange theoretically contained 4.21 pounds (lb) of the active ingredient of 2,4-D and 4.41 lb of the active ingredient of 2,4,5-T. Orange was formulated to contain a 50:50 mixture of the n-butyl esters of 2,4-D and 2,4,5-T. The percentages of the formulation typically were: n-butyl ester of 2,4-D free acid of 2,4-D n-butyl ester of 2,4,5-T free acid of 2,4,5-T inert ingredients (e.g., butyl alcohol and ester moieties) 1-3 49.49 0.13 48.75 1.00 0.62 �Some of the physical, chemical, and toxicological properties of Orange are listed in Table 1. The structures of the n-butyl esters of 2,4-D and 2,4,5-T are shown in Figure 1. 2. Herbicide White White was a dark brown viscous liquid that was soluble in water but insoluble in organic solvents and diesel fuel. One gal of White contained 0.54 Ib of the active ingredient of 4-amino-3,5,6trichloropicolinic acid (picloram) and 2.00 Ib of the active ingredient of 2,4-D. White was formulated to contain a 1:4 mixture of the triisopropanolamine salts of picloram and 2,4-D. The percentages of the formulation were: triisopropanolamine salt of picloram triisopropanolamine salt of 2,4-D inert ingredient (primarily the solvent triisopropanolamine) 10.2 39.6 50.2 Some of the physical, chemical, and toxicological properties of White are listed in Table 1. The structures of the triisopropanolamine salts of 2,4-D and picloram are shown in Figure 1. 3. Herbicide Blue Blue was a clear yellowish-tan liquid that was soluble in water, but insoluble in organic solvents and diesel fuel. One gal of Blue contained 3.10 Ib of the active ingredient hydroxydimethyarsine oxide (cacodylic acid). Blue was formulated to contain both cacodylic acid (as the free acid) and the sodium salt of cacodylic acid (sodium cacodylate). The percentages of the formulation were: cacodylic acid 4.7 sodium cacodylate surfactant 26.4 3.4. sodium chloride water antifoam agent 5.5 59.5 0.5 Some of the physical, chemical, and toxicological properties of Blue are listed in Table 1. The structure of the sodium salt of cacodylic acid is shown in Figure 1. It should be noted that cacodylic acid and sodium cacodylate contained arsenic in the form of the pentavalent, organic arsenical. This form of arsenic was essentially nontoxic to animals as can be noted by the LD^Q value for white rats. Of the total formulation, 15.4 percent was arsenic in the organic form, only trace quantities were present in the inorganic form. The term Herbicide Blue was first applied to powdered cacodylic acid in 1961 through 1964. This first Herbicide Blue contained 65 percent active ingredient 1-4 �TABLE 1. Selected physical, chemical and toxicological properties of the three major military herbicides used in South Vietnam, 1962 - 1971.a- Herbicide Code Name Orange White Blue a Molecular Mass Specific Density, 25°C Viscosity, Centipose, 23°C Weight Total Acid Ester Equivalent Ib/gal Ib/gal Soluble in Water Specific Tpxicity for Mhite Rats mg/kgb. Relative Toxicity 589 1.28 43 10.7 8.62 No 1,173 1.12 125 9.4 2.54 Yes 3,080 Very Low 296 1.32 14 10.9 3.10 Yes 2,600 Very Low 566 Low Source: (35) Milligrams of the herbicide per kilogram of body weight of the test animal lethal to 50 percent of white rats. �n-butyl ester of 2,4-dichlorophenoxyacetic acid (2,4-D) B. n-butyl ester of 2,4,5-trichlorophenoxyacetic acid (^,4,5-T) 0 0-CH0C-0~ +NH[C H ^ 3 6 03 Cl D. triisopropanolamine salt of 2,4-D - 0 -4- C-0 NH[C_H OHl 36 3 triisopropanolamine salt of 4-amino-3,5, 6-trichloropicolinic acid (picloram) CH - As - 0 Na' sodium salt of hydroxydimethylarsine oxide (cacodylic acid; FIGURE 1. ' Chemical structure and nomenclature of the major herbicides used in South Vietnam, 19621971. Formulas A and B comprised Orange, C and D - White, and E was Blue. 1-6 �cacodylic acid and 30 percent sodium chloride and was mixed in the field with water (7, 14). 4. Herbicide Orange II Orange II was the code-name of a formulation similar to Orange with the difference being the substitution of the issocytl ester of 2,4,5-T for the n-butyl ester of 2,4,5-T, The physical, chemical, and toxicological properties of Orange'II were similar to those of Orange. Orange II was produced solely by one chemical company. Approximately 950,000 gal of Oramge II were shipped to South Vietnam during 1968 and early 1969 (12). How much Orange II was returned to Johnston Island from South Vietnam in April 1972 was not determined. 5. Herbicide Purple Purple was first formulated in the mid-1950s time period. It was used in the Camp Drum, New York, defoliation test in 1959 (26). The formulation was a brown liquid soluble in diesel fuel and organic solvents but insoluble in water. One gal of Purple contained 8.6 Ib of the active ingredients 2,4-D and 2,4,5-T. The percentages of the formulation were: n-butyl 2,4-D 50 n-butyl 2,4,5-T 30 iso-butyl 2,4,5-T 20 The physical, chemical, and toxicological properties of Purple were similar to those described for Orange. 6. Herbicide Pink Pink was a formulation of 2,4,5-T used extensively in early RANCH HAND operations (7) and in the defoliation test program of 1963 and 1964 in Thailand (15). Pink was a mixture of the n-butyl and iso-butyl esters of 2,4,5-T. No data were available on the physical, chemical, or toxicological properties of Pink- However, Darrow et al (15) reported that it contained 8.16 Ib active ingredient per gal. The percentages of Pink formulation were: n-butyl 2,4,5-T 7. 60 iso-butyl 2,4,5-T 40 Herbicide Green Green was a single component formulation consisting of the n-butyl ester of 2,4,5-T. It was used in limited quantities in the 1962-1964 period (3). However, the only reported use of Green 1-7 �was in an evaluation program of herbicides for use against manioc and [(7), and correspondence between personnel of the Air Force Armament Laboratory, Eg!in AFB, Florida, and personnel of the Crops Division, Fort Detrick, Maryland, dated 5 Sep 63]. No data were available on physical, chemical, or toxicological properties of Green. Brown (7) reported that Green contained the same amount of active ingredient as Pink. 8. Other Herbicides Used in South Vietnam In addition to evaluating Herbicides Purple, Pink and Green, Brown (7) also evaluated Dinoxol, a mixture of 20 percent each of the butoxy ethanol esters of 2,4-D and 2,4,5-T; Trinoxol, 40 percent butoxy ethanol ester of 2,4,5-T; Diquat, 6,7-dihydrodipyridol (l,2-a:2'5 l'-C) pyrazidinium dibromide; and small quantities (grams) of 16 different chemicals. The latter chemicals were applied on native grasses and bamboo at the Saigon Navy Yard. Darrow et al (14) reported that small quantities of soil-applied herbicides were used on base camp perimeters, mine fields, ammunition storage areas, and other specialized sites requiring control of grasses and woody vegetation. The soil-applied herbicides evaluated for use in South Vietnam included Bromacil, 5-bromo-3-sec-butyl-methyluracil; Tandex, (3,3dimethyluneido) pheny1 -tert-butylcarbamate; Monuron, 3-(p-chlorophenyl)-!. 1-dimethylurea; Diuron, 3-(3,4-dichlorphenyl)-l, 1-dimethylurea; and Dalapon, 2,2-dichloropropionic acid. C. Quantities of Herbicides Sprayed in South Vietnam The estimated number of gal of the various military herbicides sprayed in South Vietnam from 1962 through 1971 have been obtained by examination of procurement and disposition records. The data obtained from these sources were compared to other sources when available; e.g., actual tactical mission records. Table 2 presents a summary of the available data on the number of gal of herbicides Blue, Green, Pink and Purple procured and disseminated in South Vietnam between January 1962 and December 1964. (3) Table 3 gives a comparison of the estimated number of gal procured and disseminated in South Vietnam between January 1965 and February 1971 as reported by the National Academy of Science (11), Westing (34), and Craig (12). The discrepancies in total herbicide quantity between the three sources occurred because Craig's data were from procurement records only, while the NAS and Westing data are based on both records and estimates. The latter two reports used different assumptions in calculating the total herbicide volume. These included such factors as spray line data (length and width of the spray swath), rate of application (1.5 or 3 gal/acre, and the amount of herbicide disseminated during a mission, 1-8 �TABLE 2. Number of gallons of military herbicide procured by the U.S. Department of Defense and disseminated in South Vietnam during the period January 1962 - December 1964.a Military Herbicide Gallons of Formulation Pounds Active Ingredient Blueb 5,200 10,000 Greenc 8,208 66,980 Pinkc 122,792 1,001,980 Purple 145,000 1,180,300 281 ,200 2,259,260 Total a Source document: Memorandum for Assistant Secretary of Defense from the Office of the Under Secretary, Department of the Air Force, Washington, D.C.; dated December 15, 1961. Subject: Summary of Current Status Project "RANCH HAND" Chemicals. (3) e was procured as a fine white hygroscopic powder which contained 65 percent cacodylic acid (active ingredient), 30 percent sodium chloride, 3 percent sul fates and 2 percent water. Approximately 290 1b of powder were mixed with 100 gallons of water (6). Thus, a total of 5,200 gal of Blue were probably disseminated in South Vietnam (primarily by the HIDAL Spray System). c d Pink and Green contained approximately 8.16 Ib active ingredient per gal (7). Purple contained approximately 8.14 Ib active ingredient per -gal (see Section V.A.3., Chapter I, p 1-26) 1-9 �TABLE 3. Estimated number of gal of military herbicide procured by the U. S. Department of Defense and disseminated in South Vietnam during the period January 1965 - February 1971. Military Herbicide Craig, 1974 ( 1 2 ) a NAS Report, 1974 (11 )b Westing, 1976 ( 3 4 ) c Orange 10,645,904 11,266,929 11 ,712,860 White 5,632,904 5,274,129 5,239,853 Blue 1,144,746 1,137,470 2,161 ,456 17,423,554 18,936,068 19,114,169 Total Data compiled from procurement and disposition records maintained by the San Antonio Air Logistics Center, Directorate of Energy Management, Kelly Air Force Base, Texas. The data for expenditures of Herbicide Orange, White, and Blue were based on procurement and delivery records for late FY 64 through FY 72, less those quantities of herbicides returned to Johnston Island in April 1972 or retained in the Continental United States. b See Table III C-l of the referenced National Academy of Science report (11) c See Table 3.3 of the referenced report. 1-10 �D. Land Area Sprayed with Herbicides in South Vietnam As noted, in Section C above, the estimate of acreage sprayed with herbicides was often based on spray line data and/or the quantity of herbicide expended. The National Academy of Science (11) discussed these parameters as they applied to the HERBS tape, the major source of all mission maps and tabulations of herbicide operations in South Vietnam for the period August 1965 through February 1971. Table 4 presents a comparison of data from three sources on the estimated number of acres treated in South Vietnam from January 1962 through February 1971. Included in these figures are the same areas of land counted more than once if they were sprayed more than once. Table 5 is a comparison of the data for acreage sprayed within the three major vegetational categories. These data have been corrected for multiple coverage. The National Academy of Science Report (11) concluded that herbicides were sprayed on 10.3 percent of the inland forests of South Vietnam, 36.1 percent of the mangrove forests, and 3 percent of the cultivated lands or approximately 8.6 percent of .the total land area in South Vietnam. Westing (34) estimated that approximately 10 percent of South Vietnam was sprayed. III. THE AIRCRAFT, SPRAY SYSTEMS AND MISSION CONCEPT IN OPERATION RANCH HAND Almost all herbicide used in South Vietnam was sprayed from aircraft. Irish et al (26) have described some ground delivery systems for herbicides, but noted these were used primarily for control of vegetation on minefields and perimeter defenses. U.S. military personnel were responsible for operating and maintaining the aircraft used in Operation RANCH HAND. The number and types of aircraft, their load capacity, ease of loading, and the spray system employed in them, all were important factors in determining the number of personnel required in performing the herbicide missions. Standard procedures were adopted in all herbicide handling phases of the operation. This section, then, reviews the aircraft factors where military personnel were likely to have physically contacted the herbicides. A. Historical The first aerial spray trials for herbicides were conducted by the military in 1944 and 1945 (14, 26). These early tests were accomplished using the U.S Army Chemical Corps M-10 smoke tanks hanged externally on a B-25 aircraft. By 1953, the U.S, Air Force had accomplished prove-out and acceptance testing of the large-capacity (1,000-gal) spray system known as the Hourglass or MC-1 Spray System. In 1960 and 1961, Air Force personnel assigned to the Special Aerial Spray Flight, La ITley AFB, Virginia, acquired two MC-1 Spray Systems 1-11 �TABLE 4. Comparison of data from three sources of the estimated number of acres treated in South Vietnam during the period of January 1962 February 1971. Data make n£ allowance for multiple coverage. ACRES TREATED YEAR NAS Report (11) Irish et ail. (26) Westing (34) MEAN 1962 NAa 5,68T 5,724 5,703 1963 NA 24,947 24,920 24,934 1964 NA 93,842 93,869 93,856 1965 75,50lb 221 ,559 221 ,552 221,555 1966 608,106 842 ,764 845,263 765,378 1967 1,570,114 1,707,758 1,707,784 1 ,661 ,885 1968 1,365,479 1 ,330,836 1 ,696,337 1,464,217 1969 1,365,754 NA T, 519,606 1,442,680 294,925 NA 252,989 273,982 1,259 NA 3,346 2,303 1970 1971 Total of Mean = 5,956,493 a Data not available (NA) ^Data for period August 65 through December 65. 1-12 �TABLES. The number of acres treated in South Vietnam, 1962 - 1971, with military herbicides within the three major veqetational categories. Data represent areas receiving single or multiple coverage and for 90 percent of all areas treated. ACRES TREATED Vegetational Category NAS Report, 1974 01 )a Westing, 1976 (34 )b Inland Forest 2,670,000 2,879,000 Mangrove Forest 318,000 746,000 Cultivated Crops 260,000 595,000 3,248,000 4,221,000 Total a See page II1-39 of the referenced report. b See Table 3.6 of the referenced report, Data for Inland Forest was woody subtotal, less acreage for mangrove forest. 1-13 �and modified them to spray insecticide and to interface with the newly acquired Fairchild-Hiller C-123 air transport. Irish et al (26) noted that in October 1961, six C-123 aircraft were made available to the USAF Tactical Air Command with a high-priority directive to install the MC-1 Spray System. Fabrication was accomplished-expeditiously and on 7 January 1962, three of the configured-aircraft arrived at Tan Son Nhut Air Base, Republic of Vietnam. During the early months of 1962, the C-123/MC-1 system and the HIDAL (Helicopter, Insecticide Dispersal Apparatus, Liquid) were evaluated for dissemination characteristics. The aircrews were members of the Special Aerial Spray Flight, Langley AFB, and were on temporary duty to South Vietnam as part of Operation RANCH HAND. Air Force,personnel engaged in the herbicide program did not receive permanent change of station assignments until 1964. In late 1962 and early 1963, an intensive RDT&E (Research Development, Testing and Evaluation) program was initiated between the Crops Division, Fort Detrick, and the Air Force Armament Laboratory, Eglin AFB, Florida, to provide improvements in spray system components in support of RANCH HAND (26). Concurrently, operational employment of the spray capability by the RANCH HAND units was intensified steadily with time and availability of resources. B. Spray Systems and Characteristics of the RANCH HAND Aircraft Tests and evaluations of aircraft and spray systems were conducted on the calibration grids on Test Area C-52A, Eglin AFB, Florida (6, 14, 22, 27, 35) and on the calibration grid at Pran Buri, Thailand (11, 13, 15). The C-123/MC-1 spray configuration was initially calibrated to spray 1 to 1.5 gal of herbicide per acre (gal/A) (14, 26). Thus, in 1962 and 1963 the herbicide missions conducted using this initial system resulted in the dissemination of herbicide at this lower rate. The numerous modifications and extensive evaluations of the equipment configurations at Eglin AFB and Pran Buri did not result in equipment changes for Operation RANCH HAND until 1964 (14). . Darrow et al (14) and Irish et al (26) have reported that in early 1964 the rate of 3 gal/A was obtained at first by making double passes with the aircraft but by late 1964 the modifications were complete and the system was capable of spraying 3 gal/A in a single pass. The modified 1,000-gal C-123/MC-1 spray system was capable of depositing 3 gal/A on swaths 240 feet wide when spraying at an airspeed of 130 knots at a 150 feet altitude. Two 20-hp pumps were needed to achieve the required flow rate of 430 gal/min of Purple (26). The HIDAL spray system was capable of deposits of 1.5 gal/A when flown inwind at 55 knots and at an altitude of 100 feet (26). The tank volume for this system was 200 gal. 1-14 �In early 1966, following its development, the A/A 45Y-1 Internal Defoliant Dispenser, replaced the MC-1 in all C-123 aircraft. However, completion of calibration tests and performance characteristics for this spray system did not occur until 1968 (16, 22, 27). The A/A 45Y-1 defoliant dispenser was a modular spray system for internal carriage in cargo aircraft. The module consisted of a 1,000 gal tank, pump, and engine (20 hp) mounted on a frame pallet. An operator's console was an integral part of the unit but was not mounted on the pallet. The C-123 aircraft had wing booms 1.5 inches in diameter and 22 feet long extending from the outboard engine nacelles toward the wing tips. A short tail boom 3 inches in diameter was positioned centrally near the aft cargo door. There were 16 nozzles on each wing boom and eight on the tail boom. The nozzles were check valve bodies with 3/8-inch orifices (no nozzle tips). The system was capable of spraying at the rate of 240 gal/min, which, when released at 150 feet altitude at 130 knots airspeed produced a swath 260120 feet wide with a mean deposit of 3 gal/A in a coarse spray having an MMD (mass median diameter) of 320 to 350 micron (p). Spraying time was approximately 3.5 to 4 minutes, which was adequate to dispense 950 gal of chemical on a spray line about 8.7 statute miles (14 km) in length. In order to achieve predictable deposits, it was recommended that the missions be conducted under inversion to neutral temperature situations and calm wind conditions. Craig (12) has reported that each aircraft had a crew of 3 men: the pilot, co-pilot (navigator), and flight engineer (console operator). However, observers (Vietnamese and American) frequently accompanied the aircrews on herbicide missions (32). C, Mission Concepts The objectives of the defoliation and anticrop programs in South Vietnam have been thoroughly reviewed by Huddle (23) and others (11, 14, 34). It is the objective of this section to elaborate only on the background and mechanics of a "typical" herbicide mission that would have influenced the degree of exposure to herbicides by aircrew and/or ground personnel. The following scenario of events or "standard operating procedures" has been compiled from reports by Craig (12), Darrow et al (14), Irish e't al (26) and the National Academy'of Science Report (11). 1. Each of the 11 different companies that manufactured military herbicides packed them in new ICC 17C 55-gal 18 gauge steel drums for shipment to Southeast Asia (12). Until 1967, lined drums were used only for shipment of Blue. However, because of the results of compatibility tests, lined drums were also used to ship White beginning in 1967. 1-15 �2. ^ach herbicide drum was marked with a three-inch color-coded band around the center to identify the specific military herbicide. This marking was initially a 12-inch band, but was changed to a 3-inch band in March 1966. 3. Shipping time from the arrival of the herbicide at a U.S. port until it arrived in South Vietnam varied from 47 to 52 days. 4. About 10 out of every 10,000 drums shipped were received in a damaged or defective state. This represented a damage rate of 0.1 percent. About 50 percent of these damaged drums leaked as a result of punctures or split seams. These were caused by improper loading and defective drums. Forklifts operated by stevedores also caused punctures. Redrumming was accomplished at the ports. 5. About 65 percent of the herbicide was shipped to the 20th Ordnance Storage Depot, Saigon, and 35 percent was shipped to the 511th Ordnance Storage Depot, Da Nang. Under the normal handling procedures, drums were unloaded at Da Nang and Saigon from the cargo vessel directly into semi-trailers and were placed in an upright position. The trailers were driven to the various units of the 12th Air Commando Squadron (primarily at the bases of Da Nang, Phu Cat, or Bien Hoa) for disposition. 6. Normally the contents of the drums were transferred into blocked F-6 trailer tanks through a suction tube without removing the full drums from the semi-trailers. Each F-6 trailer held 4,298 gal or about 78 drums of herbicide. If blocked F-6 trailer tanks could not accommodate the total inventory, the drums were stacked in pyramidal style until needed. 7. The transfer of the herbicides from the 55-gal steel drums to storage tanks or aircraft tanks required some precautionary measures. Personnel charged with the supervisory responsibilities of handling the herbicides were indoctrinated in appropriate safety precautions including the use of gloves and face shields as needed. Personnel handling the chemicals were encouraged to "take normal sanitary precautions and to maintain personal cleanliness and to avoid skin and eye contact with the material. Contaminated clothing were to be washed before re-use. Spillage on the skin or in the eyes was to be rinsed copiously with clea1" water" (14). 8. When the herbicide was pumped from the drums into the F-6 trailers about 0.5 to 1.5 gal remained in the drum. Hence the drum was placed on a drain rack and the "drippings" were collected from many drums in a pan-type receptacle and used for spraying base perimeter areas. 1-16 �9. Empty drums were given to the military forces (Vietnam, U.S. and Free World Military Assistance Forces) for use as barriers in defensive positions. The drums were filled with sand or concrete and used in the construction of bunkers or in foundations for runways and barbed wire perimeters (12). 10. Surface areas contaminated by spillage of the herbicides were flushed with diesel fuel or water with diversion of the drainage into settling basins or pits for incorporation into the soil. 11. The F-6 trailers were tied to plumbing and pumps so that the herbicide could be delivered to the aircraft without moving the trailers. 12. As previously noted, Orange was insoluble in water, while Blue and White were not. When Orange was mixed with either Blue or White, a gummy substance formed. The F-6 trailers were therefore color-coded to correspond to the drum color-codes and used exclusively for the herbicide to which the code applied. 13. The aircraft spray tanks, positioned in the center of the airplane, and the spray system were purged before the type of herbicide carried was changed. Particular attention had to be given to sequences involving Blue and White. .A mixture of these two herbicides resulted in the formation of a precipitate consisting of the sodium salt of 2,4-D. 14. Most of the personnel involved in the actual handling of the herbicide drums were Vietnamese. However, a USAF flight mechanic or crew chief was responsible for insuring that the aircraft wa^ properly loaded and the spray system functional. A flight mechanic was also the console operator for the spray unit. The pilot and co-pilot were officers while the flight mechanics and crew chiefs were usually enlisted personnel. 15. For record keeping purposes a herbicide "mission" consisted of several aircraft; if only one aircraft was used the operation was termed a sortie.' All missions within a target formed a project. 16. Aircraft takeoffs were normally before sunrise. From a tactical point of view, the arrival of the aircraft at the target area just prior to sunrise permitted the aircraft to approach the target from the direction of the rising sun. This afforded some degree of protection from enemy ground fire. From the standpoint of herbicidal action, application by aerial spray was most effective if accomplished prior to 0800 hours while inversion conditions existed, in the absence of precipitation, and while the wind was calm or not exceeding a velocity of 8 knots. This insured the proper settling of the spray on the target area. 1-17 �17. Within the aircraft, it was not uncommon to have herbicide leakage from around the numerous hose connections joining the spray tank and pumps with the wing and aft spray booms. In hot weather, the odor of herbicide within the aircraft was decidedly noticeable. Periodically, the spray tank and console were removed (especially with the portable A/A 45Y-1 system) and the interior flushed with surfactant or soap and with water. Because of the corrosive nature of some herbicides, it was necessary for the aircraft to also be repainted periodically. 18. In the 1966 through 1968 period, more than one sortie per day was often common. For example, during the first six months of 1968, the 24 UC-123B aircraft assigned to RANCH HAND averaged approximately 39 sorties per day. IV. PERTINENT DEPLOYMENT AND BIOLOGICAL FACTORS OF THE HERBICIDES The previous section dealt with those factors that would Influence the frequency of "physical contact" with liquid forms of the herbicide. As noted, the individuals most likely to be exposed to liquid herbicide were those charged with transport, handling, and disseminating responsibilities. This section will deal with some factors that would have influenced the likelihood of contact with the herbicides once they had been sprayed. A. Use Patterns of Individual Military Herbicides 1. Herbicides Orange, Orange II, Purple, Pink and Green Herbicides Orange, Orange II, Purple, Pink and Green were effective defoliants and herbicides on a wide array of woody and broadleaf herbaceous species. Grasses, bamboos, and other monocoiyledonous plants were less affected. The effects of these military herbicides on the forests of South Vietnam has been well documented (5, 9, 11, 13, 14, 21, 29, 32, 34). Darrow (13), and Harrow et al (14, 15) showed that at the normal use rates (3 gal/A) these herbicides, when applied to mixed woody vegetation, caused a browning and discoloration of the foliage within a period of one or two weeks. Foliage of the more susceptible species turned brown rapidly, and subsequent leaf drop occurred over a period of one to two months. Under tropical conditions, maximum defoliation occurred two to three months after the spray application. At 3 gal/A the maximum average defoliation in a single or multiple canopy was 88 and 75 percent respectively for rainy season application, or 82 and 67 percent respectively for dry season application. Under tropical forest conditions, satisfactory levels of defoliation persisted for four to twelve months or more. The National Academy of Science (11) reported that from August 1965 through February 1971, 2,962 herbicide mission^ (out Q? a total of 6,237 missions for all herbicides and all use:.) were for forest defoliation uring Orange. These 2,962 missions �accounted for 90 percent of all Herbicide Orange (including Orange II) used in South Vietnam. Likewise 90 percent of all Purple, Pink and Green sprayed in South Vietnam was for forest defoliation (26). Orange and Orange II (and Purple) were also used in control of broadleaf crops (8, 11, 34). For convenience and simplification in programming crop destruction and defoliation targets, application rates were routinely 3 gal/A (14). Annual crops; e.g., beans, gourd, jute, peanuts, and ramie, were rapidly killed by an application of Orange. Root or tuber crops; e.g., manioc, potatoes, taro, and yams, showed great reduction in yield when treated with Orange during early growth stages. Perennial and woody tropical crops; e.g., jackfruit, papaya, castor bean, and mango were susceptible to Herbicide Orange (14). From August 1965 through February 1971, crop destruction missions with Orange accounted for 8 percent of the Herbicide Orange applied (11). The remaining 2 percent of Herbicide Orange used in South Vietnam was used around base perimeters, cache sites, waterways, and communication lines (11). 2. Herbicide White Herbicide White was effective principally on broadleaf herbaceous and woody plants. Conifers (pine trees) were especially susceptible to White. However, the herbicidal action on woody plants was slow and full defoliation did not occur for several months after spray application (14). Since White was water soluble, it was frequently used in field situations where drift was to be held at a minimum (e.g., near rubber plantations). White was sprayed during 1,324 defoliation missions (21 percent of all missions) and of the total volume of White used in South Vietnam, 99 percent was for defoliation (11). The remaining one percent of White was used primarily in base perimeter applications. White was not recommended for use on crops because1' of the persistence of picloram in soils (14). 3. Herbicide Blue Herbicide Blue was the herbicide of choice for other crop destruction missions; e.g., on cereal or grain crops. For crop destruction missions, the basic rate of 3 gal/A was used. Helicopter applications were usually at the rate of one gal/A for control of grain crops. (15). Forty-nine percent of all Blue (580,000 gal) was used in crop destruction missions conducted from August 1965 through February 1971 (11). The remaining Blue was used in defoliation or in control of grass around base perimeters pi)- As a defoliant, Blue caused a rapid browning or desiccation with accompanying shriveling and leaf fall. Noticeable browning or discoloration was evident in one day, with maximum defoliation occurring within two to four weeks (14). 1-19 �B. Canopy Penetration of Defoliants As previously noted, 90 percent of all Herbicide Orange (and probably Purple, Pink and Green) was for defoliation in the forests and mangroves of South Vietnam. The quantity of herbicide that reached the forest floor is not known. However, such factors as canopy composition and time of season of application would have influenced this value. Huddle (23) recorded the following 1968 statement by Dr C.E. Minarik (Dr Minarik was at that time Director, Plant Sciences Laboratories, Fort Detrick, Maryland): "Three gallons per acre is employed. We would prefer to use less if we could get uniform deposition, but in these dense jungle areas where there may be 300 tons of vegetation per acre, this is the minimal effective volume. The three gallons contain 24 pounds of herbicide on an acid basis. Thus high dosage rate is also a requirement since much of the vegetation consists of trees 100 to 150 feet tall." In the evaluation tests of the C-123/A/A 45Y-1 Spray System, Harrigan (22) and Klein and Harrigan (27) found that in mass distribution studies (following aerial dissemination) 87 percent of the Orange Herbicide intercepted by collecting devices had a mass median diameter between 100 and 500u. The mean diameter was 367u. Harrigan (22) concluded that with altitude delivery conditions at 130 knots and 150 feet altitude, most of the Orange released would have settled onto the forest canopy in a swath approximately 260^20 feet wide within which effective defoliation was produced. Hurtt and Darrow (25) showed that the minimum biological effective deposition rate under the climatic conditions of South Vietnam was 1.0 gal/A at a mass median diameter of 350y. The minimum biological effective rate was defined as "that rate which promoted leaf fall and inhibited growth" (25). In canopy penetration studies, Tschirley (33) found (with phenoxy herbicide formulations similar to Orange) that the volume of spray reaching lower sampling levels varied proportionately with the amount deposited on the top line above the canopy. On the average, about 21 percent of the spray penetrated the upper canopy and about 6 percent penetrated to ground level. He also found that the percentage penetration remained relatively constant for drop densities greater than about 100 per square inch. Spray drops having mass median diameters of 400 to 500y would approximately equal 100 drops per square inch. Moreover, the percent spray penetration through forest canopies was inversely related to canopy density (33). 1-20 �No data were available on the number of defoliation missions conducted during the wet or dry seasons. However, as noted earlier, defoliation of forest canopy was greatest during the rainy season, when the vegetation was in full-leaf and actively growing. V. ESTIMATED QUANTITIES OF INDIVIDUAL CHEMICALS SPRAYED IN SOUTH VIETNAM For this report, the total quantities of individual chemicals become important only in reference to their potential association with dose and duration'of exposure to the population at risk. Although the National Academy of Science (11) primarily defined the population at risk as Vietnamese (especially Montagnards), our concern at this time is with U.S. military forces. The chemicals of concern are 2,4-D, 2,4,5-T and TCDD. The extreme toxicity of TCDD, however, makes it the prime chemical of concern. The toxicology of these chemicals is discussed in detail in Chapters IV and VI. The previous scientific assessments of these chemicals as applied in South Vietnam are addressed in Chapter V. A. Herbicide Orange and its Components 2,4-D, 2,4,5-T and TCDD 1• Concentrations of TCDD in Orange, Purple, Pink and Green Figure 2 shows the structure of TCDD and gives a brief description of some of its physical and chemical characteristics. Table 6 shows the available data on the concentration of TCDD (parts per million, ppm) in samples of Herbicides Orange and Purple. As noted, the mean concentration of the surplus Herbicide Orange remaining after termination of its use in South Vietnam was a value derived from data on the analyses of 492 samples. Some of these data have been previously published (4, 11). Craig (12) has reported that the Orange Herbicide maintained at the Naval Construction Battalion Center (NCBC), Gulfport, Mississippi, was probably authorized and procured during the 1968-69 fiscal year. The Orange returned from Vietnam in 1972 (to Johnston Island) was procured no earlier than late FY 64, since the first shipment of Orange did not arrive in Vietnam until early 1965, and a six months lead time was typical. Note that the mean TCDD concentration was 1.91 ppm for the Johnston Island inventory and weighted means of 1.77 and 2.11 for samples analyzed from the NCBC inventory. It is important to note the range of TCDD concentration of TCDD in both surplus Orange inventories. The maximum concentration of TCDD in Orange samples collected at NCBC was 15 ppm, while the maximum concentration of TCDD reported in samples from Johnston Island was 47 ppm. Only 4 of 200 samples from Johnston Island exceeded TCDD levels found in the NCBC inventory (4). The values of these 4 samples were 17, 22, 33, and 47 ppm (4). 1-21 �A. Structure 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) B. Physical Characteristics molecular weight melting point, °C decomposition point, °C C. 322 303 - 305 980 - 1,000 Chemical Characteristics Solubility, grams/liter ortho-dichlorobenzene chlorobenzene Orange Herbicide benzene chloroform acetone 1.40 0.72 0.58 0.57 0.37 0.11 . normal-octanol 0.05 lard oil methanol water 0.04 0.01 2 x 10 FIGURE 2. Structure and physical/chemical characteristics of 2,3,7,8-tetrachlorodibenzo-p-dioxin, TCDD or dioxin. 1-22 �TABLE 6. Concentration, ppm, of TCDD in samples of Herbicides Orange and Purple.3 Number of Samples Orange Purple Range of TCDD (ppm) Johnston Island b Inventory, 1972 200 (4)c 0.05-47 1.91 Johnston Island Inventory, 1974 10 0.07-5.3 1.68 NCBC, Gulfport d Inventory, 1972 42 0.05-13.3 1.77 NCBC, Gulfport Inventory, 1975 238 0.02-15 2.11 Source of Samples Mean TCDD, Concentration (ppm) Eglin AFB Archived Sample 45 Eglin AFB Inventory, 1972 0.04 The Weighted Mean Concentration of TCDD in Orange = 1.98 ppm Analyses for TCDD performed by Interpretive Analytical Services, Dow Chemical U.S.A., Midland Michigan; Aerospace Research Laboratories, Wright-Patterson AFB, Ohio; and The Brehm Laboratory, Wright State University, Dayton Ohio. Surplus Herbicide Orange was shipped from South Vietnam to Johnston Island for storage in April 1972. c Four of 200 samples may have been Herbicide Purple, see text. d The Naval Construction Battalion Center (NCBC) Gulfport, Missippi served as a storage site for Surplus Herbicide Orange from 1969 to 1977. e Herbicide Purple was extensively used in the evaluation of aerial spray equipment on Test Area C-52, Eglin Air Force Base Reservation, Florida, 1962-1964. 1-23 �Only one sample of Herbicide Purple has been analyzed (see Table 6). The age of the sample was not known except that it was representative of the Purple applied to Grid 1 (ARPA Grid), Test Area C-52A, Eglin AFB, Florida (Personal information, A.L. Young, and references 34 and 36), and thus, may have been from the 1962-1964 time period. The 1971 Report on 2,4,5-T by the Executive Office of the President (18) presented data on TCDD concentrations found in the analysis of Technical 2,4,5-T from one manufacturer. The data were for samples manufactured yearly from 1958 through 1969, and ranged from 1 to 32 ppm. The highest levels of TCDD were found in samples manufactured in 1965 (32 ppm) and 1968 (25 ppm). If these two samples had been used in formulating Herbicide Orange, the concentrations in the Orange would have been 16 and 12.5 ppm, respectively. If the lowest TCDD containing samples for the same two years would~Fave been used (i.e., samples containing 5 and 1 ppm TCDD) the concentrations in the Orange would have been 2.5 and 0.5 ppm, respectively. The one sample of Purple reported in Table 6 contained 45 ppm. Thus, the Technical 2,4,5-T used in that sample may have contained 90 ppm TCDD. When the Orange Herbicide was shipped to Johnston Island from South Vietnam, redrumming of the herbicide in South Vietnam was accomplished as necessary (12). The project (PACER IVY) involved U.S. military personnel. One of the individuals participating in the redrumming operation at Da Nang (redrumming also occurred at Phu Cat and Bien Hoa) has stated that drums of Purple were found (although fewer than 20) and redrummed into Orange-banded drums (personal communication, Or Michael D. Neptune, now with the U.S. Environmental Protection Agency, Washington, D.C.). In addition, an analytical chemist involved in the analyses of Orange samples for 2,4-D and 2,4,5-T, reported finding significant quantities (15 percent) of the iso-butyl ester 2,4,5-T in a few of the samples collected from Johnston Island (unpublished data, personal communication, Dr Eugene L. Arnold, now with the Clinical Sciences Division, USAF School of Aerospace Medicine, Brooks AFB, Texas). Thus, the 4 samples of Orange Herbicide containing TCDD concentrations greater than 15 ppm, may have been Purple. If these were, in fact, from drums of Purple, then the mean concentration of TCDD in 5 samples of Purple would have been 32.8 ppm. The mean value of 32.8 ppm may or may not represent the TCDD concentration of the Herbicide Purple used in South Vietnam from 1962 through 1964. Data from the 1971 Report on 2,4,5-T (18) suggests that Purple manufactured in 1958 through 1963 would have had a mean concentration of approximately 5 ppm (4.711.2 as the mean and standard deviation for the 6 samples reported for the years 1958 through 1963). However, the persistence of TCDD in soils of the two grids used for the testing and evaluation of the early RANCH HAND spray systems may indicate that Purple indeed had concentrations of TCDD from 17 to 47 ppm. Young (35) and Young et al (37) reported finding concentrations of 710 parts per trillion TCDD in the top 6 inches (15 cm) of soil collected in 1974 from the equipment-testing 1-24 �grid known to have received at least 1,894 Ib of Purple per acre during the 1962 through 1964 period. The test grid had received 16,164 gal of Purple. On an adjacent test grid, 1,168 pounds of Orange per acre had been disseminated during the 1964-1966 programs evaluating the A/A 45Y-1 Spray System. The'levels of TCDD in the soil treated with Orange at comparable depth was 30 parts per trillion. All soil samples were analyzed in 1973. Young et al (36) have reported the half-life of TCDD to be less than one year when in the presence of the phenoxy herbicides. Persistence data suggested that the levels of TCDD in Purple and Orange were significantly different. Further evidence of this is recorded by the National Academy of Science (11) for TCDD residue found in the soils of the Pran Buri Calibration Grid. They reported finding levels from <0.0012 to 0.233 ppm TCDD in the top 6 inches of soil from this testing ground. They concluded that since the grid had received approximatly 1,000 Ib/A 2,4,5-T in 1964-65, the original concentration of the TCDD in Orange would have ranged from <3 to 50 ppm. The NAS Committee (11) assumed that the material applied to the Pran Buri Calibration Grid was Orange. Darrow et al (15), responsible for the original calibration studies, reported that the Pran Buri Calibration Grid received 6,000 gal Purple, 3,800 gal Pink (all 2,4,5-T) and only 825 gal Orange. Since the majority of herbicide applied on this grid was either Purple or Pink, it further supports the contention that the four high-TCDD-containing samples from Johnston Island were Purple. Accepting the mean concentration of TCDD in Purple as 32.8 ppm and recognizing that Pink and Green contained essentially twice the active ingredient (8.16 Ib acid equivalent 2,4,5-T per gal) as Purple (4.0 Ib acid equivalent 2,4,5-T per gal), the mean concentration of TCDD in Pink and Green would have been twice that of Purple, or 65.6 ppm. Also, from the above discussion, it can be concluded with reasonable certainty that the weighted mean concentration for aVl_ Herbicide Orange sprayed in South Vietnam was 1.98 ppm: individual lots may have contained higher (<15 ppm) or lower (>_ 0.02 ppm) concentrations of TCDD, but the weighted mean was 1.98 ppm. 2- Concentrations of 2,4-D and 2,4,5-T in Orange The original military specifications for Herbicide Orange were published on 19 July 1963 as specifications MIL-H-51158 (MU) and MIL-H-51147 (MU). As written in the specifications, for the n-butyl ester of 2,4-D: "The total acid equivalent of the herbicide shall be not less than 78 nor more than 80 percent when tested as specified. The free acid content of the herbicide shall not be greater than 1.0 percent." For the n-butyl ester of 2,4,5-T the specifications noted: "The total acid equivalent of the herbicide shall be not less than 80 nor more than 82 percent when tested as specified. The free acid content of the herbicide shall not be 1-25 �greater than 1.0 percent." Orange was to be a 50:50 mixture of the products from the two specifications. These specifications were updated on 7 November 1966. Fee et al (20) and Hughes et al (24) have extensively analyzed*Herbicide Orange samples (from Johnston Island and NCPC, Gulfport, Mississippi) for composition. Table 7 .is a comparison of different manufacturers' lots for percent composition. Although the actual mean composition varied from the "theoretical" specification, the analytical method employed to test the total acid equivalent of the herbicide permitted some fluctuation in content. The parent acid portion of the herbicide molecule will remain as the herbicidally active portion of its respective ester form, while the ester appendage to the parent acid form will serve to satisfy some additional properties, such as decreased water solubility and increased surface penetration and/or translocation. The butyl ester of 2,4-P contained 79.4 percent acid 2,4-D and the butyl ester of 2,4,5-T contained 80.2 percent acid 2,4,5-T. From the data in Table 7, the mean actual weight of active ingredient per gal of Orange was 4.14 and 4.00 pounds for 2,4-D and 2,4,5-T, respectively. These values have been accepted also for the active ingredients in Herbicide Purple. 3. Quantities of Herbicides and TCDD Disseminated in South Vietnam •~-~~ Using data in Tables 2 and 3 (herbicide procurement records), Table 6 (mean TCDD concentration in Orange) the value of 32.8 ppm TCDD for Purple,the value of 65.6 ppm TCDD for Pink and Green, and Table 7 (mean, actual composition of Herbicide Orange), an estimate of the quantities of herbicides and TCDD disseminated in South Vietnam from January 1962 through February 1971, can be determined. These "estimated" quantities are in Table 8. The National Academy of Science Committee on the Effects of Herbicides in South Vietnam (11) estimated that between 220 and 360 pounds of TCDD were released over South Vietnam during the period August 1965 to February 1971. The estimate of 368 pounds in Table 8 for TCDD falls very close to their estimate. The important difference is that 143 pounds of the TCDD reported in Table 8 (or approximately thirty-nine percent of all the TCDD) was contained in Purple, Pink, and Green and was sprayed on 90,000 acres in Vietnam from 1962 through 1964» a time period when only a small force of military personnel were in South Vietnam. Herbicide Orange was sprayed on 3.5 million acres from 1965 through 1970. However, 90 percent of the Orange was sprayed on 2.9 million acres of inland forests and mangrove forests. 1-26 �TABLE 7. Composition, Percent, of Selected Samples of Herbicide Orange in Relation to Military Specifications. NCBC Inventory Number9 ASN 10 ASN 14 Mean Composition Approximate Military Specification^ Component ASN 8 Number of Gallons 123,695 383,955 145,860 Level of TCDD <0.02 ppm 0.30 +0.06 ppm <0.02 ppm n-Butyl ester 2,4-D 42.6% 46.2% 43.7% 44.2% 49.5% n-Butyl ester 2,4,5-T 39.3 44.9 42.2 42.1 48.8 Other Butyl esters of chl orophenoxyaceti c acids 7.96 4.01 ^ Octyl esters of "-1 chlorophenoxyacetic acids 5.76 0.25 Acid, 2,4-D 0.78 0.19 Acid, 2,4,5-T 0.84 Inert Ingredients0 2.76 9.05 7.0 *• 2.0 — 0.65 0.5 0.1 0.13 0.78 0.6 1.0 4.32 3.62 3.6 0.6 t—t Selected samples of Herbicide Orange were collected from the surplus inventory maintained at the Naval Construction Battalion Center (NCBC), Gulfport,, Mississippi. Samples represented lots produced by different manufacturers. Analyses for TCDD and samp]_e composition were performed by the Aerospace Research Laboratories, Wright-Patterson AFB, Ohio. [_ See Reference by Hughes et al. ( 4 . ] 2)] ^Military specifications for manufacture of Herbicide Orange were based on Specifications MIL-H-51147A (MU) and MIL-H-51148A (MU) dated 7 Nov 1966. c lnert ingredients included butanol, toluene, butylchloride, dichlorophenol, trichlorophenol, butoxydichlorobenzene, and butoxytrichlorobenzene. �TABLE 8. Estimated quantities of herbicides and TCDD disseminated in South Vietnam from January 1962 - February 1971. Chemical Pounds 2,45-Da 55,940,150 2,4,5-Tb 44,232,600 TCDDC 368 Picloram 3,041,800 Cacodylic Acid6 3,548,710 Total of Herbicides 106,763,260 2,4-D was an active ingredient in Herbicides Orange, Purple and White. From data in Table 7, the acid equivalents for 2,4-D in Herbicide Orange and White were calculated to be 4.14 Ib/gal and 2.00 Ib/gal, respectively. The acid equivalent for 2,4-D in Herbicide Purple was assumed to be 4.14 Ib/gal. 2,4,5-T was an active ingredient in Green, Pink, Purple and Orange. Approximately 276,000 gal of Green, Pink and Purple were sprayed in South Vietnam prior to 1965, when it was replaced by Herbicide Orange. Herbicides Green and Pink contained 8.16 Ib/gal 2,4,5-T. Herbicides Purple and Orange contained 4.00 Ib/gal 2,4,5-T (Table 7). G The mean TCDD concentration in Herbicide Purple was estimated at 32.8 ppm. The mean TCDD concentration in Herbicides Pink and Green was estimated at 65.6 ppm. The mean TCDD concentration in Herbicide Orange was estimated at 1.98 ppm. Picloram was an active ingredient of Herbicide White. e Cacodylic acid was the acitve ingredient of Herbicide Blue. The Herbicide Blue formulation contained 15.4 percent arsenic in the pentavalent organic form. The value includes 10,000 Ib cacodylic acid disseminated in South Vietnam from 1962-1964. 1-28 �B. Military Projects that Involved Handling Herbicides Orange, Purple, Pink or Green. Herbicide Orange was first manufactured in late 1964. It arrived in Vietnam for use in Operation RANCH HAND in early 1965. Prior to Orange, Herbicides Purple, Pink and Green were used but in far less quantities and on a limited area. All of the quantities of Orange returned from Johnston Island in 1972 and those stored at the Naval Construction Battalion Center since late 1968 were destroyed by at-sea incineration in 1977. From the first aerial spray test in 1961 through the incineration project in 1977, numerous U.S personnel directly handled the herbicide in support of specific project goals. Table 9 was assembled after an extensive search of available documents and from personal contact with eleven different individuals that had participated in one or more of the listed projects. Other than Operation RANCH HAND the most extensive handling of Herbicide Orange occurred during Project PACER HO. At the time of this latter project, analytical techniques were sufficiently developed to permit the environmental monitoring of TCDD at the parts per trillion level during all stages of the project. These data permitted an assessment of the actual exposure of personnel involved in the handling of the herbicide. Chapter II is devoted to Project PACER HO, the disposal of the surplus Herbicide Orange. VI. SUMMARY The choice of herbicides used in South Vietnam in Operation RANCH HAND, 1962-1971, was based upon those herbicides that had been widely used in world agriculture, shown to be effective in controlling a broad specturm of vegetation, and proven safe to humans and animals. * The major herbicides used in South Vietnam were the phenoxy herbicides 2,4-D and 2,4,5-T. These two herbicides were formulated as the water insoluble esters and code-named by the military as Purple, Orange, Pink and Green. A water soluble amine formulation of 2,4-D was used in Herbicide White. Two other herbicides were extensively used by the military, picloram (in White) and cacodylic acid (in Blue). An estimated 107 million pounds of herbicides were aeriallydisseminated on 6 million acres in South Vietnam from January 1962 through February 1971. Approximately 94 percent of all herbicides sprayed in Vietnam were 2,4-D (56 million pounds or 53 percent of total) or 2,4,5-T (44 million pounds or 41 percent of total). The 44 million pounds of 2,4,5-T contained an estimated 368 Ib of the toxic contaminant, 2,3,7,8-tetrachlorodibenzo-pdioxin (TCDD or dioxin). Ninety-six percent of all 2,4,5-T was contained in Herbicide Orange; the remaining 4 percent in Herbicides Green, Pink and Purple. . However, Herbicides Green, Pink and Purple contained approximately 40 percent of the estimated amount of TCDD disseminated in South Vietnam. 1-29 �TABLE 9. Project Data on the major military projects involved in the handling and/or spraying of Herbicides Orange, Purple, Pink or Green in support of military programs in South Vietnam. Dates Brief Description Selected References Project AGILE 1960-1968 Selection of herbicides, and development and evaluation of defoliation techniques. Brown, 1962 (7) Coates et a!, 1962 (10) Darrow et al, 1966 (15) Demaree and Creager, 1968(16) Operation RANCH HAND 1962-1971 Aerial spraying of herbicides in South Vietnam. Anonymous, 1961 (3) Fair, 1963 (19) Ellison, 1967 (U) Darrow et al, 1969 (14) Huddle, 1969 (23) McConnell, 1970 (29) USAF Projects 2525, 5172 5186, 5957 1962-1970 Development and testing of aerial spray equipment Biever, 1969 (6) CO o Redrumming and movement of surplus herbicide from South Vietnam to Johnston Island Craig, 1975 (12) 1972-1977 Maintenance of herbicide inventory and research on options for disposal Young, 1974 (35) Anonymous, 1974 (4) Lavergne, 1974 (28) Newton, 1975 (30) Young, et al, 1976 (37) 1977 Dedrumming of herbicide inventory and at-sea incineration of Herbicide Orange Ackerman et a l , 1978 (1) Project PACER IVY 1971 AFLC Project on Disposition of Herbicide Orange Project PACER HO Klein and Harrigan, 1969(27) Harrigan, 1970 (22) �Green, Pink and Purple were sprayed as defoliants on less than 90,000 acres from 1962 through 1964, a period when only a small force of U.S. military personnel were in South Vietnam. Ninety percent of all the Herbicide Orange (containing 38.3 million pounds of 2,4,5-T and 203 Ib of TCDD) were used in defoliation operations on 2.9 million acres of inland forests and mangrove forests of South Vietnam. The handling, transport and storage procedures employed for the herbicide generally precluded physical contact with the herbicides by most military personnel assigned to Operation RANCH HAND. However, flight mechanics (console operators for the internal spray systems) and crew chiefs (responsible for loading the aircraft) were the most likely military personnel exposed to the herbicides. The methods employed in spraying the herbicides and the geographical areas designated for dissemination of the herbicides generally precluded direct physical contact with the herbicide by military personnel assigned to other military programs. 1-31 �CHAPTER I LITERATURE CITED 1. Aekerman, D.G., H.J. Fisher, F.J. Johnson, R.F. Maddalone, B.J, Mathews, E.L. Moon, K.H. Scheyer, C.C, Shin, and R.F. Tobias, 1978. A£-4ea ^nc^tneAa-tuw oft HcAb-tcu.de Orange onboard the. M/T l/a£canai. Environmental Protection Technology Series EPA-600/2.J8-Q86. Office of Research and Development. U.S.- Environmental Protection Agency, Research Triangle Park, North Carolina. 263 p. 2. Advisory Committee on 2,4,5-T. 1971. Report of the Advisory Committee on 2,4,5-T to the Administrator of the Environmental Protection Agency. 76 p. 3. Anonymous. 1961. Memorandum for Assistant Secretary of Defense. Subject: Summary of current status project "RANCH HAND" chemicals. Department of the Air Force, Office of the Under Secretary, Washington, D.C. Win. 4 p, 4. Anonymous. 1974, Disposition of Orange Herbicide by incineration, Final Environmental Statement. Department of the Air Force, Washington, D.C. 737 p, 5. Bethel, J.S., K.J. Turnbull, D. Briggs, and J. Flores. 1975. Military defoliation of Vietnam forests. Am&t-tcan F0<te-i£6 81(1):26-30, 56-61. 6. Biever, H. 1969. Defoliant history of Test Area C-52A. Working Papers. Armament Development and Test Center, Eglin AFB, Florida. December 1969. 7. Brown, J.W. 1962, Uefle&t£t0na£ Apbcuj te4tt> -in South U.S. Army Chemical Corps Biological Laboratories, Fort Detrick, Frederick, Maryland. 119 p. Available from' the Defense Documentation Center, Defense Logistics Agency, Cameron Station, Alexandria, Virginia, DDC Number AD 476961. 8. Carrier, Hickey's in South Science, J.M. 1974. The location of herbicide missions and Informants in South Vietnam. The Effects of Herbicides Vietnam, Part B. Working Papers. National Academy of Washington, D.C. 15 p. 9. CAST. 1975. Effects of herbicides in Vietnam and their relation to herbicide use in the United States. Council for Agricultural Science and Technology. Report No. 46. Department of Agronomy, Iowa State University, Ames, Iowa. 14 p. 1-32 �10. Coates, J.H., L.M. Sharpe, and H. Pollack. 1962. The 4,to£iL6 oft ehenu.ca£ e.on&io£ ofi vegetation -in le&ttuw to need-i. Technical Notes 62-68. Institute for Defense Analyses, Department of Defense, Washington, D.C. 30 p. 11. Committee on the Effects of Herbicides in South Vietnam. 1974. Part A. Summary and conclusions. National Academy of Science, Washington, D.C. 398 p. 12. Craig, D.A. 1975. Use of Herbicides in Southeast Asia. Historical Report. San Antonio Air Logistics Center, Directorate of Energy Management, Kelly AFB, Texas. 58 p. 13. Darrow, R.A. 1973. Foliage characteristics and defoliation/ herbicidial responses in a Thailand Forest. Weed Sex.. Soc. Am. Ab*#l. 66, pp 29-30. 14. Darrow, R.A., K.R. Irish, and C.E. Minarik. 1969. HeA.b.icxxie-6 U&ed -in Soutkmut Aaxa. Technical Report SAOQ-TR-69-11078. Directorate of Air Force Aerospace Fuels, Kelly AFB, Texas. 60 p. 15. Darrow, R.A., G.B. Truchelut, and C.M. Bartlett. 1966. OCONUS de^o-tcatuM tut p/tog/iam. Technical Report 79. Crops Department, Biological Sciences Laboratory, U.S. Army Biological Center, Fort Detrick, Frederick, Maryland. 126 p. 16. Demaree, K.D. and R.A. Creager. 1968. Defoliation tests in 1966 at Base Gagetown, New Brunswick, Canada. Technical Memorandum 141. Department of the Army, Fort Detrick, Frederick, Maryland. 17. Ellison, R. 1967. C-123s defoliate jungle stronghold of Viet Cong. Aviation Week and Space Technology 86(19) :82-86. 18. Executive Office of the President. 1971. Report on 2,4,5-T. A report of the Panel on Herbicides of the President's Science Advisory Committee. C.M. MacLeod, Chairman. Office of Science and Technology, Executive Office Building, Washington, D.C. 69 p. 19. Fair, S.D. 1963. No place to hide. How defoliants expose the Viet Cong, Asuny 14:54-55. 20. Fee, D.C., B.M. Hughes, M.L. Taylor, T.O. Tiernan, and C.E. Hill. 1975. Ano£t/-ttca£ Methodology faofi HeA.bx.cx.de 0/wuage. l/o£. II. V&teAmination o$ Onig-in o& USAF S-tocfc6. Technical Report ARL-75-0110. Aerospace Research Laboratories, Wright-Patterson AFB, Ohio. 30 p. 21. Flamm, B.R., and J.H. Cravens. 1971. Effects of war damage on the forest resources of South Vietnam. J. Poie^u/ 69(11):784-789. 1-33 �22. Harrigan, E.T. 1970. Catibtuvtian Jut oh the. UC-123K/A/A45y-l Sptai/ Sy*te.m. Technical Report ADTC-TR-70-36. Armament Development and Test Center, Eglin AFB, Florida. 160 p. 23. Huddle, P.P. 1969. A Technology Assessment of the Vietnam Defoliant Matter - A Case History. Report to the Subcommittee on Science Research and Development of the Committee on Science and Astronautics. U.S. House of Representatives, Ninety-first Congress. Prepared by the Science Policy Research Division, Legislative Reference Service, Library of Congress, Washington, D.C. 73 p. 24. Hughes, B.M., D.C. Fee, M.L. Taylor, T.O. Tiernan, C.E. H i l l , and R.L.C. Vlu. 1975. Analytical Methodology iofi HeA.bi.<Ude. Oiange,. Vol. I. V<LteAmina£ian o^ Chemical Compo&ition. Technical Report ARL-75-0110. Aerospace Research Laboratories, Wright-Patterson AFB, Ohio. 357 p. 25. Hurtt, W., and R.A. Darrow. 1968. &ioloai.o.al eXXecttueneiA oX Stult SifilLud and Osianae.. Technical Report AFATL-TR-68-122. Air Force Armament Laboratory, Eglin AFB, Florida. 31 p. 26. Irish, K.R., R.A. Darrow and C.E. Minarik. 1969. manual fax. vegetation control in Bouuth<La&t k&ia. Miscl . Public. 33. Department of the Army, Fort Detrick, Frederick, Maryland. 71 p. 27. Klein, R.E., and E.T. Harrigan. 1969. CompasuAon Tut 06 Ve.Kolia.nt!>, Technical Report ADTC-TR-69-30, Vol. I. Armament Development and Test Center, Eglin AFB, Florida. 356 p. 28. Lavergne, E.A. 1974. Study oh teaAlbilitu oh HeAbicMie. O^ianpe. c.hlo>u.noluAJA . Technology Series Report EPA-600/2-74-006. Office of Research and Development. Environmental Protection Agency, Washington, D.C. 67 p. 29. McConnell, A.F. 1970. Mission: RANCH HAND. - MJI UYiivvuitg Re.vi.ew 21(2):89-94. 30. Newton, M. 1975. Environmental impact of "Agent Orange" used in reforestation tests in Western Oregon. Weed Sex.. S<?c. Am., Abstr. 144, 52 p. 31. Peterson, 6.E. 1967. The discovery and development of 2,4-D. Ag*. Hlt>t. 41:243-253. 32. Tschirley, F.H. 1969. Defoliation in Vietnam - The ecological consequences of the defoliation program in Vietnam are assessed. Science. 163:779-786. 1-34 �33. Tschirley, F . H . 1968. Reiponie ofa &iopic.at and bmb&Lopic.aJL woody p£aitt6 to c.kmic.aJL -fiea£rnen£6 . Research Report CR-13-67. Agricultural Research Services, U . S . Department of Agriculture, Washington, D . C . 197 p. 34. Westing, A.H. 1976. Ec.otoQ-ic.aJL consequence* o& the. second Indochina. Wo/i. Stockholm International Peace Research Institute. Almgrist and Wiksel Internation, Stockholm, Sweden. 119 p. 35. Young, A.L. 1974. Ec.otoQic.aJL AtudieA on a keAbi.oJ.de. - equipment teAt oA.ua, (TA C-52A). Air Force Armament Laboratory, Eglin AFB, Florida. 141 p. 36. Young, A . L . , C . E . Thalken, E . L . Arnold, J . M . Cupello, L . G . Cockerham. 1976. fate. o& 2,3,7,S-te£uiQ.hlo'LOdA.be.nzo-p-dioiu.n (TCW) -en tke. nwiA.onm2.nt', Aummany and dzzontamination H.e.commz.ndatiom, . Technical Report USAFA-TR-76-18. Department of Chemistry and Biological Sciences, USAF Academy, Colorado. 41 p. 37. Young, A . L . , C.E. Thalken, and W . E . Ward. 1975. S^udcei o& the. <LC.oloQic.aJL impact o& ^epetctcue aerial apptication* o& heAbiciideA on the. <Lc.o*yAtw ofi TeAt AA.ea C-52A, Egtin AFB, fi.oni.da. Technical Report AFATL-TR-75-142. Air Force Armament Laboratory, E g l i n AFB, Florida. 127 p. 1-35 �CHAPTER II DISPOSAL OF HERBICIDE ORANGE I. INTRODUCTION During the summer of 1977 the United States Air Force (USAF) disposed of 2.22 million gallons (gal) of Herbicide Orange by high temperature incineration at sea. This operation, Project PACER HO, was accomplished under very stringent criteria of U.S. Environmental Protection Agency (EPA) ocean dumping permits. Numerous conditions of these EPA permits required the USAF to conduct extensive environmental and occupational monitoring of the land-transfer/loading operations and shipboard incineration operations. The results of EPA permit compliance monitoring for ship board operations are reported elsewhere (1). The purpose of this chapter is to summarize the historical background leading to Project PACER HO, to briefly describe the land-transfer operations and to present a summary of industrial hygiene and ambient air monitoring accomplished during the land-based operations. At the time of this writing not all occupational and environmental monitoring data are -available; thus, the final reports of land-based monitoring for project PACER HO have not yet been published. II. 'HISTORICAL BACKGROUND In April 1970, the Secretaries of Agriculture; Health, Education and Welfare, and the Interior jointly announced the suspension of certain uses of 2,4,5-T. These suspensions resulted from published studies indicating that 2,4,5-T was a teratogen. Subsequent studies revealed that the teratogenic effects had resulted from a toxic contaminant in the 2,4,5-T, identified as 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Subsequently, the Department of Defense suspended the use of Herbicide Orange (3). At the time of the suspension, the Air Force had an inventory of 1.37 million gal of Herbicide Orange in South Vietnam and 0.85 million gal at the Naval Construction Battalion Center (NCBC) Gulfport Mississippi. In September 1971, the Department of Defense directed that the Herbici.de Orange in South Vietnam be returned to the United States and that the entire 2.22 million gal be disposed of in an environmentally safe and efficient manner. The 1.37 million gal were moved from South Vietnam to Johnston Island, Pacific Ocean, for storage (Project PACER IVY) in April 1972. The average concentration of TCDD in the Herbicide Orange was about 2 parts per million and the total amount of TCDD in the entire Herbicide Orange stock was approximately 44.1 pounds. Various techniques of destruction and recovery of the herbicide were investigated from 1971 to 1974 (AFLC Project on Disposition of Herbicide Orange). Destructive techniques included soil biodegradation, high temperature incineration, deep well injection, burial in underground nuclear test cavities, sludge burial and microbial reduction. Techniques to recover a useful product included use, return to manufacturers, fractionation and chlorinolysis. II-l �Of these techniques, only high temperature incineration was sufficiently developed to warrant further investigation. The other methods were rejected because of several considerations, including long lead times for development, inadequate assurance of success, and the lack of industrial interest. In December 1974, the USAF filed a final environmental impact statement (3) with the President's Council on Environmental Quality on the disposition of Herbicide Orange by destruction aboard a specially designed incineration vessel in a remote area of the Pacific Ocean, west of Johnston Island, The EPA held a public meeting in February 1975 to consider an ocean incineration permit application submitted by the USAF in accordance with the Marine Protection, Research and Sanctuaries Act of 1972 as amended, 33 U.S.C. 1401 et seq. During this meeting, testimony was presented which indicated that techniques for chemically reprocessing the herbicide to remove unacceptable quantities of TCDD might have been developed. The EPA indicated that the option for reprocessing should be further explored as a means of disposition prior to making a decision to destroy the herbicide via incineration (7). Subsequently, the USAF undertook an investigation into the feasibility Of reprocessing Herbicide Orange. Pilot plant studies were conducted from the fall of 1975 to July 1976 on selective activated carbon adsorption of TCDD from herbicide. This reprocessing method was shown to be technically and environmentally feasible; however, a feasible and environmentally acceptable method of safely disposing of the TCDD-laden activated carbon was not demonstrated. The USAF concluded in February 1977 that the option of reprocessing was not feasible, timely or cost effective since a technique for the ultimate disposal of the activated carbon was not currently available Or anticipated in the foreseeable future. Consequently, on 9 March 1977, the USAF requested reconvening the EPA public hearings. As a result of the public hearing held on 7 April 1977, the EPA issued a research permit to the USAF and Ocean Combustion Services, B.V. (OGS) (6). This permit authorized the transport of the Herbicide Orange from the Naval Construction Battalion Center, Gulfport MS to a designated site in the North Pacific Ocean for the purpose of atsea incineration in accordance with the provisions of the Marine Protection, Research and Sanctuaries Act of 1972, as amended. The vessel contracted for the at-sea incineration was the Dutch-owned ship, M/T Vulcanus, a ship registered in Singapore and previously used in the North Atlantic Ocean and the Gulf of Mexico to destroy chlorinated hydrocarbon wastes (12). A total of three herbicide loadings were required to incinerate the total stocks of Herbicide Orange: one loading from Gulfport MS and two loadings from Johnston Island. III. DESCRIPTION OF LAND-BASED OPERATIONS The operations at both storage sites were similar in many ways. At both sites, the 55-gal drums of Herbicide Orange were transported II-2 �short distances from their storage location to a centralized facility. The herbicide was drained from the drums and transferred to the M/T Vulcanus. Following emptying, the drums were rinsed with diesel fuel, and subsequently crushed. The rinsing from empty drum cleaning was combined with the herbicide and transferred to the ship for later incineration at sea. A. NCBC, Gulfport MS The centralized dedrumming facility at the NCBC was a temporary, enclosed facility measuring approximately 35 feet by 35 feet with an interior ceiling height of approximately 10 feet. A ventilation system capable of providing approximately 57 air changes per hour was equipped with in-line activated charcoal filters to reduce vapor emissions to the outside air. Within this enclosed facility were four identical processing lines. Each line consisted of a self-closing entry door to admit full drums, a roller conveyor along which drums were moved in an upright position, a position equipped with a heavy duty electrically operated deheading cutter, a suction wand to remove the greatest portion of the herbicide from a deheaded drum, a spray device beneath the conveyor over which the deheaded and emptied drum was inverted and rinsed with two gal of diesel fuel, a commercial, heavy duty drum crusher and a selfclosing exit door through which the crushed drums were passed. Once each drum was deheaded the con.tents were removed by the suction wand, leaving approximately three gal of liquid in the drum. The drum was then manually inverted and the remaining herbicide was collected in an open trough beneath the conveyor. Each drum was permitted to drain into the same trough for a minimum period of five minutes after which it was sprayed with two gal of diesel fuel, allowed to drain while still inverted for a minimum of two minutes, and then crushed end-to-end to approximately one-third its original volume. The rinsed and crushed drum was passed through the exit door and stacked with all other crushed drums. The liquid herbicide from the suction wands, and the herbicide and diesel fuel rinsing from the below-grade, open trough were pumped to 10,000 gal capacity rail tank cars. Air displaced from the tank cars during filling was filtered through an activated charcoal filter. The rail cars were moved along a rail spur approximately two mi.les to a dockside location where the herbicide was transferred to the incinerator ship, M/T Vulcanus. Displaced air from the ship's cargo' tanks was also filtered through activated charcoal. A total of 15,480 drums of Herbicide Orange was processed in this fashion at the NCBC between 24 May 1977 and 10 June 1977. Two 8hour shifts of approximately 55 men each accomplished the dedrumming/transfer operations. These men were all USAF officers/technicians from the five Air Logistics Center of the Air Force Logistics Command located at Kelly AFB, Texas; Hill AFB, Utah; Robins AFB, Georgia; Tinker AFB, Oklahoma and McClellan AFB, California. All workers were provided daily changes of II-3 �freshly laundered work clothes and men working within the dedrum facility were provided protective clothing including cartridge respirators, face shields, rubber aprons and rubber gloves. With only few exceptions the men rotated through all jobs involved in the dedrumming/transfer operations. All personnel were given pre-operational and post-operational physical examinations consisting of a complete medical history, complete neurological examination and the following laboratory procedures: 1. Complete hemoglobin, including hematocrit and platelet count 2. Prothombin time 3. Serum lipids 4. Serum glutamic oxaloacetic transaminase (SGOT) or 5. Serum glutamic pyruvate transaminase (SGPT) 6. Serum bilirubin 7. Blood glucose 8. Complete urinalysis 9. Chest x-ray B. Johnston Island The centralized dedrum facility at Johnston Island was a temporary, open facility measuring approximately 30 feet by 90 feet consisting of a concrete pad, roof and moveable canvas walls to exlude rain. This open facility was located adjacent to the Herbicide Orange storage site on the northwest end of Johnston Island. Nearly constant east winds ranging from 10 to 20 miles per hour provided natural ventilation and carried released vapors away from occupied areas. Two processing lines consisting of fabricated metal racks and open troughs were located in the west two-thirds of the facility. The east one-third contained pumps and drive-through for fuel trucks that were used to transport the dedrummed herbicide to the M/T Vulcanus. Full drums of herbicide were transported to the dedrum facility in sets of four using forklifts equipped with specially designed clamps. The drums were placed on the inclined metal racks in four groups of 12 drums each. Each set of 12 drums was handled independently by the dedrumming crew. Once a set of 12 drums was on the rack and the forklifts had withdrawn, a crew member would punch one hole near the top of each inclined drum as a vent hole to allow the crew's supervisory personnel to check the contents. Any drums containing other than Herbicide Orange were removed from the line and held for further testing. Three or more closely spaced holes were then punched in the bottom of each drum and the contents allowed to drain into II-4 �the open troughs. Once the herbicide had stopped flowing from the drums, they were allowed to drain for a five minute period after which the interior of each drum was rinsed twice with a total of two gal of diesel fuel. The diesel fuel rinsing drained into the open troughs, combining with the herbicide. After the 12 drums in each set had drained for a minimum of two minutes they were transported to a nearby drum crusher which consisted of a large weight suspended between two vertical I-beams. One drum at a time was crushed along its longitudinal axis and when approximately 30 drums had been crushed they were removed, banded, and stacked together near the crusher. The liquid herbicide and diesel fuel rinsing from the drums flowed into the two open troughs to a below-grade sump. The material was pumped from this sump into modified fuel tankers that transported 3,000 gal lots to dockside where the material was pumped aboard the M/T Vulcanus. A total of 24,795 drums of herbicide was processed in this fashion between 27 July 1977 and 23 August 1977. Two 10-hour shifts of approximately 50 men each were used. The workers were civilian employees of a contractor engaged to perform the dedrumming operations. USAF officers monitored all operations. As at NCBC, all workers were provided daily changes of freshly laundered work clothes, and men working within the dedrum facility were provided protective clothing consisting of cartridge respirators, face shields, rubber aprons, rubber gloves and boots. Unlike at NCBC, men on each crew remained in the same job through the dedrumming/transfer operations. A requirement of employment was preand post-operational physical examinations similar to those given the workers at the NCBC. IV. LAND-BASED OPERATIONS MONITORING PROGRAMS Detailed plans for environmental and occupational monitoring at both sites are contained in Annexes 4 and 5, kJtii Fo/ice. LciQiAticA Command VnoQfummhiQ Plan 75-19 faon the. V<it>pa&cut o& Oi&nge HeA.bi.cu.de (2). This section outlines only the industrial hygiene and ambient air monitoring programs conducted at each site. These aspects of the environmental and occupational monitoring at each site were very similar. Essentially, the same equipment, methods and procedures were used at both sites. The only significant difference between the two operations was that all sampling at the NCBC site was accomplished by members of the US Air Force Occupational and Environmental Health Laboratory (USAF OEHL), Brooks AFB, Texas, while all sampling at the Johnston Island site was conducted by Battelle Columbus Laboratories (BCL), Columbus, Ohio,under contract to the USAF. An environmental engineer from the USAF OEHL served as Project Officer and monitor of the BCL contract. In general, the industrial hygiene sampling program consisted of daily air samples within the dedrum facilities with rapid analysis (approximately 24-hour turn around time) for 2,4-D and 2,4,5-T. Samples collected for analysis of TCDD were analyzed after-the-fact. The ambient air sampling at various locations and distances from the dedrum II-5 �facilities included samples for 2,4-D, 2,4,5-T and TCDD analyses, as well as biomonitoring using rapidly growing tomato plants as indicator organisms. Pre-operational and post-operational background sampling was also accomplished. A. Monitoring Equipment and Procedures Two different methods were employed for industrial hygiene and ambient air sampling for 2,4-D, 2,4,5-T and TCDD. These procedures have been developed and field tested by the USAF OEBL. 1. 2,4-D and 2,4,5-T . , Sampling for 2,4-D and 2,4,5-T was accomplished utilizing Chromosorb*R' 102 as an adsorption medium, a granular polymer well suited for collection of chlorinated hydrocarbon vapors in air (10,11). The polymer was packed in micro-pipet tubes which were then wrapped in new aluminum foil and stored in rubber stoppered test tubes. The sampling apparatus consisted ofRa Mine Safety Appliance Model G Personnel Sampling Pump., The Chromosorb^ ' 102 tubes were connected to the pumps with Tygon^' or latex rubber tubing. A flow rate of 0.50 liters/minute (1/min) for periods ranging from five to ten hours was used, yielding an air sample volume of approximately 150 to 300 liters. This sampling time corresponded to the length of approximately one-half shift and was expected to yield sufficient adsorption efficiency to permit easy analysis. Flow rates were checked hourly with a calibrated rotameter to insure that 0,50 1/min flow rate was maintained. Where possible the pumps were maintained on constant "high" recharge by providing connections to available 110-volt power supply. When the Chromosorb(R' 102 tubes were removed from the field for lab analysis the individual tubes were wrapped in aluminum foil and returned to their respective rubber stoppered test tubes. 2. TCDD Air sampling for TCDD was accomplished using benzene as a collection medium. The sampling apparatus consisted of a train of four Greenberg-Smith impingers. The first two impingers were fritted and each contained approximately 350 ml of benzene. The third and fourth impingers were modified by removal of the fritts and contained activated carbon to adsorb vaporized benzene. The two benzene impingers were wrapped with aluminum foil providing a light barrier that would prevent any photodecomposition of the TCDD collected in the sample. Following the four impingers, an in-line paper filter was attached with TygonW tubing to prevent carbon particles from entering the Mi Hi pore pump. The pumps were operated directly from 110-volt AC power and the flow rate was one 1/min. The duration of sampling ranged from three to five hours, yielding an air sample volume from 180 to 300 liters. Flow rates were checked hourly using a calibrated rotameter and total volume of air sampled was calculated from these hourly flow rates. The maximum running time of five hours was dictated by ambient temperatures ranging from 71 to 92 degrees F and the saturation limitations of the carbon to adsorb the benzene vapors. Samples were removed from the sampling sites with II-6 �impinger trains intact in special wooden holders. The benzene was drained into new brown glass jars in a "clean" laboratory area. The impinger glassware was rinsed with benzene into the sample container to collect any materials adhering to the impinger walls. All impinger glassware was rinsed three times with acetone and once with benzene prior to reuse in the field. 3. Biomonitoring Immature, rapidly-growing, potted tomato plants, Lycop&ti>J.con ej>c.vJte.Yvt(m, ranging in size from 6 inches to 18 inches were used as indicator organisms for detecting the presence of Herbicide Orange vapors in air at various locations around the land-based dedrumming, transfer and loading operations. Young tomato plants are known to be very sensitive to phenoxy herbicide vapors (9). The symptoms typical of exposure to Herbicide Orange vapors, known as epinastic growth, is described as a curling and/or twisting of the apical portions of the plants. Depending on level of exposure these symptoms would appear within 24-hours after exposure. Normal procedures included observations, at least once daily, of the tomato plants to record the presence of the epinastic growth symptoms and to water the plants. Relative rating scales were used to describe the levels of damage noted. It was not possible to quantitate the levels of vapor exposure, but the extent to which low parts-pertrillion (ppt) herbicide vapor levels were carried by prevailing winds could be determined. B. Analytical Procedures and Methodologies The analytical procedures and methodologies used throughout Project PACER HO were developed, refined, tested and repeatedly used throughout the variety #f field exercises conducted by the USAF OEHL over the five year period from 1972 to 1977. 1. 2,4-D and 2.4,5-T Analysis of Chromosorbv(R^ 102 air samples was provided by ' two different laboratories. In the case of the NCBC, samples were analyzed by the U.S. Department of Agriculture Laboratory, Gulfport MS under an interservice agreement. All Johnston Island air samples for 2,4-D and 2,4,5-T were analyzed by the staff of the Battelle Columbus Laboratory team. The methods for analyses of herbicide will be reported elsewhere (4,5). 2. TCDD The Brehm Laboratory, Department of Chemistry, Wright-State University, Dayton Ohio, analyzed all benzene impinger samples for TCDD as well as many other types of samples and substrates in support of Project PACER HO. The Brehm Laboratory has been under contract with the USAF for II-7 �several years and has developed unique analytical capabilities in trace analysis for TCDD in a variety of substrates. The analytical methods employed for this project by the Brehm Laboratory have recently been published (8). V. LAND-BASED MONITORING RESULTS Detailed results of environmental and occupational monitoring at both sites will be reported elsewhere (4,5). This section outlines only the industrial hygiene and ambient air monitoring results for each site. Suffice to say that all other available data have indicated that there were no adverse environmental impacts on air, water or land resources at either site as a result of land-based dedrumming, transfer operations. A. NCBC, Gulfport MS The results of the industrial hygiene and ambient air monitoring programs at the NCBC are summarized below: 1. Industrial Hygiene The industrial hygiene air sampling results for 2,4-D, 2,4,5-T and TCDD are presented in Table 1. Five operational industrial hygiene samples were collected during each shift from the four corners within the enclosed dedrum facility. Four of these samples were for 2,4-D, 2,4,5-T using Chromosorb'R) 102, while the fifth sample was a benzene impinger in one corner of the facility collected for TCDD analysis. The ChromosprbW 102 and benzene impinger samplers were placed in low traffic areas near the four corners of the enclosed facility to prevent interference with work activity within the facility. As shown in Table 1, vapor concentrations of the n-butyl esters of 2,4-D and 2,4,5-T ranged from 7.76 - 141.15 ug/m3, respectively. The uniformity of concentrations of herbicide vapors within the dedrum facility is demonstrated by the lack of significant variability of 2,4-0/2,4,5-T data among the four sampling locations. All noted levels were well below the time weighted average Threshold Limit Value (TLV) of 10,000 yg/m3 for either 2,4-D or 2,4,5-T as adopted by the American Conference of Governmental Industrial Hygienists (ACGIH). No TCDD was detected in any of the 27 benzene impinger samples. The minimum detectable concentrations for TCDD ranged from 22.4 to 35.9 ng/m3. 2. Ambient Air Ambient air samples for 2,4-0/2,4,5-T and TCDD analysis were collected from three different locations. In addition, 29 groups of four tomato plants each were positioned around the dedrumming/transfer operations. The results of these monitoring efforts are presented below: a. 2,4-D, 2,4,5-T and TCDD. Sampling stations at two locations on the NCBC were established, one at the base fire station approximately 900 feet SW of the dedrum facility and one at the PACER HO Operation Center approximately 1,500 feet E of the dedrum facility. A II-8 �TABLE 1. Results of industrial hygiene air samples collected inside the dedrumming facility Project PACER HO NCBC, Gulfport, MS, 24 May - 10 June 1977. Sample Location Dedrum Facility Naval Construction Battalion Center (NCBC) • SE Corner NE Corner SW Corner NW Corner 28 28 14 14 NBEa2,4-D (yg/m3) Range Std Dev Mean 8.7-141.15 31.45 52.99 7.86-136.35 34.55 53.72 7.76-134.9 36.25 54.58 15.18-105.11 27.01 51.5 NBEa2,4,5-T (yg/m3) Range Std Dev Mean 5.52-65.11 14.98 26.40 5.70-76.36 18.57 29.93 3.01-79.62 21.02 32.39 7.59-51.31 12.79 25.93 0 0 0 Parameter No. of Samples TCDD No. of Samples Mean a 27 K NDb NBE is normal-butyl ester. ^ND is non-detectable at minimum detectable concentrations that ranged from <22.4 to <35.9 ng/m3. NOTE: The time-weighted Threshold Limit Value for either 2,4-D or 2,4,5-T is 10,000 yg/m3. (See text) II-9 �third location on the wharf approximately 300 feet north of the ship loading point was also sampled. The results of analyses of these samples are presented in Table 2. As expected, the levels of 2,4-D, 2,4,5-T were significantly (45 to 150 times) lower than were found within the dedrum facility. Filtering of exhaust air from the facility, downwind diffusion/ dispersion of released vapors, and the lack of any significant spillage of herbicide outside the facility no doubt accounted for these significantly lower levels. No TCDD was detected at any of the three ambient air sampling stations with the minimum detectable concentrations ranging from approximately 22 to 55 ng/m3. b. Biomonitoring. Tomato plants were placed in groups of four in two concentric rings around the dedrum facility at 500 feet and 1000 feet distances. Moderate to severe plant damage was noted along the axis of prevailing winds in the inner ring (500 feet). Slight to moderate plant damage was noted in the corresponding outer (1000 feet) ring. In addition, several sets of four plants were set up along the NCBC perimeterfence. In two cases test plants along the base perimeter showed only minimal damage. One set of plants was also placed on the dock 300 feet inland from the loading operations. No damage was noted at this location. B. Johnston Island The results of the industrial hygiene and ambient air monitoring programs at Johnston Island are summarized below. There were two distinct loading operations during the Johnston Island phase of the project. The first dedrum/transfer (first loading) operation was conducted from 27 July 1977 to 5 August 1977, and the second loading from 17 August 1977 to 23 August 1977. 1. Industrial Hygiene The industrial hygiene sampling of the Johnston Island operations differed from the sampling at the NCBC. The facility was larger and open to natural ventilation and the dedrum operations were far different as described earlier. Because of these and other factors the industrial hygiene sampling program was modified to include true "breathing zone" samples for 2,4-D, 2,4,5-T from selected worker positions. In general, there were three worker positions evaluated using the Chromosorb\R' 102 tubes. These positions were selected after an analysis of all positions revealed that these worker locations represented the greatest possibility of receiving a significant exposure. The first was the position occupied by those workers who punched the vent holes in each drum. When the vent holes were punched internal pressure in many drums was released, and there was a possibility of elevated exposures to workers in these positions. The second worker position evaluated was that occupied by the workers who punched the several drain holes in each drum, and the third position was the operator of the sump pump. In the latter two cases, these workers were close to open troughs of flowing Herbicide Orange. In addition to these "breathing zone" samples, air samples within the dedrum facility were also collected for ^,4-D, 2,4,5-T and TCDD. Tables 3, 4 and 5 present the results of these sampling programs. 11-10 �TABLE 2. Results of ambient air samples collected at Gulfport MS, Project PACER HO, 24 May - 10 June 1977. Sample Location NCBC, Gulf port, MS Parameter No. of Samples Fire Station Ops Center Wharf 28 29 30 NBEa2,4-Diugym3l Range Std Dev Mean 0.09-5.76 1.20 1.17 0.13-3.88 1.00 1.09 0.07-2.41 0.53 0.52 NBE a 2,4,5-T (yg/m 3 ) Range Std Dev Mean 0.04-3.36 0.85 0.52 0.34-1.97 0.49 0.34 0.01-1.45 0.32 0.21 TCDD No. of Samples Mean 27h NDb 27. NDb 23 h NDb NBE is normal butyl ester. } ND is non-detectable at minimum detectable concentrations that ranged from <21.9 to 55.2 ng/m3. NOTE: The time-weighted Threshold Limit Value for either 2,4-D or 2,4,5-T is 10,000 yg/m3. (See text) 11-11 �TABLE 3. Results of industrial hygiene air samples collected inside the dedrumming facility* Project PAGER HO Johnston Island* first loading 27 July - 5 August 1977. Sample UeatiSn Dedfum Facility deHhStbfi Islands First Loading Parameter SW Corner NW Corner E Wall 3 3 3 NBE a 2,4-D (ug/m3) Range Std Dev Mean 12.8-16,0 1,77 14.84 4.79-13*33 7,30 9.99 0.50-2.58 1.37 1.03 NBla2,.4,5-t (ug/m3) Ramge Std Dev Mean 192-8.84 1.05 8J2 2.26-8.28 3.24 4.58 - 0 0 No, of Samples TGDD No. of Samples Mean NDb a NBE is normal butyl ester, bND is non-detectable ait ifiihlfiiufri deteetSble concentrations that ranged from <8.06 to <13.89 rig/m3. NOTE: The time-weighted Threshold Limit Value for either 2,4-D or 2,4,5-T is 10,000 vig/m3. (Sfee text) 11-12 �TABLE 4. Results of industrial hygiene air samples collected inside the dedrumming facility Project PACER HO, Johnston Island, second loading, 17 - 23 August 1977. Sample Location Dedrum Facility Johnston Island, Second Loading Parameter SW Corner No. of Samples NBEa2,4-D (ug/m3) NW Corner 1 1 18.78 6.60 7.35 2.27 5 NDb 0 NBEa2,4,5-T (uq/m3) TCDD No. of Samples Mean NBE is normal butyl ester. 'ND is non-detectable at minimum detectable concentrations that ranged from <6.64 to <23.41 ng/m3. 11-13 �TABLE 5. Results of .industrial hygiene "breathing zone" samples collected inside the dedrumming facility Project PACER HO, Johnston Island. p'arsfrtete'r ' Sample' locations Dedrum Facility Johnston Island, (See Text) Veftt Drain Pump Punchers Ptine fret's O^efatof First Leading (27 July - 5 August 1977} Nd. of Samples NBEa2,4-D (ug/m3) Range Std Dev Mean NBEa2.,4,5-T (ug/m3) Range Std Dev Mean 8 10 5 2.14-30.8 8.35 17.92 7.64-19.18 5.73 19.18 . 6.11-26.78 8.18 14.36 0. 57-16. t 4.52 8.70 3.79-13.6 2.95 9.54 2.43-11.48 3.61 ' 6.32 Second Loading (17 - 23 Atigust 1977) No., of Samples 12 7 NBEa2,4-D (yg/m3) Range Std Dev Mean 8.38-40.28 10.47 23.20 .NBEa2,,4,5-T 4yg/m3J Range Std D£v Mean 6.49-22.22 6.06 13.-21 0 15.96-38.0 8.53 23.04 - 8.82-22.53 5.20 13.68 - NBE is ndrltial butyl ester. NOTE: The time-weighted Threshold Limit Value for either 2,4-D or 2,4,5-T is 10*000 yg/m3. (See text) 11-14 �The levels noted within the dedrum facility at Johnston Island were on the order of two to five times lower than those noted at the NCBC, Gulfport MS. These lower concentrations probably resulted from much greater dilution by natural ventilation of the open facility at iiohnston Island. Needless to say, the noted levels of 2,4-D and 2,4,5-T were well below the ACGIH TLV of 10,000 ug/m3. No TCDD was detected in any of the samples analyzed. 2. Ambient Air Ambient air samples for 2,4-0/2,4,5-T and TCDD analyses were collected from three different locations. In additon, 14 groups of four tomato plants were positioned at selected locations around the dedrum/transfer operations. The results of these monitoring efforts follow. a. 2,4-0/2,4,5-T and TCDD. One downwind and two upwind sampling stations were established. The downwind site was located approximately 300 feet west of the dedrum facility. The two upwind sites were the fire station approximately 4,000 feet SE and the weather station approximately 6,000 feet ESE of the dedrum facility. The results of downwind and upwind ambient air sampling sites are presented in Tables 6 and 7, respectively. As was expected, the levels of 2,4-0/2,4,5-T noted at the downwind site were somewhat lower than those levels noted within the dedrum facility. The relatively higher levels noted for the second loading as compared to the first loading are not explainable. These levels, however, are well below the TLV. No TCDD was detected in any of these samples. b. Biomonitoring. Tomato plants were placed at 14 biomonitoring stations on Johnston Island. Four of these sites were downwind of the dedrumming facility and the remaining ten locations were all upwind. Throughout the two periods of dedrumming operations all the downwind sites displayed slight to severe herbicide induced damage. There was only slight damage noted on two days at one of the upwind sites. The results of the tomato plant bioassay indicate that during the dedrumming operations concentrations of Herbicide Orange did not occur upwind of the dedrumming facility at sufficient concentrations to affect the tomato plants. VI. SUMMARY AND CONCLUSIONS As part of the environmental and occupational monitoring programs, the USAF accomplished industrial hygiene and ambient air sampling of all land-based dedrumming/transfer operations of Project PACER HO, the USAF project to dispose of 2.22 million gal of Herbicide Orange. The results of these sampling programs revealed that under the worst case noted, the levels of 2,4-D and 2,4,5-T vapors were well below the TLV for each of these materials. The noted levels were at least two and in most cases three orders of magnitude below the TLVs. TCDD was not detected in any air samples. 11-15 �TABLE 6. Results of downwind ambient air samples collected at Johnston Island, Project PACER HO, 27 July - 23 August 1977. Downwind Ambient Air Sampling Parameter No. of Samples NBEa2,4-D (yg/m3) Range Std Dev Mean NBEa2.3»5-T Cug/m3) Range Std Dev Mean First Loading (27 Jul-5 Aug 77) Second Loading (17-23 Aug 77) 14 1.92-25.5 5.99 6.21 5.79-32.67 7.73 12.51 0.82-17.1 4.33 3.27 1.89-14.0 3.46 5.12 TCDD No, of Samples Mean NDC NBE is normal butyl ester. ND is non-detectable at minimum detectable concentrations that ranged from <11.68 to <21.0 ng/m3. NOTE: The time-weighted Threshold Limit Value for either 2,4-D or 2,4,5-T is 10,000 pg/m3. (See text) 11-16 �TABLE 7. Results of upwind ambient air samples collected at Johnston Island, Project PACER HO, 27 July - 23 August 1977. Wharf Station Weather Station First Loading'3 No. of Samples NBEa2,4-D (jjg/m3) Range Std Dev Mean NBEa2,4,5-T (jjg/m3) Range Std Dev Mean TCDD No. of Samples Mean a 11 Second 0 Loading 11 First 13 Loading 11 7 Trace-0.67 0.39 0.25 ND-2.54 0.77 0.23 0 0 Trace 0.34 0.10 0 0 0 0 1 NDd 1 NDe 0 0 Trace-1.09 0.42 0.29 Second Loadi ngc 0 0 NBE is normal butyl ester. b First Loading 27 July - 5 August 1977. C 5econd Loading 17-23 August 1977. d ND is non-detectable at the minimum detectable concentration of <8.52 ng/m3. e ND is non-detectable at the minimum detectable concentration of <20.34 ng/m3. NOTE: The time-weighted Threshold Limit Value for either 2,4-D or 2,4,5-T is 10,000 yg/m3. (See text) 11-17 �Biomonitoring using tomato plants revealed that low-level vapors of Herbicide Orange were dispersed and diffused downwind of the land-based dedrumming/transfer operations at both sites. No adverse environmental impact resulted from these operations. Approximately 200 personnel carried out the dedrumming activities at the NCBC, Gulfport MS and at Johnston Island. Comparisons of available pre- and post-operational medical examinations of military personnel involved have revealed no apparent physical effects as a result of these activities. II-18 �CHAPTER II LITERATURE CITED 1. Ackerman, D.G., H.J. Fisher, R.J. Johnson, R.F. Maddalone, B.J. Mathews, E.L. Moon, K.H. Scheyer, C.C. Shin, and R.F. Tobias. 1978. At-4ea -tnc-tneAotton ofa HeAb4.cJ.de. Orange onboard the. M/T l/u£canoA. Environmental Protection Technology Series EPA-600/2-78-086. Office of Research and Development. U.S. Environmental Protection Agency, Research Triangle Park, North Carolina. 263 p. 2. Anonymous. 1977. A/iA Force Log<it>ticA Command programnujtg p£an 75-19 fan the. di&po&aJL o<j Orange Herfa.tc-t.de. San Antonio Air Logistics Center, San Antonio, Texas. Annex 4, pp 1-17, Annex 5, pp 1-23. 3. Anonymous. 1974. fl-iipo-A-ctcon o& Orange HeAb^cu.de by -imu.neAott.on. Final Environmental Statement. Department of the Air Force, Washington, D. C. 737 p. 4. Anonymous. 1977. Land-bo6ed env-tronmentat monitoring at Johnston Uland. Parts I and I I . Project PACER HO. USAF Contract No. F08635-76-D-0168 Battelle Columbus Laboratories, Columbus, Ohio. IH press. 5. Anonymous. 1978. Lewd-boused env-tAonmentod monitoring at tke. Navat Co»t6.t>t.uCxfcton Bouttation CwteJi, GutfipoKt, Mx6i4-c4AxCpp/c.. Technical Report of the U.S. Air Force Occupational and Environmental Health Laboratory, Brooks AFB, Texas. Jji press. 6. Anonymous. 1977. Mo/toie Pio.£ecxtt.on, Reieotch, and Act (Ocean Pampxjag) Re^ eaA.cn peAm-ct No. 770VH001R, United State* Protection Agency, Washington, D. C. , 15 p. 7. Anonymous. 1975. Ocean dumping, receipt of application and tentative determination. U.S. Environmental Protection Agency. Reg-cAteA 40(57): 13026- 13028. 8. Erk, S.D., M.L. Taylor and T.O. Tiernan. 1978. Env/^ionmenta£ moyUtotsing -en con/unctcon w^t^i -tnctneAa^tcon o& HeAb-tttde Orange at *ea. Activities of the Brehm Laboratory, Wright State University Dayton, Ohio. Presentation to the 1978 National Conference and Exhibition on Control of Hazardous Material Spills, Miami, Florida. 31 p. 9. M u l l i s o n , W . R . 1951. The tomato as a test plant for growth regulators. Bot. Gaz. 112:521-524. 10. Thomas, T.C. and J . N . Seiber, 1974. Chromosorb(R) 102, an efficient medium for trapping pesticides from air. Bu££. Env-cAon. Contain. and ToKicol. 12(1): 17-25. 11-19 �11. Thomas, T,C. and J.W. Jackson. 1978. A technique for sampling 2,4-D; 2,4, 5-T herbicides from air. J. A-UL VoUi-. Control tin press. 12. Wastler, T.A, , C,A. Offutt, C.K. Fltzsilflmons and P.E, Des 1975. V4J>p0Aa£ Ojf 0tycM.o£ki0JUn& um/tfci by 4.nc*Ln&t£Utin Environmental Protection Tedhnglociy Series EPA«430/9-7 Office ef Water and Hazardous Materials. Environmental Proteetion Agehcy* Washifigtdn, D,C, 223 p; II-20 �CHAPTER III ENVIRONMENTAL FATE OF 2,4-D, 2,4,5-T AND TCDD I. INTRODUCTION Chapter I was devoted to the topics of types and quantities of herbicides sprayed in South Vietnam and their handling and application. Emphasis was placed on those factors that may have influenced human exposure to the herbicides prior to actual spray applications. This chapter will focus primarily on the fate of the phenoxy herbicides sprayed in South Vietnam and on the contaminant TCDD. This is appropriate since 94 percent of all herbicides disseminated in South Vietnam were phenoxy herbicides (53 percent 2,4-D and 41 percent 2,4,5-T). The extreme toxicity of the contaminant, and its associated biological effects, require that all available data be reviewed in an attempt to determine the potential adverse human effects this compound may have had on the population at risk in South Vietnam. What happens to the individual compounds physically, chemically and biologically in the environment will significantly influence the route of exposure, the duration of exposure and the total dose (or level) of that exposure to the population at risk. Again, as noted in Chapter I, the population at risk will be confined to personnel of the U.S. military forces. The expression of units of weight, area, or volume has not been standardized between various publications cited in this Chapter. II. THE ENVIRONMENTAL FATE OF THE PHENOXY HERBICIDES A. Physical/Chemical Factors Influencing Disappearance of Herbicides 1. Fate in Air Harrigan (27) reported that in a test program evaluating the dissemination characteristics of the A/A 45 Y-l Spray System, the mean recovery of Herbicide Orange by ground sampling methods from six missions flown under operational parameters typically used in South Vietnam was 87 percent. The remaining 13 percent may have been undetected due to sampling technique or may havev failed to impact the sampling array due to drift or volatility. The mean particle size for the six missions flown was 367 micron (y). Harrigan (27) 1n the above test program with Herbicide Orange, found the following droplet size distribution in the mean percent mass recovered: Particles less than lOOy Particles 100 to 50Qy Particles greater than 500y III-I 1.9 percent 76,2 percent 21.9 percent �The recovery of 87 percent of the Herbicide Orange disseminated is in agreement with Plimmer (50) who reported that deposition of 80 percent of particles greater than 200u in size takes place in short downwind distances, whereas those of diameter less than 5y may drift for miles. The aerial application of Herbicide Orange also presented an opportunity for volatilization since spray drops evaporate during their fall. This was recognized by Grover et al (25), who examined the relative potential for drift of volatile and nonvolatile formulations of 2,4-D under conditions of typical agricultural application. The ground application system employed by Grover et al resulted in only 2.8 percent of the total spray having a particle size less than 200y. The mass of the formulation drifing- as droplets was similar (3 to 4 percent) for either the volatile (n-butyl ester) or nonvolatile (dimethylamine) formulation of 2,4-D. However, for the butyl ester, in addition to droplet drift, within the first 30 minutes after spraying 25 to 30 percent of the material was collected as vapor drift in air samplers up to 246 feet (ft) downwind from the point of application. The data by Grover et al (25) may suggest that although high percentages of Orange particles were intercepted by the vegetation, a significant amount of the material may have rapidly volatilized and moved in the air within the jungle canopy. This is in accord with what Brown (12) had first proposed in 1962 when he recommended the use of the esters of 2,4-D and 2,4,5-T for defoliation in South Vietnam. Better effect can be achieved on a susceptible tree if all its leaves receive a few drops of chemical as opposed to only one side or only the very top of the tree receiving all the chemical. In this connection, forms of the chemical known as volatile esters were requested subsequently in order to achieve more uniform coverage within a forest canopy. 2. Fate on Vegetation Approximately 85 percent of all the 2,4-D and 2,4,5-T sprayed in South Vietnam was'with the C-123/A/A 45 Y-l Spray System [estimate based on data by Irish et al (31), National Academy of Science (15), Craig (16), and Chapter I.] Klein and Harrigan (36) found that in five standard Orange missions the statistical mean value for maximum swath width having a deposition rate that would result in acceptable defoliation was 260t 20 ft. Thus, a typical 1,000 gallon (gal) sortie in South Vietnam would have effectively defoliated an area of approximately 346 acres (A). Data by Tschirley III-2 �(58) suggested that a multicanopy forest would intercept at least 94 percent of all the spray droplets. It is therefore reasonable to assume that if the entire 1,000 gal of Orange fell within the 346 A area, 940 gal of Orange would have been deposited on the canopy vegetation, and 60 gal deposited at ground-level on the soil or small herbaceous understory. The actual ground-level deposition may then • have been 0.17 gal/A or 1.4 pounds (Ib) of 2,4-0/2,4,5-T per acre (60 gal/346 A = 0.17 gal/A x 8.14 Ib active ingredient/gal = 1.4 Ib 2,4-0/2,4,5-T per A). In the United States, mixtures of these phenoxy herbicides are routinely applied at 2 Ib/A. If time after application was the same, then military personnel moving through defoliated forests in South Vietnam probably would have encountered the same amount of herbicide as would a rancher in the United States walking through defoliated brush-infested ranch land. Once the herbicide is intercepted by the vegetation, numerous physical and chemical barriers influence the amount of herbicide that is absorbed, transported and accumulated. In Volume 2 (Weed Control) of a special series on the principles of plant and animal pest control, the National Academy of Science (49) reviewed the physical and chemical barriers which intervene between application of a herbicide and its ultimate effect on the plant. They found that, in general, both the upper and lower leaf surfaces absorb herbicides. Usually, the lower epidermis is penetrated more readily, but not all areas of either surface are equally permeable. The penetration of the phenoxy herbicides into most foilage is by diffusion through the cuticle (cuticular entry). Warm temperatures that are not excessive and high humidity may actually promote the entry. Because the cuticle and the cell walls upon which the cuticle is deposited contain chemically nonpolar materials that are slightly electronegative, nonpolar herbicides (e.g., Orange and Purple) tend to be absorbed into leaves faster than polar herbicides. Cuticular penetration by the esters of 2,4-D or 2,4,5-T may occur within 30 minutes of their application. 3. Fate in Soils Hamaker (26) has reviewed the physical and chemical factors that influence fate of herbicides in soil. These include soil adsorption, hydrodynamic dispersion and diffusion, adsorption dynamics and evapotranspiration. The phenoxy herbicides, for example, have low adsorption coefficients and thus tend to leach in a soil profile. The actual amount of leaching, however, will vary from soil to soil, mainly in response to the organic carbon content. Moreover, only the herbicide free in the soil water will be carried down by descending water. Crosby (18), in reviewing nonbiological degradation of the phenoxy herbicides in soil, reported that the isopropyl, butyl and isooctyl esters of 2,4-D had a half-life of about 100 hours (h) III-3 �in neutral soil water (although hydrolysis was almost instantaneous in the presence of a base or a suspension of any of several soils at pH 7.0-7.5). Moreover, many of the phenoxy herbicides, e.g., 2,4-D, will readily undergo oxidation, reduction and substitution (notably hydrolysis) in aqueous solutions when activated by sunlight in air. The end product of the photodegradation of 2,4-D is humic acid (17). Although 2,4,5-T absorbs some ultraviolet light in sunlight, the amount is small and this herbicide is relatively unreactive (only 7 percent was hydrolyzed in 48 h). However, the presence of ferric salts or zinc oxides in the soil water will result in an increase in photolysis rate (17). Another nonbiplogical factor that determines the soil persistence of the phenoxy herbicides is their tendency to volatilize from the soil complex. Plimmer (50) noted that some volatilization will occur whether or not water is evaporating from the soil. However, a reduction in soil moisture content will decrease the pH of soil. This will favor the undissociated form of 2,4-D and 2,4,5-T and their potential for vapor loss may be increased. B. Biological Degradation of the Phenoxy Herbicides 1. Fate in Plants Loos (40) has recently reviewed the degradation of phenoxy herbicides in plants. In general, because of the widely different degradative pathways, the phenoxy herbicides do not persist in plants. However, Muzik (44) has reported that in some plants, for example, tomato, unmetabolized 2,4-D may be bound to cellular membranes and persist for two or three months. 2. Fate in Soils There is considerable evidence available to show that the phenoxy herbicides are rapidly decomposed in soils (5). Goring et al (23) in reviewing principles of pesticide degradation in soil noted that 2,4-D may undergo at least 6 different types of oxidation reactions, 1 reductive reaction, 1 hydrolytic reaction and 4 conjugative reactions. Because of this ability to readily undergo transformation, 2,4-D has been classed as a non-persistent pesticide since the estimated time required for 50 percent to disappear from soil was <0.5 months. However, 2,4,5-T has been classed as a slightly persistent pesticide since the time required for 50 percent disappearance was 0.5 to 1.5 months. III-4 �If 2,4-D were applied to a moist loam soil under summertime temperature at a rate of 0.5 to 3 pounds/acre (Ib/A), it would disappear in 7 to 30 days (37). If applied at rates of 4 to 55 Ib/A, it would probably disappear in one to three months (22). If 2,4-D were applied to the soil at a concentration of 500 ppm and disappeared at a rate proportional to the breakdown of 55 Ib/A, the calculated time would be 5.6 years. However, there is evidence that a more realistic time for inactivation of 500 ppm would be less (4). Persistence of 2,4,5-T in soils is usually two to three times longer than 2,4-D (22), and very few organisms have been identified as having the ability to breakdown the 2,4,5-T molecule (2). Newton (46) has calculated from studies on the kinetics of degradation by microorganisms that 2,4,5-T has a half-life of seven weeks in the forest floor. Investigations by Winston and Ritty (59) and Reigner et al (51) indicated that both 2,4-D and 2,4,5-T are decomposed to form carbon dioxide, inorganic chlorides and water; objectionable chlorophenols are not end-products of this decomposition. Further supporting evidence has been provided by Reinhart (52). The upper half of a 60 acre timber watershed in northern West Virginia was logged and treated with 2,4,5-T ester to kill all vegetation. The volume of herbicide that was applied was 1,325 gal on 30 acres (418 liters/ha). Almost 790 gal of this were potential contaminating materials: about 740 gal of diesel oil and 50 gal of a commercial formulation of 2,4,5-T (313 pounds acid equivalent). Reinhart found n£ odor contaminants (phenols or catechols) in the numerous water samples taken from the stream draining the treated watershed. In relation to the effects of herbicides on the soils of South Vietnam, the National Academy of Science published a report by Blackman et al (11) on persistence and disappearance of herbicides in tropical soils. The 1974 report stated a number of general conclusions, namely: 1. The behavior of herbicides in the soils of South Vietnam was similar to that reported for soils elsewhere. 2. Only where 2,4-D and 2,4,5-T were applied in very massive doses; e.g., at the Pran Buri Calibration Grid in Thailand at rates in the magnitude of 1,000 Ib/A, were there still residues (10 years following application) in concentrations above the threshold likely to induce phytotoxic symptoms in some plant species. 3. When applied to mangrove soils at total doses approaching 10 Ib/A of 2,4-D and of 2,4,5-T, the level of herbicide residue at the end of 30 weeks had no effect on the establishment of two major mangrove species. 4. In geographical areas subjected to one or two military herbicide missions 1.5 years before sampling, no soil phytotoxic residues could be detected. III-5 �5. Soils that received a directed application of Herbicide Orange at the rate of 27 Ib/A safely supported the growth of crops sensitive to 2,4-D or 2,4,5-T four to six months following application. 6. Claims that the herbicides rendered the soil sterile were without any foundation. Byast and Hance (14) have studied the degradation of 2,4,5-T by South Vietnamese soils incubated in the laboratory. Although care must be exercised in extrapolating laboratory results to field situations, their results suggested that the four Vietnamese soils studied were inherently capable of degrading 2,4,5-T at levels roughly twice the rate of military application in Vietnam. In support of feasibility tests for the soil disposal of surplus Herbicide Orange, the Air Force established a field study in 1972 on the Air Force Logistics Command Test Range, Hill Air Force Base, Utah. The study consisted of replicated plots subsurface injected with concentrations of either 1,000, 2,000, or 4,000 Ib herbicide/A. Soil samples were taken by Stark et al (56) three times throughout 1973, and microbial species present (bacteria, actinomycetes and fungi) were determined. Bacterial counts were higher for soils with greater concentrations, of the herbicide and with greater moisture content; i.e., those samples collected in midwinter from the 4,000 Ib/A plots. Herbicide Orange, in any concentration, had no significant effect on mycoflora. Arnold et al (4) monitored the herbicide levels in these plots. They sampled the plots on eight occasions from 1973 through 1975 and determined the concentrations of the n-butyl esters and free acids of both 2,4-D and 2,4,5-T. They suggested that at such massive application rates (soil concentrations greater than 10,000 ppm) and in an alkaline desert environment, the half-life of 2,4-0 and 2,4,5-T appeared to be in the range of 150 to 210 days. The cooperative studies by Stark et al (56) and Arnold et al (4) have shown that the application of 2,4-D and 2,4,5-T at massive rates not only did not sterilize the soil, but indeed stimulated the growth of certain microflora, and this stimulation may have contributed to the degradation of the herbicide. C. Accumulation and Metabolism of Phenoxy Herbicides in Animals A detailed review of the toxicity, distribution and fate of 2,4-D and 2,4,5-T in animals is provided in Chapter IV. Some general observations on the metabolism of the phenoxy herbicides have recently been published by Leng (39). She reported that residues of the phenoxy herbicides in treated food or feed crops were readily absorbed in the gut of animals and were excreted rapidly in the urine, largely as unchanged phenoxy acid. Some conjugation occurred, particularly at higher dosage levels, but the basic structure of the herbicide was III-6 �not readily altered in animals. The ether linkage can be cleaved by bacterial action in the rumen but the rate of cleavage depended on the chemical structure of the phenoxy compound. The rate of clearance of residues from the body was dependent upon dosage level, particularly if the renal threshold was exceeded. Leng (39) concluded that residue levels were considerably lower in muscle, milk, and cream than in liver and kidney, but that all residue levels rapidly declined after withdrawal of animals from treated feed. Residues of phenol metabolites were present in milk, liver and kidney of animals fed high doses of 2,4-0 and 2,4,5-T. III. THE ENVIRONMENTAL FATE OF TCDD A. Analytical Limitations Statements on the fate of TCDD in the environment are predicated upon the detection in environmental substrates. Prior to 1973, the detection limit for TCDD, was 0.1 ppb for soils and 0.05 ppm for biological tissue (60). As noted by Kearney et al (35) and Dost et al (23), a 1 Ib/A application of 2,4,5-T containing 0.1 ppm TCDD applied directly to the soil could result in a maximum of 0.1 parts per trillion (ppt) in the top 15 cm of soil. Likewise, Baughman and Meselson (9) have calculated that environmental monitoring of food chains for buildup of TCDD would require a level of detection of 1 ppt. For a 1 gram sample of biological tissue, this would require a limit of detection of 1 picogram (pg) (10-^2 gram). Highly sophisticated instrumentation is required to obtain these low detection limits. However, another one of the limiting factors, even with appropriate instrumentation, has bee,n the need for cleanup techniques applicable to a wide variety of environmental samples. Recently (1977), Hummel (30) has reported on a technique suitable for permitting the detection of ppt residue levels of TCDD. Using this technique, Hummel has analyzed a wide array of environmental substrates. These have included analyses of whole fish, fish muscle, rat and mouse liver, mouse pelts, bird liver and stomach, insects, diving beetles, seeds, soil, water, and bovine and human milk. Largely due to the analytical limitations" noted above, the quest for environmental data on TCDD began with laboratory experiments. The use of radiolabeled preparations were invaluable in these studies. There has been considerable interest placed on the analysis of TCDD in field samples; e.g., fish and human milk from South Vietnam (7), bovine fat, liver and milk from the Western United States (3,41), and rice from Arkansas (30, 55). B. Laboratory Studies of TCDD Two model ecosystem studies (33, 42) have been conducted in an attempt to simulate the mode of entry of TCDD into water with the III-7 �subsequent exposure of several organisms representing parts of natural food chains. These systems were not designed to determine the effects of TCDD on the organisms but rather, how does TCDD behave when subjected to likely environmental conditions. Matsumura and Benezet (42) introduced 14C-TCDD in the form of residues on sand into an aquatic ecosystem containing brine shrimp, mosquito larvae and fish. The results indicated that the rate of pick-up was extremely low in brine shrimp and fish under the experimental conditions, Mosquito larvae, which were bottom feeders, showed a faster rate of TCDD pick-up. They concluded that because of TCDD's low solubility in water and its low partition coefficient in liplds, it was not likely to accumulate in as many biological systems as DDT. Isensee and Jones (33) exposed several organisms to ' C-TCDD for up to 31 days to determine the distribution and bioaccumulation potential in the aquatic environment. TCDD accumulation by all organisms was directly related to water concentration (0.05-1330 ppt) and ranged from 2.0 x 104 to 2.6 x 104 times the water concentration for snail, mosquito fish and daphnids and averaged 4.9 x 103 for duckweed, algae and catfish. No metabolities of TCDD were found in submerged soil, water, snails, mosquito fish or catfish. Isensee and Jones further noted that most (85-99 percent) of the 14C-TCDD originally added to the ecosystem remained in the soil at the end of the experiment. Total recovery for the ecosystem averaged 92.2 percent, indicating that TCDD was very stable during this study. From the model ecosystem data, it has been concluded that TCDD is taken up by an organism and retained (bioaccumulation). The accumulation results in TCDD concentrations in the environment (bioconcentration). The food chain studies do not suggest, however, that TCDD is biomagnified; i.e., organisms at successive trophic levels do not exhibit an ascending order of TCDD concentrations in their tissues. Neither of the model ecosystem studies reported toxic effects from the bioconcentration of the TCDD. Both studies, however, were of short duration and the water concentration was generally low, although in one experiment by Isensee and Jones (33) the water concentration exceeded 1 ppb and'mosquito fish and catfish accumulated concentrations greater than 1.4 ppm TCDD for 3 and 6 days, respectively. Miller et al (43) conducted chronic toxicity tests to assess the hazard to aquatic organisms exposed to TCDD in water or food. They evaluated three species of fish: guppies, coho or silver salmon, and the rainbow trout; and three aquatic invertebrates: a snail, a worm and mosquito larvae. Their conclusions were that TCDD in water or food was toxic to fish. The effects of exposure for 2496 h of young salmon to TCDD in water at levels greater than 23 ng/g (23 ppb) were irreversible, and death resulted in 10-18 days. Duration of exposure was less important than level of exposure except as threshold response level was approached. The critical exposure III-8 �period was somewhat less than 24 h in static water toxicity tests in which TCDD concentrations changed markedly with time. Small fish were more sensitive than large fish on an equivalent exposure level basis. TCDD in food at 2.3 ppm markedly reduced growth of young rainbow trout (10/aquaria) exposed to 6.3 yg TCDD per tank per week for 4 weeks. TCDD at 0.2 ppb had no effect on pupation of the mosquito larvae, but reduced the reproductive successes of the pulmonate snail and the oligochaete worm. Morris and Miller (48) have conducted additional bioassay tests with guppies. Exposure of guppies to concentrations of TCDD equal to or greater than 0.1 ppb for 120 h caused complete mortality in approximately 30 days. Duration of survival was significantly and positively correlated with body lengths. Beatty et al (10) administered larval and adult forms of the American bullfrog doses of TCDD varying from 25 to 1,000 yg/kg. Doses of TCDD as high as 1 mg/kg failed to have any significant effect upon survival or completion of metamorphosis in tadpole. Doses of TCDD up to 500 yg/kg had no effect on survival of adult frogs. Histopathological examination of various tissues from the metamorphosed tadpoles and adult frogs revealed no abnormalities. In one of the first laboratory studies of TCDD in soil, Helling (28) found that TCDD was immobile when evaluated by soil thin-layer chromatography. In laboratory leaching studies, Matsumura and Benezet (42) found that virtually no TCDD leached from soil columns of sand or sandy loam. Kearney et al (34) have determined the persistence of TCDD after 20, 40, 80, 160 and 350 days in Hagerstown and Lakeland soils receiving 1, 10 and 100 ppm TCDD. After 1 year, 56 and 63 percent of the originally applied TCDD was recovered in the Hagerstown and Lakeland soils, respectively. Thus, the half-life was estimated to be about 1 year. Furthermore, TCDD could not be detected after 70 days in soils receiving 10, 100 or-1,000 ppm 2,4,5-trichlorophenol, suggesting that TCDD was not biosynthesized by microbial condensation reactions. The long half-life of TCDD suggested to Kearney et al (34) that it was not readily metabolized by soil microorganisms. This observation was in keeping with what Matsumura and Benezet (42) found. They evaluated 100 microbial strains, which had previously shown the ability to degrade persistent pesticides, for their ability to degrade TCDD. Only 5 of 100 organisms showed some ability to degrade this compound, suggesting that microbes capable of degrading TCDD were rather rare in nature. Helling et al (29), in reviewing the previous studies, concluded that persistence of TCDD was not surprising since it is an insoluble, nonpolar, chlorinated molecule, devoid of biologically labile functional groups. III-9 �Isensee and Jones (32), in laboratory studies determined the uptake of TCDD from soil by two crop species. Lakeland Sandy loam, a soil with low adsorptive capacity, was treated with ^C-T at the rate of 0.10 and 0.06 ppm, respectively. Oats or soybeans were grown in this soil and their tops were harvested at intervals to maturity. All tissue '^C-activity was expressed on the basis of the original compound. Oats and soybeans accumulated in their tissue less than 0.15 percent of the TCDD present in the soil. Isensee and Jones (32) also evaluated the fate ot TCDD when applied to foliage. Uniform quantities of '^C-TCDD were applied to the center leaflet of the first trifoliate leaf of 3-week-old soybean plants. The first leaf blade of 12-day-old oat plants was treated with '4C-TCDD only. Results indicated that TCDD was not translocated beyond the treated leaflet. An average of 94 percent of the TCDD remained on soybean leaves for 21 days, but the amount continuously decreased on oat leaves. Although Isensee and Jones suggested that volatilization was a key factor in the disappearance of TCDD from foliage, Crosby and Wong (19) have suggested that photodegradation of the dioxins was a plausible explanation. In an uptake study similar to that of Isensee and Jones (32), but using sorghum, Cupello and Young (20) found that the rate of uptake of TCDD from a Ulysses sandly loam soil was approximately one millionth of one percent of the amount of TCDD in the soil. Nash and Beall (45) have recently (1978) completed a study on the fate of TCDD in the plants, soil, water and air of a microagroecosystem. Tritium-labeled TCDD at concentrations of 44 or 7,500 ppb was applied to a bluegrass turf microagroecosystem using an emulsifiable concentrate form of the isooctyl ester of 2-(2,4,5trichlorophenoxy) propionic acid (Silvex) as a carrier. They found that: 1. TCDD concentrations in water leached through soil were below the analytical detection limit (10~'6 g/g water). 2. TCDD concentrations on grass were initially 20 ppt (10-12 g/g grass), but after four weeks were at or below 1 ppt. The half-life was approximately six days. 3. TCDD concentrations in or on soil were less than 0.2 ppt and most (80 percent) was near the soil surface (0-2 cm). 4. TCDD concentrations in air were (immediately after application) less than 100 fg/m3 (femtogram - 10~'5g/m3) and after four weeks decreased to <3 fg/m^. 5. TCDD, or its degradation products, concentrations in earthworms were less than 0.3 ppt. 111-10 �6. The major repositories for TCDD were the soil and thatch. Nash and Beall (45) concluded that volatilization (approximately 10 percent) of TCDD was a major pathway of dissipation from the microagroecosystem chamber. However, once TCDD was volatilized it dechlorinated in the direct sun and apparently even in shade outdoors or when the sun was filtered with glass in the chambers. Thus, TCDD is sensitive to photodechlorination in the vapor phase even without the presence of ultraviolet light. C. Field Studies of TCDD 1. Residue in Aquatic Ecosystems Several monitoring studies for TCDD in aquatic organisms have been conducted. Baughman and Meselson (8) reported finding TCDD concentrations of 70 to 810 parts per trillion (ppt) in fish from rivers of interior Vietnam and concentrations of 18-79 ppt in fish, and shellfish along the seacoast of South Vietnam. Their samples were collected in 1970 and analyzed 2-1/2 years later by their method and instrumentation. Zitko (65) and Zitko et al (66) did not detect dioxins in a wide assortment of aquatic organisms collected from the St. John River, New Brunswick or the Bay of Fundy, Canada. Their detection limits, however, were between 0.1 and 1.0 ug/g of tissue. Shadoff et al (55) have examined fish (bass and catfish) from a reservoir in a rice-growing region of Arkansas, where 2,4,5-T had been used annually for more than 20 years. Likewise, fish (walleyes and catfish) were obtained from a reservoir in West Texas where 2,4,5-T had been used for brush control over the past 20 years. No TCDD was detected in any of the samples with a minimum range of 10 ppt. Young et al (62) reported on species diversities and food chain studies conducted in two aquatic ecosystems draining a unique one-square mile military test area (Test Area C-52A, Eglin AFB, Florida) that received 161,000 pounds 2,4,5-T and 170,000 pounds 2,4-D herbicide during the period 1962-1970. Significant levels (10710 parts, per trillion) of TCDD were found in 1973 within the top six inches of the test area soil. Erosion of soil occurred into a pond on the test area and into a stream immediately adjacent to the area. TCDD levels of 10-35 ppt were found in 1974 in silt of the aquatic systems, but only at the point where eroded soil entered the water. Species diversity studies of the stream were conducted in 1969, 1970, 1973 and 1974. Insect larvae, snails, diving beetles, crayfish, tadpoles and major fish species (by body parts) from both aquatic systems were analyzed for TCDD. Species diversity studies indicated no significant change in the composition of ichthyofauna between these dates or a control stream. Concentrations of TCDD (12 ppt) were found in only two species of fish from the stream, sail fin III-ll �shiner and mosquito fish. The sample of mosquito fish consisted of bodies with heads and tails removed. Two samples of sailfin shiner were analyzed: one containing viscera only and the other bodies less heads, viscera and caudal fins. Only the viscera contained TCDD. Samples of skin, muscle, gonads, and gut were obtained from spotted sunfish!, from the test grid pond. Levels TCDD in those body parts were 4, 4, 18 and 85 ppt, respectively. Grass pathological observa tions Qf the sunfish revealed no significant lesions or abnormal itit r.. 2. Residues 1n Sails * The National Academy of Science (15) reported finding TCDD concentrations of <1.2 to 23.3 parts per billion (ppb) in soil of the Pran Buri Calibration Grid (Thailand), an area used in calibrating RANCH HAND aerial equipment. Wool son et al (60) found no residues in 1971 in Lakeland sand which had received 947 Ib/A of 2,4,5-T during 1962-1964. These unusually high doses resulted from testing of aerial application equipment at Eglin AFB, Florida. Although analysis of the applied material was not conducted, 2,4,5-T made prior to 1968 probably contained enough TCDD to be detected throughout the 1-yard of soil profile sampled. Wool son et al suggested that the lack of detectable residue was due probably to its decomposition on or in the soil and/or to its transportation by wind erosion. Young et al (64) conducted four years of field studies on the persistence of Herbicide Orange and TCDD when applied at massive rates to soils. Herbicide Orange "biodegradation" plots were established in Utah (Air Force Logistics Command Test Range) and in Florida (Eglin AFB Reservation) using simulated subsurface injection techniques to place the herbicide 4 to 5 inches beneath the soil surface in bands 2.5 or 6 inches wide for Utah or Florida, respectively. An application rate of 4,000 Ib herbicide/A resulted in initial TCDD residues of approximately 148 ppb and 0.375 ppb in the Utah and Florida plots, respectively. Figure 1 is a semi-logarithmic plot of the soil concentration of Herbicide Orange while Figure 2 is a semilogarithmic plot of the soil concentration of TCDD in the same field tests. Using Figures 1 and 2, the half-life data were calculated as 300 and 220 days for Orange, and 320 and 230 days for TCDD for Utah and Florida, respectively. It should be emphasized again that these data were from field plots where the herbicide and TCDD were injected as highly concentrated herbicide in narrow bands beneath the soil surface. Data on soil penetration of TCDD within the soil profile of Utah biodegradation plots receiving either 1,000, 2,000 or 4,000 Ib/A are shown in Table 1 (Unpublished data: Young, A.L., and E.L. Arnold. 1978. Report on TCDD soil penetration studies, USAF Occupational and Environmental Health Laboratory, Brooks AFB, Texas). Note that in Table 1, 98 percent of all TCDD was detected in the 0-6 inch increment of soil, the increment into which the herbicide was applied. Even in the plots receiving 4,000 Ib/A, the TCDD detected in the 6-12 111-12 �Hill AFB, Utah .Eg!in AFB, Florida 10,000 c o t. O) Q . 03 Q . 1 ,000 u -S O) a: -M (O 4-> C cu u c o o (X) 100 r ?1 200 400 600 800 1,000 Time (Days After Incorporation) FIGURE 1. Semi-logarithmic plot of soil concentrations (parts per million) of herbicide in Herbicide Orange biodegradation studies at Eg!in AFB, Florida, and Hill AFB, Utah. Source: Reference (64 ) 111-13 1,200 �20,000 Hill AFB, Utah Eglin AFB, Florida 10,000 *<• 1,000.. Q . in •»-> i. (T3 Q. Q O O c O £ •4-> C O) O c O O 100-. O 00 10 200 400 600 800 1,000 Time (Days After Incorporation) FIGURE 2. Semi-logarithmic plot of soil concentrations (parts per trillion) of TCDD in Herbicide Orange biodegradation studies at Eglin AFB, Florida, and Hill AFB, Utah. Source: Reference (.64). 111-14 1,200 �TABLE 1, Concentrations of TCDD, parts per trillion, in the Herbicide Orange biodegradation plots, AFiC Test Range, Utah, four years after applications.3 Original Rate of Herbicide Orange Applied Depth (inch) 1,000 Ib/A 2,000 Ib/A 4,000 Ib/A 0 -6 650 1600 6600 6 - 12 11 90 200 12 - 18 NAb NAb 14 a Samples collected 6 November 1976. Plots established 5 October 1972. ^Samples not analyzed. Source: Unpublished data (Young, A. L., and E. L. Arnold. 1978. Report on TCDD soil penetration studies. USAF Occupational and Environmental Health Laboratory, Brooks AFB, Texas). 111-15 �inch increment may have been there because of the mass movement of the herbicide at the time of application rather than through the movement of percolating water. These penetration data are similar to those reported by Young et al (64) for the Florida biodegradation plots (noted earlier) although the Florida site received an annual rainfall of 60 inches (vs 10 Inches annual rainfall in Utah). Young et al (63) reported TCDD data from soil analyse-* of the Eglin AFB, Florida, Spray Equipment Calibration Grid (Grid 1 5 Test Ana C-52A). As noted in Chapter I, this grid received 1,894 pounds of Purple per acre during the 1962 through 1964 period. TCDr concentrations in a soil profile from samples collected ten years after the last application of Purple are shown in Table 2. 3. .Residues in Animals The current search for TCDD in beef fat and liver in the United States may provide an indication of the possible fate of TCDD in South Vietnam. In September 1974, the Environmental Protection Agency established a Dioxrn Implementation Plan which consisted of a short term monitoring program (Part I) and a broad research plan which would take 4 to 5 years to complete (Part II) (3). Part I of the program was initiated in February 1975. The guiding principles for the sample program were: (a) the samples should be representative of beef actually prepared for human consumption and (b) the samples should be from cattle grazed on lands treated with 2,4,5-T. Control samples were to be taken from cattle grazed on non-treated areas within the same state. Between February and March 1975, 85 beef fat (peritoneal and kidney) and 43 liver samples were collected (3). Approximately 25 percent of these samples were collected from non-treated areas. One laboratory prepared all sample extracts, and identical aliquots were sent to all participating analytical laboratories. In June 1976, analytical results for these samples were announced by the EPA Dioxin Project Manager (53). TCDD was present (range of 20-60 ppt) in a small percentage (3.5 percent) of the beef fat samples taken from cattle with a known exposure of 2,4,5-T. All of the beef liver samples analyzed were negative, at a detection limit of 10 ppt TCDD. Phase II of the Dioxin Implementation Plan began in 1978, with the intended goal of providing EPA with information on the range and possible bioaccumulation of TCDD in the environment (3). Analyses of human fat and liver tissue and human milk, and additional samples of beef fat and liver were to recieve the highest priority. Mahle et al (41) have recently completed a surveillance of bovine milk samples from the states of Oklahoma, Arkansas and Missouri. Twenty-five samples were collected from cows grazing on pastures on rangeland treated with normal applications of 2,4,5-T. These samples and control samples were analyzed for TCDD by gas chromatography-mass spectroscopy (GC/MS). They found no TCDD in bovine milk 111-16 �TABLE 2. Concentration of TCDD in soil profile of Grid 1, Test Area C-52A, Eg!in AFB, Florida.3 Depth of (inch) Parts per Trillion (ppt) TCDD 1 1 -2 160 2 -4 700 4 -6 44 6-36 a 150 NDb Grid 1 received 1,894 pounds of Herbicide Purple per acre during 19621964. The soil samples were collected and analyzed in 1974. detected, minimum detection limit - 10 ppt. Source: Young et al . (63). 111-17 �from control or treated areas with a detection limit of 1 ppt. In reforestation tests in Western Oregon, Newton and Snyder (47) applied Herbicide Orange at the rate of 2-4 Ib/A. Analysis of resident mountain beaver captured inside the treated area two months after treatment showed no TCDD in livers, with a minimum detection limit of 3 ppt, and the animals appeared to be in good health in all respects. Wool son et al (60) examined extracts of 19 bald eagles from locations throughout the United,States for TCDD and higher dioxin residues. No dioxins were detected at a minimum detection limit of 50 ppb. Baughman (7) analyzed samples of human milk for TCDD from areas of South Vietnam heavily treated with 2,4,5-T during the military herbicide program. Levels of 40-50 ppt in human milk were found in samples collected in 1970 and analyzed four years later. Shadoff et al (55) analyzed samples of human milk obtained from mothers residing near the North Concho River Basin of West Texas, an area where large acreages of the watershed had been sprayed repetitively with 2,4,5-T herbicides for brush control over the past 20 years. No TCDD was found in any of the milk samples at a minimum detection limit below 10 ppt. 4. Air Force Studies Chapter I and earlier sections of this chapter have referenced studies conducted on the Spray Equipment Calibration Grids, Test Area C-52A, Eglin AFB, Florida. The soil residue studies and the aquatic studies have previously been described. Test Area C-52A offered a unique opportunity to follow the fate of TCDD in the many components of the ecosystem. Young (61), Young et al (62, 63, 64), and Bartleson et al (6) have reported on various investigations conducted on this test area. The following is a brief synopsis of the magnitude of the contamination and the subsequent effects upon the wildlife of the test area. In addition to these references, data by Young, Thalken and Harrison (unpublished - USAF Occupational and Environmental Laboratory, Brooks AFB, Texas) of recent investigations at the test site have been incorporated into the synopsis. Field investigations were conducted during 1973-1978 on the 3.0 km2 test area containing 4 different calibration grids that received a total of approximately 73,000 kg 2,4,5-T and 77,000 kg 2,4-D during the period 1962-1970. No residues of 2,4,5-T or 2,4-D were detected (detection limit of 10 ppb) in any soil samples collected during 1971-1972. However, residues of the contaminant, TCDD, were still present in 1978. Fifty-four soil samples were collected to a depth of 015 cm from throughout the test area. TCDD levels ranged from <10 to 111-18 �1,500 parts per trillion (ppt). The median concentration was 30 ppt while the mean was 165 ppt. The ecological survey extending over a five-year period documented the presence of more than a 123 different plant species, 77 bird species, 71 insect families, 20 species of fish, 18 species of reptiles, 18 species of mammals, 12 species of amphibians and 2 species of molluscs. At least 170 biological samples were analyzed for TCDD, including 30 species of animals. No TCDD was found in any of the plant species examined. However, TCDD was found in nine species of animals including two rodent species: beachmice (300-1,500 ppt, liver) and hispid cotton rat (<10-210 ppt, liver); three species of birds: meadowlark (100-1,020 ppt, liver), mourning dove (50 ppt, liver), and Savannah sparrows (69 ppt, liver); three 'species of fish: spotted sunfish (85 ppt, liver), mosquito fish (12 ppt, whole body), and sail fin shiner (12 ppt, whole body), and one reptile, the six-lined racerunner (360-430 ppt, muscle). Gross pathology was done on all species collected for TCDD residue analyses. Histopathological examinations were performed on over 300 adult or fetal beachmice or hispid cotton rats from the test area and a control field site. Examinations were performed on the heart, lungs, trachea, salivary glands, thymus, liver, kidneys, stomach, pancreas, adrenals, large and small intestine, spleen, genital organs, bone, bone marrow, skin and brain. Initially, the tissues were examined on a random basis without the knowledge of whether the animal was from a control or test area. All microscopic changes were recorded including those interpreted as minor or insignificant. The tissues v/ere then reexamined on a control and test basis, which demonstrated that the test and control mice could not be distinguished histopathologically. Similar histopathological studies were conducted on the fish and racerunner, and again no significant abnormalities were found. As a concluding remark, Young et al (64) noted that Test Area C-52A offered a unique opportunity to examine the effects of long-term, low-level exposure of biological systems to TCDD. As previously noted, histopathological examination in body organs from adult and fetal beachmice revealed only lesions which are normally observed in microscopic surveys or large numbers of field animals. The absence of liver lesions in animals that had liver levels of TCDD from 200 to 1,500 ppt was most significant in view of the quantities of TCDD that must have been applied to the test site. Although these pathologic studies were initiated in 1973, beachmice had been collected from the test area as early as 1970 for gross pathological observations. They believed the animals examined in 1973-1974 from Grid 1, the area of greatest contamination (having received 1,894 pounds of Purple per acre in 1962-1924) may have been between 24 and 40 generations removed from the mouse population first noted in 1970. Thus, these studies conducted on the mice of Test Area C-52A suggested that long-term, low-level exposure to TCDD under field conditions may in fact not be teratogenic, mutagenic nor carcinogenic. 111-19 �D. Environmental Production of TCDD In 1971, Buu-Hoi et al (14) reported that small quantities of TCDD were formed upon the pyrolysis of 2,4,5-T acid, its butyl ester, or from vegetation defoliated by these products. In their article, Buu-Hoi provided mass spectral data for TCDD (compound I in his text). In reference to these spectral data, they stated (as translated from French): There is no need to use the precise analytical techniques described in the foregoing in the case of pyrolysis of 2,4,5-trichlorophenoxyacetic acid (500-600°), because simple fractional sublimation of the pyrolysate, prewashed in diluted aqueous soda, will yield about 5 percent of compound (1). This yield is increased to 15 percent as a result of the pyrolysis of trichloro-2,4,5 sodium phenoxyacetate. The conclusion (and this has been verified) is that quantities of "dioxin" (I) are formed during the combustion, more or less forced, of materials coming from plants pretreated by 2,4,5trichlorophenoxyacetic acid, and its derivatives (2,4,5-trichlorobutyl phenoxyacetate, the base of the "Orange" defoliant, leads naturally to free acid as a result of hydrolysis attributable to humidity, or to bacterial or fungal degradation), and this is all the more so because alkaline ash appears as a result of such combustion. One then can conceive the possibility of danger, in the long or short term, to public health in areas such as South Vietnam where the people use materials that are principally of plant origin, and are local, as fuels in their homes (wood, charcoal, dry leaves and branches), and which, as a result of the intensive defoliation that took place since 1964* could contain 2,4,5-trichlorophenoxyacetic acid. In 1972, Saint-Ruf (54), a colleague of Buu-Hoi, reported on the formation of "dioxin" from the pyrolysis of Si 1 vex. He reported that although the quantity of TCDD was less than that observed from the pyrolysis of 2,4,5-T, it was nevertheless sufficiently important to render the use of Silvex extremely dangerous for man and animals, especially in areas where treated vegetable matter was likely to be used as domestic foodstuff. The data of Buu-Hoi et al (13) and Saint-Ruf (54), and their conclusions* were challenged by Langer et al (38) in 1973. Langer et al investigated conditions which might produce dioxins from salts and esters of 2,4-D, 2,4,5-T and Silvex. No dioxins were detected even when the sodium salts of 2,4,5-T and Silvex were heated to 300°C and 111-20 �3500C, respectively. However, if a mixture of 0.25 gram (g) 2,4,5-T acid, 2 g HoO and 10 g koC03 was refluxed at 100°C for 3 hr, then heated at 200°C for 15 hr, then at 400°C for 43 hr, a total yield of 0.13 percent TCDD could be detected. Furthermore, Lanaer et al found that the mass spectrum reported by Buu-Hoi et al (and used by Saint-Ruf) for TCDD was in fact not the mass spectrum of TCDD. They suggested that the mass spectrum obtained by Buu-Hoi et al was that of a polymeric matter similar to that found in their own studies. Langer et al concluded that it was extremely unlikely that dioxin {TCDD) could be produced in the field by burning plant material treated with 2,4-D, 2,4,5-T, Silvex or their derivatives. Recently (1977), Stehl and Lamparski (57) reported finding small amounts of TCDD in trapped residue from self-supported fires of grass and paper treated with different compounds containing 2,4,5-T. Under controlled, but as "natural" as feasible conditions, they analyzed the combustion products of the grass or paper after treatment with 13.3 kg 2,4,5-T per ha (12 Ib/A). Stehl and Lamparski felt that the most meaningful way to express their data was in parts per trillion (ppt) of TCDD formed per parts per million (ppm) of 2,4,5-T burned. The average of all their experiments was 0.6 ppt of TCDD formed per 1 ppm of 2,4,5-T burned. The TCDD burden added to the environment by the combustion of natural materials treated with 2,4,5-T would be no . larger than 1 ppt of TCDD per 1 ppm of 2,4,5-T residue burned. Ahling et al (1) has reported similar results when 2,4,5-T residue on wood chips is burned at 500°C; 6 ppt of TCDD formed per 1 ppm 2,4,5-T residue burned. They suggested that this would correspond to a formation of about 1 microgram (yg) TCDD per m2 in forest fire directly after application of the herbicide formulation. However, Cutler (21) recently (1978) has suggested that the burning of forested areas treated with 2,4,5-T may be of little concern, since TCDD decomposes at temperatures above 800°C (and 2,4,5-T decomposes at temperatures above 500°C), considerably below the temperatures of 1200°C or more achieved in the field with a free exchange of air. E. Photodegradation of TCDD In perhaps what can be termed as one of the most significant studies on the environmental degradation of TCDD, Crosby and Wong (19), in 1977, found that herbicide formulations (including Orange) containing known amounts of TCDD and exposed to natural sunlight on leaves, soil or grass, lost most or all of the TCDD in a single day, due principally to photochemical dechlorination. Despite the known persistence of pure TCDD, it was not stable as a contaminant in thin herbicide films exposed to outdoor light. Crosby and Wong (19) have established three requirements for significant dioxin breakdown in the environment; namely, dissolution in a light-transmitting film, the presence of an organic hydrogendonor such as a solvent or pesticide and ultraviolet light. They 111-21 �noted that all three conditions are normally met during the practical application of 2,4,5-T or other TCDD-containing chemicals. Thus, their data suggested that environmental residues of TCDD often will be considerably less than previously expected. Nash and Beall (45) concluded from their studies of the fate of TCDD in a microagroecosystem chamber, that once TCDD was volatilized, it dechlorinated in the direct sun and apparently even in shade outdoors or when the sun was filtered with glass in the chambers. They concluded further that TCDD was sensitive to photodechlorination in the vapor phase even in the absence of ultraviolet light. IV. SUMMARY Available data indicate that the vast majority of the phenoxy herbicides would impact forest canopy, the intended target. Rapid uptake (e.g., within a few hours) of the ester formulations of 2,4-D and 2,4,5-T would occur. Most of herbicide probably would undergo rapid degradation (weeks) within the cellular matrix of the vegetation. However, some of herbicide may remain unmetabolized and would be deposited on the forest floor at the time of leaf fall. Soil microbial and/or chemical action would likely complete the degradation process. Herbicide droplets that impacted directly on soil or water would probably hydrolyze rapidly (within hours). Biological and nonbiological degradatiye processes would further occur to significantly reduce these residues. Some volatilization of the esters of 2,4-D and 2,4,5-T would occur during and immediately after application. The volatile material most likely would dissipate within the foliage of the target area. Photodecomposition of TCDD would minimize the amount of biologically active volatile residues moving downwind of the target area. Accumulation of phenoxy herbicides in animals may occur following ingestion of treated vegetation. The magnitude of this accumulation would likely be at nontoxic levels. Herbicide residues in animals would rapidly decline after withdrawal from treated feed. Most TCDD sprayed into the environment during defoliation operations would probably photodegrade within 24 hours of application. Moreover, recent studies suggest that even within the shaded forest canopy, volatilization and subsequent photodecomposition of TCDD would occur. Since translocation into vegetation would be minimal, most TCDD that escaped photodegradation would enter the soil-organic complex on the forest floor following leaf fall. Soil chemical and microbial processes would further reduce TCDD residues. Bioconcentration of the remaining minute levels of TCDD may occur in liver and fat of animals ingesting contaminated vegetation or soil. However, there are no field data available that indicate that the levels of TCDD likely to accumulate in these animals would have a biological effect. 111-22 �The environmental generation of TCDD from 2,4,5-T residues, through thermal or photolytic processes, would be highly unlikely and of no consequence. 111-23 �LITERATURE CITED CHAPTER III 1. Ahling, B., A. Lindskog, B. Jansson and G. SundStrom. 1977. Formation of polychlorinated dibenzo-p-dioxins and dibenzofurans during composition of a 2,4,5-T formulation. Ckuma&ph&m 33:461-468. 2. Aly, O.M. and S.p. Faust. 1964. Studies on the fate of 2»4-D and ester derivatives in natural surface waters. J. Ag/w.c.. Food Chem. 126.541-546. 3. Anonymous. 1977. flioxot: Position document. (Draft) Dioxin Working Group. April 1977. U.S. Environmental Protection Agency; Washington, D.C. Mim. 17 p. 4. Arnold, E.L., A.L. Young and A.M. Wachinski. 1976. Three years of field studies on the soil persistence and movement of 2,4-D, 2,445-T and TCDD. Weed SCA.. Soc. Am. Meet. Atotfc. 206. p 86. 5. Audus, L.J. 1960. faioAabiotogJjCLOut breakdown. o&ft.eA.b-ccx.dei-in 4o^tA. P 1-19. In_ Herbicides and the soil. E.K. Woodford and G.R. Sugar (Eds.). Blackwell Sci. Pub, , Oxford, England. 6. Bartleson, D.D., O.D» Harrison, and J.D. Morgan. 1975. Stadia ol WiJtttJUAe. exposed to TCW zon&min&tiid 4o^ta. Technical Report AFTL-TR-75-49. Air Force Armament Laboratory, Eglin Air Force Base, Florida. 53 p. 7. Baughman, R.W. 1976. Tetrachlorodibenzo-p-dioxins in the environment. High resolution mass spectrometry at the picrogram level. P-U-6. Ab^^t. Int. 36(7):3380B. 8. Baughman, R.W. and M.S., Meselson. 1973. An analytical method for detecting TCDD (dioxin): Levels of TCDD in samples from Vietnam. EnviAdn. Health P&upa&t, 5:27-35. 9. Baughman, R.W. and M.S. Meselson. 1973. An improved analysis for tetrachlorodibenxo-p-dioxins. Advdn. Chem. SeA. 120:92-104. 10. Beatty, P.W., M.A. Helscher, and R.A. Neal. 1976. Toxicity of 2,3,7,8-tetrachlorodibenxo-p*dioxin in larval and adult forms of Rana catesbelana. 6«££. Envvwn* Cdnfaw. Taxi-tol, 16(5) :578-581 . 11. Blackman, G.E.,, J,D. Fryer, A. Lang and M. Newton. 1974. The effects of herbicides in South Vietnam. Part B» Working PapersPersistence and disappearance of herbicides in tropical soils. Nat. Acad. Sci., Washington, D.C. 56 p. 111-24 �12. Brown, J.W. 1962. l/egexUttoiaa£ bpnay ttete in South Vietnam. U.S. Army Chemical Corps Biological Laboratories, Fort Detrick, Frederick, Maryland, 119 p. Available from the Defense Documentation Center, Defense Logistics Agency, Cameron Station, Alexandria, Virginia, DDC Number AD476961 . 13. Buu-Hoi, N.P., G. Saint-Ruf, P. Bigot and M. Mangane. 1.971. Preparation, properties and identification of dioxin (2,3,7,8tetrachlorodibenzo-p-dioxin) in the pyrolysate of defoliants containing 2,4,5-T and its esters and in contaminated vegetation. C.R. Hebd. Seances Acad. Sex.., Se/t. 0. 273:708-7111. (French) 14. Byast, T.H. and R.J. Hance. 1975. Degradation of 2,4,5-T by South Vietnamese soils incubated in the laboratory. Bo££. Envision. Contam. Tovuiat. 14(1): 71 -76. 15. Committee on the Effects of Herbicides in South Vietnam. 1974. Part A. Summary and conclusions. National Academy of Science, Washington, D.C. 398 p. 16. Craig, D.A. 1975. U6e orf HeAbx.cx.de* in Southeast Mia. Historical Report. San Antonio Air Logistics Center, Directorate of Energy Management, Kelly AFB, Texas. 58 p. 17. Crosby, D.G. 1976. Herbicide. pkotade.c.ompo*ition. P 835-890. In. Herbicides - Chemistry, Degradation and Mode of Action. Vol. 2. P.C. Kearney and D.D. Kaufman (Eds.). Marcel Dekker, Inc., New York. 18. Crosby, D.G. 1976. Nonbio£ogic.cLt de.Qtiadcvtion o& heAbicideA in tk<L boiJL. P 65-97. _In_ Herbicides - Physiology, Biochemistry and Ecology. Vol. 2. L.J. Audus (Ed.). Academic Press, New York. 19. Crosby, D.G. and A.S. Wong. 1977. Environmental degradation of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Science 195:1337-1338. 20. Cupello, J.M. and A.L. Young. 1976. Radiochemical bioassay of TCDD uptake in plant material. Extract. Annual Research Progress Report No. 11. Dean of Faculty, United States Air Force Academy. 22 p. 21. Cutler, M.R. 1978. Remarks to the National USDA/EPA Symposium on the use of herbicides in forestry. USDA-SEA, Washington, D.C. 7p. 22. DeRose, H.R. and A.S. Newman. 1947. The comparison of the persistence of certain plan growth-regulators when applied to soil. PA.OC. Sci. Soa. Am. 12:222-226. 23. Dost, F. , J. Witt, M. Newton and L.A. Norris. 1975. Statement on 2,4,5-T and TCDD. J. fofi. 73(7) :410-412. 111-25 �24. Goring, C.A.I., D.A. Laskowski , J.W. Hamaker and R.W. Meikle. 1975. Psu-ndipleA o& pe6£tcxde d&gsuidation -in Ao-it. P 135-172. In_ Environmental Dynamics of Pesticides. R. Haque and V.H. Freed (Eds.) Plenum Press, New York. 25. Grover, R. , J. Maybank and X. Yoshida. 1972. Droplet and vapor drift from butyl ester and dimethyl ami ne salt of 2,4-D. Weed Sex. 20(4): 320-324. 26. Hamaker, J.W. 1975. The, witeA.pi&tation ofi *oi£ le.ac.kt.ng expetxmentb. P 115-133. ln_ Environmental Dynamics of Pesticides. R. Haque and V.H. Freed (Eds.). Plenum Press, New York. 27. Harrigan, E.T. 1970. CaUbxation TdAt o& tkz UC-123K/A/M5V-1 Sp>uu/ SyAt&m. Technical Report ADTC-TR-70-36. Armament Development and Test Center, Eg! in AFB, Florida. 160 p. 28. Helling, C . S . 1971. Pesticide mobility in soils. II. Applications of soil thin-layer chromatography. P/toc. SoJJt Sex. See. Am. 35(5):737-743. 29. Helling, C.S., A.R. Isensee, E.A. Woolson, P.D.J. Ensor, G.E. Jones, J.R. Plimmer and P.C. Kearney. 1973. Chlorodioxins in pesticides, soils and plants. 3. tnvJUion. Qual. 2(2) :171-178. 30. Hummel, R.A. 1977. Clean-up techniques for the determination of parts per trillion residue levels of 2,3,7,8-tetrachlorodibenzo-pdioxin (TCDD). J. Ag^c. Food Chm. 25(5) : 1049-1053. 31. Irish, K.R., R.A. Darrow and C.E. Minarik. 1969. InfiotLmcution manual fan. v&geJution c.on&ioi Ln SouuthnaAt faia. Miscl. Public. 33. Department of the Army, Fort Detrick, Frederick, Maryland. 71 p. 32. Isensee, A.R. and G.E. Jones. 1971. Absorption and translocation of root and foliage applied 2,4-dichlorophenol , 2,7-dichlorodibenzop^dioxin, and 2,3,7,8-tetrachlorodibenzo-p-dioxin. J. Ag/txc. Food Ckm. 19(6):1210-1214. 33. Isensee, A.R. and G.E. Jones. 1972. Distribution of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in aquatic model ecosystem. BnuAon. Sex. Techno£. 9(7) :668-672. 34. Kearney, P.C., E.A. Woolson and C.P. Ellington, Jr. 1972. Persistence and metabolism of chlorodioxins in soils. Envision, Sex.. Uchnol. 6(12):1017-1019. 35. Kearney, P.C., E.A. Woolson, A.R. Isensee and C.S. Helling. 1973. Tetrachiorodibenzodioxin in the environment: Sources, fate, and decontamination, tnv-uion. H&alth PvAApe&t. 5:273-277. 111-26 �36. K l e i n , R . E . and E . T . Harrigan. 1969. Comp<vuAon Tut o Technical Report ADTC-TR-69-30, Vol. I. Armament Development and Test Center, Eglin AFB, Florida. 356 p. 37. Klingman, G.C. 1961. Sons, Inc., New York. 38. Langer, H . G . , T.P. Brady and P.R. Briggs. 1973. Formation of dibenzodioxins and other condensation products from chlorinated phenols and derivatives. EmuAon. Health P&t6pee£. 5:3-7. 39. Leng, M.L. 1977. Companative. m&taboti&m o& phznozy k<>Abi.cA.d<Lt> <in cwxjTia&6. P 53-76. Jj^ Fate of Pesticides in the Large Animal. Academic Press, Inc., New York. 40. Loos, M.A. 1975. Phe.noxyalkano-ic. acMt>. P 1-128. In_ Herbicides Chemistry, Degradation and Mode of Action. Vol. 1. P . C . Kearney and D.D. Kaufman ( E d s . ) . Marcel Dekker, Inc., New York. 41. Mahle, N . H . , H.S. Higgins and M.E. Getzendaner. 1977. Search for the presence of 2,3,7,8-tetrachlorodibenzo-p-dioxin in bovine m i l k . Ball. EmuAon. Contam. Tazicol. 18(2) :123-130. 42. Matsumura, F. and H . J . Benezet. 1973. Studies on the bioaccumulation and microbial degradation of 2,3,7,8-tetrachlorodibenzo-p-dioxin. Envision. Health PeA6pee£. 5:253-258. 43. M i l l e r , R.A., L.A. Norris and C.L. Hawkes. 1973. Toxicity of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in aquatic organisms. Env^ion. Health Pnupuct. 5:177-186. 44. Muzik, T.J. 1976. Influence o& e.nv4Aonme.ntal factor on toKiCsity to plant*. P 203-247. j£ Herbicides - Physiology, Biochemistry and Ecology. Vol. 2. L.J. Ausus (Ed). Academic Press, New York. 564 p. 45. Nash, R.G. and M.L. Beall, Or. 1978. EnviJiom\e.ntal dlbtfu-bution aft 2,3,7,$-te&ULC.hlotLO(LLb<>.nzo-p-dioXsin (TCVV) apptiid with 4-cCvex to tunfa <in m*ioAoa.QSLoe,c.oAyAtm. Final Report EPA-1AG-D6-0054, Agricultural Environmental Quality Institue, U . S . Department of Agriculture, Beltsville, Maryland. 46. Newton, M. 1971. Disappearance of 2,4,5-T from forest ecosystems. Weed Sex.. Soc. Am. Meet. Abttn. 57. pp-30. 47. Newton, M. and S.P. Synder. 1978. Exposure of forest herbivores to 2,3,7,8-tetrachloro-p-dioxin (TCDD) in areas sprayed with 2,4,5-T. Bull. EnviAon. Con-tarn. Tozicoi. (In Press) Weed control: <u a .icx.ence. 421 p. 111-27 John Wiley and �48. Norris, L . A , and R.A. Miller. 1974. The toxicity of 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD) in guppies (Poecilia reticulatus Peters). Eatt Env.iAon. Contam. TOXA,O.O£. 12(1):76-SO. 49. Palm, C . E , (Chairman). 1968. Weed Control, Vol. 2. Principles of Plant and Animal Pest Control. Nat. Acad. Sei,, Washington, D . C . 471 p, 50. Plimmer, J,R. 1976. Vet&tA&Uy, P 891-934. In Herbicides Chemistry, Degradation and Mode of Action. P,c71<earney and D.D. Kaufman (Eds,), Vol. 2. Marcel Dekker, Inc., New York, 51. Reigner, I . e . , w . E . Sopper and R . R , Johnson. 1968. W i l l the use of 2,4,5-T to control streamside vegetation contaminate public water supplies? J, FOA, 66(12) :914-918. 52. Reinhart, K . G . 1965. Herbicidal treatment of watersheds to increase water yield. N. East Weed Contr. Conf. Proc. 19:546-551. 53. Ross, R . T . 1976. 2,4,5/Dioxins: Analytical Collaborators Meeting, June 15, 1976. June 25, 1976, Memorandum of the United States Environmental Protection Agency; Washington, D . C . p 3, 54. Saint-Ruf, 6. 1972, Formation of dioxin in the pyrolysis of sodium a-(2,3,7,8-trichlorophenoxy)'propionate. No^u/tM^am chosen 59(12) :648. (French) 55. Shadoff, L.A,, R,A, Hummel and L. Umparski, 1977. A search for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in an environment exposed. annually to 2,4,5-triehlorophenoxyacetic acid ester (2,4,5-T) herbicides. 8u££, Env-cton. Contam. Tou.o.oi. 18(4) :478-485. 56. Stark, H . E . , J.K. McBride and G.F. Orr, 1975. Soil biodtQfm.dcuU.on o£ H&ib-ctiide. 0/tang&. 1. bti.cAob<iai and <Lc.atoQ-ic.ak 4tudy a£ the. U.S, MA. FoA.ce Log<u>£icA Command TeAt HIU MA Poize. 6o4e, U-tofe. Final Report, TECOM Project No. 5-CO213'00'015, U.S, Army Dugway Proving Ground, Dugway, Utah. 73 p. 57. Stehl, R.K, and LL Umparski, 1977. Combustion of several 2,4,5trichlorophenoxy compounds: Formation of 2,3,7,8-tetrachlorodibenzop-dioxin. Science 1 97 ( 4307) :1Q08- 1009, 58. Tschirley, F.H. 1968. Reiponie ofi tfiopicjaJi and Au.b&iap<ic.at woody plante to chmic.aUi- Vieatinnnte , Research Report CR-13-67. Agricultural Research Services, U.S. Department of Agriculture, Washington, D.C. 197 p, 59. Winston, A,W., Jr. and P.M, Ritty. 1972. What happens to phenoxy herbicides when applied to a watershed area. Ind, l>eg. Manage. 111-28 �60. Woolson, E.A., P.D.J. Ensor, W.L. Reichel and A.L. Young. 1973. Dioxin residues in lakeland sand and bald eagle samples. Advan. Ckem. Svi. 120:112-118. 61. Young, A.L. 1974. Ecological &tudi&> on a heAb-icide. equipment tut ouita (TA C-52A) Egtin AFB ReAeA.vatt.an, Florida. Tech Rep. AFATL-TR-74-12. Air Force Armament Laboratory, Eglin Air Force Base, Florida. 141 p. 62. Young, A.L., P.J. Lehn and'M.F. Mettee. 1976. Absence of TCDD toxicity in an aquatic ecosystem. Weed Sex. Sec. Am. Meet. Afa-6-tt. 107. p 46. 63. Young, A.L., C.E. Thalken and W.E. Ward. 1975. Studies o& tke. ecological impact o& sie.pe£itivn a&ual appLic&tionA of, h<Lnbtcid(L& on tho, <tcoAyt>tw o& tut ouzo. C-52A, Egtin AFB, FloiLda. Technical Report AFATL-TR-74-12. Air Force Armament Laboratory, Eglin AFB, Florida, and Department of Chemistry and Biological Sciences. U.S. Air Force Academy, Colorado 80840.- 127 p. 64. Young, A.L., C.E. Thalken, E.L. Arnold, J.M. Cupel lo and L.G. Cockerham. 1976. Fate otf 2,3,7,B-t<i&iachlosiodibe.nzo-p-dAQxJ.n (TCW) -en tke. znvJJionmtLnt: Sumnasiy and de.contam<ination ie.comme.ndationA. USAFATR-76-18. Department of Chemistry and Biological Sciences, USAF Academy, Colorado 80840. 41 p. 65. Zitko, V. 1972. Absence of chlorinated dibenzodioxins and dibenzofurans from aquatic animals. 8o££. EmuAoia. Contain. Topical. 7(2/3):105-110. 66. Zitko, V., 0. Hutzinger and P. U.K. Choi. 1972. Contamination of the Bay of Fundy-Gulf of Maine area with polychlorinated biphenyls, polychlorinated terphenyls, chlorinated dibenzodioxins, and dibenzofurans. EnvxAon. Health PeAAp&ct. 1:47-50. 111-29 �CHAPTER IV ' THE TOXICITY OF 2,4-D, 2,4,5-T AND TCDD IN ANIMALS I. INTRODUCTION This review cites a major portion of the world scientific literature dealing with the toxicological aspects of 2,4-D, 2,4,5-T and TCDD in various laboratory and domestic animal species. The primary purpose was to provide a broad overview of research investigations performed to date. With this information, a more critical evaluation could be made of reported human exposures to actual and theoretical levels of 2,4-D, 2,4,5-T and TCDD as presented in other chapters of this report. In an attempt to organize this chapter the following format and sequence was followed. Each of the compounds in question was reviewed for a) acute and short-term toxicity; b) subacute and chronic toxicity; c) absorption, distribution and excretion data; d) embryotoxic, fetotoxic and teratogenic potentials; e) carcinogenic and tumorigenic potentials; and f) mutagenic and cytogenetic potentials. Where possible, the cited data were tabu! ari zed for ease of comparison and interpretation and a summary of the tabular data presented in the text. In the review of acute and short-term toxicity the primary effort was directed toward finding references establishing for each compound a no effect dose, a dose lethal to 50 percent (LD50), and a dose lethal to 100 percent (LDiOO) of the laboratory or domestic animal species studied. After the acute toxic doses were known the subacute and chronic levels were then addressed. The highest "no effect" level of repeated dosing as well as the lowest repeated dosing level causing symptoms of toxicity were collected. These two sections were followed by discussion of cited literature dealing with the absorption, distribution in various body compartments and tissues, and excretion of the 2,4-D, 2,4,5-T and TCDD. In a 1977 review of the TeAatogenxc E^e.c.t& oft Wilson (145) stated: Many chemicals with which man comes into contact are known to be overtly or potentially harmful, causing structural or functional change immediately and these effects are recognized as acute toxic responses to these chemicals. On the other hand, chemicals known to be overtly or potentially harmful, causing structural or functional change and effects, only, after some intermediate time or considerable lapse of time following exposure, are recognized IV-1 �as chemicals producing a chronic toxic response. This latter group with its subacute effects is where most of the chemicals fall the at interfere with reproduction. Reproduction effects are rarely the first or only toxic manifestations, but occasionally an embryo or fetus in ut&io is the primary or the only individual expressing the effects of the toxic material, indicating that the conceptus may have extraordinary sensitivity to certain chemicals or compounds. These so called teratogens may be naturally occurring or manufactured materials and despite its sequestered location deep within the maternal body, the embryo or fetus sometimes receives a toxic, i.e., teratogenic dose, albeit only a small fraction of the maternal dose. Dencker (31) in the introduction to his 1976 study TVcAAue Localization o& Some. T0Aatog<Lm> at EanJiy and Late. Gestation ReJLat&d to f<Ltai Ejects stated: Our knowledge concerning the mechanisms by which chemicals cause fetal damage is very sparse, and only in a few instances have generally accepted theories been presented. Most often there is no specific effect for a given chemical; rather it seems. that one agent produces a wide spectrum of mal forma tions - which indicates a nonspecific mechanism of action. Moreover, different chemicals may often produce the same type of malformation. This confusing aspect may partly be explained by the fact that the different organs have certain sensitive periods; in their development, when they are especially susceptible to external influences. With these comments in mind the literature dealing with embryotoxic, fetotoxic and teratogenic potentials of 2,4-D, 2,4,5-T and TCDD was reviewed to provide as much detail as possible as to the number of animals used, reproductive state, route of administration and toxic response as well as dose and formulation of each compound being tested. A Similar approach was used to review the carcinogenic, tumorigenic, mutagenic and cytogenetic potentials for each of the compounds. Care was taken to try and establish numbers of test animals, method and route of administration and the specific effect of a particular formulation or purity of 2,4-D, 2,4,5-T or TCDD on those animals. Where specific animal data were not available, studies dealing with animal tissue cultures or bacterial mutant strains were referenced. For simplicity in format, dosage levels of the various chemicals were expressed as mg/kg, but it should be understood that this refers to milligrams of a specific chemical or formulation per kilogram of body weight of the test animal unless otherwise specified. IV-2 �II. REVIEW OF 2,4-D TOXICITY IN ANIMALS A. The Acute and Short-Term Toxicity Potentials of 2,4-D The following review of 2,4-D toxicity was based primarily on three review articles: Rowe and Hyman (115); Dalgaard-Mikkelsen and Poulsen (29); and the International Agency For Research on Cancer (IARC) Monograph, Vol 15 (66) although other recent publications on the subject have been cited. Bucher (18) in 1946 was among the first to report the results of experiments with small animals using 2,4-D. Temporary myotonia lasting from eight to twenty-four hours or more following a single injection of 150 to 250 mg/kg was observed in mice, rats, rabbits and dogs. In 1947, Hill and Carlisle (63) published the results of acute oral studies, following single doses of 2,4-D and found the U^Q for mice to be 375 mg/kg; for rats, 666 mg/kg; for rabbits, 800 mg/kg; and for guinea pigs, 1,000 mg/kg. The largest single oral dose administered to monkeys without serious after-effect was 214 mg/kg or 428 mg/kg given intraperitoneally. An oral, plus an intraperitoneal injection in monkeys for a total dose of 500 mg/kg 2,4-D caused nausea, vomiting, lethargy, muscle incoordination and head drop. These workers observed that all species reacted similarly and that there were no significant differences in potency between crude and purified preparations, or between the sodium or ammonium salts. Deaths from large doses were apparently due to ventricular fibrillation. When death was delayed, myotonia, stiffness of extremities, ataxia, paralysis and coma were observed. Parenteral administration of 150-200 mg/kg 2,4-D caused symptoms of myotonia in mice. In those acutely intoxicated, dilatation of the blood vessels of lungs, liver and kidneys was observed by Bucher (18). Rats and guinea pigs administered lethal doses of 2,4-D exhibited congestion of the viscera. Enlarged, swollen, kidneys and microscopically .massive cloudy swelling of the proximal convoluted tubules with cast formation was noted by Hill and Carlisle (63). Florsheim and Velcoff (43) reported a decrease in both thyroid and body weights in male rats given single subcutaneous injections of 2,4-D at 100 mg/kg. Guseva (57) found the LDso for the subcutaneous injection of 2,4-D in mice to be 220 mg/kg. At 10-100 mg/kg 2,4-D in rats and mice no impairment of motor activity was seen nor did those doses alleviate strychnine spasms. In cats, 20-30 mg/kg 2,4-D given intravenously was hypotensive and that effect was not impaired by atropinization. 'Baker et al (6) administered 112 grams (g) of grass mixed with horsemeat and dog meal divided over three consecutive meals to two IV-3 �healthy one-year-old mongrel dogs. The grass had been treated two days earlier with the equivalent of 4 pounds per acre (Ib/A) of 2,4-D butyl ester, which was twice the recommended rate. The dogs readily ate the food and no ill effects were observed during the following 96 hours. Each animal was then treated with 500 mg/kg 2,4-D in a single oral dose. No deleterious effects were seen in the next 96 hours of observation. One animal, killed and necropsied at 96 hours post administration, failed to reveal any macroscopic lesions and the other animal remained healthy for 82 days following the second treatment, at which time the experiment was terminated. In dogs, Drill and Hiratzka (33) found that toxic symptoms were often delayed up to six hours following a single oral administration of lethal doses of 100, 250 and 400 mg/kg 2,4-D. The deaths were delayed and occurred two to nine days after the compounds were administered; The acute oral LDgg for (98.5 percent purity) 2,4-D was in the range of 100 mg/kg or higher. Death appeared to be due in most cases to hepatic congestion or pneumonia. Pathological changes were limited to the gastrointestinal tract, lungs and liver, and followed the development of anorexia, weight loss and myotonia (33). Dogs exhibited more evidence of hepatic congestion and moderate hepatic necrosis than was seen in other animals studied by Bucher (18). Drill and Hiratzka (33) concluded that the no effect level for a single oral dose of 2,4-D in dogs was 25 mg/kg. In a study by Shavgulidze et al (125), the single oral LDioO of 2,4-D sodium salt in sheep was 900 mg/kg. Death occurred in 2-4 days following the clinical signs of asthenia, depression, ataxia, hypothermai, dyspnea, muscle paralysis, anorexia and intense photophobia in those animals dosed at 500-1,000 mg/kg. The no effect single, oral dose of 300-400 mg 2,4-D was detoxified in 9-12 days with no traces remaining in the tissues. McLennan (88), reported on the accidental oral administration of 2,4-D in two cows. He noted that the death of one animal occurred within 12 hours following a calculated dose of 150-188 mg/kg. The toxic dose for the animal that survived, was calculated at between 105 and 132 mg/kg. In contrast Rowe and Hymas (115) noted that the 1050 of 2,4-D for cattle ranged between 500 and 2000 mg/kg body weight while a single dose of 1000 mg/kg may or may not cause illness. Rade-leff (110) cited a report in which cattle given one dose of 250 mg/kg 2,4-D showed signs of toxicity. In calves six to eight weeks old, Bjorklund and Erne (15) found that single doses of 100 to 200 mg/kg 2,4-D produced reversible signs of toxicity. Toxic symptoms summarized by Rowe and Hymas (115) included the following general observations in animals treated with acute toxic doses of 2,4-D: loss of appetite, loss of weight, depression, roughness of coat, general tenseness and muscular weakness particularly of the posterior quarters. Post mortem findings usually included irritation of the stomach of small animals and of the abomasum of ruminants, minor evidence of liver and kidney injury and in some instances congestion of the lungs. IV-4 �From data presented in Table 1, the acute 1059 as a rule was in the order of 300-800 mg/kg 2,4-D for rats, mice, guinea pigs, rabbits and cats. Analyses of data from the limited available studies supported the conclusion that the dog may be slightly more susceptible to oral doses of 2,4-D than other animals. Monkeys, sheep and cattle appeared to be somewhat more tolerant. The experiments referenced in Table 1 have also provided information on the acute oral administration of various salts and esters of 2,4-D as pure chemicals and as commercial preparations. No significant differences in the toxicity of the salt and ester forms of 2,4-D were seen when compared to the free acid (63,115). Hill and Carlisle (63) stated: In any assessment of the acute toxicity of a chemical based on data obtained from laboratory animals it should be borne in mind that considerable variation in species susceptibility may occur and that the data obtained cannot always be translated into toxic doses for humans. In the studies referenced in this section it can be concluded as Hill and Carlisle did in their studies that: all of the laboratory animals tested reacted in a similar fashion from signs and symptoms which developed and from the pathological lesions which were present at autopsy. Assuming that man is no more resistant or susceptible than the rabbit or monkey, then the largest tolerated dose for a 75 kg man would be 15 grams of 2,4-D. With the exception of dog and monkey, all of the laboratory animals used in the cited references lacked the vomiting reflex so that they were unable to relieve themselves of irritating material by vomiting. The experiments conducted in monkeys indicate that the material is a gastric irritant in large doses, so that the possibility of the occurrence of acute poisoning in humans would seem relatively remote because of the large dose which man could presumably tolerate. Assuming that man is no more susceptible than the most susceptible animal test, the mouse, then the calculated oral LDso for man would amount to approximately 28 grams (63). It is generally accepted that the oral LD5Q of 2,4-D for man is around 500 mg/kg while the accepted LD^Q of aspirin for man is around 1,500 mg/kg. B. The Subacute and Chronic Toxicity Potentials of 2,4-D Repeated once or twice daily, subcutaneous injections of 50 to 90 mg/kg 2,4-D in mice for three weeks to ninety days did not elicit a characteristic chronic syndrome of toxicity or any notable histological IV-5 �TABLE 1 . Animal Number Used Mouse 450 Summary of literature data on the no-effect, and LD levels of the acute toxicity of 2,4-D in animals Route of Administration DoseToxicity Single Dose mg/kg Reference § Gavage LD 375a'b 63 NSC Intraperitoneal LD 375a 63 NS Subcutaneous LD 220a 57 NS Subcutaneous LD 280b 18 NS Oral in olive oil LD 368a 115 NS Oral in olive oil LD 541d 115 NS Oral in corn oil LD 713e 115 NS Oral LD 380f 81 50 50 50 50 50 50 50 50 Rat L 150 Gavage LD 666b 63 NS Intraperitoneal LD 666b 63 NS Oral in water LD 805b 115 NS Oral in olive oil LD 375a 115 NS Oral in olive oil LD 700d 115 NS Oral in corn oil LD 620e 115 NS Oral LD 1 ,500f 119 NS Oral LD 2,000b 119 NS Oral LD 900f 81 125 Gavage LD 1 ,000b 63 NS Intraperitoneal LD 666b 63 NS Oral in water LD NS Oral in olive oil 50 50 50 50 50 50 50 50 50 Guinea Pig u 50 50 IV-6 50 LDcn 551-2000b 469a 115 115 �Table 1 continued NS Oral in olive oil LD50 550° H5 NS Oral in corn oil LD 50 848e 115 70 Gavage LD 50 800 63 NS Intraperitoneal LD 50 400b 63 NS Intravenous LD50 400b 63 NS Oral in corn oil LD 50 424e 115 NS Oral LD 50 820 81 • Oral LD 100d 33 1 Mh/2 F Oral No effect 25a 33 2 Oral No effect 500' 6 Oral No effect 214a 63 Intraperitoneal No effect 428b 63 Oral LD 900 125 No effect 300-400b 125 Rabbit Cat Dog 4 Fg 50 Monkey Sheep NS 100 Oral LD 100 Oral Cattle LD 50 150-188' (a calculated dose) 500-2000^ 115,132 a 2,4-D acid Sodium salt of 2,4-D C NS - number of animals in study not stated or unavailable from literature source. Isopropyl ester of 2,4-D e Mixed butyl esters of 2,4-D IV-7 �Table 1 continued Butyl ester calculated as 2,4-D 9 F - Female h M - Male n 20% w/v amine salt of 2,4-D in aqueous solution J Form not stated in available literature source IV-8 �changes. Levels of 70 mg/kg or more retarded growth, probably by reducing food intake. Mice undergoing this treatment became pregnant and bore apparently normal litters (18). Guseva (57) found that 22 daily subcutaneous injections of 0.1 mg 2,4.-D in mice caused no toxic effects. In subacute studies with rats, Hill and Carlisle (63) fed a diet containing 1,000 mg 2,4-D/kg for 30 days without severe harmful effects. Some visceral congestion and kidney edema with degenerative changes in the tubules were noted. No adverse effects were seen in groups of 5 or 6 young female rats given 2,4-D by intubation five times a week for four weeks at doses of 3, 10, and 30 mg/kg in olive oil. At doses of 100 mg/kg 2,4-D, varying degrees of gastrointestinal irritation, slight cloudy swelling in the liver and depressed growth rates were noted. At 300 mg/kg 2,4-D, the animals failed rapidly and died. The principle lesion observed at post mortem was a severe gastrointestinal irritation. In another study, matched groups of five, young, adult, female rats were placed on diets containing 100, 300, 1,000, 3,000 and 10,000 mg 2,4-D/kg of diet for 113 days. The no effect levels were 100 and 300 mg/kg of diet. At 1000 mg/kg, adverse effects were characterized by a depressed growth rate, excessive mortality, slightly increased liver weights and slight cloudy swelling of the liver. The animals on the 3,000 and 10,000 mg/kg levels in their diets were destroyed after twelve days as they were not eating and were rapidly losing weight. Increased liver and kidney weights were noted with unstated minimal pathological changes (115). No drastic damaging effects were noted when male Long-Evans rats were given 2,4-D equivalent to 2-5 g/kg over a 4 to 7-week feeding period. Response to herbicide treatment was dependent on animal age and on the duration of time that the chemical was fed. Little or no effect was noted on liver weight. Herbicide-induced enlargement of the liver was associated with increases in most of the major cellular components on a per liver basis. Isolated liver nuclei were 20-30 percent more active in the -cn-v-c^to RNA synthesis than in the control nuclei (22). Schwetz et al (122) found that oral doses of 12.5 to 87.5 mg/kg 2,4-D did not adversely affect the weight gain of rats during pregnancy. In a preliminary study, non-pregnant rats tolerated 75 mg/kg 2,4-D for 10 days while 100 mg/kg killed two rats and produced overt signs of toxicity in three survivors, Hansen et al (58) conducted a study with rats starting at 3 weeks of age, using groups of 25 female and 25 male animals, fed 0, 5, 25, 125, 625 or 1,250 mg 2,4-D/kg of diet for 2 years. During the study no significant differences in survival rates between controls and test animals were noted. The mean body weights of the different groups of IV-9 �males and females and the organ-to-body weight ratios for liver, kidney, heart, spleen and testes were not significantly different (P>0.025). The only exceptions were in two male rats, one at 625 mg/kg, and a second at 125 mg/kg dosage level in the diet. These two animals had slightly enlarged spleens. Mean values for hemoglobin, hematocrit, and total white blood cell count of controls and of rats at each dose level, at the same time interval, were similar and within normal range. The maximum no effect level for the rats in this study was greater than l»250 mg 2,4D/kg of diet, Hansen et al (58) in another study fed 0, 100, 500 or 1,5QQ mg 2,4-D/kg of diet to groups of 20 male and 20 female rats, t^o effect was observed at the 100 and 500 mg/kg of diet levels. At the 1,500 mg/kg level, there was no effect on fertility nor on the average number of pups per litter; however, significant effects on the average number of pups weaned and also on their weaning weights were noted. The no effect level is at least 500 mg/kg but less than 1,500 mg/kg of 2,4-D in the diet. Bjorklund rats at 1,000 mg/1. same dose level for health and diarrhea and Erne (15) administered 2,4-D in drinking water to Progeny from treated females were maintained on the 2 years with signs of growth inhibition, poor general as the main effects. Kay et al (72) found no significant adverse effects in a study using 112 New Zealand strain albino rabbits where 15 ml of each of three commercially available formulations of 2,4-D (dimethylarrrfne salt and the isooctyl and butyl esters) were administered 5 times a week for 3 weeks to the intact and abraded skin at 0.626 percent and 3.13 percent concentrations. Body weights, survival, hematological values, clinical chemistry values and organ/body weight ratios were all within normal ranges. Local skin inflammatory reactions occurred in all groups of animals including controls. This was especially severe in those applications where the 2,4-D esters were diluted with an unspecified oil. The water dilutions of all three forms produced less local skin inflammation. Historically, the treated animals had an increased incidence and severity of subepithelial fibre-sis and accompanying mononuclear infiltration in the skin. No peripheral or central nervous system tissues or microsections of other tissues disclosed any adverse findings. Hansen et al (58) conducted a study using groups of 3 male and 3 female beagle dogs being fed 0, 10, 50, 100 or 500 mg/kg 2,4-D in the diet (96.7 percent pure, with no detectable TCDD by GLC with a sensitivity of 1 mg/kg) for 2 years, starting at 6-8 months of age. Twenty-eight dogs surviving the 2-year period were clinically normal, in fair to good condition, with a no effect level greater than 500 mg/kg in the diet. One female at the 100 mg/kg level was emaciated at the end of the experiment; however* no significant lesions were noted. A male animal that died after 10 months on the study at the 10 mg/kg 2,4-D lev/el, shbwed a slight atrophy o,f the testes and moderate depletion of cellular elements in other tissues. IV-10 �Drill and Hiratzka (33) orally dosed (via capsule in a piece of canned dog food) adult mongrel dogs of both sexes with either 2, 5 or 10 mg/kg 2,4-D 5 days a week for 13 weeks. The 2,4-D was a commercial product of 98.5 percent purity (label stated). All dogs survived this study and no significant symptoms of toxicity were seen and no changes in body weight, organ weights, or blood count were noted. In a separate study, three of four dogs given daily doses of 20 mg/kg 2,4-D died between days 18 and 49. The signs observed in these animals differed somewhat from those seen in the acute studies. The chronically treated animals displayed stiffness of hindlegs and ataxia, weakness, difficulty in chewing and swallowing and occasionally bleeding from the gums. Weight loss occurred after 7-12% days and a terminal fall in lymphocyte count occurred prior to death. * The authors stated, "Death during the repeated administration of 2,4-D was not related to pathological changes in the liver, kidneys, or other organs examined." Seabury (123) treated three dogs experimentally infected with histoplasmosis, by intravenous injections of sodium 2,4-D at the rate of 1.17, 2.6, and 3.2 mg/kg per injection for 32-37 days without evidence of chronic toxicity. Bjorklund and Erne (15) treated young pigs at varying intervals up to 103 days with 50, 100 or 300 mg/kg of the commercial triethanolamine salt or butyl ester of 2,4-D. Exhibited symptoms of intoxication and pathology were analagous to those seen in laboratory animals. Clinical signs of anorexia and retarded growth were found in one animal given 51 doses of 50 mg/kg triethanolamine salt over 103 days. Pigs fed 500 mg/kg of diet triethanolamine salt of 2,4-D for up to 12 months developed locomotor disturbances of increasing severity after about one month. Animals sacrificed after 2-12 months had normal organ weights and no gross pathological changes. Clinical chemistry observations included lowered hemoglobin and hematocrit values, elevation of glutamic-oxaloacetic transaminase and reduced albumin and albumin: globulin ratios in the treated animals [see IARC Monograph, Vol 15 ( 6 ] 6). Shavgulidze (125) observed transient hematological changes in sheep receiving daily doses of 18 mg/kg 2,4-D sodium salt for 120 days. Mitchell et al (90) fed a cow 5.5 g of 2,4-D acid daily for 106 days with no apparent harmful effects on the health or milking performance. Post mortem examinations revealed no pathological changes in the liver, kidneys or body fat. By biological assay the presence of 2,4-D was demonstrated in the blood serum; however, 2,4-D was not found to be secreted in the milk nor was it found in the blood serum of a calf fed milk from this cow. Palmer (99) found that yearling steers needed to be given 15 daily doses of 250 mg/kg of the alkanolamine salt of 2,4-D before signs of toxicity occurred. He found that 112 daily doses of 50 mg/kg of this 2,4-D salt had no deleterious effect on the steers. IV-11 �D stated: Rowe and Hymas (115) in reviewing the chronic toxicity of 2,4The results of repeated oral administrations indicate that 2,4-D can be tolerated without adverse effects in doses only slightly smaller than those which cause toxic effects when given only once. This fact demonstrates that 2,4-D has a low degree of chronic toxicity. The same general observations of toxicity were noted in animals receiving chronic toxic doses of 2,4-D, as were seen in animals given single toxic doses. These were loss of appetite, loss of weight, depression, roughness of coat, general tenseness, and muscular weakness particularly of the posterior quarters. Post mortem findings usually included irritation of the stomach and gastrointestinal tract of small animals and abomasum of ruminants with only minor evidence of gross and histopathological injury in the liver and kidneys. Study of the data presented in Table 2 indicated that mice tolerate subcutaneous injections of 2,4-D at 50-70 mg/ka with no effect, while 70-90 rug/kg retards growth. Rats tolerated 1,000-1,250 mg/kg 2,4-D in their diet and 75 mg/kg orally without toxic effects. At levels of 1,000 mg/kg 2,4-D in the water and 1,500 mg/kg in the diet and 100 mg/kg orally, toxic signs were noted. Rabbits showed no gross differences between test and control animals, as far as skin irritation, when 3.13 percent solutions of various formulations of 2,4-D were placed on their intact or abraded skin. Dogs tolerated 500 mg/kg diet or 10 mg/kg orally with no toxic signs, while 20 mg/kg caused death in three of four animals. Oral doses of 300 to 500 mg 2,4-D/kg of diet were toxic to pigs. Rowe and Hymas (115) stated: Cattle demonstrate a similar susceptibility to 2,4-D as do the small laboratory animals. Cattle are distinctly more tolerant of 2,4-D than are dogs. Cattle can probably tolerate 30-50 mg/kg/day [(99)] for long periods without adverse effects. Daily doses of 100-250 mg/kg (99) would have to be continued for a week or longer to cause ill effects in cattle. A single dose of 500-1,000 mg/kg is not likely to cause problems; however, if repeated, serious effects and deaths are likely to occur. The chronic toxicity of 2,4-D did not differ greatly from the acute toxicity. At only slightly lower doses the same general signs, symptoms, and pathology were seen. Hansen et al (58) made the following statement on chronic exposure of humans to 2,4-D residues. (The cited values were for 1971. They have now been lowered slightly; however, in this case they were used to establish a worst-case situation.) IV-12 �TABLE 2 . Summary of literature data on the subacute and .chronic toxicity of 2,4-D in animals Route of Administration Effect Dose NSa 1-2 daily s.c. injections for 3 weeks to 90 days No effect 50-70 mg/kgb 18 1-2 daily s.c. injections Retarded growth 70-90 mg/kgb 18 NS Mouse No. Used NS Animal 22 daily s.c. injections No effect 0.1 mg/injc 57 NS 30 days in diet No severe effect 1000 mg/kg dietb 63 6Fd 5 doses/wk for 4 wks by intubation No effect 30 mg/kge 115 5 doses/wk for 4 wks by intubation Liver, G.I. growth effect 100 mg/kge 115 5 doses/wk for 4 wks by intubation Fatal in days 300 mg/kge 115 5 F 113 days in diet No effect 300 mg/kg diet6 115 5 F 113 days in diet Liver and growth effects, deaths 1000 mg/kg diet 115 Slight effect Total 2-5 g/kgc No effect 75 mg/kg' Rat 6 F 6 F 44 Mf 5 F 4 or 7 wks in diet 10 daily doses via stomach tube Referent t- 22 122 �Table 2 contumed 10 daily doses via stomach tube 2 died, overt toxicity m 3 100 mg/kgc 25 F/25 .M In diet for 2 yrs No effect 1250 ing/kg d i e t 58 W F/20 M In diet for 3 generation reproduction study in adults No effect 500 rag/kg diet 0 58 No effect on fertility or litter size. Lower no. pups weaned, lowered weight 1500 mg/kg diet 0 58 growth inhibition, poor health, diarrhea 1000 rag/ 1 water 15 No effect at gross exam. Some histopath effects in 2,4-D/oil treated animals. 3.13% solution9 72 5 f 20 F/2D M NS Rabbit 22 F/22 M In diet for 3 generation reproduction study in adults In drinking water for 2 yrs. 5 times/wk for 3 wks to intact and abraded skin Dog 122 3 F/3 M In diet for 2 yrs No effect 500 nig/kg diet c 58 3 M Oral dose via capsule 5 days/wk for 13 wks No effect on gross 10 mg/kg 33 Death in 3 at 18-49 days. Severe signs in 1 animal surviving 20 rag/kgc 33 1 F/3 M Oral dose via capsule 5 days/wk for 13 wks �Table 2 continued 1.1 mq/kg° 2.6 mg/kgj 3.2 mg/kg° 123 123 123 Toxicity, anorexia, retarded growth 300 mg/kgh 15 Locomotor problems, normal organ weights, no gross pathology 500 mg/kg1 15 Transient hematological and biochemical changes 18 mg/kg 3F Daily I.V. doses for 32 days at two higher levels, 37 days at lower level No effect NS Oral doses up to 103 days Pig NS In diet up to 12 months Sheep NS Daily oral doses for 120 days Cattle 125 1 Daily oral dose for 106 days No effect 5.5 gc 90 NS, S 15 daily oral doses Toxicity 250 mg/kg1 99 NS, S 112 daily oral doses No effect 50 mg/kg1 99 I en NS - number of animals in study not stated or unavailable from literature source Sodium salt of 2,4-D C 2,4-D acid F - Female e Butyl ester calculated as 2,4-D f M - Male ^Sodium salt, isooctyl ester and butyl ester of 2,4-D each applied separately on individual animals under the conditions described and concentration listed. Amine salt and butyl ester of 2,4-D used separately in animals at dose indicated. Vmine salt , Female lactating b S - Steer �Adequate data are not available to enable one to state conclusively what the total level of 2,4-D residues may be in foods ingested by the human population. An estimate of the greatest amount that might possibly be invested cart be made by use of the legal tolerances established by the FDA for 2*4-0 in various crops. They are 5 mgVkg pri 4 fruit Crops (apples^ citrus fruits* pe^ars and qUirices} aHd 0;5 mg/ky 6h 4 fcjraih crops (barley'} bats, fy'e ana wheat); if it is assumed that all the crop fbr Which a tdie^aHce exists always carried the" maximum amount of 2j4-D permitted; it can bis calculated that approximately Ch3 mg/kg of 2*4-0 Would be cbntribut^d to the total diet (fruit crops = 6 pertertt of the dietary intake of man ahd grain drops = 9 percent); tohe'h the maximum estimated human exposure to 2,4-D via the diet is cbtiipared to the dbsages given rats in the pr~e'sent study, it is apparent that there is an extremely wide margin of safety between 0.3 mg/kg of diet in man and the Ij250 mg/kg of diet fed to rats; C; Absorption, Distribution and Excretion of 2*4-0 Different degrees of sdditim 2,4-D poisoning were produced by Elb artd Yiitalo (35) in adult male Sprague-Dawley rats when 250 mg/kg • 2,4-0 was administered &y subcutaneous injection-. After varioU's intervals the cOncen'tratibn of intravenous 14fe-2,4-D Was cbm'pafed to the level fburtd iti the e^referbspihai fluid (CSF) and brairti At 4.5 hours 'when the sodium 2 i4-D, radioactivity in plasilia had diminished to 67 percent of control levels* ah 11-fold increase in the brain and a 39-fold increase i'n the CSF were s^fert compared to a 4.5 fold increase in the liver. All physiological and t'oxied logical parameters of this 1977 study had not been fully analyzed; however, during acute 2,4-D poisoning, the levels found in the brain were greatly increased. This increase appeared to be closely associated with the toxic symptoms. In ratsi pigs and cal'vies, 2^4-D administered in doses of 50-100 mg/kg brail y as salts ty&?$ readiiy absorbed arid eHifriMt&di mainly in the ail uHriev Wth.JpjAsflft hajf-li'ves varying from 3-12 hMrs .(^-,3^). The rate of 2-i4-D elimfnatib'n ih rats was dosage dependent-. Fbl Vowing administration of 14C-2-,4-D-, Khartna ahd Faftg (73) fouWd radioactivity in all organs and tissues examined [see IARC monograph i Vol 15 (66)]. Berridt arid Koschier (9) using J G - labeled 2-,4-D in rat and rabbit renal ddrtical tissue sliees-, JLH vijtio, noted that 2,4-D was transporlfecl. By the ciassitil retii.! organic aMon transport process j howeVer-, 'otfter 'mechanisms of tra;ns'p'ort may also have b'een involved. This study tnay h^Vp 'ek'pVafn brYe of tfe frtech'an'isms contributing to the relatively ! ;f%^j el dls'app'e'aran'c^ '6f 2\4-D 'frdm iftbst species and th'e loW levels of bi'oVO'gical deposition of this compbund. IV-16 �The esters of 2,4-D were hydrolyzed in animals and the phenoxy acids were excreted predominantly as such in the urine of rats after oral administration, although a minor portion of them may have been conjugated with the amino acids glycine and taurine and with glucuronic acid (54). No 2,4-dichlorophenol was detected, however, in the urine of C57BL/6 mice treated subcutaneously with 2,4-D or its butyl or isooctyl esters. The rates of disappearance from plasma of 2,4-D and its butyl and isooctyl esters following single subcutaneous injections of 100 mg/kg of the compounds to female C57BL/6 mice were: butyl ester > isooctyl ester > 2,4-D (147), [see IARC monograph, Vol 15 (66)]. After oral administration of 0.05 mg/kg 2,4-D to rats, Fedorova and Bel ova (42) found that traces were detected in the milk of lactating animals for six days. Within 24 hours after administration of 2,4-D to pregnant rats, 16.8 percent of the dose was detected in the uterus, placenta, fetus and amniotic fluids, [see IARC monograph, Vol 15 (66)]. Bjorklund and Erne (15) found that 2,4-D passed the placental barrier in pigs. Clark et al (23) fed 2,4-D acid (99 percent purity) to groups of 3, adult beef cattle and adult sheep at levels of 0, 300, 1,000 and 2,000 mg/kg of feed for 28 days. Animals were killed and tissues sampled one day after the last dose, others one week later. Residues of the 2,4D and its phenol metabolites were determined in muscle, fat, liver and kidney. Muscle and fat contained the lowest levels while kidneys and liver contained the highest residue level. Withdrawal from treatment for one week before killing resulted in a significant reduction in tissue residue levels. With the exception of the kidneys, 2,4-D residues averages less than 1 mg/kg in the tissue analyzed. The kidney tissue level averaged 7.82 mg/kg with 0.37 mg/kg present after a 7-day withdrawal period. No 2,4-D was detected in fat or muscle of any animals at a detection limit of 0.05 mg/kg. All treated animals showed some anorexia, weight loss or poor weight gain depending on the level 2,4-D present in the feed, due to lowered palatability. During the 7-day withdrawal period, feed consumption in all groups returned to normal. 2,4-D was rapidly eliminated from animals, mainly in the urine with plasma half-lives of 3-12 hours following a single dose. Generally, it accumulated in animal tissues when given at high doses or repeated lower doses. However, these residues declined rapidly with a half-life of 1 to 2 weeks. Because of its excretion by the kidney, kidney tissue levels were as much as twenty times greater than the level seen in other organs and tissues. D. Embryotoxic, Fetotoxic and Teratogenic Potentials of 2,4-D The embryotoxic, fetotoxic and teratogenic potentials of 2,4-D appeared to be extremely variable with observable effects dependent upon concentration, degree of purity and method of administration with some effects only occurring with doses that approached maternal toxicity. IV-17 �Bionetics Research Laboratories (12, 13, 14) reported that either the acid* or the isopropyl, butyl and isooctyl esters of 2,4-D, administered orally or subcutaneously at days 6-14 of gestation, increased the incidence of anomalous fetuses among BL6, AKR and C3H strains of mice but not among B6AK arid AIHa strains. No single strain showed a positive response to all formulations. No single formulation caused a positive response among all strains of mice. Thus, the reported effects were highly strain-specific, in addition, the Bionetics study involved parenterai administration using dimethyl sulphoxlde (DMSO) as a vehicle, which complicated the interpretation of the data* since DMSO has been shown to be a teratogen in several species of laboratory animals when administered by the route used in the Bionetics study [see Schwetz et al (122)]. Schiller (118) found no difference in fertility (defined as the number of rats weaned per female mated) of test and control animals in one experiment where rats were fed potatoes which had been treated with 2,4-D. In a combined second and third experiment, fertility of the P, Fp Fo and Fo generations was 7.2, 5.8, 6.8 and 6.1 for controls versus 7.2* 7.1, 5.4 and 5.1, respectively, for test rats. The differences between control and test groups were not significant (P>0.05). The content of 2,4-0, its form, or purity in the potatoes was not given. When 1,000 mg/1 2,4-D was given throughout pregnancy to S'pragueDawley rats via the drinking water, the gestation and parturition were normal. The litter size was not significantly reduced and no anomalies were seen in the pups (15). Hansen et al (58) stated that in unpublished work performed by T.B. Gaines and R.D, Kimbrough, female rats were fed 2,4-D acid at 0, 1,000, and 2,000 mg/kg of diet for 95 days, mated with untreated males and continued on their respective diets throughout gestation and lactation, At the highest dosage level, females gave birth to pups that were small at birth and 94 percent died before weaning. Some deaths also occurred in pups of females fed the lower level. Starting with rats three weeks of age, groups of 25 female and 25 male animals were fed for two years either 0^ 5* 25, 125, 625 or 1,250 mg 2,4-D/kg of diet. No significant effects on growth rate, survival rate, organ weights or hematologic values were noted (58). Hansen et al (58) also noted in a three generation, six litter rat reproduction study, no deleterious effect of dietary 2,4-D acid at 100 or 500 mg/kg was evident. At 1,500 mg/kgi, however, 2,4-D, while apparently affecting neither fertility of either six nor litter size, sharply reduced the percent of pups born surviving to weaning and the weights of weanlings. I* studies by Schwetz et al (122), the acid of 2,4^0, the propylene glycol butyl ether ester of 2,4-D and the isooctyl ester of 2,4-D were evaluated for effects on fetal development, neonatal growth IV-18 �and survival when administered at 12.5, 25, 50, 75 and 87.5 rag/kg orally to pregnant Sprague-Dawley (Spartan strain) rats during organogenesis (days 6-15 of gestation). Fetuses were delivered by Caesarean section on day 20 of gestation and were examined grossly, measured and weighed. Fetotoxic responses seen at high dose levels 50, 75 and 87.5 mg/kg included subcutaneous edema, delayed ossification and wavy ribs. Teratogenic responses were not seen at any dose level. 2,4-D did not affect fertility, gestation, lactation or viability of the newborn. The esters of 2,4-D decreased viability of the newborn and lowered lactation indices (Lactation Index: pups weaned/pups alive on day 4 X 100). In a second part of the experiment in which litters delivered naturally, 2,4-D and its esters had little or no effect on fertility, gestation, viability or lactation indices. There were no observable effects on neonatal growth and development. Khera and McKinley (74) observed minimal 2,4-D induced fetopathy and an increased incidence of skeletal anomalies in rat pups following single daily oral doses of 100-150 mg/kg 2,4-D from days 6 to 15 of gestation. The observed skeletal defects did not appear to be incompatible with postnatal survival. Following treatment of dams with the acid of 2,4-D and the butyl and isooctyl esters of 2,4-D, weight gain and viability of the offspring were within control limits. The findings of their study suggested that postnatal parameters were unrelated to the teratologic potential of the chemicals. No consistent embryotoxic effects were noted when 2,4-D acid was administered orally to hamsters at doses of up to 100 mg/kg on days 6-10 of gestation (24). Binns and Johnson (10) showed that 2,4-D did not have a teratogenic potential in sheep. Starting one day after breeding ewes were given 2 g/day of 2,4-D acid in an alfalfa meal/water mixture via stomach tube for 30, 60, or 90 days. No clinical signs of toxicity nor histopathologic lesions were seen in the ewes and no congenital anomalies nor histopathologic lesions were seen in the lambs. Ewes were reported to have had increased rates of stillbirths and bucks displayed reduced sexual activity and decreased sperm quality when pastures were grazed soon after treatment with 3 Ib/A of the 2,4- • dichlorophenoxybutric acid (2,4-DB) (116). When a diet containing 500 mg/kg 2,4-D was fed to a sow during the entire pregnancy, the sow was anorexic and the newborn piglets were underdeveloped and apathetic with 10/15 dying within 24 hours. When the survivors were continually fed 2,4-D at 500 mg/kg of diet until they were 8 months of age marked growth depression, persistent anemia and moderate degenerative changes of the liver and kidneys were noted (15). Erne (40) fed pregnant reindeer birch leaves that had been sprayed with a mixture of 2,4-D and 2,4,5-T at a daily dose of 1 mg IV-19 �phenoxy herbicide per kg body weight. There were no clinical or histopathological changes noted in any of the female reindeer and no fetal anomalies were seen. From the data presented in Table 3 the no effect level for embryotoxic, fetotoxic and teratogenic signs in the rat was approximately 1,000 mg/1 of the sodium salt of 2,4-D, while the no effect level from 2,4-D acid in the rat diet ranges from 1,250 to 1,500 mg/kg of food. Oral doses of 2,4-D acid and the butyl and isooctyl esters cause no effect at daily doses of 87.5 mg/kg. At 100 to 150 mg/kg 2,4-D acid and esters produced embryo and fetotoxic responses in rats and hamsters. In pigs 500 mg 2,4-D acid/kg diet caused the sow to be anorexic and produced weakened piglets with 10 to 15 dying within one day after birth. When the five surviving piglets were fed the same diet for eight months they showed a marked depression in growht. Sheep have tolerated oral doses of 2,4-D acid for 30-90 days at 2 grams per day levels, while reindeer experienced no adverse effects from daily oral doses of 1 mg/kg for 30-54 days. E. Carcinogenic and Tumorigenic Potentials of 2,4-D Studies of the carcinogenic properties of 2,4-D in mammalian biological systems are limited at best. However, in an extensive study by Innes et al (67), the tumorigencity of some 130 test compounds were tested in mice. Included in the test compounds were the 2,4-D acid and the isopropyl, butyl and isooctyl esters of 2,4-D. They were given orally, at a daily dosage rate of 46.4 mg/kg. An additional test using the dosage rate of 100 mg/kg for 2,4-D acid was included. These doses were given by stomach tube starting at 7 days of age and continued until the mice were 4 weeks of age. After weaning, the test compounds were mixed directly into the diet and the same dosage rate maintained for approximately^ 18 months of observation. The tumor incidence in any group or combination of groups in which 2,4-D was tested was not significantly different from that in control animals. Groups of male and female mice were given single subcutaneous injections of 215 mg/kg 2,4-D in dimethyl sulphoxide (DMSO) on the 28th day of life and observed up to 78 weeks of age. Tumor incidences in any group or combination of groups were not significantly different from that in controls. No increase in the incidence of tumors was observed in similar groups of mice treated with single subcutaneous injections of 21.5 mg/kg butyl or 100 mg/kg isopropyl esters of 2,4-D, both 99 percent pure. Mice treated with 21.5 mg/kg isooctyl ester of 2,4-D, 97 percent pure, had 5/17 females of one strain developing reticulum-cell sarcomas (12). Walker et al (141) demonstrated that six, daily, intraperitoneal, injections of highly purified 2,4-D (99.0 percent) at the rate of 62 mg/kg effectively inhibited development of the Ehrlich ascites tumor maintained in BALB/c mice. IV-20 �TABLE 3. Animal Rat Number Used . PFa NSb Summary of literature data on the embryotoxic, fetotoxic and teratogenic potentials of 2,4-D in amimals Route of Administration Response Dose fteferen< 1000 mg/1 water0 15 Diet for 95 days then mated and Small birth wt. 94% died continued through gestation before weaning. and lactation. 2000 mg/kg dietd 58 Some reduction in birth wt. Some deaths in pups. PF NS Drinking water during pregnancy. No effect 1000 mg/kg dietd 58 25 Fe ro In diet for 2 yrs. No effect 1250 mg/kg dietd 58 25 Mf In diet for 2 yrs. No effect 1250 mg/kg dietd 58 PF NS In diet 3 generations. Six litter reproduction study. No effect 500 mg/kg diet No effect on fertility of either sex nor litter size. Reduced % of pups born and surviving to weaning - lowered weaning weights. 1500 mg/kg diet No effect on fertility, gestation, lactation or viability of newborn. 87.5 mg/kg9 122 Fetotoxic as edema, delayed ossification, wavy ribs. No teratogenicity. 87.5 mg/kg- 122 19 PF 119 Fetuses Daily oral dose - days 6-15 of gestation. Daily oral dose to females days 6-15 of gestation. H 58 58 �Table 3 continued PF NS Daily oral dose - days 6-15 of gestation Minimal fetopathy, increased , skeletal anoma'Mes 150 mg/kg PF NS Daily oral dose - days 6-15 of gestation No consistent embryotoxic effects 100 mg/kg1 24 Via stomach tube 30, 60 or 90 days No effect 2 g/dayl 10 In diet throughout pregnancy, Female anorexic. 10 of 15 piglets died in 24 hrs. 500 mg/kg diet 15 Growth depression, anemia, moderate liver and kidney lesions. 500 mg/kg diet0 15 No effect 1 mg/kg 40 74 Hamsters Sheep PF Pig 1 PF 5 Newborn ro ro In diet for 8 months Reindeer 15 PF In diet for 1 - 1 . 5 months PF - pregnant female NS - number of animals in study not stated or unavailable from literature source c Sodium salt of 2,4-D d 2,4-D acid p F - Female f M - Male 9 2,4-D acid or molar equivalents of propylene glycol butyl ether ester of 2,4-D or the isooctyl ester of 2,4-D 2,3-D acid or butyl or isooctyl esters of 2,4-D �Hansen et al (58) studied groups of 25 male and 25 female Osborne-Mendel rats that were fed for two years on diets containing 2,4D at 0, 5, 25, 125, 625 or 1,250 mg/kg levels. The 2,4-D was 96.7 percent pure and contained no detectable levels of 2,7-dichloro or 2,3,7,8tetrachlorodibenzo-p-dioxin (limit of sensitivity of method of analysis was 1 mg/kg). No target organ tumors were observed and the individual tumor types were randomly and widely distributed and of the type normally found in aging rats of that strain. Statistical analysis of the randomly distributed tumor types indicated a tendency for the proportion of females with tumors to increase with 2,4-D dosage and a trend toward dose related increases in the proportion of males with malignant tumors. The number of treated rats with malignant tumors over controls was found only in males receiving the highest dosage level. A review of the summary of the literature on the carcinogenic and tumorigenic potentials of 2,4-D in animals presented in Table 4, revealed that 2,4-D acid, and the isopropyl, butyl and isooctyl esters of 2,4-D did not adversely affect nor increase the incidence of tumors in test animals when fed at levels of 46.4 to 100 mg/kg of diet to mice or 1,250 mg/kg of diet to rats for 18 to 24 months. Those tumors that did occur were not necessarily in target organs and were the type tumors normally seen in aging laboratory animals of the species and strain being studied. Single subcutaneous injections of 21.5 to 215 mg/kg of 2,4-D acid, isopropyl and butyl esters of 2,4-D in DMSO did not produce carcinogenic or tumorigenic responses in male or female mice, A single subcutaneous injection of 21.5 mg/kg of the isooctyl ester of 2,4-D in DMSO did produce an increased incidence of reticulurn-cell sarcomas in treated female mice. It should be noted that DMSO itself is now considered to be a potential carcinogen. At 62 mg/kg, 2,4-D acid injected intraperitoneally in mice inhibited the development of Ehrlich ascites tumor being maintained in mice. F. Mutagenic and Cytogenetic Potentials of 2,4-D in Animals Most of the mutagenic studies of 2,4-D have been conducted in bacterial cultures or in plant and animal tissue cultures; however, Styles (133) investigated the cytotoxic effects of 2,4-D on .01 u-cvo and Jin v-cfio test systems and found no increase in mutation rate and no evidence of mutagenicity in the test rats. He found serum from orally dosed rats was not mutagenic to Sa&none&ta. typkunusuium. Complete details of this study were not readily available. Pilinskaya (101) observed that treatment of cultured human lymphocytes with 2.5 X 10~7 M (0.02 yg/ml) 2,4-D increased the number of chromatid aberrations (single acentric fragments) and, to a lesser extent, the chromosomal aberrations (paired acentric fragments). In mice, Pilinskaya (101) found toxic concentrations (100-300 mg/kg) of 2,4-D administered as a single oral dose significantly increased the frequency of aberrant metaphases (2-4 fold) with single fragments being the aberration seen. IV-23 �TABLE 4 Animal Number Used Summary of literature data on the carcinogenic and tumorigenic potentials of 2,4-D in animals Route of Administration M - F NSe Single subcutaneous injections in DMSO No effect 46.4 mg/kg dietc 67 100 mg/kg diet 67 No effect 215 mg/kgd 12 No effect h 18 Ma/18 FD of Stomach tube, beginning at 7 two hybrid days of age for 21 days, then strains in diet for 18 months Dose No effect Mouse Response 21.5 mg/kgf 12 Reference 9 No effect f\ f J_ . T . T 6 daily . intraperitoneal injections Rats 25 M/25 F Diet for 2 years 12 5/17 females developed reticul urn-cell sarcomas ro 100 mg/kg 21.5 mg/kgh 12 C O m» / I «^ Erlich ascites tumor No target organ tumors, random type tumors normally seen in aging rats M - Male F - Female C 2,4-D acid and isopropyl, butyl and isooctyl esters of 2,4-D 2,4-D acid e NS - number of animals in study not stated or unavailable from literature source 1250 mg/kg diet Butyl ester of 2,4-D ^Isopropyl ester of 2,4-D h lsooctyl ester of 2,4-D 58 �Jenssen and Renberg (68) found there was no detectable increase of micronuclei in the erythrocytes of mouse bone marrow after intraperitoneal administration of 100 mg/kg 2,4-D. Because of the high experimental resolution power of the test system used in this study it was particularly suitable for the detection of weak chromosome breaking activity of 2,4-D in mammals. The lack of penetration of 2,4-D into the cells was in accordance with the rapid excretion that is known to occur in the mammalian body. This experiment did 'not in the authors opinion, consititute a reliable measure of the mutagenic potential of 2,4-D; however, in practice the lack of penetration of this substance into the cells indicated it does not constitute a cytogenetic hazard to man. Epstein et al (37) found that 2,4-D did not increase dominant lethal mutations in mice when given as a single intraperitoneal injection of 125 mg/kg or when given orally on five successive days for a total dose of 75 mg. In host-mediated assays Zetterberg et al (146) using strains TA1530 and TA1531, or Sac.c.kaAomyc&> D4, found no mutagenic effects in the organisms when host adult male mice were given 6 mg 2,4-D (200 mg/kg) by gavage. Bongso and Basrur (17) exposed embryonic bovine kidney cells and bovine peripheral blood cells, /en v-ttao, to concentrations of 1-1,000 iag/ml 2,4-D for 6-96 hours resulting in stimulation of mitosis. ChromosoMid' aberrations were not detected in the peripheral blood cells, but nucleolar irregularities and polyploid mitotic stages were observed in the kidney cells. Andersen et al (4) evaluated 110 herbicides for their ability to induce point mutation in one or more of 4 different microbial systems. The herbicide 2,4-D was included in this study. The authors did not state the purity of the compounds being tested. The 2,4-D did not cause point mutations in these microbial systems in comparison with known mutagens such as 5-bromouracil or 2-aminopurine. These observations of no mutagenicity of 2,4-D in Eiah<yu.dUa c.oti WP2 her+ or her" or in S<t£mone££a typhimuruwn strains TA1535, TA1536, TA1537 or TA1538 were also confirmed in works by Nagy et al (94), Shirasu (126) and Shirasu et al (127). A review of the literature on the mutagenic and cytoger.ic potentials of 2,4-D in animals generally supported the premise that 2,4-D was not highly cytotoxic in laboratory animals. It did not increase mutation rates nor stimulate a mutagenic response in rats and mice. In various Ln vJutiio and Jin vuvo test systems 2,4-D did cause chromatid aberrations and nucleolar irregularities in cultured human lymphocytes, bovine kidney cells and tissues of mice given single toxic doses. No mutagenic responses were seen in several studies using microbial systems for the detection of mutagenic and cytogenic responses to 2,4-D. IV-25 �III. REVIEW OF 2,4,5-T TOXICITY IN ANIMALS A. The Acute and Short-Term Toxicity Potentials of 2,4,5-T Detailed accounts of the experimental procedures used to study the acute and short-term toxicity potentials of 2,4,5-T were not available, References to acute toxicity of 2,4,5-T in small laboratory animals referred to a summary article on toxicological information on 2,4-D and 2,4,5-T by Rowe and Hymas in 1954 (115). Their literature review made reference to the 1953 work of Drill and Hiratzka (33) where acute and chronic oral toxicity studies on 2,4-D and 2,4,5-T were conducted with dogs. Apparently, the earlier research with small laboratory animals dealt primarily with 2,4-D, although some 2,4,5-T studies conducted in 1950 discussed effects on horses, dairy and beef cattle, sheep, swine and chickens immediately pastured on freshly treated alfalfa. Unfortunately, Rowe and Hymas did not detail the methodology for obtaining all the data that appeared in their article. Table 5 presents the available data from the literature dealing with the acute toxicity of 2,4,5-T in laboratory animals. Drill and Hiratzka (33) administered commercial 2,4,5-T of 98.9 percent purity (TCDD level not stated) in a single oral dose of 50, 100, 250 and 400 mg/kg to a total of 10 adult mongrel dogs of both sexes, The 400 and 250 mg/kg dosages were given to individual male dogs and both died in 2 and 3 days, respectively. One of four female animals died at the 100 mg/kg dose level; however, no other signs of toxicity were noted. All three males and one female in the 50 mg/kg dosage level survived with no signs of toxicity. The acute oral LDso for 2,4,5-T acid was in the range of 100 mg/kg or higher for dogs. Toxic doses of this level produced only mild signs of muscle spasticity. Bjbrklund and Erne (15) fed single oral doses of 100 mg/kg 2,4,5-T to pigs causing anorexia, vomiting, diarrhea and ataxia. At autopsy, hemorrhagic enteritis and congestion of the liver and kidney were found [see IARC Monograph, Vol 15 (66)]. Study of the data in Table 5 indicated that the various forms of 2,4,5-T all fall in the same range of acute toxicity for mice, rats, guinea pigs and rabbits. The dog appeared to be somewhat more susceptible, The LDso values for 2,4,5-T and its common derivatives were in the range of 380 to 940 mg/kg for the small laboratory animals. When given orally to dogs, even in fatal cases, 2,4,5-T produced only weak signs in the form of ataxia and stiff movements of the hindlegs. B. The Subacute and Chronic Toxicity Potentials of 2,4,5-T Highman et al (62) conducted a study using 978 mice including control animals. On days corresponding to days 6 through 14 of pregnancy, groups of pregnant and nonpregnant CD-I mice and male and nonpregnant IV-26 �TABLE 5 . Animal Mouse Number Used Summary of literature data on the no-effect LD5Q and LD1QO levels of the acute toxicity of 2,4,5-T in animals Route of Administration Dos e-Toxi city Single Dose nig/ kg Reference NSa Mb Oral in olive oil LD50 389C 1 15 NS Fd Oral in olive oil LD50 e 551 1 15 NS F Oral in corn oil LD50 940f 1 15 NS M Oral in olive oil LD50 500C 1 15 NS M & F Oral in ol i ve oil LD 50 495e 115 NS F Oral in corn oil LD50 481f 1 15 NS F Oral in ol i ve oil LD50 7509 1 15 NS M & F Oral in olive oil LD50 381c 1 15 NS F Oral in olive oil LD50 449e 1 15 NS F Oral in corn oil LD en 750f 1 15 NS M Oral in corn oil LD 712' 115 Rat ro Guinea Pig Rabbit 50 �Table 5 continued 1 M Oral in capsule LD 2501 33 4 F Oral in capsule LD 100C 33 1 Dog Oral in capsule F 3 M 100 50h No effect 33 Pig NS Oral Anorexia, vomiting, diarrhea, ataxia, hemorrhagic enteritis, liver and kidney congestion. 100 NS - number of animals in study not stated or unavailable from literature source. b M - Male C 2,4,5-T acid ro oo F - Female e lsopropyl ester of 2,4,5-T f Mixed butyl esters of 2,4,5-T 9 Mixed amyl esters of 2,4,5-T One of four animals died on 7th day 15 �female dihybrid cross Fg mice received, by gavage, 2,4,5-T acid doses ranging from 30 to 140 mg/kg. Some groups received a technical preparation of 2,4,5-T (97.9 percent pure, containing < 0.05 mg/kg TCDD or a purified preparation of 2,4,5-T (99 percent pure, containing < 0.05 mg/kg TCDD). Mice killed when they became moribund and at 1, 2, 4, 6, 8 and 11 days after beginning treatment. Sick or moribund mice sacrificed after 2-9 doses of 2,4,5-T often showed severe myocardial lesions, hypocellularity of the bone marrow and depletion of lymphocytes in the thymus, spleen, or lymph nodes. They also showed marked hematologic and blood chemistry changes. Treated mice remaining healthy showed few or no lesions and no blood chemistry changes, but often developed a mild anemia attributable to a hemolytic effect of 2,4,5-T. The incidence of animals becoming moribund was less than 1 percent in the CD-I mice, including those given 140 mg/kg, and ranged from 53 to 82 percent in groups of male and female F2 mice receiving 120 mg/kg 2,4,5-T. The incidence of moribund mice tended to be higher in male than in female F2 mice and in those given the purified compound. The findings of this study indicated that impairment of maternal health by severe lesions early in gestation were not the primary cause of an increased incidence of fetal abnormalities observed in mice given 2,4,5-T. The lesions appeared to be due primarily to 2,4,5-T, rather than to contaminants in the technical preparation. Finally, the importance of using more than one strain of mouse in toxicological studies was vividly illustrated. Highman et al (60) using 378 pregnant dihybrid cross F£ female mice gave either 60 or 120 mg/kg 2,4,5-T via gavage on days 6 through 14 of gestation. Both technical (97.9 percent pure with less than 0.005 mg/kg TCDD) and a more purified preparation (99 percent pure with less than 0.005 mg/kg TCDD) of 2,4,5-T were used in this study. Mice were killed when they became moribund and at 6, 24, and 30 hours, as well as at 4, 6, 8 and 11 days after beginning treatment. Mice given 60 mg/kg and many given 120 mg/kg 2,4,5-T appeared normal at the time they were terminated either in early or late pregnancy and showed few or no pathologic changes. Mice that became ill or moribund often showed severe lesions and few survived past 11 days. The histopathological lesions included myocardial rarefaction and necrosis, thymus cortical atrophy, splenic atrophy and hypocellularity in bone marrow and lymph nodes. Groups of 10 male and 10 female rats per test dose were fed for 90 days on diets containing 2,4,5-T at the daily dosage levels of 0, 3, 10, 30 or 100 mg/kg body weight. The 2,4,5-T acid was from commercial production and contained less than 1 mg/kg TCDD. No effects were noted in the animals fed 3, 10 or 30 mg/kg doses. Changes found in both sexes fed 100 mg/kg included depression in body weight gain, slight decrease in food intake and elevated serum alkaline phosphatase levels. Male rats at this dose had slightly increased serum glutamic-pyruvic transaminase levels and slight decreases in red cell counts and hemoglobin. Inconsistent hepatocellular swelling was observed upon histopathological examination in some livers. [See World Health Organization (WHO) Monograph 71.42 (143), and IARC Monograph, Vol 15 (66)]. IV-29 �Groups of 10 male and 10 female rats per test dose were fed for 90 days on diets containing 0, 100, 300, 1,000 an0 3,000 mg/kg of food, of the mono-, di-, and tripropylene glycol butyl either esters of 2,4,5-T. The 2,4,5-T acid equivalent was 62 percent. No effect levels were 100 and 300 mg/kg of diet. At 1,000 mg/kg level slight cloudy swelling of the parenchyma! cells with central lobular necrosis was noted in two of ten animals examined. Kidney weights were increased wtfth mild cellular changes noted such as cloudy swelling of renal tubular epithelium. At 3000 mg/kg a significant retardation in growth was noted in males but not females, liver and kidney weight increased in males, livers were large and light in color in both sexes, generalized cloudy swelling of liver cells and slight central lobular necrosis and cloudy swelling of renal tubular epithelium [see WHO Monograph 71.42 (143) and IARC Monograph, Vol 15 (66)]. Konstantinova (81) conducted experiments with pregnant rats using 12-13 animals per treatment group and dosing them via stomach tube for the entire gestation period with 0.01, 0.1, 0.42 and 4.2 mg 2,4,5T/kg body weight. The butyl ester of 2,4,5-T was used in this study; however, source and purity were not stated in the translation. No effects were noted at the 0.01 mg/kg dose. The threshold level in this study was at the 0.1 mg/kg dose. At 0.42 mg/kg a general toxic effect on pregnant females was noted and embryotoxic effects were of an irregular character and difficult to evaluate. The 4.2 mg/kg produced a significant increase in total embryo fatalities, a decrease in the number of live offspring (average one less per female) and a decrease in the weight of the offspring. Rip and Cherry (111) fed a group of 12, four-week-old, male, Long-Evans rats, analytical standard grade 2,4,5-T (containing no detectable TCDD at a sensitivity of 0.05 mg/kg) mixed with the diet at a rate of 10 mg/animal/day for 1-11 days. Feeding of the 2,4,5-T caused liver enlargement with no effect on the weight of the kidneys, spleen, or body weight of the animal. Increases in relative liver weight were dose dependent and were observed after the first or second feeding. Enlargement was associated with substantial increases in total RNA and total protein per liver. The increases were not restricted to any particular subcellular fraction, but appeared to represent a general induction of RNA and protein synthesis. Total DNA content per liver was not affected. The enlargement response was reversible on the removal of the 2,4,5-T from the diet. This increase did not appear to be directed toward the synthesis of 2,4,5-T metabolizing enzymes. 2,4,5-T did not stimulate production of enzymes known to be produced by hepatotoxic compounds. This suggested that 2,4,5-T did not have a strong hepatotoxic activity and in fact it demonstrated activity similar to a structurally related compound chlorophenoxyisobutyrate (CPIB) which, like 2,4,5-T, induced liver enlargement and stimulated RNA and protein synthesis while inducing a strong self-metabolizing influence in the liver. IV-30 �Drill and Hiratzka (33) administered 2,4,5-T acid via capsule to adult mongrel dogs, five days a week over a 13 week period. There was 1 male and 1 female in the 0, 2 and 5 mg/kg groups, a male and 2 females in the 10 mg/kg group and 2 males and 2 females in the 20 mg/kg group. All dogs in the 0, 2, 5 and 10 mg/kg dosage levels survived'the 90-day test period. At 20 mg/kg the dogs died between days 11 and 75. The no effect level was 10 mg/kg per day. The histopathological examination of the 20 mg/kg dosed dogs was not remarkable and did not reveal a morphological cause of death. The prominent effects were weakness, slight stiffness in the hind legs, difficulty in swallowing food and in one dog, bleeding from the gums. Study of the data in Table 6 indicated that the various forms of 2,4,5-T fell in the same general range of chronic toxicity for mice, rats and sheep. The exception to this statement were data presented by Konstantinova (81) using the butyl ester of 2,4,5-T of unstated purity. In mice there appeared to be a definite strain difference in susceptibility to 2,4,5-T toxicity. The no effect level in mice ranged from 30-120 mg/kg with an overlapping of adverse effects from 60-140 mg/kg in various strains of mice. Rats appeared to be tolerant to about 10 times the 2,4,5-T calculated dose when administered as mg/kg of diet as opposed to mg/kg body weight of the animal. The no effect level for rats fed 2,4,5-T chronically were approximately 30 mg/kg body weight and 300 mg/kg diet. Threshold toxicity levels for rats were approximately 100 mg/kg body weight and 1,000 mg/kg diet. C. Absorption, Distribution and Exretion of 2,4,5-T Single subcutaneous administration of 100 mg/kg 2,4,5-T to mice resulted in 23 percent of the dose being recovered in the body over a 24hour period (147). In rats, 85.8 percent of a single intravenous dose of 100 mg/kg was found in the urine within 6 days (117). Single oral doses to rats of 100 mg/kg of the triethanolamine salt of 2,4,5-T were readily absorbed, distributed and eliminated; excretion was primarily via the kidneys (38). Seven days after oral administration of 50 mg/kg 2,4,5-T (99.6 percent pure) to rats, 56-69 percent of the dose was recovered in the urine; 70-85 percent of the recovered dose was unchanged 2,4,5-T, and approximately 15-30 percent was found as the glycine and taurine conjugates and as 2,4,5-trichlorophenol; the two conjugates were excreted in nearly equal amounts (16, 55). Similar results were obtained in mice, except that the quantity of the taurine conjugate was greater (54). The biological half-life of 5 mg/kg 2,4,5-T administered orally to dogs (77 h) was longer than that in rats (4.7 h). When the dose of 2,4,5-T to rats was increased to 200 mg/kg the biological half-life was prolonged to 25 h, indicating that the excretory capacity of the animals could be exceeded (104). IV-31 �TABLE 6. Animal Number Used Summary of literature data on the subacute and chronic toxicity of 2,4,5-T in animals Route of Administration Reference Dose Varied by strain 30-140 mg/kgd 62 <1% moribund 53-82% moribund 111 or moribund No effect 140 mg/kgd 120 mg/kgd 60 mg/kgd 90-120 mg/kgd 62 62 62 62 Varied 60-120 mg/kgd 60 Most all animals outwardly6 normal 60 mg/kgd 60 Many animals outwardly normal Mouse Effect 120 mg/kgd 60 Daily dose per animal in feed for 90 days No effect 30 mg/kg 66 Daily dose per animal in feed for 90 days Anorexia, depressed weight gain 100 mg/kgf 66 90 days in diet No effect 300 mg/kg9 66 . 978; F PFD Mc Gavage, dosed daily for 6-14 days, corn oil vehicle CD-I strain F£ dihydrid NCTR strain CRBL strain 378; PF Gavage, dosed daily for 6-14 days, corn oil vehicle CO no Q Rat 10 M/10 F 10 M/10 F 10 M/10 F �Table 6 continued 10 M/10 F 90 days in diet 10 M/10 F 90 days in diet Toxicity; no deaths due to treatment; histopath changes were noted 1000 nig/kg diet9 66 Growth retardation in males not females', no deaths due to treatment; histopath changes were noted 3000 mg/kg diet9 66 12 or 13/PF Stomach tube, daily dosing, entire gestation. No effect 0.01 mg/kg 8T 12 or 13/PF Stomach tube, daily dosing, entire gestation. Threshold level 0.1 mg/kg 81 12 or 13/PF Stomach tube, daily dosing, entire gestation. Irregular effect on dam and fetuses . 0.42 mg/kg 81 12 or 13/PF Stomach tube, daily dosing, entire gestation. One less live pup per female, ^ toxic signs noted. 4.2 mg/kg 81 I co co 12 M In diet to provide daily dose indicated Liver enlargement only 10 mg/kg Via capsule for 90 days Via capsule for 90 days Oral for 35 days No effect All died No effect 10 mg/kgv 20 mg/kgJ 100 mg/kg 1 111 Dog Sheep 1 M/l F 2 M/2 F NSk F - Female PF - Pregnant female C M - Male 33 33 29m �Table 6 continued d Both technical and purified 2,4,5-T acid containing <0.05 and 0.005 mg TCDD/kg. e Histopathological information presented in text. 2,4,5-T acid from commercial production containing <1 mg TCDD/kg. 9 Mono-, di-, and tripropylene glycol butyl ether esters of 2,4,5-T, 62% 2,4,5-T acid equivalent, h Butyl ester of 2,4,5-T, purity not stated. Analytical standard grade 2,4j5-T acid containing <0.05 mg TCDD/kg. •Commercial 2,4,5-T acid, 98.9% purity, TCDD level not stated. NS - number of animals in study not stated or unavailable from literature source. Form not known. < CO m From table in reference (29): �Similar results were obtained with single intravenous injections of 5 or 100 mg/kg 14C-2,4,5-T in rats, where 2.3 and 7.6 percent of the radioactivity were excreted in the feces, respectively, suggesting that at the higher dose biliary excretion of 2,4,5-T and/or Hs degradation products was involved in the overall elimination of 2,4,5-T from the body (117). Marked differences in the pharmacokinetics of 2,4,5-T were seen with different species, ages and doses: clearance of 2,4,5-T from the plasma and body of dogs, mice and man was slower than that in rats. The volume of distribution after a single oral dose of 5 mg/kg also differed: in man, 0.079; in rats, 0.14; and in dogs, 0.22 I/kg (49, 104). A single dose of 100 mg/kg 2,4,5-T to pregnant mice was almost entirely eliminated in 72 h; however, after 4 daily administrations of the same dose, 2,4,5-T accumulated in maternal tissues and fetuses, and by 48 h 2,4,5-T was still detectable throughout the fetuses (34). No radioactivity was found in NMRI strain mouse embryos in an early stage of gestation after administration of ^C-2,4,5-T to the dams. When given in late gestation, the fetal tissue had a level similar to that in maternal tissue (83). Selective uptake of 2,4,5-T into the yolk sac epithelium and absence of placental transfer in early pregnancy were effects similar to those seen with trypan blue in mouse embryos (84). No radioactivity was detected in hamster embryos in a late stage of gestation after similar administration of 2,4,5-T to the dams (31).* The biological half-life of l4C-2,4,5-T was significantly longer in newborn than in adult rats (41, 64). Radioactivity was found in all tissues examined as well as in milk and fetuses after a single oral administration of 0.17-41 mg/kg l4C-2,4,5-T to pregnant rats (41). Care must be taken when making all inclusive or generalized statements on the absorption, distribution and excretion of 2,4,5-T due to the demonstrated and marked differences in the pharmacokinetics of 2,4,5-T seen in laboratory animals. Such variables as age, dosage levels, routes of administration and chemical formulations all contributed to variations in response. Single doses of 2,4,5-T appeared to be rather quickly eliminated, primarily unchanged, via the urine and feces in a few hours up to about 7 days. High doses and repeated lower doses of 2,4-D or 2,4,5-T accumulated in animal tissues. The liver appeared to take a more active role in the metabolism and excretion of higher or chronic doses of 2,4,5-T than when single lower level doses were administered. IV-35 �D. Ernbryotoxic, Fetotoxic and Teratogenic Potentials of 2,4,5-T When reviewing the literature dealing with the embryotoxic, fetotoxic and teratogenic potentials of 2,4,5-T, care must be taken to note the levels of TCDD contamination that may have been present in the 2,4,5-T tested. The TCDD contamination may very well have ranged from undetectable levels, using analytical technology available at the time, to 30 ppm or more. In an extensive 1977 review article of the teratogenic effects of environmental chemicals, Wilson (145) stated that 2,4,5-T had been intensively examined in pregnant animals of six different species. A low level of teratogenicity had been demonstrated in three rodent species: rats, mice and hamsters. Tests in pregnant rabbits, sheep and rhesus monkeys have been negative. Wilson discussed these studies in detail in the test, Handbook o& JnnatotoQg (144). Doses of more than 30 mg/kg 2,4,5-T (containing <0.1 mg/kg TCDD) increased the frequency of cleft palates in some strains of mice. When similar doses were administered to pregnant mice on days 6-15 of gestation some fetal growth retardation was observed (13). Courtney et al (26) first reported that under laboratory conditions 2,4,5-T was implicated as being teratogenic and fetotoxic. The 2,4,5-T used in the study was later found to contain 30 mg/kg TCDD. The 2,4,5-T was administered either orally or subcutaneously at a dose rate of 113 mg/kg per day on days 6-14 of gestation in C57B1/6 mice and days 6-15 in AKR mice. Oral administration caused an increased incidence of cleft palate and fetal mortality in both strains and cystic kidneys in the C57B1/6 mice. Subcutaneous injection resulted in significant increases in the incidence of cleft palate and cystic kidneys in the embryos of both strains of mice and evidence of fetal mortality in the C57B1/6 mice. Roll (112) found embryotoxic and teratogenic effects in NMRI mice exposed to 2,4,5-T, containing 0.05 ppm TCDD, administered orally at 20 to 130 mg/kg daily from 6 to 15 days of gestation. At 90 or 130 mg/kg/day the percentages of resorptions and/or dead fetuses were markedly increased relative to the controls. These levels also produced maternal toxic effects. Dose related reductions in fetal weight were observed at levels of 20 mg/kg/day and above. Cleft palate increased among fetuses exposed to 35 mg/kg/day or more. The teratogenic no effect level in mice for this particular sample of 2,4,5-T was considered to be 20 mg/kg/day. This was later confirmed with specially prepared samples of 2,4,5-T with no detectable (<0.02 mg/kg) amount of TCDD (112, 113). Neubert and Dillmann (96) found that samples of 2,4,5-T acid containing less than 0.02 mg/kg TCDD produced embryotoxic effects in NMRI mice in the form of fetal weight reductions at levels as low as 10 and 15 mg/kg per day, given orally from day 6 to 15 of gestation. The butyl ester of 2,4,5-T showed similar embryotoxic effects in mice when administered IV-36 �in the same manner. Cleft palates were produced using single doses of 2,4,5-T acid at 150-300 mg/kg. The maximum teratogenic effect was seen when mice were dosed on day 12 or 13 of gestation. A potentiation of the teratogenic effects (cleft palate) of 2,4,5-T and TCDD was obtained when teratogenic doses of one of the substances was combined with threshold doses of the other. However, for clear-cut potentiation of the effect of 30-60 mg/kg 2,4,5-T acid more than 1.5 mg/kg TCDD was required. When the level of TCDD drops below 1 mg/kg it was predicted that there would be no additional contribution to the embryotoxic effects of 2,4,5-T (i.e., cleft palate) in NMRI mice. It was concluded that in some of the 2,4,5-T preparations there must have been other contaminants present which exaggerated the teratogenic effect to some extent. Such contaminants may have been present in more than trace amounts. For example, 2,4,5trichlorophenol, did not contribute significantly to the teratogenic effect. The effect of 2,4,5-T and TCDD were studied in random bred CD-I and inbred DBA/2J and C57B1/6 strains of mice by Courtney and Moore (27). Two different samples of 2,4,5-T and one sample of TCDD were used. The 2,4,5-T technical grade contained 0.5 mg/kg TCDD and the analytical grade contained less than 0.05 mg/kg TCDD. Compounds were administered subcutaneously from day 6 to day 15 of pregnancy as solutions in 100 percent dimethyl sulfoxide (DMSO) in a volume of 100 yl/animal/injection. Both samples of 2,4,5-T and TCDD produced cleft palate in all three strains of mice when 2,4,5-T was administered at levels of 100 mg/kg and TCDD at 3 ug/kg. Kidney malformations were produced by both 2,4,5-T samples in CD-I mice and TCDD produced marked kidney anomalies in all mice strains. When 100 mg/kg 2,4,5-T and 1 yg/kg TCDD were administered in combination to CD-I mice, the activity was not potentiated at the dose levels employed. Bage et al (5) injected NMRI mice subcutaneously with 50 and 110 mg/kg 2,4,5-T containing less than 1.0 ppm dioxin on each of days 6 through 14 of gestation. At 110 mg/kg 2,4,5-T was teratogenic, causing cleft palates, rib and vertebrae anomalies as well as being fetotoxic causing 25 to 35 percent resorptions. Highman et al (61) recently reported that it was possible to detect a retardation in renal alkaline phosphatase in fetal kidneys from fetuses of mice given doses of 2,4,5-T by gavage at the rate of 60-120 mg/kg on days 6-14 of pregnancy. This retardation in renal alkaline phosphatase levels was suggested as the cause for the delay in renal functional development and indirectly supported the view that 2,4,5-T caused retarded development, rather than true teratogenesis. In this study a reduction of fetal weight and an increase in the incidence of cleft palate were seen in fetuses from treated females. Frohberg et al (45) administered 0, 20, 40, 80 and 120 mg/kg 2,4,5-T acid or butoxyethyl ester containing <0.1 mg/kg dioxin, by the oral route to NMRI mice. Oral doses of 80-120 mg/kg 2,4,5-T acid or 120 IV-37 �mg/kg butoxyethyl ester were required to produce 3 malformations and fetal deaths. In the inhalation experiments, 216 mg/m of the butoxyethyl ester showed a slight maternal toxic and fetotoxic and teratogenic effect. Ten exposures to 374 mg/m killed 5 of 15 dams, while 392 mg/m3 from day 11-15 of gestation was toxic for the dam and caused fetal deaths. Sparschu et al (130) orally administered commercial grade 2,4,5-T containing 0.5 mg/kg TCDD, to rats in daily doses of 50 and 100 mg/kg on days 6 to 15 and 6 to 10 of pregnancy, respectively. At the lower dosage level minimal fetal effects were seen with a slightly higher incidence of delayed ossification of the skull bones being observed. The higher level was toxic to the dams and caused a high incidence of maternal deaths. Only 4 of 25 rats survived with three showing complete, early, fetal resorptions and one had a litter of 13 viable fetuses which showed toxic effects but no evidence of teratogenic anomalies. Khera and MeKinley (74) found that 2,4,5-T, containing less than 0.5 mg/kg TCDD, induced some fetopathy and increased the incidence of skeletal anomalies in Wistar rats following single daily oral doses of 100-150 mg/kg on days 6-15 of gestation. The butyl ester produced no grossly observable teratologic effects when given at doses of 50 or 150 mg/kg. Various formulations of 2,4,5-T given to pregnant female rats demonstrated that a teratologic potential existed, in the form of skeletal anomalies, when repeated doses of 100 mg/kg or greater were given. At 25 mg/kg 2,4,5-T negative results were noted while at 50 mg/kg effects were noted but were not significant (P=0.05) when compared to control animals. The butyl ester produced no grossly observable anomalies and no adverse effects on the postnatal survival when pregnant females were treated at 50 and 150 mg/kg. Three of 8 females died at the 150 mg/kg dose. Skeletal deformities noted were not incompatible with life and no adverse change in reproductive performance or behavioral characteristics were detected. In the authors opinion, th£ predictive value of postnatal studies in relation to the detection of the teratogenic potential of test compounds may not be raliable on its own. Courtney et al (26) found that when 4.6, 10 or 46.4 mg/kg/day of 2,4,5-T was given orally on days 10-15 of gestation to Sprague-Dawley rats, kidney anomalies and other embryotoxic signs were seen at all levels. Some rat fetuses were reported to have had hemorrhagic gastrointestinal tracts. At the highest level there was a 60 percent fetal mortality and a higher incidence of abnormalities in the survivors. Courtney and Moore (27) reported that in CD rats, 2,4,5-T orally administered at 10, 21.5, 46.4 and 80.0 mg/kg was neither teratogenic nor fetotoxic. Prenatal administration of 2,4,5-T did not effect the postnatal growth and development of the CD rat. Sokolik (129) orally administered 2,4,5-T acid at dosage levels of 100 and 400 mg/kg per day and the butyl ester of 2,4,5-T at dosage levels of 50 and 200 mg/kg per day to rats on days 1 to 14 or 1 to 16. The purity of the 2,4,5-T in either form was not given. At 100 mg/kg IV-38 �2,4,5-T produced embryos with a combination of deformities including absence of the lower jaw, changes in the hind limbs and exophthalmos. At the level of 400 mg/kg one embryo was found with tridactyly of the upper limb combined with syndactyl, while another embryo had brachydactylia of the upper limb. Both levels of the butyl ester of 2,4,5-T were more toxic than 2,4,5-T acid, causing 30 percent embryonic mortality at 200 mg/kg. The lower dose of 50 mg/kg caused high mortality among the embryos as well. At the higher level the butyl ester induced cleft palate, hydronephrosis, hydrocephalus and extensive gastrointestinal hemorrhages along with hind limb brachydactylia. Cleft palate was the primary anomaly seen at the 50 mg/kg dosage level. Sokolik (129) concluded that the identical teratogenic action of the two preparations was probably attributable to the presence of dioxin, while the quantitative differences between the effects were attributable to differences in the concentration of the dioxin. Konstantinova (81) conducted experiments in white rats where 2,4,5-T butyl ester, purity not stated, was given orally to pregnant females for the entire period of the pregnancy at 0.01, 0.1, 0.42 and 4.2 mg/kg. The lowest level found to cause no effect was 0.01 mg/kg in the water. The threshold level was considered to be 0.1 mg/kg, with 0.42 mg/kg showing a general toxic effect on the pregnant female rat; however, the changes noted in the embryos had an irregular character. The highest dose level, 4.2 mg/kg, had a general toxic effect causing nervous system dysfunction in the female rats, changes in peripheral blood and a relative ( increase in the weight of internal organs. The embryotoxic effects were increased embryo deaths, lowered offspring weight, hydrocephaly and peritoneal cavity hemorrhages. In FW49 rats given daily oral doses of 25 to 150 mg/kg of either the TCDD-free or commercial grade 2,4,5-T (<0.1 ppm TCDD) showed no evidence of teratogenic effects (113). Emerson et al (36) confirmed the lack of teratogenic and fetotoxic effects of 2,4,5-T when containing only 0.5 ppm TCDD and when given in daily doses, by gavage, at the levels of 1, 3, 6, 12 or 24 mg/kg in Sprague-Dawley rats. Moreover, doses up to 24 mg/kg 2,4,5-T containing 1 mg/kg TCDD had no teratogenic effect in rats when given on days 6-15 of gestation. King et al (76) found no cleft palates when 93 embryos of Sprague-Dawley rats were injected in uteAo with purified 2,4,5-T on any one day ranging from 12 to 16 days of gestation at dosages of 50 to 125 yg/embryo. Two cleft palates were produced when technical grade 2,4,5-T was injected on day 15 of gestation into 118 embryos using the same techniques. In the control rats 45 females delivered 442 normal fetuses, with a 3.5 percent resorption rate and average liter size of 9.8 Commercial samples of 2,4,5-T containing TCDD in concentrations of 0.1, 0.5, 2.9 or 45 mg/kg caused fetal death and teratogenic effects IV-39 �in Syrian golden hamsters when given orally on days 6 through 10 of pregnancy at dosage levels of 20, 40, 80 or 100 mg/kg. As the dosage of 2,4,5-T increased and the TCDD content elevated, the effects were also increased. Pure 2,4,5-T containing no detectable TCDD produced no malformations when the dosage level was less than 100 mg/kg. Absence of eyelids (bulging eyes) and delayed ossification of the skull and exencephaly accounted for the main teratological abnormalities caused by 2,4,5-T containing TCDD. Hemorrhagic gastrointestinal tracts in the hamster fetuses appeared to be directly related to 2,4,5-T administration and could not be clearly linked to dose level of the compound or the dioxin content* These hemorrhages along with a marked edema noted in some of the fetuses reflected a toxic effect on fetal organs as opposed to a teratological effect (24). Gale and Perm (47) gave pregnant golden hamsters intravenous doses of 2,4,5-T on day 8 of gestation at the level of 2 mg/kg and found a 9 percent resorption rate in test animals compared to a 6 percent resorption rate in control animals. No malformed embryos were detected in this study; however, the purity of the 2,4,5-T was not given. New Zealand rabbits given oral doses of 0, 10, 20 or 40 mg/kg 2,4,5-T (containing <0,5 mg/kg TCDD) on days 6-18 of pregnancy showed no evidence of embryotoxic or teratogenic effects in their offspring (36). Dougherty et al (32) found that technical grade 2,4,5-T, containing 0.05 mg/kg TCDD was not teratogenic in rhesus monkeys, Macaco. mu£at£a, when given at 0, 0.05, 1.0 or 10 mg/kg, nor did 1t interfere with normal development of the young. Groups of 10 pregnant females were treated dally with stomach tube from days 22-38 of pregnancy. There was no evidence of toxicity to the females at these levels. In the 1971 Report of the Advisory Committee on 2,4,5-T (2), a preliminary study was cited where pregnant rhesus monkeys were orally dosed with 2,4,5-T, containing 0.05 mg/kg TCDD, at levels of 5, 10, 20 and 40 mg/kg three times weekly for 4 weeks between days 20-48 of pregnancy. After 100 days of gestation 12 fetuses were removed by hysterectomy and examined. All were found to be developmental^ normal and their weight range was not significantly different than the control animals of the same age. B1nns and Balls (11) found no congenital deformities 1n lambs from ewes daily fed 100 mg/kg 2,4,5-T add or the propylene glycol butyl ester of 2,4,5-T from the 14th to the 36th day of gestation. A third group of ewes fed 113 mg/kg of 2,4,5-T also showed no congenital deformities when fed at different periods during gestation. A summary of the literature on the embryotoxic, fetotoxic and teratogenic potentials of 2,4,5-T in animals is presented in Table 7. In reviewing the literature it was evident that embryotoxic and teratogenic responses occurred in some strains of mice* rats and hamsters when repeated oral doses of 20 to 400 mg/kg 2,4,5-T was administered. Embryotoxicity and teratogenic studies in pregnant rabbits, sheep and rhesus monkeys have been negative. The embryotoxic and teratogenic potentials IV-40 �TABLE 7 Animal Number Used Mouse NSa PFb NS PF C57B1/6 strain AKR strain Summary of literature data on the embryotoxic, fetotoxic and teratogenic potentials of 2,4,5-T in animals Route of Administration Response Dose Daily oral dose, days 6-15 of gestation Increased frequency of cleft palate in some strains. Fetal growth retardation. >20 trig/kg0 13 113 mg/kge 26 Daily oral or s.c. dose, days 6-14 of gestation Oral increased cleft palate and fetal mortality, both strains. Reference Cystic kidneys in C57B1/6 s.c. increased incidence of cleft palate and cystic kidneys in both strains. Increase in fetal mortality in C57B1/6 strain. NS PF Daily oral dose, days 6-15 of gestation No effect 20 mg/kgr 112 Cleft palate 35 mg/kg9 112 Marked increase in resorptions and "4" dead fetuses. 90-130 mg/kg9 112 �Table 7 continued Daily oral dose, day 6-15 of gestation Fetal weight reduction 10-15 mg/kg f ' h 96 Single dose during midgestation Cleft palate, maximum teratogenic effect day 12 or 13 of gestation 150-300 mg/kg 96 Daily oral dose, days 6-15 of gestation Cleft palate 30-60 mg/kg1 96 NS PF CO-1 strain OBA/2J strain C57B1/6 strain s,c. days 6-15 of gestation in a solution of DMSO at 100 yl/animal/injection Cleft palate, all three strains 100 rag/ kgJ 96 NS PF s.c. days 6-14 of gestation 50 mg/kgK 5 NS PF Kidney malformations in CO-1 strain No effect 110 mg/kg1 Teratogenic,cleft palate, rib and vertebrae anomalies, fetotoxi c ro 5 1 NS PF Savage, daily,days 6-14 of gestation Retardation in renal alkaline phosphatase in fetal kidneys, no true teratogenes i s, reduced fetal weight, cleft palate 60-120 mg/kg MS Daily oral dose,days 6-15 of gestation Toxic to females, malformations and fetal death 80-120 mg/kg 120 rag/kg1 45 Inhalation of aerosol for 10 exposures Slight maternal toxicity, fetotoxic, teratogenic 216 mg/m 3,n 45 PF m 61 �Table 7 continued Inhalation of aerosol for 10 exposures 5-15 females died 374 mg/m 3,n 45 Inhalation of aerosol for 5 exposures Toxic to females, fetal deaths 392 mg/m 3,n 45 Daily oral dose,days 6-15 of gestation Minimal fetal effects 50 mg/kg 130 Daily oral dose, days 6-10 of gestation Toxic to females, high maternal death, 4 of 25 survived, 3 had complete fetal resorptions, 1 had a litter of 13 live fetuses, toxic but no anomalies 100 mg/kg 130 Daily Oral dose,days 6-15 of gestation Fetopathy and skeletal 100-150 mg/kgp anomalies No effect at 50 and 100 mg/ 5fl , 0 ma/kaq , 9/ 9 kg. 150 mg/kg killed 3 of 8 females. 4.6, 10 or 46,4 Kidney anomalies, embryotoxi c mg/kge Rat 25, PF per test group NS PF Wistar strain Daily oral dose,days 6-15 of gestation NS PF Sprague-Dawley strain Daily oral dose,days 10-15 of gestation 74 74 26 At 46.4 mg/kg, 60% fetal mortality, many abnormalities in survivors NS PF Daily oral dose,days 1-14 of gestation Many deformities 100 mg/kg 129 Many limb abnormalities 400 mg/kg 129 �Table 7 continued Daily oral dose, days 1-16 of gestation Embryo mortality, cleft palate 50 mg/kg 129 30% embryo mortality and many anomalies 200 mg/kgs 129 No effect 0.01 mg/kgs 81 Threshold level 0.1 mg/kg 81 Toxic to female, irregular embryotoxic effect 0.42 mg/kgs 81 Toxic to female, nervous signs, embryo deaths 4.2 mg/kgs 81 Daily oral dose during pregnancy No effect No effect 25-150 mg/kgC5t 1-24 mg/kg0 Sprague-Dawley strain Gavage, daily during pregnancy No effect 24 mg/kgu 36 93 embryos Sprague-Dawley strain One -ui uteA.o injection on any one day from 12-16 days of gestation No effect 50-125 yg/kg' 76 Daily oral dose, days 6-10 of gestation No effect NS PF NS PF Daily oral dose throughout pregnancy NS PF 113 36 Golden Hamsters NS PF <100 mg/kg Fetal death, teratogenic NS PF Single intravenous dose on day 8 of gestation 20-100 mg/kg w No malformed embryos, 9% resorption - Test 6% resorption - Control 2 mg/kg r 2424 47 �Table 7 continued Rabbit NS PF Daily oral dose on days 6-18 of gestation No effect 40 mg/kgu 36 Daily stomach tube dose from 22-38 days of gestation No effect 0.05, l.O9 or 10 mg/kg 32 NS PF 3 oral doses weekly for 4 weeks between days 20-48 of gestation No effect on 12 fetuses removed by hysterectomy at 100 days gestation 5,10,20, 40° mg/kg 1 NS PF Daily dose from 14-36 day of gestation No effect 100 mg/kgr'x 11 NS PF Dosed at various periods of gestation No effect 113 mg/kg' 11 Monkey 10, PF per group Sheep en NS - number of animals in study not stated or unavailable from literature source. PF - pregnant female C 2,4,5-T acid, containing <0.1 mg/kg TCDD. s.c. - subcutaneous injection. e 2,4,5-T acid containing 30 mg/kg TCDD. f 2,4,5-T acid containing <0.02 mg/kg TCDD. 9 2,4,5-T acid containing 0.05 mg/kg TCDD h Butyl ester of 2,4,5-T, containing <0.02 mg/kg TCDD. ''z^.S-T acid, containing 1.5 mg/kg TCDD. J 2,4,5-T acid, technical grade, containing 0.5 mg/kg TCDD or analytical grade, containing <0.05 mg/kg TCDD. k 2,4,5-T acid, containing <1.0 mg/kg TCDD. 1 2,4,5-T acid containing <0.05 mg/kg TCDD. m'2,4,5-T acid, containing <0.1 mg/kg TCDD. n ButoxyethyTester of 2,4,5-T, containing <0.1 mg/kg TCDD. °2,4,5-T acid, containing 0.5 mg/kg TCDD. P 2,4,5-T acid, containing <0.5 mg/kg TCDD. q Butyl ester of 2,4,5-T, containing <0.5 mg/kg TCDD. r 2,4,5-T acid, purity not stated. s Butyl ester of 2,4,5-T, purity not stated. ^ 4 5 acid, free of TCDD. Detection level not stated. ,,^ ^2,4,5-T acid, containing 1.0 mg/kg TCDD. v Purified 2,4,5-T acid, purity not stated. w'?,4,5-T acid with oil, 0.5, 2.9 or 45 mg/kg TCDD. K Propylene glycol butyl ester of 2,4,5-T. �of 2,4,5-T in susceptible animals varied with the content of the contaminant TCDD. Levels of TCDD greater than 1 mg/kg were required to enhance the embryotoxic and teratogenic potential of 2,4,5-T. E. Carcinogenic and Tumorigenic Potentials of 2,4,5-T The industrial production of 2,4,5-T always results in some TCDD contamination, although admittedly at very low levels (<0.01 ppm) with current technology. Nevertheless, in the following review, the effects of various levels of TCDD associated with the 2,4,5-T being tested must always be considered. Innes et al (67) and the Bionetics Research Laboratories (12) reported that in groups of male and female mice receiving commercial 2,4,5-T (98 percent pure) there were no increases in any type of tumor in any group or combination of groups when compared to control animals. The treated mice were given 2,4,5-T at the dosage level of 21.5 mg/kg in 0.5 percent gelatin by stomach tube at seven days of age daily up to 28 days of age, followed by 60 mg/kg of diet until the mice were 78 weeks of age. Muranyi-Kovacs et al (92) conducted a two month study in XVII/G and C3HF mice. Beginning at six weeks of age the mice were given 2,4,5-T (containing <0.05 ppm dioxins) in the drinking water at a dosage of 100 mg/1. Following the initial two month treatment the exposure was continued throughout the animals life span by mixing 2,4,5-T directly with the diet at a concentration of 80 mg/kg. The average survival times for the XVII/6 mice was 555 days in 20 treated males and 632 days in 19 treated females, compared to 516 days in 32 control males and 40 control females. No significant differences were found in the incidences of tumors in the XVII/G strain of mice between the treated and control mice. The XVII/G strain of mice have a known high spontaneous incidence of lung tumors. In test groups of 22 male and 25 female C3HF mice studied, the average survival times were 523 days in treated males and 621 days in treated females, compared to 641 days in 43 control males and 661 days in 44 control females. The total number of tumors was 13/22 in treated males and 13/15 in treated females, which was significantly different from that in the female controls of 9/44 (P<0.01). No significance was seen when test males with tumors were compared to control males with a tumor Incidence of 22/43. The C3HF strain of mice has a known high spontaneous incidence of hepatomas. In a 1968 study (12) groups of 18 male and 18 female mice from two different crossbred strains were given single subcutaneous injections of 98 percent pure, 2,4,5-T at a dosage level of 215 mg/kg in DMSO at 28 days of age and observed up to 78 weeks of age. Tumor incidences in treated mice of any groups or combination of groups were not significantly different from any groups or combination of groups of control animals that numbered 141, 154, 157 and 161. The control animals were either untreated or were injected with DMSO, 0.5 percent aqueous gelatin or corn oil. IV-46 �Walker et al (141) demonstrated that six daily intraperitoneal injections of highly purified 2,4,5-T (99.0 percent) at the rate of 62 mg/kg effectively inhibited development of the Ehrlich ascites tumor being maintained in BALB/c mice. When the dosage of 2,4,5-T was increased to 80-85 mg/kg per day for six injections, the extent of inhibition of tumor development was doubled. From data presented in Table 8 it appeared that 2,4,5-T was not carcinogenic in most strains of mice tested at the oral dosage ranges of 21.5 mg/kg or 60 to 100 mg/kg in the diet or drinking water. Single subcutaneous doses of 2.5 mg/kg 2,4,5-T did not induce tumor formation in mice and 62 to 85 mg/kg 2,4,5-T in six daily intraperitoneal injections actually inhibited Ehrlich ascites tumor development being maintained in BALB/c mice. The only exception noted was the results reported by Muranyi-Kovacs et al (92), where treated C3HF female mice had a significantly higher incidence of tumors than did the control females. These authors stated: The carcinogenesis observed in our experiments should be attributed to 2,4,5-T per se. Nevertheless, a problem in assessing the significance of this effect was the choice of statistical analysis. Since the average survival time was different in some experimental groups, the choice of the experimental animal in assessment of carcinogenic potential is very important. For practical reasons rodents, particularly mice, are often used without scientific justification for such a choice. The problem of species specificity in the metabolism of chemical carcinogens is a known variable. The work by Gehring et al [ 4 ) on 2,4,5-T showed that the (9] kinetics of excretion of 2,4,5-T was extremely variable from one species to another. The half-life of 2,4,5*T in the plasma after a dose of 5 mg/kg was found to be 4.7 h in the rat, 77 h in the dog and 23 h in man. So the mouse being a rodent may not be the ideal experimental model for testing the carinogenicity of 2,4,5-T. Muranyi-Kovacs et al (92) further noted that in their opinion 2,4,5-T should be placed in the C group of chemical substances whose activity has been insufficiently assessed and in C2 and C3 priority groups requiring additional data, Implying that further testing in greater numbers of animals and in other species such as the rat and the dog was necessary. F. Mutagenic and Cytogenetic Potentials of 2,4,5-T As with 2,4-D, most of the mutagenic studies involving 2,4,5-T have been conducted in bacterial cultures or in plant and animal tissue cultures; however, Styles (133) investigated the cytotoxic effects of 2,4,5-T on -in vivo and Jin vi&io test systems and found no increase in IV-47 �TABLE 8. Animal Number Used Mouse . 18 Ma/18 FD of two hybrid strains 20 M/19 F XVH/G strain Summary of literature data on the carcinogenic and tumorigenic potentials of 2,4,5-T in animals Route of Administration Stomach tube, beginning at 7 days of age for 21 days, then in diet for 18 months Starting at 6 weeks of age for 60 days in drinking water, then in diet for life span Response No effect Dose . Reference 21.5 mg/kgc by stomach tube 60 mg/kg diet0 No effect 100 mg/ld for 60 days 80 mg/kg diet 5 i 22 M/25 F C3HF oo Starting at 6 weeks of age for 60 days in drinking water, then in diet for life span No effect in males, more tumors treated in females than in controls 12, 67 12, 67 92 H 92 100 mg/ld for 92 60 days 80 mg/kg diet H 18 M/18 F Single subcutaneous injections No effect 215 mg/kge in DMSO 8 sex not stated BALC/c Six daily intraperitoneal injections Inhibited Ehrlich ascites 62 mg/kg 92 tumor Doubled inhibition *M - Male 3 F - Female "2,4,5-T acid from a commercial source, TCDD level and purity not stated 80-85 mg/kg 12 141 f 141 2,4,5-T acid, containing <0.05 mg/kg TCDD "2,4,5-T acid, 93 percent pure, in dimethyl sulphoxide. 2,4,5-T acid, 99 percent pure, TCDD level not stated. �mutation rate and no evidence of mutagenicity in the test rats. He found serum from orally dosed rats was not mutagenic to SatmonMa. typhunufu.im. However, complete details of this study were not available. Jenssen and Renberg (68) found there was not a detectable increase of micronuclei in the erythrocytes of mouse bone marrow after intraperitoneal administration of 100 mg/kg 2,4,5-T containing less than 1 mg/kg TCDD. Because of the high experimental resolution power of the test system used, it was particularly suitable for the detection of weak chromosome breaking activity of 2,4,5-T in mammal cells. The lack of penetration of 2,4,5-T into the cells was in accordance with the rapid excretion that is known to occur in the mammalian body. This experiment did not, in the authors opinion, constitute a reliable measure of the mutagenic potential of 2,4,5-T; however, in practice, the lack of penetration of this substance into the cells indicated it did not constitute a cytogenetic hazard to man. In an abstract Buselmaier et al (19) reported on a large number of pesticides evaluated for mutagenic activity in mice with the hostmediated assay and to a smaller extent the dominant lethal method. These test systems took into account the mammalian metabolism and covered two different spectra of mutations: point mutations and the dominant lethal mutations which were thought to be the result of chromosomal aberrations. Back mutation systems of SaJLmonntta typhMnusuum G46 His" and SeA/uttut mot.ce4ce.n4 a21 leu" and Se/tAatLa. matce6cen4 a31 His" were used. In the host-mediated assay there was no significant increase in mutation rates after unspecified levels of subcutaneous injections of the acid or nbutyl ester of 2,4,5-T. All spot tests for this herbicide Jbi vWio was also negative. When the n-butyl ester, unspecified purity, was given to test mice by a single intraperitoneal injection, at a dose of 100 mg/kg, no increases in dominant lethal mutations were seen. Da'rving and Hultgren (30) reported that commercially available 2,4,5-T, with a TCDD concentration guaranteed on the label to contain less than 0.1 mg/kg, affected chromosomal and reproductive mechanisms in bone marrow cells from two different strains of mice. The authors concluded, however, that chromatid inter- or intra-exchanges were never observed. The study was not carried-out for sufficient time to demonstrate the effects on future generations of somatic cells. Majumdar and Hall (85) investigated the effect of 2,4,5-T -. containing no detectable TCDD, on male and female Mongolian gerbils. Test animals ranging from 50-80 days of age were given 5 consecutive daily intraperitoneal injections of 50, 150, 250, 350 or 500 mg/kg. No effects were seen on the chromosomes of bone marrow cells at doses of 150 mg/kg or less. At levels of 250 mg/kg and above, significant increases in chromatid gaps, chromatid breaks and chromatid fragmentation were observed. No exchange figures or isochromosome gaps or breaks were reported. IV-49 �Fujita et al (46) conducted studies to examine the cytogenetic effects of high purity 2,4,5-T (0.09 mg/kg TCDD) at levels of 10-' to 10-14 M on human lymphocytes in vWio. Breaks, deletions and rings were observed. Chromatid breaks increased with increasing concentrations of 2,4,5-T; however, it was not possible to distinguish if this effect was due to cellular toxicity or to a potential genetic alteration. Andersen et al (4) evaluated 110 herbicides for their ability to induce point mutation in one or more of 4 different microbial systems. The herbicide 2,4,5-T was included in this study. The authors did not state the purity of the compounds being tested. The 2,4,5-T did not cause point mutations in these microbial systems in comparison with known mutagens such as 5-bromouracil or 2-aminopur1ne. These observations of no mutagenicity of 2,4,5-T in E&che/tichia. aotL WP2 her* or her" or in Salmonella. typhirrwuum strains TA1535, TA1536, TA1537 or TA1538 were also confirmed in works by Nagy et al (94), Shirasu (136) and Shirasu et al (127). A review of the literature on the mutagenic and cytogenic potentials of 2,4,5-T in animals generally supported the premise that 2,4,5-T, like 2,4-D, was not highly cytotoxic in laboratory animals. The herbicide did not increase mutation rates nor stimulate a mutagenic response in rats and mice. In various in \)Wio and in vivo test systems 2,4,5-T did cause chromatid aberrations in cultured human lymphocytes and affected the chromosomes and reproductive mechanisms in mouse and hamster bone marrow cells. It was not determined whether these affects were due to cellular toxicity or to a potential for genetic alteration of future generations of somatic cells. No mutagenic responses were seen in several studies using microbial systems for the detection of mutagenic and cytogenic responses to 2,4,5-T. IV. REVIEW OF TCDD TOXICITY IN ANIMALS A. The Acute and Short-Term Toxicity Potentials of TCDD Studies on the extremely high acute toxicity of TCDD, the most toxic of the chlorinated dibenzo-p-dioxins, have been conducted by Carter et al (21), Greig et al (53), Gupta et al (56), Harris et al (59), King et al (76), Kociba et al (77), McConnell et al (87), Schwetz et al (121), Vos et al (140) and Zinkl et al (148). Schwetz et al (121) noted that perhaps the most striking fact about TCDD was its ability to cause death after a single'oral dose at levels as low as 0.6 yg/kg in male guinea pigs or 1000 yg/kg in the dog. Lethal doses to rabbits were in the same dose range with either oral (115 yg/kg), intraperitoneal (>252 yg/kg), or skin (275 yg/kg) administration. In mice, single oral doses of 1 to 130 yg/kg produced some deaths, however, no dose-response relationship was established. Schwetz et al (121) noted that approximately half the deaths in mice occurred between 13 and 18 days after treatment. IV-50 �Poland and Kende (108) considered TCDD to be one of the most potent low molecular weight toxins and teratogens known. They noted that most poisons act rapidly and kill by impairing the physiologic function of the nervous system. TCDD in contrast, is a "cellular poison." In the rat, deaths appeared to have resulted from hepatic necrosis and ensued weeks after a single oral dose. Harris et al (59), Schwetz et al (121), and Vos et al (140) also noted TCDD produced hepatic cell necrosis that was the probable cause of death in the rats in their studies. They also noted that in mice and guinea pigs, hepatic cell necrosis and liver insufficiency occurred only minimally. Putnam and Courtney (109) treated female Wistar rats with single oral doses of 100 yg/kg TCDD and found it caused a biphasic decline in body weight with a cessation of food and water consumption and urine production. The first phase started immediately after dosing and lasted 7-10 days followed by a recovery from 4-6 days during which time the rats ate and drank and regained about 10-15 percent of their body weight. This was followed by a second phase which occurred at 16-24 days after treatment with a weight loss of about 15-30 percent. If the loss of body weight exceeded 30 percent the rats usually died. Daily administration of water, electrolyte solution, or a balanced liquid diet did not alter or reverse the biphasic response. Cunningham and Williams (28) treated groups of 12 to 16 weanling male Wistar rats with single oral doses of 0 or 10 yg/kg TCDD. This was close to the lethal dose for when this amount was given orally to rats each day in a preliminary experiment, all died within 2 to 4 days. The lowest level in a single dosage that caused an increase in liver weight of rats in the preliminary study was 0.1 yg/kg. The TCDD had no effect on the rate of incorporation of ^H-acetate into liver lipids; however, it may have restricted the transport of lipids out of the liver. The storage of lipids reached a maximum at about 3 days after the TCDD was given and was accompanied by a significant increase in the incorporation of 14C-leucine into liver proteins. The increased synthesis of all proteins may have resulted from an induction of liver enzymes by TCDD. Harris et al (59) found the mortality pattern was very near the same in rats and guinea pigs when TCDD was given as a single oral dose or divided into daily or weekly doses over a 4 to 5 week period. He noted that this mortality pattern could be interpreted as demonstrating a cumulative toxicity from the TCDD. In rats, guinea pigs and mice, changes in the weight of the thymus appeared to be the most sensitive indicator of TCDD exposure according to work by Harris et al (59). These decreases in thymus weight occurred with doses of TCDD that had no effect on body weight. Van Miller et al (137) produced high levels of TCDD in the skin of rhesus monkeys by giving a single intraperitoneal injection of 400 yg/kg TCDD and produced clinical signs of alopecia and acne. IV-51 �A summary of the literature on the LDcn levels of the acute toxicity of TCDD for animals is presented in Table 9. TCDD was found to be an extremely toxic compound with an oral LDso range of 0.6 yg/kg in male guinea pigs to 115 yg/kg male and female rabbits. Male rats appeared to be more sensitive than females when TCDD toxicity was studied in the Sherman (Spartan) strain rat. In rabbits, essentially similar dosage levels of TCDD caused death following either intraperitoneal, oral or skin administration. Limited studies on dogs suggested that tltsy were less sensitive to TCDD than were the other laboratory animal species studied. In all species studied however, reduction in body weight was a common finding following TCDD treatment while other signs of toxicity were species dependent. B. The Subacute and Chronic Toxicity Potentials of TCDD Subacute and chronic doses of TCDD produced a variety of toxic effects, including hepatic necrosis, thymic atrophy and lesions of the myocardium in rats (20, 56), thymic atrophy, depletion of lymphoid organs and hemorrhage and atrophy of adrenal zona glomerulosa in guinea pigs (56) and hepatic necrosis in rabbits (120). The main target organs of TCDD in rats, guinea pigs and mice appeared to be the liver and thymus (56, 69, 70, 139, 140). The degree of hepatic involvement appeared to be dose dependent and the severity of the changes produced varied between species (56). A single oral dose of 126 yg/kg TCDD resulted in loss of body weight and death with an enlarged fatty liver after 21 days in C57B1/6 mice. A progressive necrotic centilobular liver lesion was seen (71). Vos and Moore (139) studied pre- and postnatal effects of TCDD in*groups of 5, 6 and 5 pregnant C57B1/6 mice dosed at 0, 2 or 5 yg/kg TCDD on days 14 and 17 of gestation and postnatally on day 1, 8 and 15. All neonates were weaned on day 23 and used for a skin graft experiment. This treatment resulted in a severe depletion of lymphocytes in the thymic cortex of the offspring. Cellular immunity was impaired and allograft rejection times were prolonged. Murray et al (93) conducted a three generation reproduction study to evaluate the effects of chronic, low-level ingestion of TCDD in Sprague-Dawley rats administered daily doses of 0, 0.001, 0.01 or 0.1 yg/kg provided via the diet for 90 days. No signs of toxicity were noted in either male or female rats during the TCDD feeding study. Vos et al (140) found the most significant findings in both mice and guinea pigs treated with sublethal doses of TCDD were in the lymphoid system where there was a supression of cell mediated immunity at doses of 2 and 5 yg/kg TCDD. Thigpen et al (134) found that low levels of TCDD did not produce overt clinical or pathological changes, however, these low levels IV-52 �Summary of literature data on the no-effect, LD5Q and levels of the acute toxicity of TCDD for animals TABLE 9 . Animal Number Used Route of Admin. Dose-Toxicity Single Dose yg/kg Reference >50 59 1-130 T21 Mouse 10 CD-I strain C57Bl/6Sch strain LD NSa Oral A few sporadic deaths 29 Mb C57B1/6 strain Oral LD 150 50 M NS T ) Oral Intraperitoneal LD 120C 138 5 M Oral No effect 8 121 5 M Oral No effect 16 121 10 M Oral LD 32 121 Oral 25 M Sherman (spartan) strain LD 22 121 Oral LD 45 121 100 100 50 Rat NS F strain 100 50d 50d �Table 9 continued Guinea Pig NS M Oral NS M Hartley strain 50 .6 2.1 121 121 Rabbit NS M/F 5 M/F 5 M/F 5 M/F 5 M/F New Zealand albino Oral Topically to skin Intraperitoneal Intraperitoneal Intraperitoneal LD 50e LD 50e No effect 2 of 5 died 3 of 5 died 115 121 275 121 32 121 >252 121 500 121 300 121 3000 121 30 121 100 121 <70 87 Dog 2 M 2 M 2 F 2 F Beagles 100 No effect No effect 1 F Rhesus I en Oral Oral Oral Oral Oral LD No effect LD Monkey 50f NS - Number of animals in study not stated or unavailable from literature source M - Male 3 "3H-TCDD A calculated LD50 cn "Responses to individual doses when ID™ could not be calculated Correlated the acute LD™ of TCDD with the clinical and pathological manifestations - not true calculated '50 LD50 �reduced host defenses. When 1 ug/kg was given orally once a week for 4 weeks to mice before infection with SaJtmon&JUa be/m, an increased mortality and decreased time from infection to death was noted. Weissberg and Zinkl (142) and Zinkl et al (148) noted hematological changes in mice, rats and guinea pigs treated with TCDD including lymphopenia and thrombocytopenia at dosage rates of 0.004 to 10 ug/kg for various repeated doses. Goldstein (50) gave TCDD orally to mice once a week over a 4 week period at a dosage of 25 ug/kg and found a 2,000-fold increase in the levels of 8- and 7-carboxyporphyrins in the liver. In a 13-week feeding study by Kociba et at (77), Sprague-Dawley rats of both sexes were given 0.001 or 0.01 ug/kg TCDD five days per week. A slight increase in relative liver weight occurred in those animals receiving 0.01 ug/kg TCDD. A steady state concentration of TCDD was attained in body tissues by the end of the study. Vos and Moore (139) in a pre- and postnatal study, treated groups of 5, 4 and 6 pregnant Fisher-334 rats with 0, 1 or 5 ug/kg TCDD prenatally on days 11 and 18 of gestation and postnatally on days 4, 11 and 18 via gastric intubation. Most of the neonates in the 5 ug/kg group 'died. Only the spleens of 25-day-old male animals from the 0 and 1 ug/kg groups were used for immunologic studies. At 1 ug/kg the pups had a depressed body and spleen weight. At 5 ug/kg, in those pups that survived, the body and spleen weights were depressed and the thymus was severely affected with marked depletion of lymphocytes in the thymic cortex. Cellular immunity was impaired with allograft rejection times being prolonged. Schwetz et al (121) found that solutions of 0.04 ug TCDD/ml of benzene was acnegenic in a rabbit ear bioassay study where the solution was applied to the inside of the ear 5 days per week for four weeks. Norback and Allen (98) fed fat, containing unspecified concentrations of chlorinated dibenzo-p-dioxins in the diet, to Macaco, mulatta monkeys for 100 days and found the monkeys developed alopecia, subcutaneous edema, anemia, progressive leukopenia and hypoproteinemia. Enlargement of the liver, hydropericardium, gastric hyperplasia and ulceration as well as hyperplasia of the lymph tissue and bone marrow was noted in the treated monkeys. Allen et al (2) found that female rhesus monkeys given a diet containing 500 ng/kg TCDD for 9 months became anemic within 6 months and pancytopenic after 9 months of exposure. Marked thrombocytopenia was associated with widespread hemorrhage. Death occurred in five of the eight animals between months 7 and 12 of the experiment at total IV-55 �exposure levels of 2-3 yg/kg TCDD body weight. At autopsy, in addition to the hemorrhage, there was a distinct hypocellularity of the bone marrow and lymph nodes. Death of these monkeys was attributed to complications from the severe pancytopenia. McNulty (89) fed one rhesus monkey a diet containing 2 yg/kg TCDD and another monkey a diet containing 20 yg/kg TCDD. The first animal died within 76 days, while the second animal died in 12 days. McNulty noted that although responses in two animals scarcely provided data for a dose-response curve, two conclusions could be drawn: (a) a total TCDD dose of less than 10 yg/kg of body weight accumulated over a few weeks period, and (b) young rhesus monkeys were among the most TCDDsusceptible animals of those that have been tested. A summary of literature data on the subacute and chronic toxicity of TCDD in animals is presented in Table 10. Subacute and chronic doses of TCDD produced a variety of toxic effects, including hepatic necrosis in mice, rats and rabbits; thymic atrophy in mice, rats and guinea pigs with adrenal gland hemorrhages and depletion of lymphoid organs also being seen in guinea pigs. Repeated oral doses of 0.001 to 10 yg/kg TCDD for four to 13 weeks did not significantly affect weight gain nor were signs of toxicity noted in mice and rats. Suppressed immune responses and changes in liver enzymes were noted, however, in mice. Repeated doses of TCDD as low as 1 yg/kg caused guinea pigs to become moribund and repeated doses of 0.04 yg/kg decreased lymphocyte counts. Rabbits developed acne of increasing severity when doses of 0.04 to 400 yg/kg were applied repeatedly to the internal surface of the ear. A total oral dose of 2-3 yg/kg over a nine month period produced severe hematological changes and death in rhesus monkeys. C. Absorption, Distribution and Excretion of TCDD Following a single oral administration of 50 yg/kg ^C-TCDD to rats, Piper et al (102, 103) found that almost 30 percent was eliminated in the feces during the first 48 h. The half-life for the disappearance of 14c activity from the body was 17.4 ± 5.6 days. After this time the excretion of ^C activity via the feces was from 1-2 percent per day. As the l^C-TCDD was absorbed into the body tissues most of the activity was localized in the liver and fat at levels about 10 times higher than that in other tissues. A total of 53.2 percent of the dose was eliminated via the feces and 13.2 percent via the urine, while 3.2 percent was expired into the air when measured over a 21 day period. Rose et al (114) found that, following daily oral administration of 0.01, 0.1 or 1.0 yg/kg l^c-TCDD five times per week for seven weeks to Sprague-Dawley rats» the major route of excretion was via the feces. Urine contained 3-18 percent of the cumulative dose of 14C activity after the seven week treatment. The half-life of 14C activity in the rats studied was 23.7 days. IV-56 �TABLE 10. Animal Mouse Number Used Summary of literature data on the subacute and chronic toxicity of TCDD in animals Route of Administration 377 Ma Once per week by gastric tube C57Bl/6JFh for 4 weeks (J67) strain Specific Pathogen free Effect Dose No effect on weight gain 0.5, 1, 5 and 10 yg/kg 134 Significant decrease in weight gain 20 ug/kg 134 Reference NSC F CD-I 134 1 yg/kg and Significant increase in mortality of mice challenged greater wi th Salmonella bern 5-6 per group C57Bl/6Sch FD strain d C57B1/6 M strain 134 No effect on mice challenged 0.5 ug/kg wi th Salmonella bern en No effect, on mice challenged 0.5, 1, 5, 10 and 20 ug/kg with Herpesvirus suis 134 2 yg/kg Oral dose given days 14 and 17 of gestation and postnatal ly on day 1, 8 and 15 No effect on weight gain Single oral dose after 8 weeks of age Hematological changes at 1 week after dose; normal at 3 weeks 1, 10 or 50 yg/kg 2000 fold increase in carboxyporphyrins in the liver 25 yg/kg 12 M Oral dose once per week for C57B1/6 strain Four weeks Suppressed cellular immunity 2 or 5 yg/kg 140 140 143 50 �Table 10 continued Rat NS M/F Sprague-Dawley strain Daily oral dose for 90 days No signs of toxicity NS M/F Sprague-Dawley Daily oral dose, 5 days per week for 13 weeks No toxicity, slight increase 0.001 or 0.01 in relative liver weight at yg/kg 0.01 yg/kg NS F CO strain Daily oral dose for 30 days Liver enzyme changes and hematological changes 10 yg/kg 148 Weekly oral doses for 8 weeks Moribund at 3 to 5 weeks 1.0 yg/kg 148 Significant decrease in lymphocyte counts 0.04 yg/kg 148 Applied to inside of ear, 5 days per week for 4 weeks in a .1 ml volume Acne with increasing severity as dose was increased 0.04 to 400 yg/kg 121 NS Macaca mulatta Fed fat containing 64% mass tetrachlorinated compounds in diet for 100 days Multiple toxic signs Unknown 8 F Macaca mulatta Fed in diet for 9 months Hematologic changes, 5 animals died 500 ng/kg of diet 2-3 yg/kg total exposure 0.001, 0.01 or 0.1 yg/kg 93 77 Guinea Pig NS F Hartley strain en 00 Rabbi t Monkey 98 �Table 10 continued 2 Macaca mulatta d Fed in diet Death in 12 days Death in 76 days M - Male b F - Female C NS- Number of animals in study not stated or unavailable from literature source Ul 20 yg/kg diet 2 jig/kg diet 89 89 �Allen et al (2) treated 40 male Sprague-Dawley rats with a single intragastric dose of 50 yg/kg of 14C-TCDD. One-half of the animals died within 25 days, 25 percent being accounted for during the first 3 days. The total amount of radioactivity in the urine was 4.5 percent of the total dose, with the highest daily levels being excreted toward the end of the experiment. A large percentage of the remaining radioactivity was localized in the liver and of this over 90 percent was located within the microsomal fraction. Fries and Marrow (44) found the half-life to be 12-15 days in rats given 7 or 20 yg/kg Mc-TCDD of diet (equivalent to 0.5 or 1.5 ya/kg per day) for 42 days. *, Vinopal and Casida (138) administered 3H-TCDO by a single intraperitoneal injection to male mice at the LDso dose of 120 yg/kg and found that it was not measurably converted to water soluble products and was eliminated primarily in the feces. Traces of tritium activity were detected in the urine. A large proportion of the administered dose persisted in the unmetabolized form in the liver, partially concentrated in the microsomal fraction for 11 to 20 days after treatment. The 3H-TCDD was not metabolized by liver microsomal fractions from mice, rats or rabbits. Gasjewicz and Neal (48) studied the tissue distribution and excretion of 14C-TCDD in adult male guinea pigs for up to 15 days following its intraperitoneal injection of 2.0 yg/kg. On day 1 the highest levels of radioactivity were located in the adipose tissue 2.36 percent, adrenals 1.36 percent, liver 1.13 percent, spleen 0.70 percent, intestine 0.42 percent and skin 0.48 percent. 14 other tissues examined contained less All than 0.3 percent. The level of C-TCDD 1n the liver Increased to 3.23 percent on day 15. An increase in 14C-TCDD was also noted in the adrenals, kidneys and lungs while adipose tissue and skin decreased in radioactivity. For the 15 days of the experiment the total urinary and fecal excretion of radioactivity was less than 1 and 5 percent respectively. The effects of 1.0 yg/kg TCDD upon plasma levels of Na, K, Cl, 003, Fe, Ca, inorganic P, alkaline phosphatase, SGOT, SGPT, LDH, glucose, urea nitrogen, creatinine, uric acid, total protein, albumin, cholesterol, triglycerides and bilirubin were determined periodically up to 14 days and compared to pair-fed control animals. Statistically significant increases in plasma albumin, total protein, Fe, urea nitrogen, cholesterol and triglycerides were observed in the TCDD-treated guinea pigs. The primary route of excretion for TCDD in animals appeared to be the feces, with urinary excretion occurring at a much reduced rate. Liver and fat accumulated about 10 times higher levels of TCDD than did other body tissues. The half-life for TCDD in rats following a single or repeated exposure was 12-24 days after termination of treatment. Large proportions of an administered dose of TCDD remained unmetabolized in the liver microsomes and were slowly excreted over an extended period. IV-60 �D. Embryotoxic, Fetotoxic and Teratogenic Potentials of TCDD The embryotoxic and teratogenic effects of TCDD in mice have been described by Courtney and Moore (27), Neubert and Dillmann (96), Neubert et al (97), and Smith et al (128) where doses as low as 1-10 ug/kg» given in a single or repeated dose, caused significant increases in the frequency of cleft palate and kidney anomalies. Neubert (95), and Neubert et al (97) noted a dose-response relationship for producing cleft palates in mice with TCDD. They also observed increased incidences in the frequency of cleft palate in mice,1 apparently caused by the synergistic effect of combining 'sub-threshold and 'threshold1 levels of TCDD with similar low levels of other known teratogens such as the weak teratogen 2,4,5-T when administered during days 6-15 of gestation. Moore et al (91) confirmed that exposure to TCDD via the milk was a major factor in the development of renal hydronephrosis in mouse pups when the nursing dam received a single oral dose of 1, 3 or 10 ug/kg TCDD at parturition. This effect was also seen in mouse pups nursed by a foster mother treated with TCDD during pregnancy or at the time of parturition. The common etiology of these kidney anomalies, whether prenatal or postnatal, was TCDD interference with development of the metanephric kidney and/or subsequent maturation. The incidence and degree of hydronephrosis was a function of dosage and length of target organ exposure. The dose effecting 50 percent of the test organisms (£050) for cleft palate production in NMRI mouse pups was estimated by Neubert et al (97) to be 40 ug/kg TCDD per day. The no effect level during days 6 to 15 of gestation was estimated at 2 ug/kg TCDD per day with no pronounced fetal mortality occurring when 3 ug/kg TCDD was given from day 6 to day 15 of gestation. Becker (8) has concluded that the influence of a teratogenic substance closely related to the critical developmental period of a particular tissue or organ. After this critical period passed, damage to other tissues may have occurred even if no significant malformations were observed. Unspecified doses of TCDD produced an extremely fatty degeneration of the liver in adult female rats when they were treated on days 13 to 15 of gestation. Fatty inclusions were seen in the liver of embryos from these treated females; however, no structural anomalies were noted in any of the embryo livers. Courtney and Moore (27) produced cleft palates in three strains of mice by giving 1 or 3 ug/kg TCDD subcutaneously on days 6 to 15 of pregnancy, while Courtney (25) found TCDD to be the most fetotoxic and teratogenic of several dioxin compounds when given at 25, 50, 100, 200, and 400 ug/kg per day orally and 25, 50, 100, 200 ug/kg per day subcutaneously IV-61 �in CD-I mice on days 7 to 16 of pregnancy. Fetal mortality increased with the dose: up to 97 percent in orally treated dams and up to 76 percent in dams receiving subcutaneous administration of the highest levels of TCDD. Other anomalies observed were hydrocephalus, lack of eyelid formation (open eye) and clubfoot with edema and internal hemorrhages being noted in fetuses of dams receiving the highest doses. Smith et al (128) administered 0.001, 0.01, 0.1, 1.0 and 3.0 wg/kg TCDD per day to CF-1 mice by gavage from days 6 to 15 of pregnancy. Only at the 1.0 yg/kg dose was the percentage of resorption sites per implantation sites significantly higher than in the control animals. At 3.0 ug/kg, cleft palate occurred in 71 percent of the treated litters and at 1.0 yg/kg, 21 percent had cleft palate. Renal anomalies*occurred in 28 percent of the litters treated at 3.0 yg/kg and in 5 percent of the litters treated at 1.0 yg/kg. No significant anomalies were seen at the other dosage levels. Embryo lethal effects have occurred in rats under experimental conditions imposed by Sparschu et al (131). Courtney and Moore (27) have observed kidney anomalies in rats, while Khera and Ruddick (75) observed intestinal hemorrhages and general edema in rat fetuses when oral or subcutaneous doses ranging from 0.03 to 16.0 yg/kg TCDD were administered daily to dams on days 6 to 15 of gestation. Sparschu et al (131) administered 0.03, 0.125, 0.5, 2.0 and 8.0 yg/kg TCDD per day to Sprague-Dawley rats on days 6 to 15 of gestation. At 8.0 yg/kg per day all fetuses were resorbed. Fetal weights were significantly (p<0.05) depressed at the 0.125 and 2 yg/kg per day level. Internal hemorrhages were observed at the 0.125, 0.5 and 2.0 yg/kg per day level. No adverse effects were noted in the fetuses of dams treated at the 0.03 yg/kg per day level. The authors suggested that 0.03 yg/kg per day was the no effect level for fetal and embryotoxic effects in rats. Khera and Ruddick (75) studied the perinatal effects of TCDD in Wistar rats in a two part experiment by giving daily oral doses of 0.125, 0.25, 0.5 and 1.0 yg/kg TCDD on days 6 to 15 of pregnancy. Visceral lesions were observed at 0.25 yg/kg per day and above with slight decreases 1n fetal weight also being observed. Postnatal effects of prenatal exposure to TCDD were studied by allowing offspring of treated dams to be reared by untreated dams until weaning. At maternal levels of 0.5 and 1.0 yg/kg per day, reduced survival, lowered body weight and reduced reproductive ability in the offspring were observed. At levels of 0.125 yg/kg per day no fetotoxic effects were observed. In the second part of the Khera and Ruddick study (75), rats were treated with daily oral doses of 1, 2, 4, 8 and 16 yg/kg TCDD on days 6 to 15 of pregnancy. At doses of 1.0 and 2.0 yg/kg per day, visceral lesions, reduction in fetal weight, and lowering of the number of live fetuses per litter were observed. Doses of 1 yg/kg per day or more IV-62 �produced maternal toxicity with all doses of 4 ug/kg or more producing 100 percent embryo lethality. The fetotoxic no effect level in Wistar rats appeared to be 0.125 ug/kg per day with any level of 0.25 ug/kg per day or more on days 6 to 15 of pregnancy adversely affecting fetal rat development. Courtney and Moore (27) administered TCDD to CD rats at the rate of 0.5 ug/kg per day subcutaneously in solutions of 100 percent DMSO on days 6 to 15 of gestation. Kidney anomalies were seen in 67 percent of the litters of treated females. At this level, TCDD did not affect fetal mortality or fetal weight, nor were cleft palates observed in any of the fetuses. • A summary of literature on the etnbryotoxic, fetotoxic and teratogenic potentials of TCDD in animals is presented in Table 11. It was apparent that TCDD caused birth defects and embryo mortality. Repeated daily oral doses of 0.1 to 2 yg/kg in pregnant mice produced no effect on the embryos; however, 3 ug/kg was the threshold level for production of cleft palate and kidney abnormalities. Single or repeated oral doses of 6.5 to 40 ug/kg TCDD were required to produce cleft palate in 50 percent or more of some strains of mouse embryos being studied. Daily subcutaneous injections of 1 to 3 ug/kg TCDD produced cleft palate and kidney abnormalities in 50 percent or more of three different strains of mouse embryos studied. Repeated oral doses of 25 to 400 ug/kg TCDD produced increasing fetotoxic and teratogenic responses in mice. Repeated daily oral doses of 0.03 to 0.125 ug/kg TCDD produced no effect in some strains of rat embryos while repeated oral doses of 0.125 to 2 ug/kg TCDD depressed fetal weight, lowered fetal survival and caused internal hemorrhages in fetuses. Repeated daily oral doses of 4 to 8 ug/kg TCDD produced 100 percent fetal mortality in rats. Signs of embryo toxicity and fetal death occurred in rats more frequently than did any signs of teratogenicity. When teratogenic lesions did appear in rats, kidney abnormalities were more common than cleft palate. E. Carcinogenic and Tumorigenic Potentials of TCDD In a preliminary report by Toth et al (135), 50 ten-week old male random bred Swiss H/Riop mice received gastric intubations of 7 ug/kg TCDD in sunflower oil for 12 months. No tumors were observed in 19 mice receiving post mortem examinations at the end of the treatment period. The livers from three animals showed histological evidence of cirrhosis and eight animals had developed dermatitis and showed histological evidence of increased amyloid in the tissues. Weekly doses of 0.007 and 0.7 ug/kg TCDD were given for 12 months to similar groups of mice. No pathological lesions were observed in five animals killed two months after the end of treatment. All surviving mice were kept for life-span studies and observation for the development of tumors. IV-63 �TABLE 11. Summary of literature data on the embryotoxic, fetotoxic and teratogenic potentials of TCDD in animals Mouse 700 total /PFa NHRI strain, 7000 fetuses examined 100 total/PF Route of Administration Response Dose yg/kg References Daily oral dose, days 6-15 of gestation No effect 96 CP - ED5Qd 2 (estimated) 3C 6.5 96 96 Daily oral dose, days 9-13 of gestation , Animal Number Used CP CP - ED5Qd 9C <9 96 96 Single oral dose, day 13 of gestation CP 15C 97 97 K D CP - Threshold CP 40 ED - 50 5C Single oral dose, day 11 of gestation 01 35 litters total from CD-I, DBA/2 J, and C57B1/60 strains CP Daily doses given subcutaneously on days 6-15 of gestation CD-I - CP effect, 1 litter only - CP, Threshold - CP, ED50 - KAe, Threshold - KA, ED5Q CP 15 ED * 50 DBA/ 20 - CP, Threshold 1 3C >3 c lc 1 -3 3C 97 97 27 27 27 27 27 - CP, ED5Q >3 - KA, ED5Q >3 27 27 27 27 C57B1/6J - CP, Threshold 3C >3 c 3C <3 27 27 27 27 - KA, Threshold - CP, ED50 - KA, Threshold - KA, ED50 c 3C �Table 11 continued 17 PF 19 PF Daily oral dose, days 7-16 of gestation Fetotoxic, teratogenic, increasing w/dosage up to 97% at highest dose 25, 50, 100, 200, and 400 25 Daily dose given subcutaneously on days 7-16 of gestation 31 PF CD-I strain Fetotoxic, teratogenic, increasing w/dosage up to 76% at highest dose 25, 50, 100, and 200 25 Daily oral dose, by gavage, days 6-15 of gestation No effect 0.1 128 Increased fetal resorption sites, 21% CP, 5% KA 1 128 71% CP, 28% KA 3 128 14 PF 18 littersf Single oral dose, day 10 of gestation No effect, CP 34% KA 1 91 16 littersf Daily oral dose, days 10-13 of gestation 1.9% CP 58.9% KA 1 91 14 littersf Daily oral dose, days 10-13 of gestation 55.4% CP 95.1% KA 3 91 NS9/fetuses Females given oral dose at parturition Renal hydronephrosis, 12, 71 or 75% depending on dose Daily oral dose, days 6-15 of gestation No effect 0.03 131 Depressed fetal weight 0.125 and 2 131 Internal hemorrhages in fetuses 0.125, 0,5 or 2 131 All fetuses died 8 131 cr> en ,il, 3 or 10 91 Pat 51 total/PF Sprague-Dawley (Spartan) strain �Table 11 continued 103 total/PF Daily oral dose, days 6-15 of gestation 0.25 75 0.5 and 1 75 Visceral lesions, reduced fetal weight, increased fetal death with maternal toxicity 1 and 2 75 100% embryo death en 75 Reduced fetal survival, lower body weight and lowered reproductive ability in progeny Daily subcutaneous dose, days 6-15 of gestation 0.125 Slight decrease in fetal wei ght 6 PF 48 fetuses CD strain No effect 4 75 No effect on fetal mortality 0.5 or CP 67% KA PF - Pregnant Female CP - Cleft palate b °Lowest dose with which a significant teratogenic effect has been produced. In some cases this is the only dose level tested and does not necessarily represent the lowest dose which could result in teratogenic effects.. EDg0 - Dose required to produce an effect in 50% of animals g KA - Kidney abnormalities f C57Bl/6 strain 9 NS - Number of animals in study not stated or unavailable from literature source Dose given in 100 percent dimethylsulfoxide solution (DMSO) 27 �Van Miller et al (136) recently reported the results of a two year study where ten groups of 10 male Sprague-Dawley rats were fed a laboratory diet-containing 0, 1, 5, 50, 500 or 1,000 yg/kg TCDD of food or 1, 5, 50 or 500 ng/kg TCDD of food for 78 weeks. All rats receiving the 50, 500 or 1,000 yg/kg TCDD of food died between the second and fourth week of treatment. In seven remaining groups, only one animals died before the 30th week and that death occurred in the 500 ng/kg TCDD of food at the 17th week. In the 1 and 5 yg/kg TCDD of food groups, all animals died between the 30th and 90th weeks of the experiment. The number of animals dead at the 95th week of the experiment were: 0 dose 6/10, 1 ng/kg 2/10, 5 ng/kg 4/10, 50 ng/kg 4/10, 50 ng/kg 4/10 and 500 ng/kg 5/10. Those animals surviving after the 95th week were killed and subjected to complete necropsy examinations. In all rats surviving past the 65th week laparotomies were performed and biopsies of any tumors were taken. After the 78th week on treated diets, the rats were placed on the same diet used to feed the control animals. Tumorigenie and toxic effects were observed in rats from the lowest six dosage groups. The overall incidence of neoplasms in these six experimental groups was 23/60 (38 percent) compared with 0/20 (0 percent) in both the 1 ng/kg and the control groups. Neoplastic nodules and cholangiocarcinomas of the liver were observed in 40 percent of the rats ingesting 5 yg/kg TCDD of food; two animals had both neoplastic nodules of the liver and cholangiocarcinomas, Van Miller et al (136) also found that tumors developed in 24/50 (46 percent) of the rats ingesting 5, 50 or 500 ng/kg TCDD-of food and 1 or 5 yg/kg TCDD of food, compared to none (0/10) in the control animals. The tumors seen were carcinomas of the ear duct, kidney and liver. Three retroperitoneal histiocytomas were described as metastasizing to the "lungs, kidney, liver and skeletal musculature." Three of the ten deaths which occurred in the 5 yg/kg TCDD of food dose group were attributed to aplastic anemia. One animal in the 500 ng/kg TCDD of food group had a severe liver infarction. Kociba et al (78) conducted a chronic study of TCDD toxic effects to Sprague-Dawley rats fed 0.1, 0.01 or 0.001 yg/kg TCDD daily for two years to groups of 50 rats of both sexes. Eighty-six animals of each sex served as controls. Discernible increases were noted in the incidence of hepatocellular carcinomas of the liver and of squamous cell carcinomas of the lung, hard palate/nasal turbinates and tongue in rats fed at the rate of 0.01 yg/kg. They also reported decreased incidences of pituitary, uterine, mammary gland, pancreatic and adrenal gland tumors at the 0.01 yg/kg level. The squamous cell carcinoma of the hard palate observed in one female rat receiving this dose was considered unrelated to TCDD treatment since a similar tumor had occurred in other unrelated studies. At 0.001 yg/kg TCDD, no significant lesions were seen in male rats and the only lesion of significance in female rats at the 0.001 yg/kg TCDD was swollen hepatocytes, considered to be a reversible lesion. IV-67 �Many chemically nonreactive carcinogens ai-e eiizymaLiu-a I ly converted to biologically active carcinogens. The enzyme aryl hydrocarbon hydroxylase (AHH) has been strongly implicated in this process (86). Kauri et al (32) studied AHH induction in human lymphocyte cultures by TCDD. The authors stated; TCDD itself is not a potent carcinogen in mice; however, the synergistic action of TCDD with 3-methylcholanthrer.e (MC) produces cancer in different strains of mice in direct proportion to the degree of elevation of the induced hy/droxylase activity and associated cytochrome content. Their study showed a positive correlation between basal enzyme activity and enzyme levels maximally inducible by either TCDD or MC. They also found that TCDO WAS about 40 to 60 times more potent than MC as an inducer of hydroxy/lase activity in cultured human lymphocytes. The implication, of TCDD in AHH inducibility had also been reported t>y Poland and Glover (105, 106) and Poland et al (107) in their studies on chick embryo livers. They found that all dioxins which were potent inducers have halogens at three of the four lateral ring positions and at least one noft-halagenateti carbon atom. When TCDD potency, as an inducer of hepatic AHW activity » was compared with that of MC by a computer bioassay technique, data reflected that TCDD may be 28,640 times as potent as MC on a molar basis. Allen et al (2) conducted a study in which female rhesus monkeys were fed diets containing 500 ppt TCDO for nine months. Anemia, thrombocytopenia and leuikapenia were the most debilitating changes noted. The altered, lymphopoiesis cotild be associated with immune suppression. Epithelial changes, including hypertrophy, hyperplasia, and metaplasia were reported in these TCDD exposed monkeys. A summary of the literature on the carcinogenic and tumori genie potentials of TCDD in animals is presented in Table 12. It was noted that in a preliminary study where O.Q07, O..Q7 and 7 yg/kg TCDD was given in weekly oral doses for 12 months to. mice* no tumors were produced. In "'ats, levels o>f 1 and! 5 wo/kg TCDO of diet and; 1, 5, 50 and 500 ng/kg 1CD0 of diet fed for 78 weeks produced an overall tumor incidence of 38 percent in the test amiraals. At 0.001 ug/kg TCDD, given via the diet to rats far 2 years, nS effect was produced. A level of 0.01 yg/kg TCDD given via the diet to rats* for 2 years, produced liver nodules and hyperplasia of the epithelium of the lungs. An increase in liver and lung carcinomas was seen when O.I ug/kg TCDD was fed to rats for 2 years via the diet. An interesting unexplained observation, however, was the reduction of pituitary, uterine, niaranary/,, pancreas and adrenal tumors. Monkey/s fed 500 n§/k§ TCDO of diet for 9 months did not develop tumors but died of marked hetnatological alterations. IV-68 �TABLE 12. Animal Number Used Summary of literature data on the carcinogenic and tumorigenie potentials of TCDD in animals Route of Administration Response Dose Gastric intubation weekly for 12 months starting with 10 week old animals No effect in 5 animals examined 2 months after treatment ended 0.007 ug/kgb 135 No effect in 5 animals examined 2 months after treatment ended 0.07 ug/kgb 135 No tumors in 19 animals examined at end of treatment 7 yg/kgb 135 All died in 2 to 4 weeks 50, 500 or 1000 ug/kg diet 136 All died in 30 to 90 weeks 1 and 5 yg/kg diet 136 50% dead at 95th week 500 ng/kg diet 136 50 ng/kg diet 136 Mouse 50 M per group Swiss H/Riop strain I CTi Reference Rat 10 groups of 10 M In diet for 78 weeks 38% tumors < 40% dead at 95th week 40% dead at 95th week '20% dead at 95th week No tumors 5 ng/kg diet 1 ng/kg 136 < 60% dead at 95th week Controls 136 �Tafrle 112 continued 10; Met fswr 2 years No, effect Live* - 540; ng/TOW' k§e Fat - 540 ng; JIQT lH€.reasedi urinary ex.Ofeti?<m erf? ptiqDfry/irins in; females Liver - noduTes 5® ararfcmaTs LQn! tag/kg Liver - 5,100 ng Fat - IJQQ n§ d Increaseefc incidence off eell carcinQmas evidence' ©f Ltterlnfi * mcanmary pancreas aiatdi adrenaJ Fat ~-J - 24,800 nig: TCBi^ltg; - ajtfO ng: o Monkey 8 Maeaca ff diet far § msrrtfos M - Male ""Preliminary report remaining animals to be kept for life span study and observation for tumor development wfthiro 6roanthis Pancytopenia after 5 months Rarked thrombocytapenia Tissue hemorrhages 5 of 8 died between 7 and 12 months Epithelial tissue changes ag/kg diet This is the dose supplied to each animal via the diet: 0.001 yg TCDD/kg body weight = 22 ng TCDD/kg diet 0.01 yg TCDD/kg body weight = 210 ng TCDD/kg diet 0.1 ug TCDD/kg body weight = 2200 ng TCDD/kg diet : F - Female "Terminal samples of liver and fat indicating accumulated levels of TCDD/kg of tissue after two years of treeiment at the respective dosage levels Total exposure, 2-3 yg/kg body weight �F. Mutagenic and Cytogenetic Potentials of TCDD Again, as with 2,4-D and 2,4,5-T, most of the mutagenic studies involving TCDD have been conducted in bacterial cultures or in plant and animal tissue cultures. Khera and Ruddick (75), however, have conducted dominant lethal tests in which male Wistar rats received TCDD, orally, at dosages of 4, 8 or 12 yg/kg per day for seven days. TCDD did not induce dominant lethal mutations during or in the 35 days following treatment. This 35 day period corresponded to the postmeiotic stages of spermatogenesis Green and Moreland (52) conducted a short-term investigation of several dioxins, using male Osborne-Mendel rats, to determine what potential these substances had to cytogenetic damage in rat bone marrow. In one study, all of the dioxins were tested via gavage in the rats for five consecutive days at 10 yg/kg per day. A second study involved TCDD being given separately by two routes. A single oral dose of 20 yg/kg TCDD or oral doses of 10 yg/kg TCDD for five consecutive days, and in other rats, single intraperitoneal doses of 5, 10 or 15 yg/kg TCDD were given. No evidence was found that any of the substances tested produced cytogenetic damage in the bone marrow of male rats under the conditions of the experiment. However, when rats of both sexes were treated twice weekly with TCDD at a dosage level of 4 yg/kg for 13 weeks, a significant increase in the number of chromosome aberrations was found by 6r,een (51). Hussain et al (65) evaluated the mutagenic activity of TCDD (99 percent pure) of three different microbial test systems. In the first study, TCDD significantly increased the incidence of reverse mutations in EAdieAdua. coti Sd-4 when 2 yg/ml TCDD caused the bacteria to change from streptomycin dependence to streptomycin independence. This dosage was the only dose at which mutations were clearly observed. In a second study, Hussain et al (65) examined reverse mutation from histidine dependence to histidine independence in So£mone££a typkmuA^u strains TA1530 and TA1532. TCDD caused positive changes in TA1532 strain but negative results were seen in TA1530 strain which indicated that TCDD may act as a frameshift mutagen in this bacterial strain. In a third study conducted by Hussain et al (65) slight prophage induction in E4cAa>u.cA-ta c.otl K-39 was observed. However, in this study the solvent DMSO was used which.itself causes cellular effects. Seiler (124) using plate assays to study the mutagenicity of TCDD found a positive response in Satmonatta. typkunufuum strain TA1532, doubtful responses in strains TA1531 and TA1534, and negative responses in strains G46 and TA1530. Metabolic activation systems were not included in any of these microbiological assays. Beatty et al (7) conducted a study with -en \>Ww cultures of the mammalian cell types Hela, Balb-3T3, virus (SV-40) transformed 3T3 IV-71 �mouse fibroblasts, human foreskin fibroblasts and human lymphocytes. In all cases TCDD added in a final theoretical concentration of 10'° to the culture medium prior to the addition of cells resulted in no significant inhibition of growth measured after a period of four days. Electron microscopic examination of the TCDD-treated cells did not reveal any changes in morphology as compared to untreated cells. Incubation of human fibroblasts and SV-101 cells with 14C-labelled TCDD showed that incorporation of the TCDD into the cells did occur. Kondorosi et al (79) found that TCDD did not impair the transfectivity of QB-RNA, thus confirming the assumption that TCDD did not react chemically with nucleic acid. Whatever mutagenic property it had must have occurred by the forming of a physical complex by "intercalation" in DNA, leading, to frameshift mutation. In summarizing the limited literature dealing with the mutagenic and cytogenic potentials of TCDD in animals, it was noted that daily oral doses of 4, 8, or 12 yg/kg TCDD given to rats for seven days did not induce dominant lethal mutations. Five daily oral doses of 10 yg/kg TCDD and a single oral dose of 20 yg/kg TCDD did not produce cytogenetic damage in bone marrow cells of male rats. Chromosome aberrations were detected when male and female rats were dosed twice weekly at 4 yg/kg TCDD for 13 weeks. Using microbiological systems, TCDD has been shown to induce mutagenic changes in some strains of bacteria. V. SUMMARY OF THE LITERATURE REVIEW OF THE TOXICITY OF 2,4-D, 2,4,5-T AND TCDD IN ANIMALS In summarizing the literature on the toxicity of 2,4-D, 2,4,5-T and TCDD in animals, the following general statements provided a concept of the overall toxicity of each compound as they related to each other and the effects they produced in experimental animal studies. Where possible, inclusive statements were given rather than individual species responses. A. 2,4-D 1. The LDcn for single oral doses of 2,4-D in animals ranged from 100-2,000 mg/kg with the majority of LDso values in the 300-800 mg/kg range. 2. Signs of chronic 2,4-D toxicity did not differ greatly from those seen in acute toxicity. No effect levels, seen when 2,4-D was given in repeated oral doses, ranged from 30 to 75 mg/kg. 3. Being a strong acid, 2,4-D was rapidly eliminated from the body mainly via the urine. The plasma half-life of a single oral dose was in the 3-12 h range. After high doses or repeated lower doses, 2,4-D accumulated in the tissues; with residue levels rapidly declining as evidenced by a half-life of 1 to 2 weeks. IV-72 �4. No teratogenic signs were seen in rats fed repeated doses of 1,250 to 1,500 mg/kg 2,4-D of diet, nor when repeated daily doses of 8.75 mg/kg were given. Embryo toxic and fetotoxic responses appeared in rats and hamsters at repeated daily oral doses of 100 to 150 mg/kg. 5. Tumors were not produced in mice fed 46.4 to 100 mg/kg 2,4D of diet nor in rats fed 1,250 mg/kg 2,4-D of diet for 18 to 24 months. Single subcutaneous injections of 21.5 to 215 mg/kg 2,4-D did not produce carcinogenic or tumorigenic responses in mice. 6. The 2,4-D was not highly cytotoxic in laboratory animals and did not cause increased mutation rates nor did it stimulate a mutagenic response in rats and mice. No mutagenic or cytogenic responses were seen in several studies using microbial systems for the detection of such toxicity. B. 2,4,5-T 1. The acute toxicity for 2,4,5-T was in the same general range as for 2,4-D in most animal species. The 1050 values for single oral doses of 2,4,5-T ranged from 380 to 940 mg/kg in small laboratory animals. 2. Chronic toxicity studies in mice using repeated oral doses of 30-120 mg/kg 2,4,5-T produced no effect. An overlapping of adverse effects were seen, however, in doses of 60-140 mg/kg 2,4,5-T, depending on the strain of mouse studied. The no effect level for rats orally administered repeated doses of 2,4,5-T was approximately 30 mg/kg while as much as 300 mg/kg of diet could be fed with no adverse effects being noted. Threshold toxicity levels for adverse effects of repeated oral doses of 2,4,5-T in rats was approximately 100 mg/kg or 1,000 mg/kg of diet. 3. Single doses of 2,4,5-T were eliminated in animals, primarily unchanged, via the urine and feces over a period of a few hours up to about 7 days. 4. It was evident that 2,4,5-T induced embryotoxic and teratogenic responses in some strains of mice, rats and in hamsters when repeated oral doses of 20 to 400 mg/kg were administered. However, doses of 20 to 150 mg/kg in the same laboratory animal species produced a negative or no effect response. This indicated a great species and strain variation in response to 2,4,5-T as well as the fact that the embryotoxic and teratogenic potential of 2,4,5-T varied with the concentration of TCDD present. Levels of TCDD greater than 1 mg/kg were required to enhance the embryotoxic and teratogenic potential of 2,4,5-T. Embryotoxicity and teratogenic studies in pregnant rabbits, sheep and rhesus monkeys have been negative. 5. In most strains of mice, oral doses of 21.5 mg/kg or repeated doses of 60 to 100 mg/kg in the diet or drinking water and single subcutaneous doses of 2.5 mg/kg of 2,4,5-T did not induce tumor formation. IV-73 �6. In animals, 2,4,5-T, like 2,4-D was not highly c>totoxic and did not increase mutation rates nor stimulate a mutagenic response in rats and mice. It produced, however, chromatid abnormalities in cultured human lymphocytes and affected the chromosomes and reproductive mechanisms in mouse and hamster bone marrow cells. These effects may have been due to cellular toxicity rather than genetic alterations. No mutagenic responses were seen in several studies using microbial systems for the detection of such toxicity. C. TCDD 1. TCDD was an extremely toxic material with a single oral dose LDgg range of 0.6 yg/kg in male guinea pigs to 115 yg/kg in rabbits. 2. Chronic toxicity was manifested by hepatic necrosis, thymic atrophy and depletion of lymphoid organs. In mice and rats, repeated oral doses of 0.001 to 10 yg/kg for four to 13 weeks produced a no effect response for weight gain and no signs of toxicity were noted. Repeated oral doses as low as 1 yg/kg caused guinea pigs to become moribund and a repeated dose of 0.04 yg/kg decreased lymphocyte counts. Acne of increasing severity was produced in rabbits when doses of 0.04 to 400 yg/kg were applied repeatedly to the internal surface of the ear. A total oral dose of 2-3 yg/kg over a nine month period produced severe hematological changes and death in rhesus monkeys. 3. The primary route of excretion for TCDD in animals appeared to be the feces, with urinary excretion occurring at a much reduced rate. Liver and fat accumulated about 10 times higher levels of TCDD than did other body tissues. The half-life for TCDD in rats, following repeated exposure, was 12-15 days after termination of treatment. 4. It was apparent that TCDD caused birth defects and embryo mortality. Repeated daily oral doses of 0.1 to 2 yg/kg TCDD in pregnant mice produced no effects on the embryos; however, 3 yg/kg was the threshold level for production of cleft palate and kidney abnormalities. Single or repeated oral doses of 6.5 to 40 yg/kg TCDD were required to produce cleft palate in 50 percent or more of some strains of mouse embryos. Daily subcutaneous injections of 1 to 3 yg/kg TCDD produced cleft palate and kidney abnormalities in 50 percent or more of three different strains of mouse embryos. Repeated daily oral doses of 0.03 to 0.125 yg/kg TCDD produced no effect in some rat strains while doses of 0.125 to 2 yg/kg TCDD depressed fetal weight, lowered fetal survival and caused internal hemorrhages in fetuses. When teratogenic lesions appeared in rats, kidney abnormalities were more common than cleft palate. 5. No tumors were produced in a preliminary study where 0.007, 0.07, or 7 yg/kg TCDD was administered to mice in weekly oral doses for 12 months. When levels of 1 and 5 yg/kg TCDD of diet and 1, 5, 50 and IV-74 �500 ng/kg TCDD of diet were fed to rats for 78 weeks, an overall tumor incidence of 38 percent was present in the test animals. No effects were produced when 0.001 yg/kg TCDD was given to rats via the diet for 2 years. A level of 0.01 yg/kg TCDD given via the diet for 2 years produced liver nodules and hyperplasia of the lung epithelium. A level of 0.1 yg/kg TCDD in the rats' diet for 2 years produced an increase in liver and lung carcinomas. Monkeys fed 500 ng/kg TCDD of diet for 9 months did not develop tumor but died of marked hematological alterations. 6. Daily oral doses of 4, 8 or 12 yg/kg TCDD given to rats for seven days did not induce dominant lethal mutations. Five daily oral doses of 10 yg/kg TCDD and a single oral dose of 20 yg/kg TCDD did not produce cytogenic damage to bone marrow cells of male rats. 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Cekanova and K.S. Larsson. 1973. Teratogenic and embryotoxic effects of the herbicides di- and trichlorophenoxyacetic acids (2,4-D and 2,4,5-T). Acta PkoAmacLot. Tou.c.ol. 32(6) :408-416. 6. Baker, D.L., F.K. Ramsey and E.P. Sylvester. 1953. Suspected poisoning of dogs from eating grasses treated with 2,4-D. Month Am. Vet. 34:194. 7. Beatty, P.M., K.J. Lemback, M.A-. Holseher and R.A. Neal . 1975. Effects of 2,3,7,8-tetrachlorodibenzo-p-dioxiri (TCDD) oh mammalian cells in tissue cultures. TOJO.CO£. App£. PhoAwaco£; 31:309-312. 8. Becker, D. 1973. The effects of folate overdose and of 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD) on kidney and liver respectively of rat and mouse embryos. Teratology. 8:215. 9. Berndt, W. 0. and F. Koschier. 1973. InvJL&uo uptake of 2,4dichlol^ophenoxyacetic acid (2,4-D) and 2i4,5-trichlorpphenoxyacetic acid (2i4 4 5-T) by renal eortical tissuis df rabbits artd rats. Tox^cot. Phafmacai. 26:559-570. 10. Binns, W. and A.E. Johnson. 1970. 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Herbicides and wild animals - several recent findings: Starting point of the investigations - reindeer deaths in Lapland. Z. Jagdwu*. 20(1):68-70. 41. Fang, S.C., E. Fallin, M.L. Montgomery and V.H. Freed. 1973. The metabolism and distribution of 2,4,5-trichlorophenoxyacetic acid in female rats. Toxx.c0£. App£. Phanmacol. 24:555-563. 42. Fedorova, L.M. and R.S. Belova. 1974. Incorporation of 2,4-dichlorophenoxyacetic acid into the organs of animals: paths and dynamics of its excretion. Gig.j. SCLVU£, 2:105-107. 43. Florsheim, W.H. and S.M. Velcoff. 1962. Some effects of 2,4dichlorophenoxyacetic acid on thyroid function in the rat: effects on iodine accumulation. EndocsUnoZogy. 71:1-6. 44. Fries, G.F. and G.S. Marrow. 1975. Retention and excretion of 2,3,7,8-tetrachlorodibenzo-p-dioxin by rats. J. Agti. food Chm. 23:265-269. 45. Frohberg, H., J. Gleich and A. Hofmann, 1975: Investigations on the embryotoxic effect of 2,4,5-T in NMRI mice. Tznatology. 10(3) :309. 46. Fujita, K, H. Fujita and Z. Funasaki . 1975. Cytogenetic studies of 2,4,5-T related substances. Nippon NoAon Igakktu. la&bki. 24(3):432-433. (Japanese). 47. Gale, T.F. and V.H. Ferm. 1973. Effects of the herbicide 2,4,5-T and Pyrazon on embryogenesis in the hamster. Awot. Rec. 175(2) :503. 48. Gasiewicz, T.A. and R.A. Neal . 1978. Tissue distribution and excretion of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and effects upon clinical chemical parameters in the guinea pig. fe.d. PA.OC.. 37(3) :501. 49. Gehring, P.O., C.G. Kramer, B.A. Schwetz, O.Q. Rose and V.K. Rowe. 1973. The fate of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) following oral administration to man. Tox^.co£. App£. Phtvunacoi. 26:352-361. IV-79 �50. Goldstein, J , A . , P. Hickman, H. Bergman and J.G. Vos. 1973. Hepatic porphyria induced by 2,3,7,8-tetrachlorodibenzo-p-dioxin in the mouse. Re,i. Commun. Chm. Path. PhaAjnaaol. 6:919-928. 51. Green. S. 1977. Cytogenetic effect of 2,3,7,8-tetrachlorodibenzop-dioxin on rat bone marrow cells. FDA By-lines, Washington, D . C . , Food arid Drug Administration (in press). 52. Green, S. and F.S. Moreland. 1975. Cytogenetic evaluation of several dioxins in the rat. Toxxc.o£. App£. PkaAmac.ol. 33:161. 53. Greig, J.B., G. Jones, W.H. Butler and J.M. Barnes. 1973. Toxic effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin. Food Cotmet. Toucot. 11:585-595. 54. Grunow, W. and C. BShme. 1974. Uber den Stoffwechsel von 2,4,5-T und 2,4-D bei Ratten und Ma'usen. A/icA. Toxxco^.. 32:217-225. 55. Grunow, W . , C. Bb'hme and B. Budczies. 1971. Renale Ausscheidung von bei Ratten. Food Co^mot. Toiu.c.ol. 9:667-670. 56. Gupta, B.N., J.G. Vos, J.A. Moore, J.G. Zinkl and B . C . Bullock. 1973. Pathologic effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin in laboratory animals. EmuAon. Health ?&upe.ct. 5:125-140. 57. Guseva, E.N. 1956. Moscow 9(4):41-44. 58. Hansen, W.H., M.L. Quaife, R.T. Habermann and Q.G. Fitzhugh. 1971. Chronic toxicity of 2,4-dichlorophenoxyacetic acid in rats and dogs. Tox.4.c.ol. App£. Pkanmacol. 20:122-129. 59. Harris, M . W . , J.A. Moore, J.G. Vos and B.N. Gupta. 1973. General biological effects of TCDD in 'laboratory animals. EnvJAon. 5:101-109. Pharmacology of 2,4-D. (Russian). FaAmakol. Tokiikol. 60. Highman, B., T.B. Gaines and H.J. Schumacher. 1976. Sequential histopathologic, hematologic and blood chemistry changes induced in mice by a technical and a purified preparation of 2,4,5-trichlorophenoxyacetic acid. J. TaiUc.o£. EmuAon. Health. 1(3): 469-484. 61. Highman, B., T.B. Gaines and H.J. Schumacher. 1977. Retarded development of fetal renal alkaline phosphatase in mice given 2,4,5-trichlorophenoxyacetic acid. J. To?u,co£. Envision. Health 2:1007-1018. 62. Highman, B., T.B. Gaines, H.J. Schumacher and T.J. Haley. 1976. Strain differences in histopathologic, hematologic and blood chemistry changes induced in mice by a technical and a purified preparation of 2,4,5-trichlorophenoxyacetic acid. 3. Tox^col. . Hza&th 1 (6): 1041 -1054. IV-80 �63. Hill, E.V. and H. Carlisle. 1947. Toxicity of 2,4-dichlorophenoxyacetic acid for experimental animals. J. Ind. Hwg. To5uco£. 29(2):85-95. 64. Hook, J.B., M.D. Bailie, J.T. Johnson and P.J. Gehring. 1974. In \}Wio analysis of transport of 2,4,5-trichlorophenoxyacetic acid by rat and dog kidney. Food Co^me/C. Tox^co£. 12(2) :209-218. 65. Hussain, S., L. Ehrenberg, G. Lofroth and T. Gejvall . 1972. Mutagenic effects of TCDD on bacterial systems. Amb^o. 1:32-33. 66. International Agency for Research on Cancer. 1977. IARC Monographs on the Evaluation of the carcinogenic risk of chemicals to man. Vol 15, Some fumigants, the herbicides 2,4-D and 2,4,5-T, chlorinated diobenzodioxins and miscellaneous industrial chemicals. Lyon, France. 67. Innes, J.R.M., B.M. 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App£. 1977. PCB poisoning in Rhesus monkeys. Ptujmate. New*. 35(1) -.139-140. 94. Nagy, Z., I. Mile and F. Antoni. 1975. The mutagenic effect of pesticides on Eacke/u.akca c,oti WP2 try. Acta Mxc/Lofaxo£. Acad. Sox. Hang. 22:309-314. 95. Neubert, D. 1976. Some remarks to the toxicity of polychlorinated dibenzo-dioxins. In. Proceedings of the Congress of the European Teratology Society, Gaspiano, 1976 (in press). 96. Neubert, D. and I. Dillmann. 1972. Embryotoxic effects in mice treated with 2,4,5-trichlorophenoxyacetic acid and 2,4,7,8-tetrachlorodibenzo-p-dioxin. Maun(/n-Sdtnu.edebe/u} '& M.c.k. Phmasikot. Exp. ?outkot. 272 (3): 243-264. 97. Neubert, D . , P. Zens, A. Rothenwallner and H.-J.Merker. 1973. A survey of the embryotoxic effects of TCDD in mammalian species. . Heo&th PeMpect. 5:67-79. 98. Norback D.H. and J . R . Allen, 1973. Biological responses of the nonhuman primate, chicken and rat to chlorinated dibenzo-p-dioxin ingestion. EnvxAon. Heotth P&tApect. 5:233-240. 99. Palmer, O.S. 1963. Chronic toxicity of 2,4-D alkanolamine sales to cattle. J. Am. l/et. Med. A^oc. 143(4): 398-399. IV-83 �TOO. Palmer, J.S. and R.D. Radeleff. 1964. The toxicologic effects of certain fungicides and herbicides on sheep and cattle. Ann. M. V. Acad. Su. 111:729-736. 101. Pilinskaya, M.A. 1974. Cytogenetic effect of the herbicide 2,4-D on human and animal chromosomes. J&Ltot. Genei. 8(3) :202-206. (Russian) . 102. Piper, W.N. and J.Q. Rose. 1971. The excretion and tissue distribution of 2,3,7,8-tetrachlorodibenzo-p-dioxin in the rat. Amer. Chem. Soc., Abstr. Pap., 162nd Nat. Meet., Pe-6-ttc. Cheat. Sue.., No. 88. 103. Piper, W . N . , J.Q. Rose and P.O. Gehring. 1973. Excretion and tissue distribution of 2,3,7,8-tetrachlorodibenzo-p-dioxin in the rat. Aduan. Chum. SeA. • 120:85-91. 104. Piper, W . N . , J.Q.. Rose, M.L. Leng and P.J. Gehring. 1973. The fate of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) following oral administration to rats and dogs. Tox^co£. App£. 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Rip, J.W, and J.H. Cherry. 1976. Liver enlargement induced by the herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). J. \gtUc.. food Ckm. 24(2):245-250. 112. Roll, R. 1971. Studies of the teratogenic effect of 2,4,5-T in mice. Food CaAm<Lt. Tox^cot. 9(5) :67l-676. 113. Roll, R. 1973. Toxicological evaluation of special organochlorinated compounds. Enu^Aon. Qvuti. Sa^. 2:117-124. IV-84 �114. Rose, J.Q., J.C. Ramsey, T.H. Wentzler, R.A. Hummel and P.O. Gehring. 1976. The fate of 2,4,7,8-tetrachlorodibenzo-p-dioxin following single and repeated oral doses to the rat. TOJO.CO£. App£. Phasunacot. 36:209-226. 115. Rowe, V.K. and T.A. Hymas. 1954. Summary of toxicological information of 2,4-D and 2,4,5-T type herbicides and an evaluation of the hazards to livestock associated with their use. AmeA. J. Rei. 15: (57)622-629. 116. Sadykov, R.E., V.K. Rabochev and Yu. N. Strokov. 1972. The effect of 2,4-DB used for the treatment of pastures on the reproductive function of sheep. IkivotnovodAtvo 34(2):73-74. (Russian) 117. Sauerhoff,. M.W., W.H. Braun, G.E. Blau and P.O. Gehring. 1976. The dose-dependent pharmacokinetic profile of 2,4,5-trichlorophenoxyacetic acid following intravenous administration to rats. Toxxco£. App£. PkaAmac.o£.. 36:491-501. 118. Schiller, K. 1964. Beeinflussung der Fertilit'at von Ratten durch Stoffe mit Sonderwirkung im Kartofelbau. 14(2):111-114. (German). 119. Schillinger, J.I. 1960. Hygienische Wertung von landwirtschaftlichen Erzeugnissen, angebaut unter Anwendung von Herbiziden. J. Hyg. EpUe.miol. 4:243-252. (Czech). 120. Schulz, K.H. 1968. Zur Klinik und Atiologie der Chlorakne. Arbeitsmed. Soz-uLtmed. M.b<i£ti>hyg. 3:25-29. (German). 121. Schwetz, B.A., J.M. Morris, G.L. Sparschu, V.K. Rowe, P.J. Gehring, J.L. Emerson and C.G. Gerbig. 1973. Toxicity of chlorinated dibenzo-p-dioxins. EMUAOPI. Heo£#i Pmpeet. 5:87-99. 122. Schwetz, B.A., G.L. Sparschu, P.J. Gehring. 1971. The effect of 2,4-dichlorophenoxyacetic acid (2,4-D) and esters of 2,4-D on rat embryonal, fetal and neonatal growth and development, food CoAmnt. To?o.c.o£.. 9:801-807. 123. Seabury, J.H. 1963. Toxicity of 2,4-dichlorophenoxyacetic man and dog. M.ch. EmuAon. HeotCfc. 7:202-209. acid for 124. Seiler, J.P. 1973. A survey on the mutagenicity of various pesticides. Expe*x.mtui 29:622-623. 125. Shavgulidze, M.M., V.I. Nanobashvili and M.N. Mirianashvili . 1976. Toxicity of the herbicide 2,4-D. -Vzt<iru.naMycL 4:103-104. (Russian). 126. Shirasu, Y. 1975. Significance of mutagenicity testing on pesticides. Envlton. Qual. Satf. 4:226-231. 127. Shirasu, Y., M. Moriya, K. Kato, A. Furuhashi and T. Kada. 1976. Mutagenicity screening of pesticides in the microbial system. Mutation R&6. 40:19-30. IV-85 �128. Smith, F.A., B.A. Schwetz and K.D. Nitschke. 1976. Teratogenicity of 2,3,7,8-tetrachlorodibenzo-p-dioxin in CF-1 mice. Tox^col. App£. 38:517-523. 129. Sokolik, I. Yu. 1973. 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Metabolic stability of 2,3,7,8-tetrachlorodibenzo-p-dioxin in mammalian liver microsomal systems and in living mice. M.oh. Emu/ton. Contain. Tox*cco£. 1:122-132. IV-86 �139. Vos, J.G. and J.A. Moore. 1974. Suppression of cellular immunity in rats and mice by maternal treatment with 2,4,7,8-tetrachlorodibenzo-p-dioxin. Int. M.ch. MZeAgy App£. Immanol. 47:777-794. 140. Vos, J . G . , J.A. Moore and J . G . Z i n k l . 1974. Toxicity of 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD) in C57B1/6 mice. Toxico£. App£. PhaAmacol. 29:229-241. 141. Walker, E . M . , Jr., R . H . Gadsden, L . M . Atkins and G . R . Gale. 1972. Some effects of 2,4-D and 2,4,5-T on Ehrlich ascites tumor cells Jun VM.VO and <in \jWio. Ind. Mecf. 41(l):22-27. 142. Weissberg, J.G. and J.G. Zinkl. 1973. Effects of 2,3,7,8-Tetrachlorodibenzo-p-dioxin upon hemostasis and hematologic function in the rat. Environ. Health Pmpea*. 5:119-123. 143. World Health Organization. 1971. 1970 Evaluations on some pesticide residues in food. The Monographs. WHO/Food Add./71.42, pp 459-477. 144. W i l s o n , J . G . 1977. Envvtomzntal c.kzm.c.atb . P 357-386. In_ Handbook of Teratology. J . G . Wilson and F . C . Fraser ( E d s . ) . Vo-1 . 2. Plenum Press, New York. 145. W i l s o n , J . G . 1977. Teratogenic effects of environmental chemicals. Fed. Ptoc. 36 (5): 1698-1 703. 146. Zetterberg, G. 1977. Experimental results of phenoxy acids on microorganisms. ln_ Chlorinated Phenoxy Acids and their Dioxins: Mode of Action, Health Risks and Environmental Effects. C. Ramel , ( E d ) , Ecol. Bull. (Stockholm), 27: ( i n press). 147. Z i e l i n s k i , W . L . , Jr. and L. Fishbein. 1967. Gass chromatographic measurement of disappearance rates of 2,4-D and 2,4,5-T acids and 2,4-D esters in mice. J. Ag/u.c. food Cfiem. 15:841-844. 148. Z i n k l , J . G . , J . G . Vos, J . A . Moore and B . N . Gupta. 1973. Hematologic and clinical chemistry effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin in laboratory animals. Env&ion. H&altn PeAApe,c.t. 5:111-118. IV-87 �CHAPTER V 2,4,5-T/TCDD EPISODES I. INTRODUCTION The current controversy over the potential adverse human effects of 2,4,5-T and TCDD stem from a chain of events that occurred in the 1960s. The presence of TCDD as a contaminant, potent acnegen and acute toxin in the production of 2,4,5-trichlorophenol was documented in 1957 by Kimmig and Schulz (58). However, it was not until 1964 that concern over the levels of TCDD in 2,4,5-T herbicide was reported. In that year, the Dow Chemical Company experienced contamination problems during its expansion in production of 2,4,5-T to meet the requirements for Herbicide Orange by the U.S. military. They closed their production facilities and made extensive modification in the reaction conditions for the synthesis of trichlorophenol. By late 1965, the new technology developed by Dow Chemical Company permitted production of 2,4,5-T containing no more than 1 ppm TCDD (36). Simultaneously, in 1964, the National Cancer Institute contracted for a screening study of a number of pesticides to determine if they were tumorigenic, teratogenic or mutagenic. Among the pesticides evaluated was 2,4,5-T herbicide. By 1967-68, preliminary data on 2,4,5-T from this screening study indicated that 2,4,5-T was teratogenic (15). The data were apparently provided to the press prior to actual publication. [When the manuscript eventually appeared in the scientific literature, in 1970, it contained a footnote indicating that the original sample of 2,4,5-T used in the screening tests contained approximately 30 ppm TCDD (23).] The press releases in the U.S. on the teratogenicity of 2,4,5-T were occurring in the same time period that South Vietnamese newspapers were publishing reports of an alleged increased occurrence of birth defects in areas sprayed with Herbicide Orange. These releases elicited far-reaching reactions from governmental agencies, segments of the scientific community and various lay groups concerned with environmental problems (2). On October 29, 1969, the President's Scientific Advisor announced that a series of coordinated actions was being taken by several governmental agencies to restrict the use of 2,4,5-T herbicide. Additional animal experiments performed early in 1970 confirmed that pregnant mice did deliver some malformed offspring. The question then was one of whether, or to what extent, such animal data could be extrapolated to man. On April 14, 1970, the Secretary of Health, Education and Welfare (HEW) advised the Secretary of Agriculture that: "In spite of these uncertainties, the Surgeon General feels that a prudent course of action must be based on the decision that exposure to this herbicide may present an imminent hazard to women of child-bearing age." Accordingly, on the following day, the Secretaries of Agriculture; HEW, and Interior jointly announced the suspension of 2,4,5-T for "all uses around the home, recreation areas, and similar sites" and "all uses on crops intended for human consumption." Immediately thereafter, the Department of Defense suspended the use of Herbicide Orange in South Vietnam (7). V-l �Numerous incidents involving suspected 2,4,5-T/TCDD poisoning of humans or livestock have been reported since this initial controversy. The most recent alleged episode involved veterans of the Vietnam Conflict. In March 1978, WBBM, a CBS-owned television affiliate in Chicago, Illinois, aired a special report on "Agent Orange: Vietnam's Deadly Fog". In the film, a number of past episodes allegedly involving 2,4,5-T and TCDD were examined. This chapter will review the available scientific data on these and other episodes, including industrial episodes, assessments in South Vietnam and the incident that occurred in Seveso, Italy, in July 1976. The medical data on many of these episodes are reviewed in Chapter VI. The expression of units of weight, area, or volume has not been standardized between the various publications cited in this Chapter. II. INDUSTRIAL EXPERIENCES A. Industrial Processes The herbicide, 2,4,5-T, was first commercially produced in the United States in 1944 (79). The quantity o'f 2,4,5-T produced and used in the United States and in world agriculture increased steadily until 1968-69, after which a sharp decline in its use occurred. Table 1 shows total U.S. Production data for 2,4,5-T, and how it was subsequently used, during the period 1961 through 1969. Approximately 34 percent (53 million pounds) of the total U.S. production was procured by the Department of Defense for use in South Vietnam. However, 8.9 million pounds of the 53 million pounds were not sprayed in South Vietnam, but rather destroyed by at-sea incineration in 1977 (see Chapter II). During the same period, 1961 through 1969, 50.6 percent (78.1 million Ib) of the total U.S. 2,4,5-T production was used in domestic herbaceous and woody plant control programs. The synthesis scheme for the industrial production of 2,4,5-T herbicide is shown in Figure 1. Forth (40) has described two different processes for the manufacture of the herbicide. The "Dow" process is a pressureless, high temperature process (>160°C but <200°C) requiring the alkaline hydrolysis of 1,2,4,5-tetrachlorobenzene to sodium trichlorophenate in the presence of ethylene glycol (an alcohol) and caustic soda (e.g., sodium hydroxide). The second process, the "Boehringer" process uses high pressure (19.5 atmospheres) but low temperature (157°C) conditions in the presence of methanol, caustic soda, and 1,2,4,5-tetrachlorobenzene. Both processes will result in the formation of sodium trichlorophenate. The sodium trichlorophenate can be acidified to form trichlorophenol or may be used directly in the production of 2,4,5-T by adding chloroacetic acid. The production of the n-butyl ester (NBE) of 2,4,5-T is accomplished by V-2 �TABLE 1. Total United States production and use of 2,4,5-T herbicide for the period 1961 through 1969.a Use Million Pounds Herbicides Green, Pink and Purple^ Percent of Total 1.6 1.04 Herbicide Orange0 51.4 33.27 Exports 23.4 15.15 Domestic Use 78.1 50.55 154.5 100.01 Total a Total production and export data were from The Pesticide Review, 1970 and earlier issues, U.S. Department of Agriculture, Agricultural Stabilization and Conservation Service, U.S. Government Printing Office, Washington D.C. Data expressed in acid equivalents. Data based on estimated number of gallons of Herbicides Green, Pink and Purple used in South Vietnam, 1962-1964. c Data based on estimated number of gallons of Herbicide Orange used in South Vietnam (10,645,904 gallons) plus the surplus 2,215,125 gallons remaining after termination of Operation RANCH HAND. V-3 �methanol or ethylene glycol caustic in«0 / socja Cl' " X "Cl 1 c n O - 180° C \" 160° 1,2,4,5-tetrachlorobenzene - where R = CH or OUCH Chloroacetic acid,^ sodium hydroxide sodium trichlorophenate > 230°C 0 0-CH^C-OH 2,4,5-T butanol, anhydrous hydrochloric acid 0-CH2C-0-CH2CH2CH2CH3 Cl n-butyl ester 2,4,5-T FIGURE 1. Synthesis scheme for production of the n-butyl ester 2,4,5-T (NBE 2,4,5-T) and site where formation of TCDD may occur. V-4 �esterification using butanol and anhydrous hydrochloric acid. TCDD is formed only, during the formation of the phenol. Dimerization of the sodium trichlorophenate to form TCDD will occur in the reaction vessel during the alkaline hydrolysis of 1,2,4,5-tetrochlorobenzene. Maintaining low temperatures, J160°-'I800C, will minimize the formation of TCDD. The reaction temperatures during the "Dow" process may become difficult to maintain. If the temperature of the hydrolysate rises above the normal ,180°C, an exothermic reaction occurs after any residual solvent, e.g., glycol, is removed by distillation. This reaction, attributed to the decomposition of sodium-2-hydroxethoxide, starts at a temperature of 230°C and continues to 410°C. The heat generated by this reaction assists in the formation of TCDD through the dimerization of two molecules of sodium trichlorophenate. The rapid temperature increase in the reaction vessel, results in a pressure increase; failure to release the pressure has resulted in some of the industrial accidents that have been reported (46). B. Industrial Episodes In the years since the first commercial production of 2,4,5-T herbicide (1946-47), there have been numerous industrial episodes involving exposure to TCDD (and/or other chlorinated dibenzo-p-dioxins). The exposure to TCDD normally occurred during the handling of contaminated intermediate products (e.g., trichlorophenol, TCP). Fifteen of 23 episodes recorded in the literature were apparently associated with this "occupational" exposure. However, on eight occasions, explosions occurred, generally during the production of sodium trichlorophenate, and personnel were exposed to TCDD at the time of the accident, during the clean-up of the accident or from subsequent contamination of the workshop environment. The first reported industrial accident occurred in Nitro, West Virginia, in 1949 (51). A total of 228 people were poisoned by the reactor residue during and/or immediately after the accident. No measures were taken to decontaminate the factories or to control the residue from the reaction vessel. In 1953, an accident occurred at a TCP factory in Ludwigshafen, Federal Republic of Germany (43). The 55 workers that showed chloracne and other acute toxic effects were exposed to the residue of the reaction vessel either during the accident or in the subsequent clean-up work. By 1957, Kimmig and Schulz (55) implicated TCDD as the causative agent of at least the chloracne seen in these workers. The most thoroughly documented episode of occupational exposure has been by Oirasek et al (54,55) and occurred in Czechoslovakia between 1965 and 1969. In 1965, two technicians developed chloracne during the evaluation of a new production process for the manufacture of 2,4,5-T. At the time, it was assumed that they were exposed because of careless work and defective equipment under the pilot plant conditions. During the following two years, after the plant became operational, an additional V-5 �76 people developed chloracne. An investigation and study of the entire problem finally resulted in a shutdown of the operation and abandonment of the production in 1968. Jirasek et al have carefully described the afflicted individuals and have continued to monitor their health since the onset of the disease. The above two episodes and other episodes involving occupational chloracne associated with the manufacture of chlorinated phenols are presented in Table 2. The clinical features of the affected cases described in the 23 episodes listed in Table 2 are described in Table 3. Note that most features observed were inconsistent with the exception of chloracne. Certainly, extended exposure to the major chemicals [TCP, pentachlorophenol (PCP), 2,4-D or 2,4,5-T] must have complicated the observed clinical features. In addition to TCDD, it should also be noted that TCP may also contain significant concentrations of hexachlorodibenzop-dioxin, while PCP may contain hexa-, hepta- and octachlorodibenzo-p-dioxin. An extensive review of occupational chloracne has been prepared by Crow (24) and Kimbrough (56). With one exception, men have been almost exclusively affected by the disease due to the occupational position they have historically maintained in the factories producing the chlorinated phenols. The few women and children that have been afflicted were exposed because of contact with clothing worn by the men. Goldmann (43) reported that a female animal nurse developed chloracne by contact with contaminated test animals. The one industrial incident where a large number of women were afflicted with chloracne was reported by Braun (17) in 1959. Braun examined 114 women and 9 men, who in the course of a year became afflicted with chloracne in a condenser factory where chloronaphthalenes of different degrees of chlorination were used as dip-waxes. The reporting of this incident is important because of contradictory statements in the literature on the differential sensitivity of different people (including^-sexes) to chloracne. From the examination of the women Braun concluded the following: 1. Age was of no importance within the range of 20 to 45 years. 2. Strongly adiposed persons were more likely to be afflicted. 3. Seborrhoic types with greasy skin and open pores and scars of previous Ac.ne vutg<wit> were sooner and more severely afflicted. 4. Non-affliction was definitely extremely rare under the circumstances. Only four women (2 of them sisters) with a very smooth and fine skin through which the veins showed bluish when they were at rest remained free from the alterations due to the disease. 5. The occurrence of chloracne had no real relationship to hair color and skin pigmentation. V-6 �TABLE 2. Industrial incidents Year Country associated with the manufacture of chlorinated phenols. Primary Production Source of Manufacturer/Location3 Productr Exposure Monsanto/ Nitro, West Virginia . / / Nordrhein, Westfalen / / TCP Explosion PCP, TCP 1952- West Germany 53 1953 West Germany Years from Number Incident to of Last Cases Observation0 Reference 228 4 Occupational 17 1 TCP Occupational 60 12 DUcrir 1 liyt:i / TCP Occupational 37 46 BSAF/ Ludwigshafen TCP Explosion 55 24 51, 43 Boehringer, Ingleheim/ Hamburg TCP, 2,4,5-T Occupational 31 9 58, 12 1956 France Rhone Poulenc/Grenoble TCP Explosion 17 2 30 1956 United States Diamond Alkalai/ Newark, New Jersey 2,4-D, 2,4,5-T Occupational 29 13 1956 United States tlUUKci/ TCP Occupational (?) 46 1960 United States Diamond TCP Occupational (?) 46 1949 United States 1949 West Germany 1952 West Germany 1954 West Germany Ch amv»ni~ \r t 51, 73 11 16, 68 �Table 2 (continued) 1962 Italy 1963 Netherlands 1964 USSR 1964 United States / 5 TCP Explosion Philips-Duphar/ Amsterdam / / TCP Explosion ' 50 2,4,5-T Occupational 128 Dow Chemical/ Midland, Michigan 2,4,5-T Occupational 60 6 38 TCP Occupational 78 6 54, 55 67 1965- Czechoslovakia Soolana/ 69 Rhone Poulenc/ Grenoble 47, 51 14 14, 26 51 50, 74 1966 France TCP Explosion 21 1968 United Kingdom Coalite and Chemicals TCP Products/ Bolsover, Derbyshire Explosion 79 9 51, 60 1970 Japan PCP, 2,4,5-T Occupational 25 3 64 1972 USSR TCP Occupational 1 1 81 2,4,5-T Occupational 50 40, 46 00 1973 Austria / / Linz Nitrogen 46 Un i-l-i: / worKs/ 1974 West Germany Bayer/Uerdingen 2,4,5-T Occupational 5 40, 46 1975 United States Thompson-Hayward/ TCP Occupational - 46 Kansas City, Kansas �Table 2 (continued) 1976 Italy ICMESA/Meda TCP Explosion 134 2 69, 80 a The name of the factory or company and its location was cited whenever it was available because considerable confusion exists in the published literature as to what incident is addressed. The absence of data indicates the information was not available. b TCP = trichlorophenol, PCP = pentachlorophenol Frequently individuals involved in an incident, and who were examined initially, may have also been examined at a later date. The years that lapsed from the exposure until the most recent examination are cited in this column. The absence of a number indicates that only an initial examination was reported in the referenced literature. �TABLE 3. Some clinical features observed in cases of chloracne associated with production of 2,4,5-T and other chlorinated phenols. Frequency observed Clinical Features Consistent Chloracne Additional Notes In worst cases, chest and inguinal area affected and scarring generally increased. Occasional Prophyria cutanea tarda Increased excretion of urinary uroporphyrin or coporporphyrin or both. -^ o Inconsistent Hyperpigmentation of the skin Usually prominent on face and consisted of grayish or brownish tone to the complexion. Hirsutism Noticeable between the outer edge of the eyebrow and the temple hair margin. Enlarged, tender liver Excessive mechanical fragility of the skin Neuromuscular symptoms Severe pains in the chest and pain and weakness in extremities �Table 3 (Continued) Mucous membrane irritation Itching of the eyes and frequent tearing, hyperemia of the nasal mucosa, and inflammation of the buccal mucosa. Irritability Nervousness and insomnia. �6. A simultaneous psoriasis or a systemic eczema in the previous case history, or a pregnancy, did not make any difference and had no perceptible effect on the course of the chloracne. One woman reported that she had noticed a worsening of her chloracne after her delivery. 7. During the menstrual period, the pimples on the cheeks of some of the women were temporarily more prominent. 8. Dirty and untidy women took ill sooner and more severely than those who placed great importance on cleanliness and hygiene. The persistence of dioxins in the environment of an industrial plant has been documented by Jensen (53). He reported on two cases of chloracne in employees of an outside contractor that had been working on a piece of equipment exposed (but thought to have been decontaminated) to TCDD three years earlier in an industrial explosion in Derbyshire, England in 1968. A young son of one of these employees also develeoped chloracne. The presumed source of the child's contamination was the father's working clothes. An episode involving the deliberate synthesis of TCDD has been reported by Oliver (65). This episode involved three young (male) scientists working with pure TCDD in the laboratory. Two of the men were exposed to the dioxin while attempting to synthesize it by heating trichlorophenol in an alkaline solution in the presence of a catalyst or by heating prepared potassium trichlorophenate in a closed system. Both men wore overalls and plastic gloves and allegedly took the utmost care to avoid inhalation or skin contact. The third man was a colleague of the other men and had been working with the diluted dioxin standards they had prepared. His work also had been done with the utmost caution and with special care to avoid personal contamination. Three clinical features were common to the three men, namely, chloracne, hyperpigmentation and hypercholesterolemia (increased levels of cholesterol). None of the three patients had evidence of acquired porphyria. However, two patients developed hirsutism (excessive facial hair) two years after the exposure. These same two also reported that when the hirsutism developed, other symptoms occurred, e.g., loss of appetite, oppressive headaches, and an unusual loss of vigor and drive with excessive fatigue. Oliver concluded from the evidence that those accidentally exposed to dioxin (TCDD) may be subject to delayed toxic effects for at least two years. III. VIETNAM EPISODE As noted in Chapter I, approximately 53 million Ib of 2,4,5-T were in the 13.2 million (gal) of Orange, Purple, Pink and Green procured by the Department of Defense. However, 8.9 million lb of 2,4,5-T were in the surplus Herbicide Orange. Thus, approximately 44 million pounds of 2,4,5-T were sprayed in South Vietnam from 1962 through 1970. As noted in Chapter I, an estimated 368 lb of TCDD were probably present in Herbicides Orange, Purple, Pink and Qreen. V-12 �Irish et al (52) have stated that among all the controversial subjects that were part of the conflict in Vietnam, the use of vegetationcontrol chemicals received an undue amount of publicity that was generally critical. They noted that the Department of Defense was not insensitive to the critics' pronouncements; justification for continuation of the RANCH HAND program had been periodically reviewed. The conclusions of all the evaluations prior to 1969 recognized that defoliation had reduced the incidence of ambushes, saved lives and disrupted enemy tactics. The issues of long-term ecological damage or potential adverse human health effects due to the herbicides were little discussed until the late 1960s. These issues when viewed in context with the realities of the military conflict were of minor concern, especially since the available scientific data did not support the justification for greater concern. It should be noted that in 1967 the Department of Defense had contracted with the Midwest Research Institute (MRI), Kansas City, Missouri, for an in-depth report on the assessment of ecological effects of extensive or repeated use of herbicides (49). Following its publication in December 1967, both the National Academy of Science (NAS) and the American Association for the Advancement of Science (AAAS) reviewed the document and concluded that MRI had "done a creditable job of assessing the scientific literature related to herbicides and their ecological effects." However, both organizations felt that the report represented "only a first step in investigating further the ecological effects of intensive use of herbicides" (3). Some of the conclusions that the MRI reported (49) included: 1. The greatest short-term or long-term direct ecological consequence of using herbicides in Vietnam or anywhere else is the destruction of vegetation. As long as soil sterilization is not an objective, destruction of vegetation by herbicides is a selective process, denuded earth does not occur especially in forest spraying. Furthermore, the end result of the use of herbicides from an ecological standpoint is that the ecosystem is set back to an earlier sere, i.e., an earlier stage of plant succession. 2. The long-term effects on wildlife may be beneficial or detrimental. Studies in other countries have shown that herbicidal treatment of forested areas improves wildlife habitat and is favorable to animal populations. The extent and pattern of herbicide treatment in Vietnam have no precedent; therefore, it is difficult to predict effects on wildlife with any accuracy. 3. The herbicides used in Vietnam will not persist at a phytotoxic (plant toxic) level in the soil for a long period of time. On the basis of the average temperatures and rainfalls in Vietnam, it would be reasonable to expect that the chlorophenoxy acid esters will be dissipated quickly. 4. The possibility of lethal toxicity to humans, domestic animals or wildlife by use of the herbicides used in Vietnam is highly unlikely and should not be a matter of deep concern. V-13 �5. Herbicides seldom persist in animal or insect tissues. Toxic transfer to the next higher animal in the food chain is minimal. In fact, biological concentration does not occur with most herbicides, since they are readily excreted from animals. In September 1968, the U.S. Department of State released an assessment of the ecological consequences of the defoliation program in Vietnam. Tschirley (75), a plant ecologist and the author of the Department of State report, published his assessment in Sconce (the Journal of the AAAS) in February 1969. The major conclusions reached by Tschirley after his fourweek visit to South Vietnam included: 1. The defoliation program has caused ecologic changes. These changes are not irreversible, but complete recovery may take a long time. Regeneration of the mangrove forest to its original condition is estimated to require about 20 years. 2. The effects of defoliation on animals is not known, but it does not appear to have been extreme. There is no evidence to suggest that the herbicide used in Vietnam will cause toxicity problems for man or animals. In March 1969, the Society for Social Responsibility in Science, sponsored a five-week trip, for two zoologists to Vietnam with the objective of supplementing Tschirley's observations. The subsequent report, written by Orians and Pfeiffer (66), was published in May 1970. Their conclusions included: 1. The ecological consequences of defoliation were severe, especially in areas receiving repetitive applications of defoliants. 2. Evidence was found of moderate to severe defoliation of trees and herbs in areas many miles removed from sites of application. 3. Little evidence of toxic effects of the herbicides to animals was found, although one report was received (through an interview) of many sick and dying birds and mammals in forests following defoliation. The report was not investigated. 4. No evidence was found that the herbicides had direct adverse effects on human health. The defoliation program however, has had tremendous psychological impact upon the Vietnamese people, and the crop destruction program may have impacted on the availability of food for women, children and elderly people in the highland regions of South Vietnam. The first Herbicide Orange and July 5, 1969 reports resulted reports of human birth defects allegedly attributed to appeared in Vietnamese newspapers between June 26, 1969 (2). The public and scientific furor caused by these in two surveys of South Vietnamese hospital records V-14 �conducted independently by Cutting et al (25) and Meselson et al (63). An evaluation of both documents in 1971 by an advisory Committee on 2,4,5-T to the Administrator of the Environmental Protection Agency (2) concluded with the following summary: Summarizing the Vietnam data on human embryotoxicity, it can be said that (1) the sample of births surveyed was from year to year a variable but usually very small fraction of the total number, (2) it was quite unrepresentative of the geographic and ethnic distributions, (3) the heavily sprayed and otherwise exposed areas were greatly underrepresented, and (4) the birth records were not trustworthy and, therefore, the rates of stillbirth, and especially of congenital malfoVmation, derived from them were equally unrealiable. For example, the overall congenital malformation rate found in South Vietnam, 4.91 per 1000 livebirths, is about half of what was reported in other studies in various parts of Asia, and possibly a quarter of what might actually exist at term. A further indication that the newborn children were not carefully examined is the absence of Down's syndrome in the list of specific malformations compiled by the Army survey [Cutting et al (25)] despite the fact that some Oriental populations have been reported to have an incidence of this condition not unlike that in Western populations. Finally there is, and can be, no precise knowledge or reasonable approximation of the exposure to 2,4,5-T (and hence, TCDD) experienced by pregnant Vietnamese women, including what amounts they ingested or absorbed and when this may have occurred during pregnancy. Thus, any attempt to relate birth defects or stillbirths to herbicide exposure is predestined to failure. It can only be concluded that the birth records that have been surveyed, and probably any that will be surveyed in the future, for South Vietnam for the period 1960-1970 cannot answer positively the questions about possible adverse prenatal effects following human exposure to 2,4,5-T. It must be emphasized, however, that the searches that have been made almost certainly would have revealed any marked increase in the incidence of birth defects or the introduction of a striking defect such as that produced by thalidomide. In spite of considerable effort, no such occurrences were found. Following the publication of the above two surveys, some additional reports of birth defects in South Vietnam were released. One of these was by Tung et al (77) of North Vietnam (Democratic Republic of Vietnam). They reported that out of a total of 903 South Vietnamese taking shelter in the North and grouped in hospitals and lodgings in Hanoi, 19 adult women, including 4 mothers, and 70 children between the ages of 6 and 14 had been directly hit by herbicidal sprays while living in South Vietnam. The report went on to state that of the above four mothers, two had given birth to children with Down's Syndrome (Trisomy 21). In addition, among V-15 �the 70 children between the ages of 6 and 14, numerous cases of deformations were evident, e.g., ocular lesions, exaggerated lumps on the forehead, valgus feet (i.e., feet that are bent outward) and a high frequency of chromosomal aberrations in lymphocytes and leucocytes. Following a summary of their data, Tung'et al (77) concluded by stating: Though still limited in number, our clinical observations confirm the results obtained on animals by American researchers. The massive and prolonged utilization of defoliants besides permanent ocular lesions, can cause chromosomic alterations among a population obliged to cling to ancestral soil and these alterations can provoke among* their progeny congenital malformations the importance of which remains to be determined. In the abominable history of wars, have we ever seen such an inhuman fate reserved for the survivors except in the case of atomic war? In reviewing the report by Tung et al (77), the Dow Chemical Company (8) noted that basically, the whole study was a result of a seemingly hit and miss clinical examination of some refugees from South Vietnam who had lived in regions where defoliants had been applied. There was no record of exposure except that most had been sprayed at one time or another with something. Dow further stated: "Trying to correlate cause and effect from the published data is completely frustrating and futile. There is no doubt that these authors saw some ill people, but to reach the conclusion that their problems were caused by 2,4,5-T rather than the ravages of war is speculation." A study similar to Tung et al (77) was reported by Rose and Rose (71) in 1972. They interviewed 98 refugees in Hanoi who claimed to have been repeatedly sprayed with defoliants while in South Vietnam. Abortions were reported for humans and domestic animals and monstrous births were said to have occurred. Deaths evidently occurred among human, domestic animals, fish and fowl. The charge by Tung et al that TCDD in 2,4,5-T was reponsible for much of the Down's Syndrome seen in South Vietnam was also made by Grumner as reported by Honoroff (48). Grumner, apparently of Rockstock University, German Democratic Republic, claimed to have observed high incidences of children with Down's Syndrome while on a trip through North and South Vietnam. Honoroff quoted Grumner: Provided that it be understood that this estimate cannot be anything but a cautious one, it may be assumed that there are at least 25,000 children with hereditary defects in South Vietnam. This does not include all the unborn babies whose mothers were sprayed during the missions that were flown in recent months. It does not include those who were stillborn, or died soon after birth, on account of their serious chromosomatic defects. Even V-16 �after the war, it will probably be possible to arrive at only an approximation of the entire scale of this crime since one will only be able to examine the survivors when the time comes. In 1973, Tung et al (78) reported an increase in the number of persons with primary liver cancer in proportion to all cancer patients admitted to Hanoi hospitals during the period 1962-1968 (790 liver cancer cases out of 7,911 cancer cases, 10 percent) as compared to the period 1955-1961 (159 liver cancer cases out of 5,492 total cancer cases, 2.9 percent), which was prior to the start of herbicide spraying. The authors attributed this increase to exposure as a result of the spraying of herbicides containing TCDD in South Vietnam during the 1960s [however, a recent IRAC monograph (50) noted that limitations in the reporting of the study make impossible an adequate assessment between the incidence of liver cancer and herbicide spraying in South Vietnam]. A further factor of importance has -been suggested by Ford et al (39). They noted that at least in Thailand, consumption of aflatoxin-contaminated food was highly correlated with liver cancers. Aflatoxin is a naturally occurring contaminant of cereal crops. In 1974, the National Academy of Science (NAS) (21) announced the results of studies conducted in South Vietnam in 1972 and 1973. The NAS Committee could find no conclusive evidence of association between exposure to herbicides and birth defects in humans. Available records of two major Saigon hospitals and evaluation of records in a third, as far as they went, showed no consistent pattern of association between rates of congenital malformations and annual amounts of herbicides sprayed. The Committee recognized, however, that the material was not adequate for definite conclusions. The Committee was also unable to confirm or deny reports that some humans (especially the Montapnards) and domestic animals became ill or died after exposure to herbicide sprays or after eating treated plants or drinking contaminated water. The Committee also attempted to assess the social, economic and psychological effects of the herbicide program. The impact of the program on the population "appeared relatively trivial as compared with other aspects of the upheaval in that country." Evidence was obtained that numbers of families moved away from their traditional homes because of the herbicide spray program but few were actually identified. In a letter of transmittal for the NAS report (21), the President of NAS stated: "On balance, the untoward effects of the herbicide program on the health of the South Vietnamese people appear to have been smaller than one might have feared." IV. EASTERN MISSOURI HORSE ARENA EPISODE In August 1972, the Missouri Division of Health, St. Louis, Missouri, and The Center for Disease Control, Atlanta, Georgia (59) reported an investigation of a horse arena in eastern Missouri where 54 of 57 horses exposed to the arena had died of an illness characterized V-17 �by skin lesions, severe weight loss and heptotoxicity. Birds, dogs, cats, insects and rodents were also found dead in and around the arena, and one 6-year-old girl exposed developed epistaxis, gastrointestinal complaints, and severe hemorrhagic cystitis (characterized by blood in the urine). Analysis of urine cultures for bacterial and viral pathogens was negative. Three other persons developed milder illnesses consisting primarily of transient headaches and nausea after exposure to the arena. The toxic substance(s) responsible for the illness was not at that time identified. In the investigation of the illness, Lobes et al (59) found that the outbreak coincided with treatment of the arena floor for dust control with approximately 2,000 gal of salvaged motor oil. The treatment occurred on May 26, 1971. On May 30, the stable owners reported that "hundreds" of birds were found dead on the floor of the arena barn. Within the next few weeks, cats, dogs, rodents and horses began to die. The four people cited above [2 adults and 2 children (both girls)] had more than occasional exposure to the arena barn during the six months following the oil spraying. These individuals were first examined in mid-August 1971, The report (59) also noted that similar horse illnesses and deaths occurred in two other horse arenas in the eastern Missouri area sprayed by the same salvage oil company. The three arenas had been sprayed within one month of each other. Subsequent to investigation, soil from all three arenas was excavated and disposed. No further problems occurred following the excavations. In 1974, laboratory analysis of soil samples taken from the initial arena implicated 2,4,5-trichlorophenol (TCP) and TCDD as the probable toxic substances (29). The actual levels of TCDD in these soils however were not published until 1975, when Carter et al (19) provided more details on the exposure and the probable source of the TCDD in the salvage oil. The horse arena soil was found to contain 31.8 to 33 yg of TCDD per gram (ppm) of soil. In addition, further investigations revealed that the sludge used to spray all three arenas came from a common storage tank at the salvage oil company. It was suspected that TCDD and TCP were in distillate residues collected by the salvage company from a hexachlorophene producer in southwestern Missouri. Between February 1971 and October 1971 the salvage oil company obtained and stored 18,000 gal of the distillate in a storage tank from which the sludge for spraying the three arenas was obtained. In late 1971 the hexachlorophene plant and subsequently the salvage oil company both discontinued operations. The residue remaining in the tank originally used to store the distillate residue at the plant site was sampled in 1974. It contained TCDD in concentrations of 306 to 356 yg/g (19). Case (20) has described some of the clinical studies performed on the horses involved in this episode. Kimbrough et al (57) has recently (1977) detailed the epidemiology and pathology associated with the poisoning episode. V-18 �Commoner and Scott (22) have reviewed the Missouri Horse Arena Episode in an attempt to provide consultative data to the Italian Government in the wake of the Seveso, Italy episode. Their,review focused on the human reactions (symptoms) to accidental TCDD exposure and the problem of soil degradation of TCDD. They also provided an excellent chronological account of the episode. Beale et al (13) have recently re-examined the young girl who had developed hemorrhagic cystitis following repeated exposure to TCDD in one of the horse arenas sprayed with the waste oil. In the 5-year interval since exposure, the patient had grown normally, and both her height and weight were above the 75th percentiles. Detailed physical, chemical and neurological examinations were also conducted and found to be normal. The same studies were done on the patient's sister and mother, exposed simultaneously, but less extensively to dioxin, and the results were also normal. Beale et al (13) concluded: "Our experience demonstrates that people exposed to dioxin can recover completely with no apparent sequela from the toxin. It remains to be determined whether -the exposure to dioxin in these children will result in abnormal pregnancies or affect their offspring." V. THE SEVESO, ITALY EPISODE Perhaps the most publicized chemical accident in modern times is the TCDD episode in Seveso, Italy. This episode has attracted worldwide interest and concern. Hundreds of scientists, physicians and veterinarians have participated in either on-site inspections, conferences, or consultations into the various facets of this episode. Although the Seveso, Italy episode did not involve 2,4,5-T herbicide, it did involve the production of trichlorophenol. The trichlorophenol was in this case used in the production of hexachlorophene. Nevertheless, this episode represents to many people the inherent danger associated with the industrial production of 2,4,5-T. Data on levels of TCDD found, the magnitude of the contamination and the extent of human and animal illness have just recently begun to appear in the scientific literature. The following scenario of the episode has been assembled from this literature. The episode of TCDD poisoning occurred on 10 July 1976 in Seveso, Italy, a small town 40 kilometers (km) north of Milan (40,46). The source of the TCDD was a chemical factory that produced trichlorophenol through the alkaline hydrolysis of tetrachlorobenzene (see Figure 1). When the temperature in a steam-heated reaction vessel rapidly increased, a safety disk ruptured sending a plume of trichlorophenol, TCDD and other products 30 to 50 meters (m) high above the factory. The cloud apparently rose into the air, cooled and came down over a cone-shaped area about 2 km long and,700 m wide. V-19 �The chemical plant involved was the Givaudan ICMESA (Swiss-owned) chemical plant. At the time of the incident, there were some 2,000 kg of reagents and reaction products in the reactor (sodium trichlorophenate, soda, sodium chloride, ethylene glycol, tetrachlorobenzene and secondary reaction products) (9). Based on determinations made by production officials it was estimated that 4,000-500 kg of reaction product was discharged into the atmosphere (9,27). The amount of TCDD dispersed with the other reaction products has been estimated to have ranged from 650 grams to 1,700 grams (27,69). A sample of the escaped product taken from the reactor head for analysis revealed the presence of 3.5 percent TCDD (35,000 parts per million TCDD) (9). The accident occurred on a Saturday. By the following Monday, a site inspection of the area revealed phytotoxic effects (brown discoloration and drop-like perforation of the leaves) for a distance of some 1,000-1,300 m in a triangle with a base of approximately 400 m and a vertex of 100 m centered on the factory (9). Several measurements of TCDD on vegetation in this area and areas adjacent to the factory were in the 1 to 15 ppm range, with one reading as high as 50 ppm (69). • Reggiani (69) reported that animals (birds, rabbits and chickens) were beginning to die 2-3 days after the accident. A few children and some adults who had been directly seized by airborne dust consisting of the reactor content were complaining of nausea and presenting skin lesions of various aspects and extension but mainly redness and swelling. Some of the children were hospitalized and the physicians in charge warned that beyond overt signs of injury pointing to the action of caustic material causing burns and blister formation, they also had to consider the possibility of a contact or ingestion of a still unknown quantity of TCDD. In the meantime numerous Italian laboVatories and the Givaudan Laboratories cooperated in mapping out the polluted zones, determining TCDD on soil, vegetation and buildings by gas chromatographic-mass spectrometric techniques (9,41,69). In addition, the Regional Veterinary Service assisted in drawing up the map, working from animal death patterns and TCDD levels in the liver of surviving animals. Highest TCDD levels were found in herbivorous animals (41). About 1,000 assays led to the area being divided into two zones. Giovanardi (42) reported that the first zone, Zone A, was a triangularshaped area covering approximately 1000 hectares (ha). This area, located south south-east of the ICMESA factory and downwind at the time of the accident, had estimated soil levels of TCDD greater than 0.001 ppm [Reggiani (69) later described this area as having TCDD levels greater than 10 ppb]. The 700 inhabitants of this area were evacuated in three stages, on 26 July, 28 July and 2 August 1976. In the second zone, Zone B, soil levels of TCDD were detectable but less than 0.001 ppm [Reggiani (69) defined the soil levels of TCDD as between 0.1 and 10 ppb]. This area covered approximately 250 ha and was divided between a large urban center and an extensive rural area with some small residential V-20 �aggregates (42). This area had a population of 4,900 and was not evacuated. For the people in Zone B, recommendations were issued to reduce the possibilities of exposure in particular for the children and the women (69). A third zone, Zone C or "Respect Zone," covering a total of about 1,430 ha was also delineated. Occasional concentrations of less than 0.1 ppb TCDD in soil were found in this zone. The population of this area was approximately 40,000 people (69). By late August 1976, an extensive surveillance system of the health of the population was established covering the acute and mid-term effects of the exposure as well as the long-term effects. General and special medical examinations, laboratory tests at given intervals, course and outcome of pregnancies, examinations of abortions, rate of stillbirths, followup of newborns, morbidity and mortality of the population, and a cancer registry were all set up to detect any abnormality of the health of the community for which an exposure to TCDD could be postulated. The medical health surveillance program was extended to 11 districts with a total population of 216,000 (9,14,37,69). Periodically, reports of clinical damage to the population of Seveso have appeared in the press and scientific literature (38,40,41, 46,80). However, the most complete analyses of health data have been recently published by Reggiani (69). He concluded: The Seveso accident has not revealed up to now toxic effects in humans, which have not been observed in other episodes. Chloracne, the typical skin lesion, has occurred in children with tendency to spontaneous and rapid healing. The peripheral nervous system has perhaps been attacked and reacted with subclinical signs of impairment. Signs of involvement of the liver without apparent functional disorders have occurred. No other organs or functions have been impaired. There has been no derangement of the gestation, no foetal lethality and loss, no gross malformations, no growth retardation at term and no cytogenetic abnormalities. The immunocapability of the population, not even of the,children with chloracne, has not been attained. VI. GLOBE, ARIZqNA_EPISODE_ Globe, Arizona was another site of possible human exposure to TCDD. In 1969, the U.S. Forest Service applied 3,680 Ib of 2 (2,4,5-trichlorophenoxy) propionic acid (Silvex) and 120 Ib 2,4,5-T in the Kellner Canyon-Russell Gulch spray project near Globe (76). The reports of harmful effects to animals and people from the spraying began during and immediately after the spray treatment. The complaints included damage to vegetation off the spray project area, deformed animals and human illnesses. Although the Forest Service investigated the allegations, many of the local citizens were dissatisfied with the V-21 �reports and the case continued to fester until, in February 1970, it attained national attention. Television newscasts showed deformed animals alleged to have been caused by the herbicides. On February 13, 1970, a public hearing was held in Globe. As Tune Ma.ga.zwie. (4) reported, the local veterinarian insisted that he had noticed nothing out of the ordinary in local animals. Doctors too were puzzled. Said one: "I keep trying to see the relationship between the spraying and the illnesses, but I have simply not found anything." T-unn (4) also reported that: "The investigators holding the public hearing ended up perplexed and incredulous. In a paranoid outburst, the investigators were accused of being impostors, really representatives of chemical manufacturers in clever disguise." To look further into this episode, The Office of Science and Education, USDA, established an investigating team to assess the allegations against the Kellner Canyon-Russell Gulch Spray Project. Tschirley et al (76) published the results of the investigating team following on-site inspections of the spray project area, February 16-20, 1970. Tschirley et al, attempted to assess numerous parameters that would contribute to a comprehensive assessment of the episode. Some of these parameters included: (1) assessment of herbicide damage to plants off the project area, (2) effects of plant diseases, (3) effects of air pollution, (4) residue analyses of soils, plants and animal tissue, (5) observations of fish and wildlife, (6) evaluations of the health of domestic animals and (7) interviews with many of Globe's citizen and physicians. Some of the conclusions reached by Tschirley et al (76) were: 1. There was clear evidence of drift of herbicide outside the project area. 2. There was evidence of woody plant mortality from root rot, and also visible damage to certain yard trees from several kinds of birds and insects. 3. Reports from wildlife specialists indicated no significant effects on birds, deer and other wildlife. 4. With the exception of soil from the site where the herbicide was loaded aboard the helicopter, no residues of 2,4-D, 2,4,5-T, Si 1 vex or TCDD were found in any of the substrates analyzed. 5. Information obtained from owners of livestock and observations of animals did not indicate any illnesses that do not commonly occur in other regions. No association was found between the herbicides and the deformed animals shown on the television newscasts. 6. Human illnesses had been reported by several residents in the Globe region. Many of the residents with complaints were interviewed V-22 �by a medical member of the panel. The complaints were those that commonly occurred in the normal population; no cases of chloracne were reported. One individual had an eye irritation from steam cleaning an empty herbicide drum. Nine doctors serving the area of Globe were interviewed and there was general agreement that there had been no significant increase in human illness related to the spraying. Tschirley et al (76) summarized their panel report by stating: "Significant in evaluating the Globe situation was the emotional peak of its inhabitants. The complaints offered were those occurring in normal populations, with many of them (especially in the adults) being quite subjective. With the exception of the skin rash and eye irritation experience by one subject, it is highly unlikely that the ailments described were related directly to the spraying. However, the psychosomatic effect of an aroused public very likely has played a role. It is also important to note that except for three subjects all of the complaints dated only from the June 1969 spraying, despite the Forest Service having sprayed the same area three other years." A subsequent report was published by Roan and Morgan (70) of analytical results of selected human tissue collected by Tschirley et al (76) and of an epidemiologic study of the hospital records. Roan and Morgan concluded: We cannot find any evidence that there was long-term exposure of residents of the Globe, Arizona area to chlorophenoxy herbicides, or significant contamination of water supplies in this area with 2,4-D, 2,4,5-T, Si 1 vex or metabolites of these herbicides. Nor have we found contaminants such as TCDD that may be associated with one or more of the above technical grade products. Statistics on reproductive mortality and morbidity for the period 1960 through the first six months of 1970, from one hospital serving this area, do not indicate any trends that are suggestive of adverse influences on human reproductive function that might be associated with herbicide use during the years 1965, 1966, 1968 and 1969. Even though the analytical data available to us apply only to the years 1969 and 1970, the rate of disappearance of these compounds in the environment leads us to believe that gross, protracted contamination was probably absent in prior years as well. Although samples of. human tissues and body fluids, obtained through the cooperation of the medical profession in the area, are few in number, we believe the analytical results (which were all negative) are very probably representative. V-23 �VII. THE SWEDISH LAPLAND EPISODE In the spring of 1970, Swedish newspapers reported an accumulation of sudden deaths of reindeer grazing in the Visttrask area of Lapland. Approximately 30 reindeer, mainly young animals, died within a week after a heavy, wet snowfall, without any previous signs of illness. It was also reported that about 10 reindeer cows aborted their fetuses. Examination of several reindeer by veterinarians showed inanition (empty stomachs). When given additional feed, the deaths stopped. The case was of particular interest since it was learned that the area where the reindeer grazed had been treated with a mixture of 2,4-D plus 2,4,5-T (2). Analyses performed on liver and kidney samples (33,35) from one of the cows and three aborted fetuses noted above indicated traces of 2,4-D (0.2 to 0.5 ppm) and 2,4,5-T (0.3 to 1.0 ppm). Tree leaves contained 25 and 100 ppm of 2,4-D and 2,4,5-T respectively. However, no herbicides could be found in the ground vegetation. Although it was generally accepted that the deaths of the reindeer were attributed to starvation rather than exposure to 2,4,5-T and/or TCDD, Erne (34) initiated a controlled experiment on female reindeer and phenoxy herbicides. Erne's experiment involved thirty pregnant reindeer, where half of the animals were given birch leaves from an area that had been aerially sprayed with one of the products that was used in the Visttrask area, the rest received untreated birch leaves. The average daily intake of leaves for both test and control groups was about 1 kg per animal, which for the test group corresponded to a daily dose of phenoxy acid of 1 mg/kg body weight. After the feeding experiment, the reindeer were sacrificed and necropsied just before the expected parturition. During the course of the investigation, no clinical hematological or chemical signs were observed of injurious effects attributable to the sprayed leaves. The necropsy of the sacrificed animals showed nothing at all remarkable. All were pregnant (except one in the control group) and all the embryos were alive and normally developed. In histological investigations of the female reindeer and the fetuses, no pathological changes were observed that could be attributed to the prolonged consumption of sprayed leaves as fodder. Thus, Erne (34) concluded that the toxic manifestations noted in the Lapland incident were probably not caused by ingestion of herbicides. Immediately following the report of reindeer deaths (and concurrent with press reports on alleged health effects from 2,4,5-T and TCDD in Vietnam), two cases of congenital malformations in human infants were also attributed to alleged exposure of pregnant women during application of phenoxy herbicides in Lapland forests (2). However, competent medical scientists at the Institute of Hygiene and the Teratological Laboratories of the Karolinska Institute of Stockholm and at the Institute of Human Genetics at Munster, Germany, were unable to find temporal or clinical evidence to suggest that the occurrence of these human birth defects was more than coincidentally related to the herbicide operations. V-24 �The publicity given to the Lapland incident resulted in additional reports of alleged adverse human health effects due to the phenoxy herbicides. For example, in early 1972, Swedish newspapers reported excess lung cancer mortality among railroad workers exposed to 2,4-D and 2,4,5-T. These reports prompted the Swedish National Board of Occupational Safety and Health to request an epidemiological evaluation of the stated excess mortality and its relation to herbicide exposure (10). The subsequent investigation as reported by Axel son and Sundell (10) in 1974 found that a slightly dose-dependent and significantly increased tumor incidence and mortality among workers exposed to the herbicide amitrol (3-amino-l,2,4-triazol) whereas those exposed to 2,4-D or 2,4,5-T had about normal tumor incidence and mortality. The study comprised 2,978 person-years at observation in the total cohort. The study has been recently reanalyzed with a case-control approach and through stratification on amitrol when considering the effect from phenoxy acids and vice versa (51). The results showed a possible and previously masked tumor inducing effect also from phenoxy acid. By 1976 an Intense debate was in progress in Sweden over the use of phenoxy herbicides. This debate prompted Harden (45) to examine the occupational history of 87 patients who had malignant mesenchymal tumors and who had visited the oncological clinic in Umea during the years 1970-76. Nine of the 87 patients were forestry workers, four worked in farming and forestry and six in sawmills or the pulp industry. The implication by Harden was that these 19 individuals were in occupations where exposure to phenoxy herbicides was relatively common. Based on the official statistics of Sweden, the expected fraction of tumors has been calculated for these occupations: the expentancy was 11 cases versus the 19 observed. Harden (45) however, cautioned making any conclusion about the possible casual connection between exposure to phenoxy acids and contaminants and the occurrence of malignant tumors, solely on the basis of the reported cases. In February 1977, the debate climaxed when the Royal Swedish Academy of Sciences organized a conference on "Chlorinated Phenoxy Acids and their Dioxins, Mode of Action, Health Risks and Environmental Effects" (31). The conference participants concluded that (1) there was no evidence that dioxins could be formed in nature, (2) there was no evidence of bioaccumulation of TCDD at levels of application used in Sweden and (3) that if the concentration of TCDD can be kept below 0.1 ppm in all phenoxy formulations the risks involved can be disregarded and the safety factors based on the phenoxy acids themselves. In the March 1978 WBBM television report on "Agent Orange: Vietnam's Deadly Fog", reference was made to a report from Sweden on birth defects (e.g., spina bifida) in children born to 65 women allegedly exposed to 2,4,5-T herbicide. The only reference to such an incident was that reported by Hailing (44) in 1977. Hailing studied the malformations V-25 �in children born to mothers exposed to hexachlorophene soap during early pregnancy. All of the mothers were employed as nurses in a hospital and thus came in contact with the hexachlorophene in performance of this job. A group of 65 children born to this group showed six slight malformations and five severe malformations, whereas only one slight case in 68 children was observed in the unexposed group. VIII. TE AWAMUTU, NEW ZEALAND EPISODE The New Zealand episode had many similarities to the episode in Sweden; once the initial report was publicized, additional cases were forthcoming. In January 1972, Sare and Forbes (72) reported the following in the New Zealand Medical Journal: "Sir, - Two babies, born within a month of each other at our local maternity hospital, had congenital defects incompatible with life. Both had a gross myelo-meningocele. Post-mortem was performed on only one and other congenital abnormalities were brought to light. What intrigued us was that the families concerned live on adjoining hilly country farms, where for several years aerial spraying has been carried out with a chemical called 2,4,5-T, designed to kill useless vegetation. Inquiries into the nature of this chemical revealed that it contains an impurity called dioxin, which is apparently one of the most powerful poisons ever discovered. It has been investigated in the United States, partially banned in all states, and totally in others. It was likewise banned in Vietnam when its potential danger was discovered " The suggested relationship between 2,4,5-T/TCDD and the two deformed babies quickly received national and international attention. Accusations that 2,4,5-T/TCDD were indeed responsible for the congenital defects soon appeared in articles in the United States (1, 32). The circumstances surrounding these cases at Te Awamutu were thoroughly investigated by a subcommittee of the Agricultural Chemicals Board of New Zealand (6). In the subcommittee report it was noted: The women who gave birth to deformed babies had both been exposed to 2,4,5-T during pregnancy, one person by assisting at the airstrip during spraying and the second person by helping to free the spray truck which was stuck on the property and was exposed to 2,4,5-T when spraying was done to lighten the load. It was not possible to ascertain the degree of exposure in either case. V-26 �The deformity common to both babies is spina bifida, caused by a failure of the end of the neural tube to close completely during early development. This deformity is one of the commonly occurring deformities, with overseas averages of about 1 per 1,000 total births. In New Zealand during the period 1964-70, 515 live births and 151 stillbirths affected with spina bifida were recorded. In the light of present embryological knowledge it may be stated that the neural tube is usually closed by the fourth week after conception and definitely by the sixth week. Medical records show that in one case, exposure to 2,4,5-T during the spraying operation occurred after the neural tube would have normally closed. It is concluded that in one of these cases the reported exposure to 2,4,5-T could not have caused the birth deformity. It is not possible to state definitely in the second case whether exposure to 2,4,5-T was in any way a factor causing the deformity, and thus the subcommittee was unable to arrive at any information of value to the general topic of 2,4,5-T toxicity to human foetuses. In April 1977, the New Zealand televison program "Dateline Monday" suggested that the occurrence of "clusters" of neural tube defects in the South Taranaki, Northland and Waikato areas of New Zealand were related to the use of 2,4,5-T (61). The New Zealand Department of Health, Division of Public Health, appointed a committee of experts to investigate the allegations. In the Committee report, McQueen et al (61) noted that the three "clusters" represented 20 cases of birth defects. Seven of the cases were anencephaly (congenital defect of the cranial vault) and 13 were spina bifida (congenital defect of the bony encasement of the spinal cord). McQueen et al noted that although this group of defects may well have occurred entirely by chance, the possibility of a common causal factor must be considered. After a thorough investigation of each of the 20 cases reported, McQueen et al (61) concluded: It is obvious from an inspection of the data for the three "clusters" that 2,4,5-T cannot reasonably be implicated in the causation of neural tube defects. It is true that in one or two cases there may have been some "exposure" to 2,4,5-T around the critical period. However, considering 2,4,5-T is the most used pesticide in New Zealand, this is'not unexpected. In short, the data permit the conclusion that there is no evidence to implicate 2,4,5-T as a causal factor in human birth defects. As a final note in relation to this episode, the following brief article appeared in the New Zealand Medical Journal (5): V-27 �Publicity on certain chemicals as causation of malformations of the human fetus has been widespread. Some of the publicity has been sensation mongering and not all the remarks from the profession have been in keeping with a balanced assessment of scientific evidence. It is proper that there should be intelligent public awareness of the various environmental hazards that may come from the use of chemicals in farming ....however, those who would write of their experiences in medical journals must remember that disasters are the staple of the sensation mongers in the news media industry. Until recent publicity there had been no suggestion that 2,4,5-T, which has been used for over 20 years in New Zealand, was responsible for congenital malfunctions either in man or in farm animals. It is the duty of the physicians (and scientists) who have any concern for science to attempt to make valid observations which can be repeated. In the problem at issue, fetal malformations are natures common mistakes which we have no desire to perpetrate or to increase, although they are the inevitable price that is paid for our place on the evolutionary scale. There are extensive gaps in our knowledge but they will be filled only by patient work. Unresolved problems of fetotoxicity can only be solved by accurate record keeping at all stages of pregnancy. IX. DISCUSSION OF LITERATURE AND CONCLUSIONS The episodes described in this chapter have provided much of our knowledge of the adverse effects to human health of the phenoxy herbicides, other chlorinated phenols and the associated dioxins. The only episodes however where TCDD was actually confirmed as a caustive agent were those involving some of the industrial accidents, the Eastern Missouri horse arena episode and the Seveso, Italy episode. Mercier (62) estimated that in the industrial accident in 1963 at the Philips-Duphar Company, Amsterdam, The Netherlands, up to 200g of TCDD were released into a factory hall. The incident in the horse arenas in Missouri may have involved 5,000g of TCDD (69). The quantity of TCDD involved in the Seveso, Italy episode has been estimated at 650-1,700g (69). In these three episodes, the TCDD was confined to a relatively limited area. The exposure of the people involved was from days (Philips-Duphar) to weeks (Seveso) to months (Missouri). Nevertheless, no human deaths were reported, although in both Missouri and Seveso, numerous animal deaths did occur. The clinical experience from these three episodes (and the other industrial episodes involving at least 1,000 individuals) support the opinion that patients without chloracne are extremely unlikely to have suffered the toxic effects of TCDD. In general, only in the most severe cases of chloracne has symptomatology persisted, admittedly for many years in a few instances. V-28 �The available scientific literature suggests that the episodes in Arizona, New Zealand and Sweden were primarily the result of emotionalism associated with zealous press coverage. Although each incident began subsequent to field applications of phenoxy herbicides, it was highly unlikely that the symptoms reported were attributable to actual pesticide or TCDD exposure. The behavior in the environment of 2,4,5-T and TCDD following normal field applications (see Chapter III) lends little credence to accusations that significant bioaccumulations occurred in humans to initiate the t-oxic symptoms reported. Furthermore, the absence of confirmed illness in domestic livestock or wildlife in these three episodes also addresses the issue of whether an actual toxic exposure occurred. Chapter IV defined the concentrations of herbicide and TCDD that were toxic to animals. The magnitude of the dosage required to elicite toxic symptoms in animals might be obtained only under the most extreme cases (e.g., spills or sequential repetitive applications). These extreme situations were not noted in the episodes in Arizona or New Zealand. The human responses associated with these episodes show a similarity to what occurred in Michigan involving exposure to polybrominated biphenyls (PBB). In 1973 and 1974, more than 10,000 Michigan farm residents were exposed to PBB when several hundred pounds were accidentally introduced into a nutritional supplement that was subsequently fed to numerous herds of dairy cattle. Budd et al (18) conducted an epidemiological study in an effort to determine whether or not exposure to PBB had caused illness in Michigan residents. Three groups were invited to participate in a prospective cohort study: (1) all persons who had been identified as living on PBB-contaminated farms at the time of quarantine; (2) all persons who had received food products directly from such farms; and (3) workers and their families who had been exposed occupationally to PBB in a chemical manufacturing plant. All subjects were administered a questionnaire requesting information on the occurrence in the years before and since 1973 of 17 symptoms and conditions potentially related to PBB. Venous blood samples were also obtained on the subjects. An evaluation of dose-response relationships revealed that symptom-prevalence rates were higher in persons with no detectable PBB in serum than in those with measurable quantities. These observations suggested that factors other than PBB absorption were responsible for the production of symptoms and that selection factors (e.g., selecting from a list of given symptoms by the subject) may have played an important role in the observed distribution of complaints. The episodes in Arizona, New Zealand and Sweden all occurred in the same time period; a period when numerous articles appeared in the world press on the alleged human health effects of Herbicide Orange and TCDD in South Vietnam. The effects these articles had on the actual episode can only be speculated. V-29 �The wide publicity that was given to the use of defoliants, especially Herbicide Orange in South Vietnam, appeared to have exceeded concerns of human health or the environment. Political issues may certainly have been a major reason for much of this publicity. Consider, for example, the data in Table 1 of this chapter; more 2,4,5-T and hence TCDD, was disseminated in the United States during the same period than in South Vietnam. If the assessment of canopy penetration is reasonably accurate in Chapters I and III,then the actual groundlevel deposition of Herbicide Orange in South Vietnam (1.4 pounds 2,4-0/2,4,5-T per acre) would have been approximately equal to the concentrations of herbicides encountered at ground-level following brush applications in the United States. The Committee on the Effects of Herbicides in South Vietnam of the the National Academy of Sciences (21) attempted to assess the effects of propagandists activities on the attitudes of the South Vietnamese towards the use of herbicides. The following statements are quotations from the 1974 report: Our findings indicate that there is a major dichotomy between,the views of the rural population and those of the urban middle-sector regarding the use of herbicides in SVN. Contrary to what might be expected, the herbicide missions are much less emotional issue among the peasants, who bore the brunt of the effects, than it is among urban intellecturals for whom it has become a symbol. Despite extensive propaganda and counter-propaganda campaigns waged by the RVN and the NLF, peasant views regarding herbicide effects seem to be based upon their own experience. The RVN stressed that herbicides were used as a military measure to deprive the guerrillas of their hiding places, that the herbicides might damage crops but could also have beneficial effects, and that people and livestock would not be adversely affected by spraying. NLF statements emphasized the dangerous nature of herbicides. They claimed that the chemicals caused the death of people as well as livestock and crops, resulted in increased numbers of miscarriages and stillbirths, and caused numerous diseases, especially leprosy and conjunctivitis. Further, it was said that the U.S. had deliberately introducted "chemical bacteria" into the spray which could penetrate peoples bodies and cause disease. The fact that the villagers did not appear to subscribe blindly to the propaganda claims of either side does not mean that they lacked political opinions nor that they were uninfluenced by information derived through the mass media. Rather it seems to mean that their opinions on this issue came mainly from their own observations. V-30 �The degree to which the above referenced propaganda influenced world opinion is illustrated by Dmitriyev (28) in articles published in 1974 in a Russian medical journal. The following quotation is a translation from that journal: Often in South Vietnam, chemical substances were used not only in the forest regions but also close to populated areas; this resulted in injury to a considerable part of the peaceful population. According to the data of the Provisional Revolutionary Government of the Republic of South Vietnam in 1961-1969, 1,293,000 persons were subjected to the effect of poisonous chemicals. In the first ten months of 1970, 185,000 cases of persons being poisoned were recorded. Three hundred persons died and a significant number of those injured became chronic patients. Persons injured by herbicides and defoliants noted perceiving a sharp odor of chlorine or DDT, sharp pain, burning in the nasopharynx and sneezing (91%), crying and vomiting (73%), headache and vertigo (38%), a burning sensation in the area of the eyelids and the skin (41%). These clinical symptoms were apparent after a 2.4-hour incubation period. Improvement in the patients, if they did not die, began after 3-4 days. However, they continued to suffer from asthenic symptoms in the form of sleeplessness, sexual weakness, and weakening of the vision. Similar quotations are available in American or European literature. Mercier (62), in reviewing the literature on TCDD for a conference in Milan, Italy in 1976, stated of the National Academy of Science Report (21): Considerable information is contained in a NAS report (1974) about the effects of herbicides, and especially 2,4,5-T, so-called "Agent Orange" and the contaminant TCDD on humans, animals and vegetation in Vietnam where they have been used during military herbicide operations. It contained reports of death to children, diarrhea, skin rashes looking like insect bites, and abdominal pain following spray missions. The use of the materials also significantly increased the incidence of congenital malformations among children. The point to be made is that the scientific studies that have been conducted in Vietnam; Globe, Arizona; Eastern Missouri, Sweden; New Zealand; Seveso, Italy; and the numerous industrial accidents do not document deaths of children or adults due to the herbicides or TCDD, nor do they substantiate increased incidence of congenital malformations among children. The reports published by North Vietnamese scientists provide insufficient data on which to draw contrary conclusions. V-31 �X. SUMMARY Increased industrial production of the phenoxy herbicides parallelled the rapid acceptance of these materials in world agriculture. The demands upon the industrial production however, resulted in at least 23 industrial incidents involving'over 1,100 people (almost all adult males). Although medical examinations were initially conducted on these individuals, few long-term studies are available. The use of herbicides by the United States military in South Vietnam precipitated numerous allegations of adverse health effects upon the human population. Review of the scientific literature of the few available studies conducted in Vietnam do not confirm the allegations. Episodes of TCDD poisoning in Eastern Missouri in 1974 and in Seveso, Italy in 1976 resulted in adverse effects to primarily women and children. Although the acute symptoms of poisoning have dissipated, long-term effects remain to be determined. Episodes of alleged poisoning from 2,4,5-T and TCDD in Globe, Arizona (1969-70), Sweden (1970) and New Zealand (1972) occurred in a period of time when intense publicity was given to the use of herbicides in South Vietnam. The available scientific studies of these incidents suggest that factors other than herbicide exposure may have been responsible for the symptoms reported. V-32 �CHAPTER V LITERATURE CITED 1. Adamson, L. 1974. Spray Now - Pay Later? EmuAon. Action, p 9-13; July 6, 1974. 2. Advisory Committee on 2,4,5-T. 1971. Report of the Advisory Committee on 2,4,5-T to the Administrator of the Environmental Protection Agency. U.S. Environmental Protection Agency, Washington, D.C. Mim. 76 p. 3. Anonymous. 1968. A preliminary assessment of herbicides and defoliation. EnuxXon. Sex.. Te.chno£. 2(3): 176-181. 4. Anonymous. 1970. Globe's Mystery. T^nie 95(8):42. 5. Anonymous. 1972. Fetotoxicity. N.Z. Med. 3. 75(480):304-305. 6. Anonymous. 1972 Report of the Subcommittee on 2,4,5-T. Agricultural Chemicals Board; Wellington, New Zealand. Pp 1-10. 7. Anonymous. 1974. Disposition of Orange Herbicide by incineration. Final Environmental Statement. November 1974. Department of the Air Force, Washington, D.C. 737 p. 8. Anonymous. 1974. Comments of the Dow Chemical Company on the paper by Lucile Adamson, Spray Now - Pay Later? Published in Environmental Action July 1974, p 9-13. The Dow Chemical Company, Midland, Michigan. 79 p. 9. Anonymous. 1977. Activity of the Laboratorio di Igiene e Profilassi (LPIP) in testing consequent to the ICMESA Incident.. Report of 5 November 1977 to the Seveso Authority. Reporto Chimico, Laboratorio di Igiene e Profilassi, Milano, Italy. (Italian) 10. Axelson, 0., and L. Sundell. 1974. Herbicide exposure, mortality and tumor incidence. An epidimiological investigation on Swedish railroad workers. Wolfe. Envision., HeaJttk 11(1):21-28. 11. Baader, E.W. and H.J. Bauer. 1951. Industrial intoxication due to pentachlor phenol. Iwd. Meci. SUA.Q. 20(6):286-290. 12. Bauer, H., K.H. Schulz, and U. Spiegelberg. 1961. Occupational intoxications in the manufacture of chlorophenol compounds. Arch. Gewerbepathol. GejMeA.be.hyg. 18:538-555. (German) 13. Beale, M.G., W.T. Shearer, M.M. Karl, and A.M. Robson. 1977. Longterm effects of dioxin exposure. Letter to Editor. lanc.zt 1(8014):748. 14. Berlin, A., A. Buratta, and M.Th. Van der Venne. 1976. Proceedings of the expert meeting on the problems raised by TCDD pollution. Milan Italy, 30 September and 1 October. 179 p. V-33 �15. Bionetics Research Laboratories, Inc. 1969. Evaluation of the carcinogenic, teratogenci and mutagenic activity of selected pesticides and industrial chemicals. Vol. III. Teratogenic Study in Mice and Rats. Submitted under contracts PH 43-64-57 and PH 4367-735 with the National Cancer Institute. Document No. PB-223160, National Technical Information Service. 16. Bleiburg, J., M. Wall en, R. Brodkin, and I.L. Applebaum. 1964. Industrially acquired porphyria. A/ic/i. Vesunatol. 89:793-797. 17. Braun, W. 1959. Clinical observations on the origin of chloracne. 10:126-129. (German) 18. Budd, M.L., N.S. Hayner, H.E.B. Humphrey, J.R. Isbister, H. Price, M.S. Reizen, G. van Amburg, and K.R. Wilcox, Jr. 1978. Polybrominated biphenyl exposure - Michigan. Motb. Molt. 27(14) :115-1 16, .121. 19. Carter, C.D., R.D. Kimbrough, J.A. Liddle, R.E. Cline, M.M. Zack, Jr. W.F. Barthel, R.E. Koehler, and P.E. Phillips. 1975. Tetrachlorodibenzo: an accidental poisoning episode in horse areans. Science 188:738-740. 20. Case, A. A. 1976. Tetrachlorodibenzodioxin (TCDD) - clinical aspects of poisoning. 1976. Ctin. TOXA.C.OI. 9(6): 963-967. 21. Committee on the Effects of Herbicides in South Vietnam. 1974. Part A. Summary and conclusions. National Academy of Science, Washington, D.C. 398 p. 22. Commoner, B. and R.E. Scott. 1976. Accidental contamination of soil with dioxin in Missouri: Effects and Countermeasures. Center for the Biology of Natural Systems. Washington -University St. Louis, Missouri. Mim. 27 p. 23. Courtney, K.D., D.W. Gaylor, M.D. Hogan, H.L. Falk, R.R. Bates, and I. Mitchell. 1970. Teratogenic evaluation of 2,4,5-T. Science 168(3933): 864-866. 24. Crow, K.D. 1970. Sec. 56:79-99. Chloracne. Trans. St. John's Hosp. t?eAJwuto£. 25. Cutting, R.T., T.H. Phuoc, J.M. Ballo, M.W. Benenson, and C.H. Evans. 1970. Congenital malformations, hydatidiform males and stillbirths in the Republic of Vietnam, 1960-1969. Document No. 903.233. Government Printing Office, Washington, D.C. 26. Dalderup, L.M. 1974. Safety measures for taking down buildings contaminated with toxic materials. II. T. Sec. Ganaeife. 52:616-623. (Dutch) V-34 �27. di Domenico, A. 1977. Valiuta.z4.one. dsJULa. TCVD net teM.e.no. Rapporti ISTISAN 1977/4. Istituto Superiore di Sanita, Roma. 101 p. (Italian) 28. Dmitriyev, V.I. 1974. Harmful effects of chemical substances used by the U.S. Army in Indochina l/oen. Med. In. 1:88-90. (Russian) 29. Donnell, H.D., and P. Phillips. 1974. Illness associated with TCDD contaminated soil - Missouri. Moib. Mont. 23(34) :299. 30. Dugois, P., J. Marshal, and L. Colomb. 1958. Chloracne caused by 2,4,5-trichlorophenol. M.ch. Mo£. Piotf. 19:626-627. (French) 31. Emmelin, L. 1977. Conference on phenoxy acids. Current Sweden Environment, Planning and Conservation. Swectcih Institute., Bait No. 72. Him. 5 p. 32. Environmental Defense Society. 1972. The case against 2,4,5-T. W. Z. EHVMACW. 2:16-21. 33. Erne, K. 1972. lexicological aspects of phenoxy herbicide usesome recent results. Jn_ Weeds and Weed Control. Swed. Weed Conf. 13.-C1-C2. Weed Afa^. 22(2):38, 1973. 34. Erne, K. 1973. Toxicity studies with phenoxy herbicides on reindeer. Swen. t/e^. 24:273-275. (Swedish) 35. Erne, K. 1974. Phenoxy fietiu.cute. te^-tdueA <tn Swe.d>ti>k f^h and wu£cttc($e. P 192-195. .In. Environmental Quality and Safety Supplement. Vol. III. Pesticides, International Union of Pure and Applied Chemistry. 3rd International Congress. Helsinki, Finland; 3-9 July 1974. F. Coulston and F. Korte (Eds.). 36. Executive Office of the President. 1971. Report on 2,4,5-T. A report of the Panel on Herbicides of the President's Science Advisory Committee. Executive Office of the President, Office of Science and Technology. Washington, D.C. 69 p. 37. Fara, G.M. 1976. Health Surveillance program. Medical - epidemiclogical commission. Milan, Italy, August 27, 1976. Mim. 10 p. 38. Firestone, D. 1977. The 2,3,7,8-tetrachlorodibenzo-para-dioxin problem: A review, jn. Chlorinated Phenoxy Acids and Their Dioxins: Mode of Action, Health Risks and Environmental Effects. Ec.o£. 8od£. (Stockholm), 27 (In press). 39. Ford, R.E.* B.J. Jacobsen, and D.G. White. Myc.atoxA.nt> - e.nv<inom<>.ntaJt contaminants Jbi natusui. Illinois Research, Winter 1978, pp 10-11. 40. Forth, W. 1977. 2,3,7,8-tetrachlorodibenzo-l ,4-dioxin (TCDD): The Seveso incident. Oeoticfie^ biztitblatt 44(3) -.2617-2628. (German) V-35 �41. Garattini, S. 1977. TCDD poisoning at Seveso. Blome.dicA.ne. 26:28-29. 42. Giovanardi, A. 1976. Decontamination program for the dioxin - contaminated areas of Seveso and Media. Giuhta Regionale Delia Lombardia. Ministero Delia Sanita. Milan, Italy. August 18, 1976. Mim. 17 p. 43. Goldmann, P.J.. 1973. Severe acute chloracne, a mass intoxication due to 2,3,6,7-tetrachlorodibenzodioxin. HawtaAzt 24:149-152. (German) 44. Hailing, H. 1977.' Suspected link between exposure to hexachlorophene and birth malformed infants. LakaKtidnAnge,n 74:542-546. (Swedish) 45. Hardell, L. 1977. Malignant Mesenchymal tumors and exposure to phenoxy acids - a clinical observation. LafeoAXufrutngen 74(33) :27532754. 46. Hay, A.W.M. 1977, Tetrachlorodibenzo-p-dioxin release at Seveso. 1(4): 289- 308. 47. Hofman, M.F., and C.L. Meneghini. 1962. A proposito delle follicolosi da idrocarburi clorosostituito (acne clorica). G. Ital. VeAm. 103:427-450. (Italian) 48. Honoroff, I. 1973. Down's Syndrome - it can happen here. A Report to the Consumer 111(50) :l-4. Sherman Oaks, California. Mim. 4 p. '49. House, W.B., L.H. Goodson, H.M. Gadberry, and K.W. Dockter. 1967. Assessment of ecological effects of extensive or repeated use of herbicides. Midwest Research Institute (Kansas City, Missouri). Sponsored by Department of Defense. ARPA Order No. 1086. 369 p. 50. International Agency for Research on Cancer. 1977. IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Man. Vol. 15. Some Fumigants, the Herbicid.es 2,4-D and 2,4,5-T, Chlorinated Dibenzodioxins and Miscellaneous Industrial Chemicals. World Health Organization; Lyon, France. 354 p. 51. International Agency for Research on Cancer. 1978. IRAC Internal Technical Report No. 78/001. (Draft). Coordination of Epidemiological Studies on the Long-Term Hazards of Chlorinated Dibenzodioxins/Chlorinated Diobenzofurans. World Health Organization; Lyon, France. 48 p. 52. Irish, K.R., R.A. Darrow and C.E. Minarik. 1969. Incarnation manual faott, vegetation c.onfao£ in Southeast ktxia.. Misc. Public. 33. Department of the Army, Fort Detrick, Frederick, Maryland. 71 p. 53. Jensen, N.E. 1972. Chloracne: Three cases. PJLOC.. R. See. Med. 65(8):687-688. V-36 �54. Jirasek, L., J. Kalensky, and K. Kubec. 1973. Acne chlorina and porphyia cutanea tarda during the manufacture of herbicides. Ce-afe. 48(5): 306-31 7. (Czech) 55. Jirasek, L., J. Kalensky, K. Kubec, J. Pazderova, and E. Lukas. 1974. Acne chlorina, porphyria cutanea tard and other manifestations of general intoxication during the manufacture of herbicides. Part II. Cwfe. VvumaXat. 49(3):145-157. (Czech) 56. Kimbrough, R.D. 1974. The toxicity of polychlorinated polycyclic compounds and related chemicals. Ctc£. Rev. Topical. 2:445-498. 57. Kimbrough, R.D., c.D. Carter, J.A. Liddle, R.E. Cline, and P.E. Phillips. 1977. Epidemiology and pathology of a tetrachlorodibenzodioxin poisoning episode, kick. EnviJion. Heo&tfi 28:77-85. 58. Kimmig, J. and K»H. Schulz. 1957. Occupational acne (so-called chloracne) due to chlorinated aromatic cyclic ethers. VeAmcutolog^cja. 115:540-546. (German) 59. Lobes, L.A., R.E. Koehler, W.F. Barthel , R.A. Feldman and J.V. Bennett. 1972. Toxic illness, Lincoln Gouty, Missouri. CDC No. EPI-72-13-2. U.S. Public Health Service. Center for Disease Control. Atlanta, Georgia. Mim. , 16 p. 60. May, G. 1973. Chloracne from the accidental production of tetraclorodibenzodioxin. &*.. J. Ind. Med. 30:276-283. 61. McQueen, E.G., A.M.O. Veale, W.S. Alexander, and M.N. Bates. 1977, 2,4,5-T and human birth defects. New Zealand. Dep. Health, Div. Publ. Health. Mim. 41 p. 62. Mercier, M.J. 1976. 2,3,7 ,S-t&tMLC.ktotiodib<inzo-p-d<LoxAn, an \jJim. P 141-157 In Proceedings of the expert meeting on the problems raised by TCDD pollution. A. Berlin, A. Buratta and M.Th. Vander Venne (Eds.). Milan, Iialy, 30 September and 1 October. 63. Meselson, M.S., A.H. Westing, and J.D. Constable. 1971. Background material relevant to presentations at the 1970 annual meeting of the AAAS concerning the Herbicide Assessment Commission for the American Association for the Advancement of Science. Washington, D.C. Min. 47 p. 64. Mivra, H., A. Omori , and M. Shibue. 1974. The effect of chlorophenols on the excretion of porphyrins in urine. Jpn. J. Ind. Health 16(6): 575-577. (Japanese) 65. Oliver, R.M. 1975. Toxic effects of 2,3,7,8-tetrachlorodibenzo-l ,4dioxin in laboratory workens. &Ut. J. Ind. Med. 32(1): 49-53. V-37 �66. Orians, G.H. and E.W. Pfeiffer. 1970. Ecological effects of the War in Vietnam. Science 168:544-554. 67. Pazderova, J., E. Lukas, M. Nemcova, M. Spacilova, L. Jirasek, J. Kalensky, J. John, A. Jirasek, and J. Pickova. 1974. Chronic poisoning by chlorinated hydrocarbons formed in the production ot 2,4,5-trichlorophenoxyacetate. P*AC. Lefe. 26(9):332-339. (Czech) 68. Poland, A. P., D. Smith, G. Metter, and P. Possick. 1971. A Health survey of workers in a 2,4-D and 2,4,5-T plant. M.c.k. 22:316-327. 59. Reqgiani, G. 1978. The estimation of the TCDD toxic potential in the light of the Seveso accidpnt. Pane*' presented at the 20th Congress of the European Society ot 1:0x1 coiogy. Berlin ^West), June 25-28, 1978. 70. Roan, C.C., and D.P. Morgan. 1972. Alleged effects on human health of the use of herbicides in the area around Globe, Arizona. Arizona Community Pesticides Studies Project, March 6, 1972. University of Arizona, Tucson, Arizona. Mim. 7 p. 71. Rose, H.A. , S.P.R Rose. 1972. Chemical spraying as reported by refugees from South Vietnam. Science 177:710-712. 72. Sare, W.M. and P.I. Forbes. 1972. Possible dysmorphogenic effects of an agricultural chemical: 2,4,5-T. Mew Zeo&md. Mc.d. J. 75(476): 37-38. 73. Suskind, R.R. 1976. A review of occupational exposures to dibenzop-dioxins. Presentation to a Conference on Dibenzodioxins/Dibenzofuran. November 18, 1976. Rougemont, N.C. 74. Telegina, K.A. and L.I. Bikbulatova. 1970. Affliction of the follicular apparatus of the skin in workers occupied in the production of butyl ether of 2,4,5-trichlorophenoxyacetic acid. l/e6^Cn. Vwmeutol. 44:35-39. 75. Tschirley, F.H. 1969. Defoliation in Vietnam. Science 163:779-786. 76. Tschirley, F.H., W. Binns, C. Cueto, B.C. Eliason, H.E. Heggestad, G.H. Hepting, P.F. Sand, and R.F. Stephens. 1970. Investigations of spray project near Globe, Arizona. Investigation conducted February 1970. U.S. Department of Agriculture, Office of Science and Education. Mim. 29 p. 77. Tung, T.T., T.K.anh, B.Q. Tuyen, D.X. Tra, and N.X. Hugen. 1971. Clinical effects of massive and continuous utilization of defoliants on civilians. lAtetnomeAe Studies 29:53-81. V-38 �78. Tung, T.T., T.T., An, N.D. Tarn, P.H. Phiet, N.N. Bang, T.T. Bach, H. vanSon and O.K. Son. 1973. Le cancer primaire due foie au Viet-nam. CklnuAQ^n 99:427-436. (French) 79. United States Tariff Commission. 1946. Synthetic organic chemicals: U.S. production and sales, 1944. Report No. 155, Second Series. U.S. Government Printing Office, Washington, D.C. 80. Walsh, J. 1977. Seveso: The questions persist where dioxin created a wasteland. Science 197(4308) :1064-1067. 81. Zelikov, A. Kh. and L.N. Danilov. 1974. Occupational dermatoses (acnes) in workers engaged in production of 2,4,5-trichlorophenol. Sov. Med. 7:145-146. (Russian) V-39 �CHAPTER VI HUMAN EFFECTS OF HERBICIDE ORANGE I. INTRODUCTION This chapter will discuss the human effects of Herbicide Orange. There has been considerable medical literature published on the constituents of Herbicide Orange, i.e., 2,4-D, 2,4,5-T, and the contaminant TCDD. The pharmacokinetics of these chemicals will be discussed along with their adverse effects. Most of the reports in the literature have involved occupational experiences. However, several episodes involving general populations from selected localities throughout the world will also be discussed. II. PHARMACODYNAMICS Little work has been done regarding the pharmacodynamics of 2,4-D, 2,4,5-T or TCDD in humans. The available studies are summarized below. A. Percutaneous Entry of Phenoxy Herbicides Feldmann and Maibach (27) in 1974 in studies using radioactive tracers showed that 2,4-D was able to penetrate the skin. Indirect evidence resulting from the numerous occupational exposures to 2,4-D and 2,4,5-T (and TCDD) in industry and herbicide spraying described later further supports percutaneous entry. B. Ingestion of Phenoxy Herbicides Kohli et al (46, 47) in two separate studies gave purified 2,4-D and 2,4,5-T in capsules to human volunteers. Each herbicide was orally administered to six men as the acid at a dose level of 5 mg herbicide per kg body weight (mg/kg). The 2,4-D was quickly absorbed and appeared in the plasma within one hour after ingestion. Seventy-five percent of the administered dose was excreted unchanged in the urine within 96 hours (h). The 2,4,5-T was also readily absorbed, being present in the plasma one hour after ingestion. After 96 h, 63 percent to 72 percent of the herbicides had been excreted unchanged by the kidney. Plasma levels peaked between seven and twenty-four hours for both 2,4-D and 2,4,5-T and the half-lives for plasma clearance were 33 and 18 h respectively. In a study by Saueroff et al (70) in 1977, five male humans ingested 5 mg/kg of 2,4-D. Essentially all was absorbed from the gastrointestinal tract. It was eliminated from the plasma with an average half-life of 11.6 hours and from the urine with an average half-life of 17.7 hours. Eighty-two and three tenth percent was excreted unchanged and 12.8 percent in a conjugated form for a 95.1 percent total recovery. Utilizing this rate of clearance, 99 percent of the steady state would be reached in about three days making body accumulation of repeated exposure unlikely. Gehring et al (28) in 1973 and Matsamara (52) in 1970 found similar results in comparable studies of 2,4,5-T. It should be noted VI-1 �that no short-term adverse effects were found in any of the above studies with 5 mg/kg being the highest dose. The fate of Silvex [2-(2,4,5-trichlorophenoxy) propionic acid] was studied by Saueroff et al (71). Seven men and one woman ingested a dose of 1 mg/kg. Peak plasma levels were reached two to four hours after ingestion. The Silvex was excreted in the urine both in the unchanged and conjugated forms. The mean recovery in the urine was 64 percent of the orally administered dose after 24 hours and 79.8 percent after 144 hours. Recovery of Si 1 vex in the feces accounted for not more than 3.2 percent of the administered dose. The half-life for plasma clearance was biphasic, 4.0 +. 1.9 h and 16.5 ±. 7.3 h for initial and terminal periods respectively. No adverse effects were noted. Park et al (60) described clinical and pharmacokinetic observations in a 39-year-old male following ingestion of the amine salts of 2,4-D and [2-(2-methyl-4-chlorophenoxy) propionic acid] (MCPP). Following forced alkaline diuresis, the plasma half-half of 2,4-D was greatly reduced from 220 to 4.7 h. The renal clearance of 2,4-D increased up to greater than 100-fold during the period of alkaline diuresis. I'lrinary recovery studies confirmed absorption of about 70 ml of the herbicide. ,fthough the patient initially demonstrated a mild proximal neuropathy and myopathy, full recovery occurred in two months. C. Tissue Analyses for the Phenoxy Herbicides Levels of phenoxy herbicides found in human tissue or body fluids following ingestion of a fatal dose are shown in Table 1. The data are reported in parts per million: it was assumed that all tissues (removed during the autopsy) were analyzed on a fresh weight basis and that 1 ml of blood or urine was equal to 1 g. Frequently, no description of the handling procedures was reported; thus, fluid may have been present within the organ (e.g., liver) at the time of the analyses. This fluid contamination may have resulted in high values for a given tissue. Coutselinis et al (20) in 1977, reported on the analyses of herbicide in the organs of a woman who died 16 hours after ingesting a large dose of a mixture of 2,4-0 and 2,4,5-T. Levels of the two herbicides found in selected tissues at the time of death are shown in Table 1. The formulation ingested was a mixture in a 3:2 ratio, 2,4-D to 2,4,5-T. Nielson et al (56) reported a more complete investigation of herbicide residue in body tissue resulting from an autopsy of a 23-year-old male who ingested 2,4-D. The levels of 2,4-D in parts per million for selected tissue are also shown in Table 1. The herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA) has been associated with two deaths. Johnson and Koumides (39) reported the death of a 65-year-old man following the ingestion of 250 mg MCPA/kg body weight. VI-2 �TABLE 1 Levels (part per million) of Phenoxy Herbicides in Human Tissue or Body Fluid Following Ingesfion of Fatal Dosea Patiert Herbicide Coutselinis et al. (20) Young Wcmsn 2,4-D/ 2,4, 5-T "Large" Nielson et al. (56) 23 Yr Old Han 2,4-D Time Level of Herbicide (Parts Per Million) in Tissueb Ingestion Gastric Fatty - Death Blood Urine Liver Kidney ! Brain Spl een Muscle Heart Washings Tissue ;• 18 hrs 826 210 82 12 182 48 5 22 Dose (mg/kg) >80 Source i Dudley and Thapar (23) 669 264 183 63 13 2,4-D 76 Yr Old Man >2,000C 5 days 58 408 194 i 20 hrs 250 180 1 1 2,500 j 800 t I 440 20 hrs 230 970 i . i ! 32 Yr Old Han '• MCPA : I 118 93 ! MCPA 83 : 70 134 ( i 65 Yr Old Han Johnson and Koumides (39). Popham and Davies (63) 24 hrs 146 154 33 3,000 i I ^Tissue/fluid removed during autopsy. °Ip convert parts per million to mg/dVor to mg/100 ma, multiply tabulated values by 0.1 . e Tne 55 kg patient consumed one pint of a presumed ester formulation (kerosene-like, water insoluble formulation) of 2,4-D. tster formulations containing the least amount of active ingredient 2,4-D are two pound/gallon formulations. If a pint contained 113 g 2,4-D acid, then the dose would have been >2,000 mg 2,4-D/kg body weight. * �Popham and Davis (63) report the death of a 32-year-old man following a MCPA dose of 440 mg/kg. The levels of MCPA found in selected organs or body fluids following death are reported in Table 1. The high level of MCPA in the urine suggests that this herbicide, like 2,4-D, was rapidly excreted unchanged by the kidney. D. Pharmacodynamics of TCDD There is almost a complete lack of information concerning the Pharmacodynamics of the dioxins in man. In November 1977, Fanelli (2)-in a letter to the Mario Negri Institute of Pharmacologic Research in Italy found no TCDD in samples of the liver, mesenteric fat, or cerebral fluid in the necropsy of a woman who had been included in a follow-on study of the Seveso, Italy, TCDD episode. The lower limits of detection were 0*4 ng TCDD/ml of fluid and 0.25 ng/gm of tissue. The cause of death was not given. Reggiani (65) described the case of a 55-year-old woman who died of pancreatic carcinoma with liver involvement seven months after the Seveso episode. Children living with her suffered severe caustic burns of the skin and, subsequently, chloracne. Neither the patient nor the mother of the children developed chloracne. It is almost certain that the entire family ate food contaminated with TCDD. TCDD detected in the analysis of tissue obtained during the autopsy is shown in Table 2. No TCDD was found in the same tissues taken from autopsies of three persons who were certainly not related to a TCDD exposure. The samples were run concurrently with those of the case described above. III. ADVERSE EFFECTS A. Limitations of Referenced Studies There is considerable information in the world literature regarding the adverse effects of 2,4-D, 2,4,5-T, 2,4,5-trichlorophenol (TCP) and TCDD in humans. Most of it is the result of studies on worker experience, industrial accidents or individuals poisoning. Unfortunately, there are very few controlled studies and only generalizations can be made regarding a causeeffect relationship. In most cases all that can be said is that an association exists. There are several other important limitations of the studies that must be kept in mind when reviewing them. These include: 1. The populations were biased toward the adult male of working age. 2. Examinations were post-exposure, and therefore, pre-existing disease often was not known or reported. 3. Exposures frequently were to mixtures and, therefore, one cannot be certain which chemical produced which effect. 4. An accidental or intentional ingestion or an exposure from an industrial accident would result in a dose much higher than would be expected in the general population in the region of a herbicide spraying program. VI-4 �TABLE 2 TCDD Levels in a Human Body Date Sampl e b 28, 7, 7 Liver Limit of Origin Quantity Detection Recovery TCDDa 10 g 10 PPT 64% 0.15 PPB Autopsy 10 g 10 PPT 59% 1.84 PPB Pancreas Autopsy , Autopsy 5g 10 PPT 59% 1.04 PPB Fat Lung Autopsy 10 g 10 PPT 60% 0.06 PPB Kidney Autopsy 10 g 10 PPT 60% 0.04 PPB Brain Autopsy 10 g 10 PPT 60 0.06 PPB i a - Total body weight:, kg 70 - Calculated total amount at time of death: 40 yg b - Vacuum Generator Micromass Laboratory, Altrincham (Manchester, U.K.) Source: Reggiani (65). VI-5 �5. Although the routine occupational exposure would in most cases be at a dose rate lower than that of accidents, the exposure would be prolonged effectively raising the total dose. 6. The actual dose received in most instances was not known. B. Phenoxy Herbicides That Do Not Contain TCDD As was explained in a previous chapter, TCDD is a contaminant of phenoxy herbicides made from TCP. TCP is not a precursor of 2,4-D. This permits the evaluation of health effects of 2,4-D (or 2,4-D-like herbicides) as an entity separate from TCDD. 1. Experimental Exposure to 2,4-D There have been at least three reports of no-effect exposure where the precise dose was known. Assouly (4) in 1951 reported on a man who ingested 0.5 g of 2,4-D daily for three weeks without adverse effects. Kohli (46) in 1974 in his pharmacodynamic study of 2,4-D reported no effect after a single oral dose of 5 mg/kg. In 1962, Seabury (74) treated two cases of disseminated coccidiomycosis with 2,4-D. The first patient received a total of 40 mg of the sodium salt by intramuscular injection over a period of four days. The patient died on the fifth day without evidence of 2,4-D toxicity. In the second patient, approximately 13 g were given intravenously over a period of one month, the last 2 g in one dose. No adverse effects were noted. When the dose was increased to 3.6 g over a period of two hours the patient became semi-stuperous and exhibited fibrillary movements about the mouth and in both hands and forearms. The stupor deepened to a point where the patient responded only to painful stimuli. Forty-eight hours after the dose was given he returned to his pre-reaction state. There was no evidence of neurologic or muscular change in the next seventeen days after which he died from the primary disease. 2. Exposure in the Production of 2,4-D or MCPA Bashirov (8) in 1969, examined 292 workers including 44 women employed in the production of the amine salt and the butyl ester of 2,4-D. This report is of particular significance in that the butyl ester is the form found in Herbicide Orange. Table 3 shows the various responses along with the percentage of occurrence. Several organ systems were involved with emphasis on headaches, the asthenic syndrome, and gastrointestinal complaints. Fifty persons from the above group were selected for controlled studies involving the liver and stomach. Bashirov indicated that there were significant differences between the control and test groups in amount of gastric secretion and the antitoxin and carbohydrate functions of the liver. In addition, they noted a correlation between the length of service and the changes in the functional state of the stomach. The authors did not state their level of confidence. Telegina and Bikbulatova (78) in 1970 reported on 158 workers employed in the production of MCPA. Telegina and 'Bikbulatova found contact VI-6 �TABLE 3. Distribution of symptoms in 292 workers employed in the production of the amine salt and the butyl ester of 2,4-D. Percent of workers describing symptoms Symptoms 1. Weakness, fatigability, headaches 63 2. Asthenic Syndrome with vegetative dysfunction 61 3. Anorexia, bitter taste in mouth, dyspepsia abdominal pains, constipation 51.7 4. Vertigo 33 5. Dyspnea on exertion 26.7 6. Tachycardia, precordial pain 17.8 Source: Bashirov (.8) VIr7 �dermatitis or history of same in 55 individuals in the first examination and in 65 in a second examination a year later. Irritation of mucous membranes was also found in a majority of these individuals. 3. Accidental or Intentional Exposure to 2,4-D, MCPA, 2.4-DP or MCPP Another major group of persons exposed to 2,4-D or the analogs MCPA, 2,4-DP [2,4-dichlorophenoxy) propionic acid] and MCPP, are those involved with accidental or intentional ingestion of the substance. Table 4 is a summary of many such cases along with the estimated dose of herbicide (where available), major effects and outcome of the intoxication. Popham and Davies (63) reported the case of a 32-year-old man who ingested an estimated dose of 440 mg MCPA/kg. There were signs of severe meningoencephalitis including grand mal and focal seizures with death within hours. Necropsy showed no evidence of damage to the gastrointestinal tract, but the liver showed signs of early necrosis. The brain and meninges showed marked congestion but otherwise were normal. Johnson and Koumides (39) described a similar MCPA episode without the severe central nervous system signs and with death in hours. The dose was estimated at 250 mg/kg. Nielson et al (56) published a paper describing a 23-year-old man who committed suicide by ingesting an unknown amount of 2,4-D. Tissue analysis indicated, however, that at least 80 mg/kg must have been absorbed. Unlike the cases of Johnson and Koumides (39) and Popham and Davies (63), this subject was in good physical health prior to the ingestion. The others were suffering from chronic illnesses. There was evidence that this subject had at least one convulsive episode before dying, implicating the central nervous system. In the necropsy, small amounts of 2,4-D were found in the brain tissue (see Table 1). There was also evidence of degeneration of ganglionic cells in the brain. If the degeneration was due to 2,4-D and not hypoxia, it would have indicated that the cellular elements of the central nervous system were quite sensitive to 2,4-D as the tissue analysis showed the brain to have a much lower level of herbicide when compared with other organs of the body. Other episodes of poisoning by 2,4-D or MCPA have been reported by Jones et al (40), Berwick (12), Brandt (15), Dudley and Thapar (23), and Park et al (60). Findings, other than those involving the central nervous system, included abnormal enzyme levels, anemia, thrombocytopenia, skeletal myositis with myoglobinuria, myocardial irritability, loss of color vision, peripheral nervous system disorders, pulmonary edema, and renal disorders. The subject reported by Dudley and Thapar (23) died; the remainder survived with varying degrees of recovery. The case reported by Brandt (15) had a complete recovery after an estimated dose of 300 to 600 mg/kg; however, this individual had ingested a mixture of 2,4-D and 2,4-DP. The case reported by Berwick (12) was noteworthy because the individual involved accidentally ingested a dose of 110 mg 2,4-D/kg. The herbicide was formulated as the isooctyl ester of 2,4-D. Although the individual demonstrated numerous symptoms (Table 4), he fully recovered. VI-8 �TABLE Distribution of Adverse Effects in Case Reports Following the Ingestion of Non-TCDD Containing Phenoxy Herbicides c to c O O — 4_> .— 4J ._ *-* in >- — U 4) O *J OJ fD -C <U 4-1 O 4-1 X aj *- — i_ Q. (LI (0 Q- i/l — 4-t Q_ ••-» r— 4_l O I- ( U - C Q - O u i O <U O O (0 <0 O _c ra ^D ~ " I 0) *J 5 41tOmg/kg MCPA 1965 250mg/kg . ^ " 2 Q 4 toSI -C - 1 Nielson et al . (56) 1965 >80mg/kg 2.4-D Jones et al . (40) Berwick (12) g ( ? Z l G, O Z + 1967 <1 900mg/kg MCPA + 1970 HOmg/kg 2,4-D + + Brandt (15) 1971 300-600 mg/kg 2,4-D/ 2,4-DP Dudley and Thapar (2k) 11--A -2000mg/kg 2.4-D Total Number o f Reports Listing Effect Unkn 2.A-D/ MCPP 2 ^ (J (U d> 4-* a.— ^n < CL O -o 1_ 01 Death- + Death Death + •*- + + + + + * + + - + + 1 ) 8 2 + 2 Ful 1 Recovery + -t + Ful 1 Recovery + + + 6 Residual * * Peripheral Sensory Defect Death Full Recovery + 3 Outcome (_> | + 1377 - + + (fcn.) O 03 + •I- Park et ai. *j .— >-C 1 MCPA • Johnson and Koumides (39) tfl >- Q. 1964 Popham and Davies (63) Q o — Senses ion c •Q 0) -i-" 3 ^ 1 1 �The patient was routinely observed over a three year period and no signs of peripheral neuropathy occurred. 4. Exposure to 2,4-D in Spray Operations A fourth group of exposed individuals is those who were involved in spraying operations contacting either the spray or the liquid. Table 5 summarizes these cases where individuals were exposed to 2,4-D. In 1959, Goldstein et al (31) first reported on three patients who developed peripheral neuropathies manifested by pain, paresthesias and paresis. There had been previous skin contact with liquid 2,4-D indicating a probable percutaneous route of entry. Recovery from the neuropathy was incomplete for the three patients during the periods of observation which were 1, 2 and 3 years, respectively for a 65-year-old male, 50-year-old female and a 52-year-old male. The 65-year-old male was exposed during the course of spraying a field with an ester of 2,4-D wetting his arms and legs. He was reported to have been in ill health prior to exposure. The 50-year-old female was exposed twice, one year apart, to an ester of 2,4-D wetting hands and legs. The 52year-old male was exposed first when he spilled 60 ml 2,4-D ester on his arms and failed to wash it off. His second exposure was two months later, wetting his legs with the same formulation. In 1961, Monarca and di Vito (55) reported a case where the entry route may have been at least partially respiratory, the subject having stayed downwind during much of the spraying operation. The immediate toxic symptoms consisted of asthenia, autonomic hyperactivity, gastrointestinal irritation and alterations of the central nervous system. Some days later he developed a hemorrhagic enterocolitis. After a period of five months recovery was complete except for hyporeflexia of the lower limbs. Berkley and Magee (11) described the development of peripheral neuropathy in a 39-year-old farmer who had significant hand contact with 2,4-D. At the end of one year the only residual effect was mild hypoalgesia on the fourth and fifth fingers of the right hand. Todd (80) reported a case in which the subject presented with anemia and leukopenia as well as peripheral neuropathy. The subject had two separate contacts with liquid 2,4-D experiencing gastrointestinal symptoms each time. The neuropathy lasted almost two years. In 1966, Tsapko (81) reported headache, retrosternal pain, general weakness, vertigo, nausea, vomiting, and mild leukopenia in a group of field workers who entered an area immediately after it was sprayed with 2,4-D. Kotlarek-Haus et al (48) described an autoimmune hemolytic anemia in a pesticide applicator. However, DDT, Lindane and Fenthion were routinely sprayed by this individual, as well as was 2,4-D VI-10 �TABLE 5 Distribution of Reported Adverse Effects Following Exposure of Field Workers and Applicators to 2,4-D 4-1 VI to 4_t in — u O a Yc-> of if.^.. of Source Number numoer Episode Of Cases ? b~D i,t u Formulation Primarv — rrimary Rnnfp o r ( ) / nouie nf z Exposure O 3 nc/)i/l 2>. " OQ + 1<<55 3 Ester Percut Monarca anddi Vito (55) HoO 1 Sodium Sal t inhal o 0) (0 -C CL Q. _ O J: U3 ua) °-z 4-. O c— *> <U <0 a . * ->- — - 4J (/itO JEQ. >-O n j u QJ ra i- IQ z UuO 1 N/Ab Percut + Berkley and Magee (11) IS61 1 Amine Salt Percut Tsapko (81) 1S66 Group Sodium Salt Percut Wai Us et al. ( ? 8) 1?S6 1 N/A Inhal Paggiaro et al . (58) 1972 1 Ester Inhal Total Number of Reports Listing Effect Percut = Percutaneous; Inhal = Inhalation Formulation description not available. ">- 10 Q. O 41 _1-c -—o . c «Q. <g 1- z + + °1 >—O <u o i-v) -O Remarks + + + + + One case of neuropathy for 3 Yr 5 Mos Residual hyporeflexa 2 Yrs + 3 Vrs Full recovery but neuropathy lasted two Yrs 1 Yr + + + oju + + + ID e ° °- ° + + + «-^ ° •* + + Todd ( 0 8) b <u c C + Goldstein et a!. ( ! 3) a C Mild hyperalgesia in two finger N/A No comment 2 Yrs + + + Full recovery 1 Mo Ful 1 recovery �Sare (69) reported on a subject who complained of diplopia toward the end of days in which he sprayed 2,4-D. In 1974, Barthel (7) related three cases of pulmonary fibrosis in workers engaged in weed control programs using MCPA. It is more probable, however, that the fibrosis was related to the carrier substances which were slatemetal, kaolin, and talcum. In a letter to the editor, Taylor (76), reported a suicide in a young farmer who became depressed over an illness possibly resulting from exposure to 2,4-D and 2,4,5-T. The illness was not specified nor was it clear whether the depression was a primary response to the herbicides or entirely secondary to the illness. However, this was the only reference found in which a psychiatric disorder was attributed to 2,4-D. Paggiaro et al (58) described an individual intoxicated by inhalation of 2,4-D. The individual manifested headaches, constipation, urinary incontinence, myalgia, muscular hypotonia, proteinuria and tachyarrhythmia. Despite these numerous symptoms, the patient fully recovered in one month. Palva et al (59), in 1974, reported a case of aplastic anemia in a 64-year-old farmer after exposure to MCPA. Recovery was complete after five months. C. Trichlorophenol (TCP), 2,4,5-T and TCDD Since TCDD is formed in the production of TCP (see Chapter V), both TCP and 2,4,5-T are contaminated with TCDD. As a result, TCDD must be considered when discussing either TCP or 2,4,5-T. Although other dioxins are usually formed in the production of pentachlorophenol (PCP), small amounts of TCDD may also be produced and, therefore, exposure to PCP will be included in this section. 1. Industrial Exposure and Symptomatology Since the first commercial production of 2,4,5-T there have been numerous industrial episodes involving exposure to TCP, 2,4,5-T and TCDD. Chapter V discussed these industrial episodes in depth. Fifteen of the 23 episodes recorded in the literature were apparently occupational exposures that occurred during industrial production of chlorinated phenols. However, on eight occasions, explosions occurred and personnel were exposed during the clean-up of the accident or from subsequent exposure to an improperly decontaminated workshop. The symptomatology reported for various occupational episodes are presented in Tables 6, 7 and 8. Table 6 is a summary of the organ systems affected during episodes of occupational exposure to chlorinated phenols and/or TCDD. Table 7 is a summary of the signs, symptoms and disorders reported for these episodes. Table 8 is a summary of special clinical studies conducted in support of physical examinations given to selected VI-12 �TABLE 6 Organ Systems Reported Affected After Occupational Exposure to PCP, TCP, 2,4,5-T or TCDD <u z (1) u> .c 3 Q. O Source Chemical Baader and Bauer (6) Bauer et al. (9) PCP TCP/2,4,5-T Bleiberg et al. (14) TCP/2,4.5-T/2.4-D Po.land et al . (62) TCP/2,4,5-T/2.4-D Dugois et al. ( 4 2) TCP Phenoxy Acid TCP/2,4,5-T Hardell (33) Kimmig and Schulz (44) • c a 17 8 21 48 c <a o CP o. 3 20 PCP/2.4.5-T 10 23 76 PCP/2.4.5-T PCP/2,4,5-T PCP/2.4.5-T 53 + TCDD 2,4,5-T TCP Same p]ant as Bleiberg 1964 after improved conditions. Chloroform odor from skin. Same plant as Bauer 1961. 10 No significant difference in findings from control. 2 persons had porphyria without acne. Subjects taken from group examined in Jiracek et al. (37) 13 3 489 278 20 Comment Examined June 1950, 16 months after last exposure 31 workers exposed. Examined 5 years after exposure ceased. 7 17 31 3 Number of cases in which organ system affected1" a E O E O w ±J c/1 2,4,5-T Kramer ( 9 4) Jirasek et al, (37) Jirasek et a!. (38) Pazderova et al (61) Miura et al. (54) Oliver (57) Ter Beek et al. (79) Zelikov and Danilor (88) -Q E 3 Lab workers synthesizing TCDD. 4 40 36 11 24 10 0 10 Number entries in table reflect the number of cases in which a disorder of the organ system was reported. * -»• = Organ system involvement reported; however, number of cases not given. Numbers do not include cases represented by "+" and totals may represent some double counting due to overlap of studies by Jirasek et al . and Pazerova et al. �TABLE 7 Signs. Symptoms, and Disorders Reported After Occupational Exposure to TCP. 2,4,5-T or TCDD c O m to > > 10) -C U ~O 0) 4^ U . U 0) o> . — O> <B — .- (D I/1JI . - ! _ 1" u ~ 0)C Q ) > ~ ( 0 0) 4J 0) (0 T3 4->£ (0 >-<0 L - O (Din Z in- L. 4-1 V (0 CU1 <u • — £ 4J — l_ > . Ol 3 .— in Q.L. . _ 1O V) •— Q <u (0 -C c in »- — ( 3 (0 0 l _ ID .— C lf> Q. Q . d > X tt) (0 O ^ : (U 0) O O 0) (U J-> I/I (D Ifl C Ul — 0) OQ_Q S_ Source 8 4a Bauer et al . (9) 2 6 9 17 Poland et al. (62) 8 Dugois et al . (24) 4-J 4) 18 20 1 7 30 48 i + 22 i + + t (33) 9 5 87 Kimmig and Schulz (44) 31 + Kramer (49) Jirasek et al. (37) i | +• Pazderova et al. + + 12 + Jirasek et al . (38) 2 19 2 i + 78 + + 23 + 3 3 i + + (£]) + + Miura et al . (54) 2 \ 27 53 8 + + 1 1 1 + O l i v e r (57) 2 Ter Beek et al . (79) 1 + 1 + 17 6 15 18 0 47 75 2 3 1 + 1 3 Zelikov and Danilov (88) cases + : 4 3 Total number of reportedc 6 17 2 Q i 8 +b a »-.— CO 5 1 Hardell (0 O) •— C X— 11 3 Bleiberg et al . (14) -fc- 0 — ^ Baader and Bauer (6) < ( - C O - ( U Z Q U « _ >. — 3 •> • O >~l- fD u — + + 47 17 275 0 91 + 6 23 6 Number entries in table reflect the number of cases in which sign, symptom or disorder was reported. + = Sign, symptom or disorder reported but number of cases not given. c Numbers do not include cases represented by "+" and totals may represent some double counting due to the overlap to studies by Jirasek et al. and Pazderova et al. �TABLE 8 Special Clinical Studies Following Occupational Exposure to TCP, 2,4,5-T or TCDD Liver Funct Source Renal Funct Baader and Bauer (6) 6a 2 2 1 6 1 1 1 B 1 ood Elements 1 Poland et al. Proteins 2 Bauer and Schulz (9) Lipids (62) Kramer ( 9 . ^) a 0 2 7 1 k 5 ]k +b 11 11 Oliver (57) Total number of cases with abnormal study B 1 ood Pressure 6 Jaracek et al . (37) Pazderova et al . (61 )c EEG 6 Carbohydrates 37 8 9 3 28 5 18 **7 9 ' 13 15 Number entries in table reflect the number of cases in which the special study was reported as abnormal. °+ * Special study reported as abnormal but number of cases not given. C The results include studies reported in Jiracek et al. (AO). The two studies complement each other. - Numbers do not include cases represented by "+". 18 �individuals following or during occupational episodes. The data in these tables are probably representative of the over 520 individuals that were reported in Chapter V to have been medically examined following the various occupational episodes. Approximately 600 individuals were adversely affected by exposure to TCDD following eight reported industrial accidents (see Chapter V). These individuals were either involved in the accident, responsible for clean-up after the accident, or returned to work in the plant following the accident. Table 9 is a summary of organ systems affected after .an exposure to TCP and TCDD following these industrial accidents. Table 10 is a summary of the signs, symptoms and disorders noted in the individuals following exposure to TCP and TCDD. Table 11 is a summary*of the few available data on special clinical studies on those individuals involved in the industrial accidents. Armstrong et al (3) and Robson et al (67) have reported on extensive medical data (organ systems affected, symptoms, disorders and clinical examinations) from newborn infants exposed to sodium pentachlorophenate in a hospital episode of PCP poisoning. Since these data involved newborn infants and PCP in a hospital environment, they were not included in the Tables. The data in Tables 6 thru 11 list the effects reported in the industrial environment where TCDD may be produced in the course of trichlorophenol production. The absolute numbers must be looked upon with caution for the reasons expressed earlier. There were no controls and preexisting conditions in most cases were not described in the articles. This limitation is demonstrated nicely by the study of Reggiani in 1977 (64) on the workers of the ICMESA plant in Seveso, Italy. As will be explained in more detail later there appears to be minimal if any development of systemic disorders if chloracne or a history of the same is not also present (64, 65). (Personal communication: Crow, K. D., Princess Margaret Hospital, Swindon, England. Holder, B. B., Dow Chemical Company, Midland, Michigan.) Out of 176 ICMESA workers examined immediately after the accident and more thoroughly four weeks after, only one displayed a doubtful case of chloracne. Yet, there were 29 subjects with liver disorders, 28 with lower respiratory problems, and nine with disorders involving the heart. In this case, the caustic products and TCDD exited the plant through a stack resulting in minimal, if any, exposure to the workers in the plant. This is contrasted with other accidents where the formed material remained in the plant providing major exposure to TCDD. If the premise that chloracne will be present before or during the time systemic symptoms are present is accepted, the abnormalities seen in this case must be due to some etiology other than TCDD. It is a matter of speculation as to why the one worker developed chloracne. There are at least two possibilities. He may have had a low threshold or the chloracne may have preceded the incident, being present as a result of his routine work. This raises the question of how many of the systemic problems listed were also completely or partially unrelated to TCDD. From the data available, the question cannot be answered. VI-16 �TABLE 9 Organ Systems Reported Affected After Exposure to TCP and TCDD Following an Industrial Accident tn >- a> tfi <U i" O > 3 O > ui CO »- <0 U O > <1) Z I4) <1) </> <U — u — co +•> C •— +J U «o E (0 I - X ui i— c — ja Q. E >* i- i- Source in tO "O _a E 3 z 3 c .^ ~ ^ a) > • •— 1 - (/) a) c£ a) 2: c i- a> 3 o 1 O — ^ Dugois et al. (25) 21 83 83 13 1 Goldman U9,30) 42 42 6 1 Anonymous (2) (Seveso, Italy) 176 1 29 Suskind (75) 228 + + Number of cases in which organ system affected0 550 147 48 i- L. z z <u >- c <1> i/> — <u E i / i f D E - C E O E 10 — < l ) ( D o 3 u C ro ^ *-• -tJ .— j-i o 4-1 iCirt Uui 4JO1 to a/ > > ^ ( u > - 3 > » < u ) 0t Q.CO <co or o. u Q. 0) to Comments 21a Jensen and Walker (36) - 3 +b Includes family members of exposed worker 1 -xj a 7 4 1 6 6 28 35 1 3 + + 4 1 6 Includes 14-yr old son of employee Includes only workers at ICMESA Plant 9 + 2 1 6 10 1 3 Number entries in table reflect the number of cases in which a disorder of the organ system was reported. b + = Organ system involvement reported. c Number of cases not given. Numbers do not include cases represented by "+". �TABLE 10 Signs, Symptons and Disorders Reported After Exposure to TCP and TCDD Following an Industrial Accident C C <D E O in t/1 (U V) JT 0 ( a) Source U O <U •— — +j 0 0)O> »— 3 ( 0 3 1 - a) z ^ >- a) zz tn — (D °- Q) U) <U <U •— -C 1 . E <u = •*-* fl3 L . O °- O1 —i_ °-° 1 CD (75) Number of cases reportedc a ( •— C C u ** 4 J to "^ 6 O f C W — 0) § - ja L. <o 7 k2 3 1 5 + 5 ; + + 11 + + + + 0 Bk ]k 0 + + 1 6 7 + 00 ^ a. O +b 21 a 1 »3 D O •""" 13 Reggiani (64) Suskincf -*- i4-»tfl > - C l - Dugois, P. et al . (25) Goldmann (29,30) (X d) 1 Number entries in table reflect number of cases in which sign, symptom or disorder was reported. °+ = Sign, symptom or disorder reported. c Numbers do not include cases represented by "+". �TABLE 11 Special Clinical Studies After Exposure to TCP and TCDD Following an Industrial Accident Llver Funct Renal Funct Carbohydrates 13a 1 Goldmann ( 9 3 ) 2,0 + + Reggian! (64) +b Suskind (75) Total number of cases with abnormal studyc + Lipids 3 Source May, G. (53) 13 Blood Pressure + 17 + 1 3 a 0 ' 17 Number of entries in table reflect the number of cases in which the special study was reported as abnormal. ^Special study reported as abnormal but number of cases not given. c Numbers do not include cases represented by "+H. �Still, even with the limitations the data do allow for an evaluation of trends. Chloracne is by far the most common finding. Also appearing frequently are disorders involving the liver, nervous systems, and mental state, the latter primarily in the form of asthenia. Early symptoms such as respiratory tract and mucous membrane irritation as well as headaches and nausea probably result from the primary substance and not TCDD (75). Lipids are frequently evaluated, but due to the normal large day-to-day variation within an individual, the findings are difficult to evaluate. Chloracne, asthenia, and liver disease in the form of porphyria cutanea tarda will be discussed in greater detail. a. Chloracne. Chloracne is the hallmark of exposure to the highly chlorinated dibenzodioxins and dibenzofurans. Kimmig and Schulz (44, 45) in 1957 and Schulz in 1968 (73) showed that it was TCDD and not TCP that produced Chloracne. The history of chloracne since its first description in the late 1800's has been well documented, in numerous review articles (16, 21, 43, 44, 74, 77). The problem peaked about the time of World War II as the result of a large production of chlorinated napthalenes. It also has been a major problem with the polychlorinated biphenyls and the associated dibenzofurans, particularly in Japan. The incidence of chloracne has been decreasing as production techniques and housekeeping methods have improved resulting in a reduced level of TCDD. Chloracne is a disorder of the pilosebaceous mechanism with the overproduction of keratin in the sebaceous ducts. This results in the development of the comedone or blackhead seen in all types of acne. In mild cases this may represent the full extent of the disorder. However, the natural progression is the formation of cysts and in severe cases to the development of inflammatory lesions and scar formation. Inflammation, however, tends to be less prominent than that found in acne vulgaris (common or juvenile acne). Frequently associated with the chloracne are hyperpigmentation and hirsutism manifested by excessive facial and body hair. In the mildest cases acne may only appear in the area of the outer canthus of the eye and pre- and post-auricular regions. In somewhat more severe cases, the rest of the face and neck may be involved with a sparing of the nose. In even more pronounced cases, the trunk and extremities, except for the hands and feet, may be affected. A preferential site of involvement not usually seen in other forms of acne is the genital region. In the worst cases the skin of the entire body gives the appearance of a homogeneous covering of comedones and small cysts. Severity of the acne does not necessarily reflect the degree of exposure to TCDD (14). Acne may appear as early as two to three weeks after the first exposure; however, there may be a delay of several months. The delay could represent a time for the development of a skin burden of TCDD. (Personal communication: Holder B. B., Dow Chemical Company, Midland, Michigan.) This burden would represent a threshold below which acne does not appear. VI-20 �Oliver in 1975 (57) reported two laboratory workers who developed very greasy skin, one of whom developed acne. This picture is contrary to the usual finding in chloracne where the skin is typically very dry. (Personal communication: Crow, K. D., Princess Margaret Hospital, Swindon, England.) Why these workers developed the greasy skin cannot be explained and must at this time be considered an anomaly. Experience from the industrial episodes (and from the Seveso, Italy episode) confirm that mild chloracne may clear quickly (e.g., in months). Severe chloracne is known, however, for its recidivism. Cases with active lesions have persisted for up to fifteen years after exposure ceased (53). Many of the studies of systemic effects used populations presenting with chloracne as a point of entry. This probably is not a major weakness, however, because chloracne is one of the earliest indicators of disease (13). Nevertheless, it could have resulted in an artifically lowered incidence of systemic effects present without acne. b. Porphyria Cutanea Tardia. Porphyria cutanea tarda (PCT) is a disorder of heme pigment metabolism characterized by skin sensitivity, accumulation of excess pigment in the liver, and the build-up of the various porphyrin pigments. Skin findings include skin fragility, bullous lesions, pigmentation, and photosensitivity. It may be either hereditary or acquired. The latter is usually associated with hepatic disorders. Bleiberg et al (14), in 1964, discovered eleven cases of PCT in workers involved in the production of 2,4,5-trichlorophenol. In 1973, Pazderova et al (61) reported on twenty-three additional cases. Liver biopsies were obtained in five subjects and liver tissue from necropsies in two. All showed fluorescence under ultraviolet light indicating high levels of porphyrins. In 1971, Poland et al (62) studied the workers described by Bleiberg and noted only one asymptomatic urine uroporphyrin. Changes in the plant had greatly decreased the exposure to TCP and TCDD. The hyperpigmentation and skin lesions found in PCT are independent of those found in chloracne. Pre-existing liver disease appears to predispose a subject to PCT when challenged by another agent such as TCDD. Based on the majority of studies, systemic disease does not result unless chloracne is present either before or during the course of the disease. However, Bleiberg (14) found porphyria was present in two cases without acne, and Oliver (57) noted that one laboratory worker synthesizing TCDD developed rather severe systemic symptoms but never any acne. It is accepted that chloracne can result from external exposure to TCDD. The role of systemic absorption of TCDD in the development of chloracne has been a matter of debate. Similarly, it is even less clear what role percutaneous absorption of TCDD plays in the development of systemic disease. Regardless, the basic observation is true enough so that an etiology other than TCDD should be diligently searched for in any case where symptoms developed without acne. VI -21 �c. Asthenia. Many asthenic and other vegetative symptoms have been described in 2,4,5-T, TCP and TCDD intoxication. For purposes of this report, asthenia includes the following: headache, apathy, fatigue, anorexia, weight loss, sleep disturbances, decreased learning ability, decreased memory, dyspepsia, sweating, muscle pain, joint pain and sexual dysfunction. True pathology is closely interwoven with the depression which undoubtedly exists as a result of other disorders, particularly the disfigurement of chloracne, therefore causing difficulty in interpretation of these symptoms. This problem is well demonstrated in a report on polybrominated biphenyl (PBB) exposure in the April 7, 1978, issue of the Center for Disease Control MoibM<ti;y and mofttattty Weefe£</ Repoit (17). Several hundred pounds of PBB were accidently introduced into animal feed. Three cohorts were studied, the first involving all persons who had been identified by the Michigan Department of Public Health as living on PBB contaminated farms at the time of quarantine, the second including persons who had received food products directly from such farms, and the third included workers (and their families) who had been exposed occupationally to PBB in a chemical manufacturing plant. Two additional groups with low level PBB exposure were also evaluated. Highest PBB levels were found in those groups in whom one would expect the exposure to be the greatest. However, symptoms occurred most frequently in volunteers and in persons from nonquarantined farms with low level PBB contamination. Symptoms were least prevalent in quarantined farm families and in chemical workers, just the opposite of what one would expect. Symptoms and conditions included fatigue, rashes, joint pains, hepatitis, diabetes, benign tumors, and cancer. The point to be made is that signs and symptoms of asthenia are common and need not be related to chemical exposure. There is little question that asthenic symptoms can develop following TCDD exposure. In an early plant accident in which exposure is felt to have been massive, workers developed fatigue and severe muscle pain (75). Impotency was present. As it was one of the first such episodes, the symptoms of TCDD or TCP exposure had not been delineated, and therefore the effect of suggestion would have been minimal. It needs to be emphasized, however, that the exposure was massive and the symptoms did clear. One must be very careful in transposing the results of this accident to another where exposure was much less. One is on particularly tenuous ground if he attempts to attribute the symptoms to the exposure levels found in herbicide spraying. 2. Special Case Studies a. Exposure resulting from spraying operations. The study by Londono in 1966 (51) is of special interest in that he reported on five subjects who were involved in herbicide spraying as opposed to industrial exposure. The herbicides included the butyl ester of 2,4-D and the methyl ester of 2,4,5-T. All five developed chloracne. One of the workers manifested the acne seventeen days after the onset of spraying, three after two months, and one after eighteen months. No clinical systemic disease was reported, although liver function tests were mildly abnormal. b. Controlled study on 2,4,5-T plant workers. In contrast with the episodes just described, which were in effect case studies, Kramer in VI-22 �1970 and revised in 1974 (49) in an unpublished report described a control study on the health of employees exposed to 2,4,5-T at Dow Chemical Company. The control population of 4,600 non-exposed Dow employees did not vary significantly from the general population. Fifty clinical parameters were investigated including both history and laboratory studies. Parameters included were those which would be indicative of disorders of the central nervous system, mucous membrane irritation, pulmonary disease, cardiovascular disease, gastrointestinal and hepatic disorders, renal disease, asthenia, and psychiatric disorders. No significant differences were found between the study and control groups. 3. General Population Exposures The discussion up to this point has generally related to the occupational hazards of TCP, 2,4,5-T and TCDD. In recent years there has been considerable interest expressed by a number of groups concerning the public health aspects of the phenoxy herbicides and TCDD. The remainder of this section will concentrate on several incidents in which the general population was involved. Chapter V has provided more extensive details on each of these episodes. a. South Vietnam Episode. In the latter part of 1969 newspapers in South Vietnam reported that there were an unusually large number of malformed babies being born among the Montagnards, This was followed by a publication by Tung et al (85) of the Democratic Republic of Vietnam in T971 in which they reported 179 people who had lived in sprayed areas from two months to five years or had been in direct contact with the spray. He did not specify the type or composition of the spray material. Disorders were divided into three major groups: asthenia, ocular syndrome and genetic effects. The general asthenia was accompanied by insomnia, headache, sexual impotence and menstrual problems in females. A specific form of the asthenia, visual asthenia,was characterized by early onset of eye fatigue (5-15 minutes) when reading. The ocular syndrome consisted of the visual asthenia (mentioned above) as well as a decrease in visual acuity and corneal scarring. The genetic syndrome consisted of chromosomal alterations in seriously affected adults, congenital malformations (particularly Trisomy 21) in the new born, and unclassifiable multiple congenital malformations with multiple chromosomic alterations. In 1973, Tung et al (86) reported an increase in the number of persons with primary liver cancer in proportion to all cancer patients admitted to Hanoi hospitals during the period 1972-1968 (790 liver cancer cases out of 7911 cancer cases, 10 percent) as compared to the period 19551961 (159 liver cancer cases out of 5492 total cancer cases, 2.9 percent), which was prior to the start of herbicide spraying. The authors attributed this increase to exposure as a result of the spraying of herbicides containing TCDD in South Vietnam during the 1960's; however, a recent IARC monograph (34) noted that limitations in the reporting of the study make impossible an adequate assessment between the incidence of liver cancer and herbicide spraying in South Vietnam. VI-23 �A National Academy of Science (NAS) committee (18) was established in 1972 to investigate the effects of herbicides in Vietnam. in their report, published in 1974, they described an earlier study by Cutting et al (22) in 1970 reviewing congenital malformations, hydatidiform moles, and stillbirths in 22 hospitals in the Republic of Vietnam for the periods between 1960-1965 and 1966-1969. The first time period involved light spraying of Herbicide Orange, the second, heavy. Neither the NAS nor Cutting et al were able to demonstrate any influence of the herbicides on the development of these disorders. It must be pointed out that all studies in Vietnam were limited by poor and incomplete reporting, and most important by the politics of the area. Large segments of the population in question were not available to the investigating groups. b. Eastern Missouri Horse Arena Episode. Following the spraying in 1971 of three horse arenas in Lincoln County, Missouri, with salvage oil contaminated with TCDD, a number of people who worked or played in the arenas developed medical disorders (10, 19, 43, 50). The most serious war> a six-yearold girl who developed hemorrhagic cystitis and focal pyelonephritis. The urinary tract symptoms were preceded by headache, epistaxis, diarrhea and a general malaise. Her urinary tract symptoms cleared after a few days. Three months later examination was normal except for punctate hemorrhages of the bladder seen on cystoscopy. The father of the child had developed headaches and nausea while working in the arena. Her mother reported severe headache, nausea, diarrhea and abdominal pains, and arthralgia. A ten-year-old sister developed easy fatigability, epistaxis, headaches, abdominal pain, and diarrhea. All developed at least mild acne lesions (64). Follow-up studies on the mother and two children performed five years later were normal (10). Chloracne developed in two three-year-old boys who played in another arena (19, 43). One case lasted more than a year. Commoner and Scott (19) in 1976 mentioned one additional case of chloracne in a veterinarian who obtained samples in a third arena. The symptoms in all seven of the humans were relatively mild with the most severe being the hemorrhagic cystitis and focal pyelonephritis seen in the six-year-old girl. The symptoms had cleared on re-examination several years later. Exposure, at least to the four children must have been significant in that they regularly played in the soil of the arenas. Contrast this with the disastrous effects the dioxin had on the horses and other animals that were in the arena often for only a short period (43). This gives strong support to the contention that man is relatively resistant to TCDD or absorbs it to a much lesser extent. c. The Seveso, Italy Episode. The details of the Seveso, Italy, incident where an industrial accident resulted in the exposure of the general population to a cloud of TCP and other toxicants are described in the previous chapter. This incident is most significant in that it represents the first episode where a cross section of a community received a definite exposure to TCDD, although the degree of exposure can only be estimated. As in any such situation confusion reigns, and a great deal of information is passed VI-24 �consisting of a mixture of truths, half-truths, and untruths. This confusion was amplified by the fact that the caustic nature of the cloud produced serious irritative effects including skin burns in many of the people who came in direct contact with the cloud. Very early after the incident an organized program was established to follow the general populace to determine what if any effects, both long and short-term, resulted (26). The findings for the first two years have been reported and are summarized as follows (2, 64, 65, 83, 84): (1) Chloracne--A massive screening program was initiated in 32,000 school children below the age of ten. Seventy-nine cases of chloracne were confirmed, only eight of which were severe. Many of the victims were not present in the area until weeks or months after the accident, indicating that the TCDD remained in the environment outside the zone of evacuation at a level high enough to produce chloracne. Except for the eight severe cases, the acne cleared in a few months. Two years after exposure some of the severe cases still showed active lesions and had severe scarring (65). In October 1977, six new cases were found in children who returned to their homes after decontamination, bringing the total to 85. No systemic abnormalities have been found in the children with acne. It is of interest that nearly all cases of acne were found in children. There are several possible explanations" for this. A massive systematic, search for chloracne was undertaken for children under the age of ten. No such search was undertaken for adults. It may be that children are more sensitive than adults. This is a phenomenon frequently seen with chemicals and drugs. It may also simply be that the children's daily routine results in greater exposure. (2) Spontaneous Abortion and Fetal Malformation—Information concerning the birthrate, abortions and fetal malformations for the two ylars following the accident revealed no significant changes (2, 64, 65, 83, 84). There were several problems regarding the evaluation of the results. First and most important was the lack of reliable background data for the area. Worldwide figures and figures from the Lombardy region of which Seveso is a part were used. Data were also biased by the fact that therapeutic abortions were offered to women who were pregnant at the time of or immediately after the accident. Nevertheless, it was the opinion of the evaluators that significant increases in spontaneous abortions and fetal malformations could not be demonstrated. Chromosomal studies were performed on the fetuses of thirty pregnancies interrupted between August 13 and December 10, 1976. No abnormalities in number of pattern beyond the expected rate were seen (2, 64, 65, 83, 84). (3) Immunology—No differences in imrnunoglobulins and B lymphocytes were found between a study and a control group of children, even though twenty of the children in the study group had chloracne (65). Hospital admissions and disease classification data evaluation revealed no significant changes from the previous year. There was an increase in VI-25 �infectious diseases compared to the previous year, but this increase was also seen in the nonex.posed districts (2, 64, 65). (4) Summary—Except for the initial irritative effects of the caustic substances and the presence of eighty-five cases of chloracne, no adverse effects to the chemicals in the toxic cloud have been confirmed. It must be remembered, however, that in many instances the findings were not conclusive and that long-term effects such as cancer and hidden congenital malformations have not yet had time to manifest themselves. It will be several years before all the data are published on the Seveso incident. d. Globe, Arizona Episode. In 1969, a number of residents in the Globe, Arizona area alleged that numerous physical ailments resulted from the spraying of the surrounding area with 2,4-D, 2,4,5-T and Silvex. Symptoms and disorders mentioned included headaches, fatigue, chest and arm pain, worsening of pre-existing nasal allergies and asthma, loss of the sense of smell and taste, severe diarrhea, spasms of the arms and legs, anemia, irregular and painful menses, spontaneous abortions, fetal malformations and cancer (82). An investigation in 1970 by Tschirley et al (82) was unable to connect the disorders with definite exposure; however, he recommended further studies. As a result of this recommendation Roan and Morgan (66) in 1972 reported on the results of an epidemiological study of the hospital records in the area and a pesticide analysis of several body tissues and fluids including adipose tissue. The technique of analysis allowed minimum detection of TCDD at 2 ng/gm tissue and of 2,4,5-T, 2,4-D or Silvex at 0.01 ng/gm tissue. No 2,4,5-T, 2,4-D, Silvex or TCDD was found. They concluded that the probability of chronic human exposure in the area in question was very minimal. e. The Swedish Lapland Episode. As noted in Chapter V, this episode involved a series of public debates on the risks to humans (and animals) of the phenoxy herbicides, especially 2,4,5-T. In the March 1978 WBBM television report on "Agent Orange: Vietnam's Deadly Fog," reference was made to a report from Sweden on birth defects (e.g., spina bifida) in children born to 65 women allegedly exposed to 2,4,5-T herbicide. The only reference to such an incident was that reported by Hailing (32) in 1977. Hailing reported on the presence of malformations in children born to mothers exposed to hexachlorophene soap during early pregnancy. A group of 65 children born to this group showed six slight and five severe malformations. This contrasted with one slight malformation in 68 children born to a group of nonexposed mothers. It needs to be emphasized that the chemical in question was hexachlorophene and not phenoxy herbicide. f. Te Awamutu, New Zealand Episode. In 1972 Sare and Forbes (68) reported on two babies born within a month of each other in the same hospital, each presenting with meningomyelocoeles. They lived in farm country where spraying with 2,4,5-T had been routinely carried out for several years. The possibility that the malformations may have been related to the herbicide was suggested. Because of this report and other allegations that neural tube deformities were the result of 2,4,5-T exposure, a thorough, although retrospective, investigation of the problem was undertaken by the VI-26 �Department of Health in 1977. The investigating committee (1) concluded that there was no evidence to implicate 2,4,5-T as an etiologic factor. D. Cancer There are a number of individual case reports and geographically limited studies of herbicide workers, both in manufacturing as well as application, that suggest an associative relationship between exposure to either 2,4,5-T, TCP or TCDD and subsequent development of a variety of neoplasms. Of 75 workers exposed in a TCP factory accident in 1953, most were affected by chloracne, 42 were listed as severe. All of the 75 workers could be traced 25 years later and whfle the mortality rate was no higher than expected, there had been 6 deaths due to cancer versus the 4 that could have been expected from national averages. Three of the deaths were due to stomach cancer in the 60-69 year age group, which was significantly more than expected (35). One worker involved in an accident in a 2,4,5-T producing factory in the Netherlands in 1963 died of carcinoma of the pancreas in 1964 (35). Because of the extremely short time span between the exposure and the death, it is not likely that the two are related. In 1973 Tung (86) reported an increased incidence of hepatic cancer in Vietnamese allegedly exposed to the spray of Herbicide Orange. A lack of details in the reporting make evaluation of the claim difficult. Jirasek et al (37, 38) and Pazderova et al (61) reported the presence of two bronchiogenic carcinomas at ages 47 and 59 during the first five years of the follow-up of 75 workers occupationally exposed to 2,4,5-T and pentachlorophenol. They noted that only 0.12 lung cancer deaths were expected from national mortality statistics. Again, the latent period was short and no smoking statistics were given. In 1972, newspapers in Sweden reported an excess mortality due to lung cancer in railroad workers exposed to herbicides. As a result, Axelson and Sundell (5) initiated a controlled study and in 1974 reported that although there appeared to be an increased incidence with Amitrol there was no significant increase with 2,4-D or 2,4,5-T. However, a re-evaluation of the data indicated a possible and previously masked tumor inducing effect from the phenoxy acids (35). A similar study on workers involved with spraying 2,4-D and 2,4,5-T on brushwood in Finland showed no increase in overall mortality. There were, however, four cases of cancer in the age group younger than 45 years as opposed to the expected two(35). Hardell (33) reported that of 87 mesenchymal tumors seen from 1970-1976 in the Department of Oncology, Regional Hospital, Umea, Sweden, 19 had been in men whose employment (farmers and forestry workers) may have resulted in exposure to the phenoxy herbicides. The expected mesenchymal VI-27 �cancers for this group was eleven. Seven cases with known sporadic herbicide exposure 10-20 years before diagnosis were presented. Hardell noted the difficulty in establishing a causal relationship but suggested that the deviation from national averages for these relatively uncommon tumors could perhaps be linked to extensive use of the phenoxy herbicides in the Umea region. Five leukemia deaths have been reported in the area of Meda, Italy, since the Seveso episode in July 1976. No more than 1.4 were expected. One of the cases was found to predate the accident (35). Additionally, the interval from exposure to diagnosis appears to be too short to ascribe causation. The case of pancreatic carcin'oma in the 55-year-old woman described by Reggiani (65) and mentioned previously in the section on the pharmacodynamics of TCDD was also felt not to be related to the exposure to TCDD. To quote Reggiani "A causal relationship with the malignancy can be excluded owing to the lapse of time required by tumor growth to reach the size, weight and diffusion of this case. The exposure to TCDD has occurred at a time when the growth of the tumor had already reached the stage of occult spreading throughout lymphatic and blood vessels to the adjacent tissues and organs." (65) As noted above, these studies should be viewed only as preliminary evidence of a statistical relationship between exposure to the phenoxy herbicides, TCDD and TCP and subsequent cancer development. Except in cases such as the angiosarcoma caused by vinyl chloride where the type of cancer is rare and the association with exposure irrefutable, it is virtually impossible to differentiate a cancer caused by a specific chemical agent from a similar cancer caused by some other etiology. This is certainly true with the retrospective studies currently available and may be true even with meticulously controlled prospective studies. There are, however, a number of cohort studies either ongoing or planned which may help clarify the present uncertainty concerning the role of the phenoxy herbicides in cancer causation in humans (35). IV. CONCLUSIONS A. Pharmacodynamics 1. 2,4-D and 2,4,5.-T are readily absorbed via the cutaneous, and gastrointestinal routes, distributing throughout the body. The respiratory tract may also be a point of entry although of lesser importance, 2. Liquid phenoxy-herbicide contact to the skin can produce systemic reactions. 3. 2,4-D and 2,4,5-T have relatively short half-lives in the human body and persistent body burden is unlikely to develop, at least in short-term or intermittent exposures. VI-28 �Other than the knowledge that TCDD may enter the body ly, the pharmacokinetics of TCDD in man are essentially unknown. Sasud on the way ot;her_p«-c.t,icides are handled, it is reasonable to assume that t^e use of 2,^,5-T has resulted in considerable skin-liquid contact. In spite of this, reports of 2,4,5-T toxicity and therefore TCDD toxicity are minimal considering the degree of use. This may indicate that man is more resistant to the effects of 2,4,5-T and TCDD than other animals, but it could also indicate that percutaneous absorption is less. The apparent relative lack of toxicity or percutaneous absorption is further supported by the Missouri incident where there was a marked difference between the degree of toxicity in man and animals. B. Effects of the Herbicides 1. The use of 2,4-D and 2,4,5-T worldwide since the middle 1940s, with minimal reports of adverse effects indicate that they jre generally saf" chemicals if properly used. Large total doses or 2,4-D have been given tc humans in controlled circumstances without adverse effects. 2. The ne-vous system is p-: v - r icui at i,> sensitive to 2,4-D. If peripheral neuropathy developed following exposure to 2,4-D, it normally disappears in a matter of months. However, in some reported incidents, it "nd persist for on? to three years. 3. Symptoms present within the first few days after exposure are probably due to the herbicide and not TCDD. 4. Adverse effects of 2,4-D and 2,4,5-T should manifest themselves shortly after exposure. Symptoms arising for the first time, months to years after the last exposure are probably due to an etiology other than 2,4-D and 2,4,5-T, 5. The hematopoetic system may be an important target organ for 2,'-i-D in some people. C. Effects of TCDD 1. If there is not a history of chloracne, it is highly unlikely that systemic changes will be due to TCDD. However, the acne may be minimal and, therefore, the historical search must be meticulous. 2. The presence of active chloracne months to years after exposure does not necessarily mean continuing exposure. 3. Skin lesions of porphyria cutanea tarda are independent of those associated with chloracne. 4. The development of porphyria cutanea tarda following exposure to TCDD suggests an adverse liver response to the TCDD. VI-29 �5. Although asthenia is difficult to interpret, it probably represents a symptom of TCDD intoxication. 6. A rise in serum lipids may occur after exposure to TCDD. However, because of large individual variations, the finding is difficult to interpret. 7. Claims of carcinogens!s, teratogenesis, and mutagenesis in man have not been confirmed at this time for the phenoxy herbicides or TCDD. However, the topic remains open. • 8. The preliminary information from the Seveso episode and the study by Kramer on the health of 2,4,5-T workers indicate that incidental nonoccupational exposure to small amounts of TCDD is unlikely to produce symptoms. 9. The long-term effects of large acute doses of TCDD or small intermittent or chronic exposures are not known. V. SUMMARY The pharmacodynamics and adverse effects of the phenoxy herbicides, trichlorophenol and TCDD were reviewed, primarily through reports of occupational exposure and accidents as well as reported exposures to the general public. A number of organ systems may be involved if the dose is significantly high with emphasis on the skin, liver, CNS and peripheral nervous system. Adverse effects of 2,4-D and 2,4,5-T should manifest themselves shortly after exposure. Symptoms arising for the first time months to years after the last exposure are probably due to an etiology other than 2,4-D and 2»4,5-T. The hallmark of TCDD is chloracne and its absence makes it unlikely that systemic disorders present are related to TCDD. Asthenic and vegetative symptoms are often present in overexposure but are difficult to interpret. They would normally be expected to clear with time. There is no conclusive evidence at this time that the phenoxy herbicides or TCDD are mutagenic, teratogenic or carcinogenic in man. VI-30 �LITERATURE CITED CHAPTER VI 1. Anonymous. 1977. 2,4,5-T and Human Birth Defects. Report prepared in the Division of Public Health, Department of Health, New Zealand. Mim. 42p. 2. Anonymous. 1977. 28th Technical Report to the Seveso Authority. Mario Negri Institute of Pharmacological Research. Milan, Italy. November 1977. 3. Armstrong, R.W., E.R. Eichner, E.D. Klein, W.F. Barthel , J.V. Bennett, V. Jonsspn, H. Bruce, and I.E. Loveless. 1969. Pentachlorophenol poisoning in a nursery for newborn infants. II. Epidemiologic and toxicologic studies. J. PzdLLa&L. 75(2) -.317-325. 4. Assouly, M. 1951. Desterbants selectifes et substances de croissance. Apercu technique. Effet pathologique sur Thomme au cours de fabrication de Tester du 2,4-D. AtcA. Mo£. P/torf. 12:26-30. 5. Axelson, 0. and L. Sundell. 1974. Herbicide exposure, mortality and tumor incidence. An epidemiological investigation on Swedish railroad workers. Wo/ife, Enutton. , Heotth ll(l):21-28. 6. Baader, E.W. and H.J. Bauer. 1951. Industrial intoxication due to pentachlorophenol. Ind. Med. SotgeAt/ 20(6) : 286 -290. 7. Barthel, E. 1974. Pulmonary fibroses in persons occupationally exposed to pesticides. Z. &ikA.. ktmungAoig 141:7-17. (German) 8. Bashirov, A. A. 1969. The state of health in workers manufacturing the herbicides, the amine salt and the butyl ester of 2,4-D acid. (//uzcAebnoe t?e£o Wo. 10:92-95. (Russian) 9. Bauer, H., K. H. Schulz and U. Spieqeioerg. 1961. Occupational intoxication in tne manufacture of chiorophenol compounds. A/tcA. GzweA.be.path.ot. 18:538-555. (German). 10. Beale, M.G., W.i. Shearer, M.M. Karl and A.M. Roboon. 1977. Longterm effects of dioxin exposure. Ltr to Editor. Lancat(l) (8014) :748. 11. Berkley, M.C. and K.R. Magee. 1963. Neuropathy following exposure to a diethylamine salt of 2,4-D. A/ich. Intern. Med. 111:351-352. 12. Berwick, P. 1970. 2,4-Dichlorophenoxyacetic acid poisoning in man. Some interesting clinical and laboratory findings. 3. Am. Med. VI-31 �13. Birmingham, D.J. 1964. Occupational dermatology: current problems. 3:38-42. 14. Bleiberg, J., M. Wallen, R. Brodkin and I.L. Applebaum. 1964. Industrially acquired porphyria. M.c.h. Vejuncutat. 89:793-797. 15. Brandt, M.R. 1971. Herbatox poisoning, a brief review and a report of a new case. Ugtekn. La&g. 133(11) :500-503. (Danish) 16. Braun, W. 1970. Chloracne. TkeA.. Umck. 27(8) :541-546. (German) 17. Budd, M.L., N.S. Hayner, H.E.B. Humphrey, J.R. Isbister, H. Price, M.S. Reizen, G. van Amburg and K.R. Wilcox. 1978. Polybrominated biphenyl exposure - Michigan. Mo-tb. Matt. 27(14) :115-116, 121. 18. Committee on the effects of herbicides in South Vietnam. 1974. Part A. Summary and Conclusions. National Academy of Science, Washington, D.C. 398p. 19. Commoner, B. and R.E. Scott. 1976. Accidental contamination of soil with dioxin in Missouri: Effects and countermeasures. Center for the Biology of Natural Systems. Washington University; St. Louis, Missouri. Mim. 27p. 20. Coutselinis, A., R. Kentarchou and D. Boukis. 1977. Concentration levels of 2,4-D and 2,4,5-T in forensic material. Foimdxlc Science 10:203-204. 21. Crow, K.D. 1970. 56:79-99. Chloracne. Trans. St. John's Hosp. Vexmcutol. Sco. 22. Cutting, R.T., T.H. Phuoc, J.M. Ballo, M.W. Benenson and C.H. Evans. '1970. Congenital malformations, hydatidiform moles and stillbirths in the Republic of Vietnam, 1960-1969. Document No. 903.233. Government Printing Office, Washington, D.C. 23. Dudley, A.W. and N.T. Thapar. 1972. Fatal human ingestion of 2,4-D, a common herbicide. M.c.k. ?cuthol. 94(3):270-275. 24. Dugois, P., J. Mare'chal and L. Colomb. 1958. Chloracne caused by 2,4,5-trichlorophenol. hick. Mat Ptorf. 19:626-627. (French) 25. Dugois, P., D. Amblard, M. Aimard and G. Deshors. 1968. A collective and accidental Chloracne of a new type. Bo££e£tn de. to. Soc^e^e'Ctcn-tque do. VexmcutoioQle. <tt SyphJJUgHaphie. 75:260-261. (French) 26. Fara, G.M. 1976. Health surveillance program. Medical -Epidemiological . Commission. Milan, August 27, 1976. Mim. lOp. 27. Feldmann, R.J. and H.I. Maibach. 1974. Percutaneous penetration of some pesticides and herbicides in man. Tozicoi. App£. Phasunacoi. 28(1):126-132. VI-32 �28. Gehring, P.J., C.G. Kramer, B.A. Schwetz, J.Q. Rose and V.K. Rowe. 1973. The fate of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) following oral administration to man. TOJO.CO£. App£. VhaJwac.ot. 26:352-361. 29. Goldmann, P.J. 1972. Extremely severe acute chloracne due to trichlorophenol decomposition products. A contribution to the perna problem. Atfae^&med. Soz-ta6ned. Afi.b<ut&hyg. 7(1):12-18. (German) 30. Goldmann, P.J. 1973. Severe acute chloracne, a mass intoxication due to 2,3,6,7-tetrachlorodibenzodioxin. Huutaft.zt laJit. 24:149-152. (German) 31. Goldstein, N.P., P.H. Jones and J.R. Brown. 1959. Peripheral neuropathy after exposure to an ester of dichlorophenoxyacetic acid. J. Am. Med. A44oc. 171:1306-1309. 32. H a i l i n g , H. 1977. Suspected l i n k between exposure to hexachlorophene and birth malformed infants. LakafcUdninge.n 74:542-546. (Swedish) 33. Hardell, L. 1977. Malignant mesenchymal tumors and exposure to phenoxy acids - A clinical observation. Lafea/t£cdcu.ngen 74(33): 2753-2754. (Swedish) 34. International Agency for Research on Cancer. 1977. I ARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Man. Vol. 15. Some ^umiQantA, the. koAb<icMizA 2,4-1? and 2,4,5-T, c.kio^inate.d and mit>c.<Mane.ouA induA&tijot chenu.co£a. Lyons, France. 35. IARC. 1978'. IARC Internal Technical Report No. 78/001. Coordination of epidemiological studies on the long-term hazards of the chlorinated dibenzo-dioxins/chlorinated dibenzofurans. Joint NIEHS/IARC Working Group Report. Lyon, France. 36. Jensen, N.E. and A.E. Walker. 1972. Chloracne: Three cases. Royal Soc. Meet. 65:687-688. P/coc. 37. Jirasek, L., J. Kalensky and K. Kubec. 1973. Acne chlorina and porphyria cutanea tarda during the manufacture of herbicides. Vesunatal. 48(5): 306-31 5. (Czech) 38. Jirasek, L. , J. Kalensky, K. Kubec, J. Pazderova and E. Lukas. 1974. Acne chlorina, porphyria cutanei. tarda, and other manifestations of general intoxication during the manufacture of herbicides. II. C&sfe. Vfwnalol. 49(3):145-157. (Czech) 39. Johnson, H.R.M. and 0. Koumides. 1965. A further case of M.C.P.A. poisoning. B/i. Meet. J. 2:629-930. 40. Jones, D.I.R., A.G. Knight and A.J. Smith. 1967. Attempted suicide with herbicide containing MCPA. M.c.k. Env<tiion. H&atth. 14:363-366. VI-33 �41. Kimbrough, R.D. 1972.. Toxicity of chlorinated hydrocarbons and related compounds. hick. Evwifian. Health 25(2) :125-131 . 42. Kimbrough, R.D. 1974. The toxicity of polychlorinated polycyclic compounds and related chemicals. CJut. Rev. Toiu,c.ol. 2:445-498. 43. Kimbrough, R.D. , C.D. Carter, J.A. Liddle, R.E. Cline and P.E. Phillips. 1977. Epidemiology and pathology of a tetrachlorodibenzodioxin poisoning episode. hick Env-inon H&cuLth 28:77-85. 44. Kimmig, J. and K.H. Schulz. 1957. Chlorinated aromatic cyclic ether as cause of so-called chloracne. Na£uAw^en4cha££en ,44:337-338. (German) 45. Kimmig, J and K.H. Schulz. 1957. Occupational acne caused by chlorinated aromatic cyclic ethers. V&ima£ol.OQ4.ca 115:540-546. (German) 46. Kohli, J.D. , R.N. Khanna, B.N. Gupta, M.M. Dhar, J.S. Tandon and K.P. Sircar. 1974. Absorption and excretion of 2,4-dichlorophenoxyacetic acid in man. Xeno b-iotic.a 4(2):97-100. 47. Kohli, J.D. , R.M. Khanna, B.N. Gupta, M.M. Dhar, J.S. Tandon and K.P. Sircar. 1974. Absorption and excretion of 2,4,5-trichlorophenoxyacetic acid in man. 'hich. Int. Phasunacodyn. TheA. 210:250-255. 48. Kotlarek-Haus, S., W. Dzierkowa-Borodej and B. Lawinska. 1971. Autoimmune hemolytic anemia after handling insecticides and herbicides with simultaneous detection of the Australian antigen (AT) in the serum, fotia. Hamcutol. 95(3)240-253. (German) 49. Kramer, C.G. 1970, revised 1974. Health of employees exposed to 2,4,5-T. Dow Chemical Company, Midland, Michigan. Mim. Unpublished data. 19p. 50. Lobes, L.A. , R.E. Koehler, W.F. 1972. Administrative report to Control (CDC) on toxic illness, EPI-72-13-2, U.S. Public Health Barthel , R.A. Feldman and J.V. Bennett. the director of the Center for Disease Lincoln County, Missouri, CDC No. Service, CDC, Atlanta, Georgia. 51. Londono, F. 1966. Occupational acne: Five cases produced by weed killers. Medicxjoo. Cwtanae. 3:225-232 (Spanish) 52. Matsumura, A. 1970. The fate of 2,4,5-trichlorophenoxyacetic acid in man. Jap. J. Ud. Hea&th 12(9):20-25. (Japanese) 53. May, G. 1973. Chloracne from the accidental production of tetrachlorobenzodioxin. B-t. J. Ind. Mad. 30:276-283. 54. Miura, H., A. Omori and M. Shibue. 1974. The effect of chlorophenols on the excretion of porphyrins in the urine. Sangyo Igafeu 16(6) :575,, (Japanese) VI-34 �area, G. and G, di Vito. 1961. Acute poisoning from weed killer ,4-dichlorophenoxyacetic acid), fotia Med. 44:480-485. 56. Hielson, K. , B. Kaempe and J. Jensen-Holm. 1965. Fatal poisoning in in man by 2,4-dichlorophenoxyacetic acid (2,4-D): Determination of the agent in forensic materials, kcta ?kamac.ol. TOJO.CO£. 22:224-234. 57. Oliver, R.M. 1975. Toxic effects of 2,3,7, 8-tetrachlorodibenzo-l ,4dioxin in laboratory workers. St. J. Ind. Meet. 32(l):49-53. 58. Paggiaro, P.L., E. Martino and S. Mariotti." 1974. A case of 2,4-dichlorophenoxyacetic acid (2,4-D) intoxication. Meci. Lav. 65 (3-4.) :128-135. (Italian) 59. Palva, H.L.A., 0. Koivisto and I. P. Palva. 1975. Aplastic anaemia after exposure to a weed killer, 2-methyl-4-chlorophenoxyacetic acid. Haemato£. 53(2) :105-108. 60. Park, J., I. Darrien and L.F. Prescott. 1977. Pharmacokinetic studies in severe intoxication with 2,4-D and mecoprop. Ctot. To>u.c.o£. 18:154-155. 61. Pazderoz, J., E. Lukas, M. Nemcova, M. Spacilova, L. Jirasek, J. Kalensky, J. John, A. Jirasek and J. Pickova. 1974. Chronic poisoning by chlorinated hydrocarbons formed in the production of 2,4,5-trichlorophenoxyacetate. Piac.. Ltk. 26(9) :332-339. (Czech) 62. Poland, A.P., D. Smith, G. Wetter and P. Possick. 1971. A health survey of workers in a 2,4-D and 2,4,5-T plant. A/icfo. Envision. \\<LaJWi 22:316-327. 63. Popham, R.D. and D.M. Davies. B*. Med. J. 1:677-678. 1964. A case of MCPA poisoning. 64. Reggiani, G. 1977. Medical problems raised by the TCDD contamination in Seveso, Italy. Presentation to the 5th International Conference on Occupational Health in the Chemical Industry (Medichem), San Francisco, California, September 5-10, 1977. 65. Reggiani, G. 1978. The estimation of the TCDD toxic potential in the light of the Seveso accident. Paper presented at the 20th Congress of the European Society of toxicology. Berlin (West), June 25-28, 1978. 66. Roan, C.C. and D.P. Morgan. 1972. Alleged effects on human health of the use of herbicides in the area around Globe, Arizona. Arizona Community Pesticide Study Project, March 6, 1972. University of Arizona, Tucson, Arizona. Mim. 7p. 67. Robson, A.M., J.M. Kissane, N.H. Elvick and L. Pundavela. 1969. Pentachlorophenol poisoning in a nursery for newborn infants. I. Clinical features and treatment. J. PzdMi. 75(2) :309-316. VI-35 �68. Sare, W.M. and P.I. Forbes. 1972. Possible dysmorphogenic effects of an agricultural chemical: 2,4,5-T. W.Z. Med. J. 75(476):37-38. 69. Sare, W.M. 1972. The weedicide 2,4-D as a cause of headaches and diplopia. N.A. Med. J. 75(478) :173-174. 70. Sauerhoff, M.W. , W.H. Braun, G.E. Blau and P.J. Gehring. 1977. The fate of 2,4-dichlorophenoxyacetic acid (2,4-D) following oral administration to man. Toiu.c.ot.ogy 8:3-11. 71. Sauerhoff, M.W., M.B. Chenoweth, R.J. Karbowski, W.H. Braun, J.C. Ramsey, P.J. Gehring and G.E. Blau. 1977. Fate of Silvex following oral administration to humans. J. ToiU.c.ol. Envision Hea&tk 3:941-952. 72. Schulz, K.H. 1957. Clinical and experimental studies on the etiology of chloracne. M.C/I. K&tn. Ex.p. V<ywatot. 206:589-596. (German) 73. Schulz, K.H. 1968. Clinical picture and etiology of chloracne. . Sozxu&ned. Atbexx&hyg. 3(2):25-29. (German) 74. Seabury, J.H. 1963. Toxicity of 2,4-dichlorophenoxyacetic acid for man and dog. A/tch. EmuAon. Health 7:202-209. 75. Suskind, R.R. 1978. Chlorinated hydrocarbon acne. Presentation at the American Occupational Health Conference, New Orleans, Louisiana, April 10-14, 1978. 76. Taylor, C.C. 1974. Chemical toxicity and mental disorder. Am. J. 131(5):609., 77. Taylor, J.S. 1974. Chloracne - A continuing problem. Cu£u 13:585-591 78. Telegina, K.A. and L.I. Bikbulatova. 1970. State of the skin in persons in contact with methoxone during its industrial production. l/ei£n. Vvwatol. VzneAol. 44(8):76-79 (Russian) 79. Ter Beek, R. , R. Bokhorst, M.V.D. Plas, K. Olsthoorn, P. Vergragt and G. Van Der Zwan. 1973. Dioxin, a dangerous contaminant in a much used herbicide. Cfiem. We.efefa£ 69(23) :57 (Dutch) 80. Todd, R.L. 1962. A case of 2,4-D intoxication. J. Iowa Med. Soc.. 52:663-664. 81. T.sapko, V.P. 1966. The herbicide 2,4-D as a health hazard in agriculture. GA&. Saute. 31:449-450. 82. Tschirley, F.H., (Chairman) W. Binns, C. Cueto, B.C. Eliason, H.W. Heggestad, G.H. Hepting, P.F. Sand and R.F. Stephens. 1970. Investigation of spray project near Globe, Arizona. Investigation conducted February 1970. Mim. , U.S. Dep Agric Office of Science and Education. Mim. 29p. VI-36 �83. Tuchmann-Duplessis, H. 1977. Embryo problems posed by the Seveso accident. Le. Conc.onfu> Medico£ No. 44, November 26, 1977. Translation. Mim. 17p. (French) 84. Tuchmann-Duplessis, H. 1978. Environmental pollution and offspring: With relation to the accident at Seveso. MecL &t Hyg. 36:1758-1766. (French) 85. Tung, T.T., T.K.A.B.Q. Tugen, D.X. Tra and N.X. Huyen. 1971. Clinical effects of massive and continuous utilization of defoliants on civilians. W.etnome4e Stu.di.tA. 29:53-81. 86. Tung, T.T. , T.T. An, N.D. Tarn, P.M. Phiet, N.N. Bang, T.T. Bach, H. vanSon and O.K. Son. 1973. Le cancer primaire du foie au Vietnam. e. 99:427-436. (French) 87. Wallis, W.E., A. Van Posnak and F. Plum. 1970. Generalized muscular stiffness, fasciculations and myokymia of peripheral nerve origin. A/icfc. NeuAo£. 22:430-439. 88. Zelikov, A. Kh and L.N. Danilov. 1974. Occupational derma toses (acnes) in workers engaged in production of 2,4,5-trichlorophenol . Sov. Meet. 7:145-146. (Russian) *U.S. GOVERNMENT PRINTING OFFICE: 1980-671-1H3/2S VT- 1 }? � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 046 Folder The folder containing the original item. 1165 Series The series number of the original item. Series III Subseries I Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Young, Alvin L. John A. Calcagni Charles E. Thalken James W. Tramblay Description An account of the resource <strong>Corporate Author: </strong>United States Air Force Occupational and Environmental Health Laboratory, Aerospace Medical Division (AFSC), Brooks Air Force Base, Texas Date A point or period of time associated with an event in the lifecycle of the resource 1978-10-01 Title A name given to the resource The Toxicology, Environmental Fate, and Human Risk of Herbicide Orange and its Associated Dioxin Subject The topic of the resource Ranch Hand biodegradation herbicide disposal herbicide toxicology ao_seriesIII https://www.nal.usda.gov/exhibits/speccoll/files/original/3f4bef0956a64c1c127a1b2894821266.pdf 3181b7d44f6de47aef9776417196ede7 PDF Text Text Item ID Number 00193 Author Young, Alvin L. Corporate Author Department of Chemistry and Biological Sciences, USA Report/Article TitlO Fate of 2,3,7,8-Tetrachlorodibenzo-P-Dioxin (TCCD) in the Environment: Summary and Decontamination Recommendations Journal/Book Titlo Year Month/Day Color Number of Images October [J 49 Monday, January 22, 2001 Page 205 of 341 �USAFA-TR-76-18 FATE OF 2, 3, 7, 8-TETRACHLORODIBENZO-P-DIQXlN (TCDD) IN THE ENVIRONMENT: SUMMARY AND DECONTAMINATION RECOMMENDATIONS CAPTAIN ALVIN L. YOUNG MAJOR CHARLES E. THALKEN LT COLONEL EUGENE L. ARNOLD CAPTAIN JAMES M. CUPELLQ MAJOR LORRIS G. COCKERHAM DEPARTMENT OF CHEMISTRY AND BIOLOGICAL SCIENCES USAF ACADEMY, COLORADO 80840 OCTOBER 1976 APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED Prepared for: HEADQUARTERS AIR FORCE LOGISTICS COMMAND WRIGHT-PATTERSON AIR FORCE BASE, OHIO 4S433 DEAN OF THE FACULTY UNITED STATES AIR FORCE ACADEMY COLORADO 80840 �Editorial Review by Lt Colonel J. M. Shuttleworth Department of English and Fine Arts USAF Academy, Colorado 80840 This research report is presented as a competent treatment of the subject, worthy of publication. The United States Air Force Academy vouches for the quality of the research, without necessarily endorsing the opinions and conclusions of the author. This report has been cleared for open publication and/or public release by the appropriate Office of Information in accordance with AFR 190-17 and DODD 5230.9. There is no objection to unlimited distribution of this report to the public at large, or by DDC to the National Technical Information Service. This research report has been reviewed and is approved for publication. PHILIP J/QZRDLET Colonel, USAF Vice Deah of the Faculty Additional copies of this document are available through the National Technical Information Service, U. S. Department of Commerce, 5285 Port Royal Road, Springfield, VA 22151. �UNCLASSIFIED SECURITY CLASS'FICATION OF THIS »AGE (When Data Entered) READ INSTRUCTIONS BEFORE COMPLETING FORM REPORT DOCUMENTATION PAGE 1. REPORT NUMDER 2. GOVT ACCESSION NO 3. RECIP'FN'T'S CATALOG NUMBER USAFA-TR-76-18 4. TITLE (and Subtitle) 5. TYFE OF REPORT ft PERIOD COVERED Fate of 2,3,7,8-TetracMortdibenzo-p--dioxin (TCED) in the Environment: Surtmary and Decontamination Recxxtmendations Summary Report 6. PERFORMING ORG. REPORT NUMBER 8. 7. AUTHOR?.) Alvin L. Young, Capt, USAF, PhD; Charles E. Thalken, Maj, USAF, VC, DVM, MS; Eugene L.Arnold, LtCpl, USAF, BSC, PhD; James M, Cupello, Capt, USAF, PhD; Lorris G. CocTcerham, Maj, USAF, MS CON1 RACT OR GRANT NUMBERf»> 10. PROGRAM F.LEMENT. PROJECT, TASK AiHTA ft WORK UNIT NUMBERS 9. PERFORMING ORGANIZATION N A M E AND ADDRESS Department of Chemistry and Biological Sciences DFCBS-R USAF Academy, Colorado 80840 t. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE October 1976 Department of Chemistry and Biological Sciences DFCBS-R USAF Academy, Colorado 80840 13. NUMBER OF PAGES 14. MONITORING AGENCY NAME & ADDRESSf// different from Controlling Otlice) 15. SECURITY CLASS, (of thla report) 44 UNCLASSIFIED 15«. DECLASSIFICATION/DOWNGRADING SCHEDULE 6. DISTRIBUTION STATEMENT (ot thla Report) Approved for public release: distribution unlimited. 7. DISTRIBUTION STATEMENT (of the abstract entered In Block 20, II different from Report) 8. SUPPLEMENTARY NOTES 9. KEY WORDS (Continue on reverse aide It necessary and Identity by block number) Animal SUTVey; Aquatic Studies; Bic>accumulation; Biodegradation of Herbicides; Biodegradation of TCDD; Ecological Effects; 2,4-dichlorophenoxyacetic acid (2,4-D); Fish Studies; Herbicide; Histopathology; Insect Studies; Maranals; Necropsy; Orange; Reptile Study; Soil Microbial Studies; TCDD; Teratogenic; 2,3,7,8-tetxochlorodibenzo-pdioxin (TCDD); Test Area C-52A, Eglin AFB Reservation; 2,4,5-trichlorophenoxyanifl \rf f ^ * *rf__ jfr f T Vegetative Succession. • —• irtffrYftrr H-hM HiVfAM ^r^-VT^_ _* ^y VMV^ ^ * ^- - «''*^^ *' -. *"^ ' " — -..,..-— ———.... , —, 0. ABSTRACT (Continue on rovora* aide (/ ri «vt** «ry ant/ I ((entity by bjpck number) . . /msmr\\ i* U.^ Studies on the fate of 2,3,7,8-tetrachiorodibenzo-p-dioxin (TCDD) have been conducted on biodegradation plots and field test areas that have received massive quantities of Orange herbicide (a 50:50 mixture of the n-butyl esters of 2,4lichlorophenoxyacetic acid [ , 4 D and 2,4,5-trichlorophenoxyacetic acid 2'-] 2,4,5-T]). From the studies reviewed in this report, it is apparent that 1) TCDD may persist (in biotic and abiotic components) for long periods of time when initially present at extremely high concentrations on the soil surface, 2) TCDD will accumulate in the tissues of rodents, reptiles, birds, fish, and W DD , FORM73 1473 JAN M >l EDITION OF 1 NOV 65 IS OBSOLETE Mg F i rs UNCLASSIFIED �SECURITY CLASSIFICATION OF THIS PAGEfWhen Data Entered) 20. Abstract (Continued) insects when these organisms are exposed to TCDD contaminated soils (however, the levels of TCDD in the tissues apparently do not exceed the levels of TCDD found in the environment), (3) organisms tolerate, i.e., based on no observed deleterious effects, soil levels between 10-1,500 ppt TCDD, (4) TCDD is degraded by soil microorganisms, especially when in the presence of other chlorinated hydrocarbons, (5) TCDD is degraded in the presence of sunlight, (6) movement of TCDD in the abiotic portions of the environment can be by wind or water erosion of soil particles, but leaching by water alone does not appear to occur, and (7) TCDD is probably not readily released or degraded in the environment when bound to activated coconut charcoal. SECURITY CLASSIFICATION OF THIS PAGE(Wien Date Entered) �TABLE OF CONTENTS Title Page Introduction 1 Soil Incxjrporation/Biodegradation Studies 6 Fate of TCDD in an Ecosystem Geographical and Vegetative Features Sampling Grids and Herbicide Deposition Preliminary Ecological Studies Soil Studies of TCDD Residues Rodent Studies Trapping Data/Histopathology Liver and Pelt Analysis Burrow and Diet Studies TCDD Laboratory Uptake Experiment Hepatic Ultrastructural Study Reptile Studies TCDD in Aquatic Organisms TCDD in Birds of TA C-52A Vegetative Succession Studies on TA C-52A 17 ... 18 18 18 .21 23 23 25 25 26 27 29 30 31 32 Laboratory and Greenhouse Experiments with TCDD 34 Recormiendations 39 �LIST OF TABLES Number 1 2 3 Page Analyses of the Top 15-on Layer From Each of the Soil Biodegradation Sites 7 Descriptions of Three Biodegradation Studies Involving Use of Herbicide Orange 8 Concentrations of Herbicide Orange and TCDD in Plots Originally Treated with 4,480 kg/ha, AFLC Test Range Complex, Utah, at Various Sampling Dates After Application. (TCDD in parts per billion) 9 4 Concentrations of Herbicide Orange and TCDD in Plots Originally Treated with 4,480 kg/ha, Garden City, Kansas, at Various Sampling Dates After Application. (TCDD in parts per trillion) . 9 5 Concentrations of Herbicide Orange and TCDD in Plots Originally Treated at 4,480 kg/ha, Eglin AFB, Florida, at Various Sampling Dates After Application 10 6 Movement of Herbicide Orange and TCDD in a Soil Profile, Eglin AFB, Florida. (TCDD in parts per trillion) 12 7 Comparison of Herbicide Orange Degradation Rates in Plots at the Eglin AFB, Florida, Site, Receiving Either Herbicide, Herbicide Plus Soil Amendments, or Herbicide Plus Amendments and Charcoal .14 8 Approximate Amounts of 2,4-D and 2,4,5-T Herbicides Applied to Test Area C-52A, Eglin AFB Reservation, Florida 9 10 11 19 Concentration of TCDD in Soil Profile (1974) of Grid I, Test Area C-52A, Eglin AFB, Florida 22 Numbers of Beach Mice Collected During the 1973 and 1974 Studies of Test Area C-52A 22 Concentration (Parts Per Trillion) of 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD) in Liver and Pelt Samples from Beach Mice, Peromyscus polionotus, Collected from Control and TCDD-Exposed Field Sites, 1973 and 1974 24 11 �UST OF TABLES (Continued) Nottogr 12 13 14 Page Concentration (Parts Per Trillion) of 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD) in Liver and Pelt Samples from Beach Mice, Peronyscus polionotus, Dusted with Alumina Gel Containing No TCDD (Control) or 2.5 Parts Per Billion TCDD (Test) 28 Concentration (Parts Per Trillion) of 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD) in Composite Samples of Viscera or Trunk from Six-Lined Racerunners, Cnemidophorus sexlineatus, Collected from Control and TCDD-Exposed Field Sites 28 Degradation of TCDD (Parts Per Trillion) in a Greenhouse Experiment, Eglin AFB, Florida 37 111 �INTRODUCTION The heterocyclic organic molecule 2,3,7,8-tetrachlorc-dibenzop-dioxin (TCDD) has received a great deal of attention in the last 6 years because of its highly toxic properties and the possibility of it being widespread in the environment by the use of products made from trichlorophenol, especially the herbicide 2,4,5trichlorophenoxyacetic acid (2,4,5-T). Although TCDD may occur as a contaminant in products made from trichlorophenol, the levels of TCDD found in any given lot of trichlorophenol is dependent upon the manufacturing process. TCDD may be produced as a by-product during an alkaline hydrolysis reaction when the temperature for making 2,4,5-trichlorophenol from tetrachlorobenzene exceeds 160°C. However, there is less likelihood of TCDD formation in the manufacturing process which starts with phenols and chlorinates them to form trichlorophenol since little or no heat is required in this reaction. Public interest in TCDD originated in 1970 when the herbicide 2,4,5-T was implicated as a potential teratogen in pregnant rats ( ) Later tests indicated that the teratogenesis may have been 1. caused by 27 ± 8 ppm of TCDD present as a contaminant in the 2,4,5-T. As more data have been obtained (2), it has become apparent Courtney, K.D., D.W. Gaylor, M.D. Hogan, J.L. Falk, R.R. Bates, and I. Mitchell. Teratogenic evaluation of 2,4,5-T. Science 168:864-866, 1970. 2 Schwetz, B.A., J.M. Norris, G.L. Sparschu, V.K. Rowe, P.J. Gehring, J.L. Oner son, and C.G. Gerbig. Toxicology of chlorinated dihenzo-pdioxins. Biviron. Hlth. Perspect., Experimental Issue No. 5:87-100, September 1973. �that TCDD is one of the most toxic chemicals known; the oral LD5Q for many animal species is in the range of micrograms per kilogram. Purthermore, the known effects of TCDD include anorexia, severe weight loss, hepatotoxicity, hepatoporphyria, vascular lesions, chloracne, gastric ulcers, and teratogenicity ( ) The 2. hazard posed by the presence of even a small amount of this substance in the environment has therefore been of concern. For a person or animal to be poisoned with TCDD, a rare set of circumstances would be required. Since present production methods are able to reduce the TCDD level to less than 0.1 ppm, it is unlikely that contaminated 2,4,5-T herbicide or even contaminated trichlorophenol would be implicated in such a poisoning. Nevertheless, two accidental poisoning episodes involving TCDD have been recently reported. In 1975, Carter et al. (3) identified TCDD as the apparent cause of an outbreak of poisoning in humans, horses, and other animals on a horse breeding farm in eastern •H .• , Missouri in 1971. Exposure to TCDD followed the spraying of contaminated industrial waste oil on riding arenas for dust control. An investigation concluded that a hexachlorophene (made from trichlorophenol) factory in southwestern Missouri had accumulated distillate residues containing 306 to 356 ppm TCDD. It was this distillate residue that was subsequently disposed of via a salvage oil company and sprayed on the horse arenas. 3 Carter, C.D., R.D. Kiiribrough, J.A. Liddle, R.E. Cline, M.M. Zack, Jr., W.F. Barthel, R.E. Koehler, and P.E. Phillips. Tetrachlorodibenzodioxin: an accidental poisoning episode in horse arenas. Science 188:738-740, 1975. �The second incident of TCDD poisoning occurred in July 1976 in Seveso, Italy ( ) The source of the TCDD was a chemical 4. factory that produced trichlorophenol through the alkaline hydrolysis of tetrachlorobenzene. When the temperature in a steamheated reaction vessel rapidly increased, a.safety disk ruptured sending a plume of trichlorophenol, TCDD anici other products 30 to 50 m high above the factory. The cloud apparently rose into the air, cooled, and came down over a cone-shaped area about 2 km long and 700 m wide. An area of 110 hectares (ha) was evacuated after hundreds of animals had died and many people had reported skin disorders. Several measurements of TCDD on vegetation in an area adjacent to the factory were in the 1 to 15 ppm range, with one reading as high as 51.3 ppm. An Italian government commission (5) recommended: "removal of topsoil to a depth of 10 cm in an area of 113 ha, the. dismantling of all buildings in the Seveso area, and the total disruption of all wildlife." The need for data on the fate of TCDD in the environment is not confined to solving problems associated with the above two incidents. During the latter portion of the last decade, a program of aerial application of herbicides was conducted in Southeast Asia by the United States Air Force. In 1969, at the conclusion of this program, considerable amounts of herbicide were left unused. 4 Rawls, R.L., and D.A. O'Sullivan. Italy seeks answers following toxic release. Chem. Engr. News 54(35):27-35, August 23, 1976. Itay, A. Toxic cloud over Sevesco. Nature 262(5570):636-638, August 19, 1976. �One of the herbicides used extensively in this project was a herbicide designated "Orange" which was formulated as a 50:50 mixture of the n-butyl esters of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-T. In 1970, approximately 2.3 million gallons of this material was placed in storage by the Air Force. An analysis of TCDD in the Orange herbicide stocks (6) indicated that the range in concentration was 0.1 to 47 ppm TCDD. The weighted average concentration of TCDD for the 42,015 55-gallon drums of herbicide was 1.859 ppm. Because of the TCDD concentration, the herbicide could not merely be declared surplus and disposed of on the agricultural markets. Many methods have been evaluated for disposing of this material. However, regardless of the final method selected for its disposition, the storage sites where the material is currently stored (Naval Construction Battalion Center, Gulfport, Mississippi, or Johnston Island, Pacific Ocean) will need to be decontaminated. At the request of Headquarters, Air Force Logistics Command, Wright-Patterson AFB, Ohio, in April 1972, the Department of Chemistry and Biological Sciences, United States Air Force Academy, initiated studies on herbicide Orange and TCDD. The objectives of these studies were: (1) to investigate soil incorporation/ biodegradation as a disposal method for herbicide Orange; (2) to investigate the ecological effects associated with past uses of Department of the Air Force. Disposition of orange herbicide by incineration. Final Environmental Statement, November 1974, pp. 36-37. �herbicide Orange; and (3) to investigate the soil persistence and food chain accumulation of TGDD. This report documents the available data on TCDD from these studies. Furtherxnore, using these data, recommendations for decontamination of an area exposed to TCDD are presented. �SOIL INCORPORATION/BIODEGRADATION STUDIES One potential method proposed for the disposal of herbicide Orange was subsurface injection or soil incorporation of the herbicide at massive concentration rates. The premise for such studies was that high concentrations of the herbicides and TCDD would be degraded to innocuous products by the combined action of soil microorganisms and soil hydrolysis. In order to field test this concept, biodegradation plots were established in three climatically different areas of the United States; Northwest Florida (Eglin AFB), Western Kansas (Garden City), and Northwestern Utah (Air Force Logistics Command Test Range Complex). A comparison of the soils of the three sites is given in Table 1. The Utah site had a mean annual rainfall of 15 on, while the Kansas and Florida sites had 40 and 150 cm, respectively. Table 2 describes the experimental protocol for the three sites to include when the plots were established, the method of herbicide incorporation, the experimental design and the initial calculated herbicide concentration, ppm, at the time the plots were established. Further details on the experimental protocol can be obtained from Young, Arnold and Wachinski ( ) 7. Tables 3, 4, and 5 compare the rate of disappearance of TCDD with that of Orange herbicide for selected plots at the Utah, Young, A.L., E.L. Arnold, and A.M. Wachinski. Field studies on the soil persistence and movement of 2,4-D, 2,4,5-T, and TCDD. Appendix G. Department of the Air Force. Disposition of orange herbicide by incineration. Final Environmental Statement, November 1974. �TABLE 1. ANALYSES OF THE TOP 15-CM LAYER FROM EACH OF THE SOIL BIODEGRADATION SITES ORGANIC MATTER (%) SAND (%) SILT (%) CLAY (%) 5.6 0.5 91.6 4.0 4.4 Garden City, KS^ 7.0 1.7 37 42 21 Silt loam AFLC Test Range Complex, UT0 7.8 1.4 27 53 20 Clay loam LOCATION pH Eglin AFB, FLa SOIL DESCRIPTION Sandy loam located on Test Area C-52A, Eglin AFB Reservation, Florida T>lots located on the Kansas Agricultural Experiment Station, Garden City, Kansas °Plots located 75 miles west of Salt Lake City, Utah �TABLE 2. LOCATION Eglin AFB, Florida CO Garden City, Kansas DESCRIPTIONS OF THREE BIODEGRADATION STUDIES INVOLVING USE OF HERBICIDE ORANGE DATE ESTABLISHED 2 Apr 1972 10 May 1972 AFLC Test 2 Oct 1972 Range Complex, Utah METHOD OF INCORPORATION TREATMENT CALCULATED INITIAL HERBICIDE CONCENTRATION (PPM)C 4,480 kg Herbicide/haa 4,480 kg Herbicide/ha, plus soil amendments^ 4,480 kg Herbicide/ha plus soil amendments and activated charcoal 5,000 5,000 Preplant Incorporate (Rototiller) 2,240 kg Herbicide/ha 4,480 kg Herbicide/ha 1,000 2,000 . Simulated Subsurface Injection (8 cm band width) 1,120 kg Herbicide/ha 2,240 kg Herbicide/ha 4,480 kg Herbicide/ha Simulated Subsurface Injection (30 cm band width) 5,000 10,000 20,000 40,000 of herbicide calculated as active ingredient. Herbicide injected at 10-15 cm level or preplant incorporated in the 0-15 cm level. All plots duplicated. xhe amendments included 4.5 kg lime, 13.5 kg organic matter, and 1.4 kg fertilizer (12:4:8 for N,P,K, respectively) uniformly mixed within the top 0-30 cm of soil in the plot. °Contained in the top 0-15 cm layer. �TABLE 3. CONCENTRATIONS OF HERBICIDE ORANGE AND TCDD IN PLOTS ORIGINALLY TREATED WITH 4,480 KG/HA, AFLC TEST RANGE COMPLEX, UTAH, AT VARIOUS SAMPLING DATES AFTER APPLICATION. (TCDD IN PARTS PER BILLION) DAYS AFTER APPLICATION TOTAL HERBICIDE3 (PPM) TCDD ., (PPMxlO ) 282 8,490 15.0 637 4,000 7.3 780 2,260 5.6 1,000 2,370 3.2 1,150 1,150 2.5 a Composite sample from replicated plots, 0-15 on increment TABLE 4. CONCENTRATIONS OF HERBICIDE ORANGE AND TCDD IN PLOTS ORIGINALLY TREATED WITH 4,480 KG/HA, GARDEN CITY, KANSAS, AT VARIOUS SAMPLING DATES AFTER APPLICATION. (TCDD IN PARTS PER TRILLION) DAYS AFTER APPLICATION TOTAL HERBICIDE3 (PPM) TCDD3 , (PPMxlO~°) 8 1,950 ~b 77 1,070 225 189 362 210 600 40 659 a 490 <:L —b —b —b 42 Composite sampling from replicated plots, 0-15 cm increment HSbt determined �TABLE 5. CONCENTRATIONS OF HERBICIDE ORANGE AND TCDD IN PLOTS ORIGINALLY TREATED AT 4,480 KG/HA, EGLIN AFB, FLORIDA, AT VARIOUS SAMPLING DATES AFTER APPLICATION DAYS AFTER APPLICATION TOTAL, HERBICIDE (PPM) TCDDa , (PPMxlO~b)C 5 4,897 375 414 1,866 250 513 824 75 707 508 46 834 438 -b 1,293 <10 b — Composite sample from the plot containing only herbicide (i.e., no lime, organic matter, or fertilizer added). Sample from the 0-15 cm increment. Analysis not completed. °TCDD in parts per trillion. 10 �Kansas, and Florida sites, respectively. Although the number of analyses have been limited, the data have indicated that TCDD (and phenoxy herbicide) degrade more rapidly in the Kansas soils (Ulysses Silt Loam) than in the Florida soils (Lakeland Sandy Loam), and least rapidly in the Utah desert soils (Lacustrine Clay Loam). The levels of TCDD and herbicide in a soil profile from one of the Bgl.in AFB, Florida, biodegradation plots are shown in Table 6. Initially (e.g., day 414), the data indicate that both the herbicide and the TCDD may be leaching down into the lower soil increments. However, note that the analysis for herbicide in a soil profile obtained on day 557 shows no leaching. The method of collecting soil samples, i.e., by the use of a soil auger contaminated the lower soil increments whereas the trenching technique showed no contamination. The analysis of soil profiles at all three locations for biodegradation indicated that neither the herbicide nor the TCDD appreciably penetrated below the 15-30 cm level. Thus, we believe that the disappearance of the herbicide and the TCDD can be attributed to the action of soil microorganisms, rather than leaching. Data for TCDD are not available at this time (analysis in progress) on the influence of soil amendments (e.g., lime, fertilizer, and organic matter) on the degradation of TCDD in the Eglin AFB, Florida, biodegradation study. However, preliminary indications are that the addition of these amendments in these Florida soils does appear to slightly enhance herbicide degradation. On the other hand, the presence of activated coconut charcoal in 11 �TABLE 6. MOVEMENT OF HERBICIDE ORANGE AND TCDD IN A SOIL PROFILE, EGLIN AFB, FLORIDA. (TCDD IN PARTS PER TRILLION) DAYS AFTER APPLICATION3 4l4b 557C HERBICIDE (PPM) DEPTH (CM) HERBICIDE (PPM) 0-15 1,866 250 824 15-30 263 50 11 30-45 290 <25d <10d 45-60 95 <25d <10d 60-75 160 <25d <10d 75-90 20 <25d <10d TCDD ,. (PPMxlO ) a Composite sample from the plot containing only herbicide r~ Increments obtained by use of a soil auger having cup dimensions of 7.6 x 15.2 on, diameter and length, respectively £i Increments obtained by use of porcelain spatula from the side of 90 cm deep trench < T)etection limit 12 �the Eglin plots, at the 12 on level, prevented degradation of the herbicide and probably also prevented degradation of the TCDD. These data are shown in Table 7. In no instance can it be shown that TCDD levels reached a non-detectable level (less than 10 parts per trillion) within the designated time periods (see Tables 3, 4, and 5). Although biodegradation appears to reduce the level of herbicide and TCDD, the data did not follow simple exponential decay curves. For the mixture 2,4-D and 2,4,5-T herbicides, disappearance was rapid initially, but slowed substantially in the later portions of the test period. With this type of decay kinetics, meaningful half lives are difficult to calculate; however, a reasonable estimate appears to be in the range of 150-210 days. The degradation of TCDD followed a similar decay pattern. However, it appears at this time that the decreased rate of degradation of TCDD as a function of time may be even more pronounced than for the herbicides. One might speculate that the enzymes responsible for herbicide metabolism are inducible and also are involved in TCDD breakdown. If this is the case, it is not surprising that TCDD metabolism slows or ceases when the initial massive concentrations of herbicide are removed. Microbial studies have been conducted in the biodegradation plots in both Utah and Florida ( , ) For the Utah plots, 89. Q Stark, H.E., J.K. McBride, and G.F. Orr. Soil incorporation/ biodegrada.tion of herbicide orange. Vol I. Microbial and baseline ecological study of the U.S. Air Force Logistics Command Test Range, Hill AFB, Utah. Document No. DPG-FR-C615F, US Army Dugway Proving Ground, Dugway, Utah 84022, February 1975. 13 �TABLE 7. COMPARISON OF HERBICIDE ORANGE DEGRADATION RATES IN PLOTS AT THE EGLIN AFB, FLORIDA, SITE, RECEIVING EITHER HERBICIDE, HERBICIDE PLUS SOIL AMENDMENTS, OR HERBICIDE PLUS AMENDMENTS AND CHARCOAL TREATMENT HERBICIDE PLUS HERBICIDE PLUS AMENDMENTS 3 HERBICIDE AND CHARCOAL" AMENDMENTS DEPTH (CM) DEPTH (CM) DEPTH (CM) DAYS AFTER 0-15 15-30 0-15 15-30 0-15 15-30 APPLICATION (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) 5 4,897 302 5,703 232 3,074 134 98 4,280 580 5,422 <50 414 1,866 263 2,015 193 2,767 c <50 c 463 1,217 222 c 824 11 161 c c 557 1,796 c 707 508 <10 c c 2,660 c <50 c 834 438 <10 184 <10 c c 1,293 <10 <10 <10 <10 1,556 <10 amendments included 4.5 kg lime, 13.5 kg organic matter, and 1.4 kg fertilizer (12:4:8 for N,P,K, respectively) uniformly mixed within the top 0-30 cm of soil in the plot. A 1 cm layer of activated coconut charcoal was applied to the trench prior to application of the herbicide. ^ °Not determined. 14 �samples were taken three times throughout the year (summer, winter and spring, 1973-1974), and nacrobial species present (bacteria, actlncmycetes and fungi) were determined. Bacterial counts were higher for soils with greater concentrations of the herbicide and with greater moisture content, but the herbicide, in any concentration, had no significant effect on the mycoflora. For the Florida plots (9), soil samples were taken from all plots in June and August 1974, and in April 1975. Although bacterial and fungal levels were similar for control plots or plots receiving either herbicide or herbicide plus the soil amendments lime, fertilizer, and organic matter, the levels were significantly higher in the plots receiving the activated charcoal. Microorganisms tended to be concentrated in the level which contained the charcoal (0-15 cm), but greatly reduced in number at depths immediately below the charcoal. This effect of increasing the number of microorganisms may have been due to adsorption of growth promoting substances (e.g., nutrients and water) on the surface of the charcoal particles. Although the number of organisms were greater in these plots, the level of herbicide residue was also greatest (Table 7). Apparently, the binding of the herbicide by the charcoal prevented it from being degraded by the microorganisms. These two microbial studies have shown that the application of 2,4-D and 2,4,5-T at massive rates (5,000-40,000 ppm) not only Q Cairney, W.J. Determination of soil microorganism populations in the Eglin AFB, Florida, biodegradation plots. Department of Chemistry and Biological Sciences, United States Air Force Academy, CO, 1975, unpublished. 15 �does not sterilize the soil, but indeed stimulates the growth of certain rnicroflora. That these bacteria, actinomycetes and fungi are proliferating to such an extent indicates that they are probably using the herbicide and TCDD as a carbon source (the exception being the charcoal plots at Eglin), and, as such, are conjxibuting to their degradation. 16 �FATE OF TCDD IN AN ECOSYSTEM The biodegradation plots offered little opportunity to evaluate the ecological effects associated with the use of herbicide Orange or to investigate food chain acramulation of TCDD. Although studies were conducted on the microorganisrns, plants and dominant resident vertebrate and invertebrate animals on and adjacent to these plots (8,9), they were limited to studies of less than 0.5 ha. Therefore, concurrent with the biodegradation studies/ an investigation was initiated on the much larger ecosystem (terrestrial and aquatic) of a unique military test area in Northwest Florida. In support of programs testing aerial dissemination systems, Test Area (TA) C-52A, Eglin AFB Reservation, Florida, received massive quantities of military herbicides. The purpose of these test programs was to evaluate the capabilities of the equipment systems, not the biological effectiveness of the various herbicides. Nevertheless, after several applications, test personnel began to express concern over the potential ecological and environmental hazards that might be associated with continuance of the test program. This concern led to the establishment of a research program in the fall of 1967 to measure the ecological effects produced by the various herbicides on the plant ccnniunity of TA C-52A (10). Ward, D.B. Ecological records on Eglin AFB Reservation—the first year. AFATL-TR-67-157, Air Force Armament Laboratory, Eglin AFB, Florida, 1967. 17 �Geographical and Vegetative Features In 1962, the Armament Development and Test Center (ADTC), Eglin AFB, Florida, established an elaborate testing installation designed to measure deposition parameters of aerially applied herbicides on the Eglin Reservation. The direct aerial application 2 was restricted to an area approximately 2.6 km within TA C-52A in the southeastern part of the reservation. The entire test area 2 covers approximately 5 km and is a grassy plain surrounded by a forest stand that is dominated by long leaf pine (Pinus palustris), sand pine (Pinus clausa), and turkey oak (Quercus laevis). The actual area of test flight paths and herbicide application is in 4 a mechanically cleared area now occupied mainly by broomsedge (Andropogon virginicus), switchgrass (Panicum virgatutn), and other low growing herbaceous vegetation. Sampling Grids and Herbicide Deposition Four separate test grids were established on the 2.6 km2 test area during the 1962 through 1970 testing period. Table 8 indicates the approximate total amount of herbicides (active ingredients) applied on each test grid and the time periods of those applications. Preldmnary Ecological Studies The first in depth animal survey was initiated on the herbicide equipment test grids and surrounding area in 1970 ( 1 . This 1) T>ate, B.D., R.C. Voight, P.J. Lehn, and J.H. Hunter. Animal survey of test area C-52A, Eglin AFB Reservation, Florida. AFATLTR-72-72, Air Force Armament Laboratory, Eglin AFB, Florida, April 1972. 18 �TABLE 8. APPROXIMATE AMOUNTS OF 2,4-D AND 2,4,5-T HERBICIDES APPLIED TO TEST AREA C-52A, EGLIN AFB RESERVATION, FLORIDA TEST GRID GRID AREA (HECTARES) 1 37.25 39,540 (1962-1964)a 39,540 (1962-1964) 2 37.25 15,885 (9416) 16-96 15,885 (1964-1966) 3 37.25 4 97.0 HERBICIDES (KILOGRAMS ACTIVE INGREDIENT) 2,4-D 2,4,5-T 1,263 (97 16) 19,959 (9817) 16-90 19,959 (9817) 16-90 When the major portion of the herbicide was applied. 19 �survey was conducted during the time that aerial spray equipment was actively being tested. The purpose was to determine species variation and distribution patterns on the test grids and surround2 ing 28.5 km . Of the 86 species of vertebrate animals observed or collected, it was concluded that the beach mouse (Beromyscrus polionotus) and the six-lined racerunner (Cnemidophorus sexlineatus) were present in sufficient numbers to conduct population studies. In the spring of 1973, analyses of random soil samples from the test area indicated that low levels (e.g., parts per billion or parts per trillion) of TCDD were persisting in areas (i.e., the flight paths) that had received repetitive aerial applications of 2,4,5-T. Based on the beach mouse populations and the residue information a study was initiated in the summer of 1973 to obtain rodents for analysis of TCDD in body tissues and for examination of TCDD in body tissues and for examination of gross and microscopic evidence of teratogenic and mutagenic effects. A trapping survey was also conducted to study habitat preference of the beach mouse to determine if population distribution was related to vegetative cover. Data from these studies (12) indicated a correlation between the levels of TCDD in rodent liver and soil; however, there was no evidence of toxic histopathology in any rodent tissue. It was also found that indeed the population distribution was related to vegetative cover. *oung, A.L. Ecological studies on a herbicide-equipment test area (TA C-52A) Eglin AFB Reservation, Florida. AFATL-TR-74-12, Air Force Armament Laboratory, Eglin AFB, Florida, 1974. 20 �In the sunnier of 1974 a team of military and civilian scientists undertook a more extensive investigation of the numerous components of the ecosystem of TA C-52A. Using the information from previous studies, they obtained data on the fate of TCDD in soils, rodents, reptiles, aquatic organisms, birds, and vegetation. These results have been published by Young, Thalken and Ward (13), and are summarized in the following sections of this report. Soil Studies of TCDD Residues Soil samples (the top 0-15 cm increment) were collected from all four of the test grids on the test area and analyzed for TCDD. With the exception of Grid I, TCDD residues were in the range of <10 (minimum detection limit) to 30 parts per trillion (ppt, 1x10-12) Soil analysis of 20 separate samples from Grid I detected levels of TCDD in the range of <10 to 1,500 ppt. This wide fluctuation in TCDD concentrations was attributable to the locations of the actual flight paths on the test grid ( . . not all of the 37 ha ie, received the same amount of aerially applied herbicide). It was • also apparent that the massive amounts of herbicides applied to this area in 1962-1964 contained very high levels of the TCDD contaminant. Further analysis of a duplicate soil core, obtained from a site having 110 ppt TCDD, indicated that TCDD was stratified within this top 0-15 cm of soil (Table 9). Young, A.L., C.E. Thalken, and W.E. Ward. Studies of the ecological impact of repetitive aerial applications of herbicides on the ecosystem of test area C-52A, Eglin AFB, Florida. AFATLTR-75-142, Air Force Armament Laboratory, Eglin AFB, Florida, 1975. 21 �TABLE 9. CONCENTRATION OF TCDD IN SOIL PROFILE ( 9 4 17) OF GRID I, TEST AREA C-52A, EGLIN AFB, FLORIDA SOIL PROFILE GRID I APPLICATIONS OF HERBICIDES ( 9 2 1 6 ) 16-94 PARTS PER TRILLION ( P ) TCDD PT 0-2.5 on 150 2.5-5 on 160 5-10 on 700 10-15 on 44 Below (15-90 on) None detectable TABLE 10. NUMBERS OF BEACH MICE COLLECTED DURING THE 1973 AND 1974 STUDIES OF TEST AREA C-52A CONTROL 1973 1974 TOTAL Male 5 12 17 Female 5 10 15 12 11 33_ Fetuses Subtotal 65 TEST 1973 1974 TOTAL Male 26 17 43 Female 18 13 31 Fetuses 25 9 34 Subtotal 108 TOTAL 173 22 �Rodent Studies TRAPPING DATA/HISTOPATHOLOGY. In the 8 weeks of trapping beach mice during the summer of 1973 and 6 weeks during the summer of 1974, 106 specimens were collected from Grid I. Many of the females were pregnant at the time of collection, providing 67 fetuses for examination. Table 10 indicates the numbers of males, females and fetuses collected from Grid I during 1973 and 1974. The only significant lesions seen on histopathologic examinations of 173 adult and fetal beach mice were two instances of moderately severe, multifocal, necrotizing, hepatitis (one test, one control animal) and a single test mouse with severe venous ectasia of the renal veins in one kidney. All other lesions were of the minor or insignificant type normally observed in microscopic surveys of large numbers of field animals. The absence of liver lesions (necrosis and porphyria) in mature animals that had liver levels of TCDD from 20 ppt to 1,300 ppt (Table 11) is most significant in view of the massive quantities of both 2,4,5-T and TCDD that must have been applied to the test site. There was no evidence to indicate that TCDD was mutagenic nor carcinogenic in the field at the concentrations noted in Table 11. None of the 34 fetuses examined from animals captured on the test grid showed teratogenic defects. This leads one to the conclusion that the levels of TCDD encountered in the field failed to induce observable developmental defects. An analysis of the organ to body weight ratios of each of the control (males and females) and 23 �TABLE 11. COSfCENTRATiai (PARTS PER TRILLION) OF 2,3,7,8-TETr'RACHLORODIBENZOP-DTOXIN (TCDD) IN LIVER AND PELT SAMPLES FROM BEACH MICE, PEROMySCUS IE. IOUONOTLJS, COLLECTED FROM CONTROL AND TCDD-EXPOSED FIELD S T S , 1973 AND : PELT TREATMENT SEX Control 1973 Male and Female 20a ND13 Control 1974 Male 51 40a Control 1974 Female 83 40a Grid I to .fc- YEAR 1973 Male and Female 540 NDb Grid I 1974 Male Grid I 1974 Female a Minimum level of detection determined LIVER 1,300 960 130 140 �test (males and females) using the Wilcoxon Rank Sum Test indicated no statistical differences between field control males and field test males nor field control females and field test females (P^O.05). LIVER AND PELT ANALYSIS. The presence of TGDD in the liver samples of both male and female mice collected from the control site in 1974 may have been due to high levels in one or more specimens in the pool of samples. Mice from the test area could have migrated to the periphery of the grid and wandered into the area designated as control. The closest point from the control site to the test area was 200 m. However, it is emphasized that a mouse (or mice) could have been contaminated in this way, and thus have contaminated pooled samples analyzed for TCDD. Therefore, the use of these data as truly control data must be viewed with caution. The levels of TCDD in the liver of beach mice collected from Grid I substantiated bimccumulation of TCDD; i.e., an accumulation of TCDD in an organism from its environment. In general, levels of TCDD in the livers were no greater than the most concentrated zones of TCDD in the soil. There are no data from these studies to support biomagnification of TCDD; i.e., an increase in concentration of TCDD in successive organisms ascending the trophic food chain. BURROW AND DIET STUDIES. In all burrows that contained mice a consistant finding was a plug of soil pushed up into the tunnel within the first 2.5 to 25 on of the entrance. Frequently an "escape tunnel" would extend from the nest area to within 2.5 to 25 �15 on of the soil surface. Although the concentration of TCDD on the pelts of beach mice from the test area was only 10-15 percent of that In their livers, Table 11, it was apparent that the mice were continually contaminating themselves as they repeatedly moved in and out of their burrows. The soil data, Table 9, substantiated the presence of a zone of TCDD within the region of the tunnel entrance. Likewise, the location of the escape tunnel suggested that even the nest itself may contain detectable levels of TCDD. An examination of the plant and insect litter within the nests indicated that the beach mouse diet was made up of about 90 percent seeds (based on caryopsis hulls) and about 10 percent insects (based on insect exoskeletons and wings). Four composite seed samples were analyzed for TCDD with no TCDD being detected in any sample (at a minimum detection limit of 1 ppt TCDD). The insect remains are currently being analyzed for TCDD. TCDD LABORATORY UPTAKE EXPERIMENT. Twenty-two beach mice from the designated control area were brought into the laboratory and divided into a "control" group of 10 animals and dusted with 100 mg of alumina gel 10 times over a period of 28 days while the "test" group of 12 animals was dusted with 100 mg alumina gel containing 2.5 ppb TCDD 10 times over the 28 day period. Table 12 indicates control levels and test levels of TCDD in the composite liver samples and on the composite pelt samples of the alumina gel and alumina gel plus TCDD dusted animals. These animals were given complete histopathologic examinations at the completion of the experiment with no differences being 26 �seen between control and test animals. An analysis of the organ to body weight ratios of each of the control males to test males and control females to test females using the Wilcoxon Rank Sum Test indicated a statistical difference involving only the spleens of control male and test male animals at the 95 percent confidence level. This difference was not supported by either histopathological evidence nor by morphometric data as indicated in the Hepatic Ultrastructural Study section which follows. HEPATIC ULTRASTRUCTURAL STUDY. After the liver was removed from 30 beach mice (15 control and 15 from the test area) and weighed, a section was taken from the center of the median lobe. Representative electron micrographs were made from the liver tissue of each animal and the data obtained from each micrograph using a stereology technique. This method of quantitative analysis of the cell ultrastructure used morphometric procedures based on the techniques developed by Weibel et al. (14), as modified by Buchanan (15) With this method, a transparent grid of intersecting lines was placed at random over the micrographs and all the line intersections (points) which were over the required cell structures were counted. All of the points lying over the mitochondria, the damaged (swollen and ruptured) mitochondria, the granular vfeibel, E.R., G.S. Kistler, and W.F. Scherle. Practical stereological methods for morphometric cytology. J. Cell. Biol. 30: 23-38, 1966, Buchanan, G.M. Effect of high dietary molybodenum on rat adrenal cortejc. Unpublished thesis. University of Colorado, Boulder, CO, 1973. 27 �TABLE 12. CONCENTRATION (PARTS PER TRILLION) OF 2,3,7,8TETRACHLORPDIBENZO-P-DIOXIN (TCDD) IN LIVER AND PELT SAMPLES FROM BEACH MICE, PEROMYSCUS POLIONOTUS, DUSTED WITH ALUMINA GEL CONTAINING NO TCDD (CONTROL) OR 2.5 PARTS PER BILLION TCDD (TEST) TREATMENT SEX Alumina Gel Malea Female Alumina Gel + TCDD Male3 Femalea LIVER PELT NDb NDC NDb NDC 125 45 125 89 a Male and female livers composited for analysis Minimum detection level - 10 ppt detection level - 8 ppt TABLE 13. CONCENTRATION (PARTS PER TRILLION) OF 2,3,7,8TETRACHLORODIBENZO-P-DIOXIN (TCDD) IN COMPOSITE SAMPLES OF VISCERA OR TRUNK FROM SIX-LINED RACERUNNERS, CHEMIDOPHORUS SEXLINEATUS, COLLECTED FROM CONTROL AND TCDD-EXPOSED FIELD SITES LOCATION VISCERA Control Site NDa Test Site 360 TRUNK 370 a Minimum detection limit - 50 ppt Tiinimum detection limit - 40 ppt 28 �endoplastnic reticulum (RER) and the agranular endoplasmic reticulum (SER) were then counted. The total area of the cytoplasm was then measured in the same manner. The volume fraction of each structure was determined to be the ratio between the point count of that structure and the total point count of the cytoplasm. In this manner the ratio of mitochondria volume to cytoplasm volume of the hepatic parenchyma! cell was determined for each animal, as was the ratio of damaged mitochondria volume to total mitochondria volume, RER to cytoplasm, SER to cytoplasm, and RER to SER. Using these volume fractions or ratios as quantitative measurements of the structures in question, the hepatic parenchymal cells from treated animals were compared with those from control animals. Similar data were collected from 22 mice brought from the field into the laboratory and exposed to 30 days of external dusting with alumina gel (with or without 2.5 ppb TCDD) . Analysis of the morpheme-trie data using the Wilcoxon Rank Sum Test indicated no statistical differences between field control and field treatment animals, nor were there statistical differences between the control and treatment animals of the dusting study Reptile Studies ANALYSIS OF REPTILE TISSUE. Chemical analysis for TCDD in body parts of the six-lined racerunner indicated significant levels of TCDD in both the visceral mass and in the trunk, Table 13. 29 �Gross post-mortem examinations were performed on 19 racerunners collected from either a control site or from Grid I with no evidence of gross abnormalities seen in any of the specimens. TCDD In Young, Lehn and Mettee (16) conducted species diversities and food chain studies in two aquatic ecosystems draining TA C-52A. Erosion of soil occurred in to a pond on the test area and in to a stream irrmediately adjacent to the area. TCDD levels of 10-35 ppt were found in silt of the aquatic systems, but only at the point where eroded soil entered the water. Species diversity studies of the stream were conducted in 1969, 1970, 1973 and 1974. Insect larvae, snails, diving beetles, crayfish, tadpoles, and major fish species from both aquatic systems were analyzed for TCDD. Species diversity studies indicated no significant change in the composition of ichthyofauna between these dates or a control stream. Concentrations of TCDD (12 ppt) were found in only two species of fish from the stream, sailf in shiner (Nbtropis hypselopterus) and mosquitofish (Gambusia affinis) . The sample of mosquitofish consisted of bodies with heads and tails removed. Two samples of sailf in shiner were analyzed; one containing viscera only and the other bodies less heads, viscera, and caudal fins. Only the viscera contained TCDD. Samples of skin, muscle, gonads, and gut were obtained from spotted sunfish (Lepomis punctatus) Young, A.L., P.J. Lehn, and M.F. Mettee. Absence of TCDD toxicity in an aquatic ecosystem. Weed Sci. See. Amer. Abst. 107, p. 46, 1976. 30 �from the test grid pond. Levels of TCDD in those body parts were 4, 5, 18, and 85 ppt, respectively. Gross pathological observations of the sunfish revealed no significant lesions or abnormalities. TCDD In Birds of TA C-52A Bartleson, Harrison, and Morgan (17) have conducted an extensive survey of the birds of TA C-52A. Between March 1974 and February 1975, they visited study areas twice each week at various times of day and night, and observed a total of 77 species of birds. Of this number, 44 species were observed on Grid I, the area of greatest TCDD residue. The remaining birds were seen in the surrounding clearing and bayheads projecting into the clearning. A small collection of specimens was made for species identification and for TCDD analysis. Only three species could be classified as residents which nest on the test grids. These were southern meadowlark (Sturnella magna), morning dove (Zenaidura macroura), and bobwhite quail (Colinus virginianus). TCDD residues were found in meadowlark livers (100-1,020 ppt) and in the stomachs and stomach contents (46 ppt) of these same birds. An analysis of liver and fat tissue from doves indicated concentrations of 50 ppt. An analysis of seed in the crop of the doves showed no detectable residue of TCDD. Two routes of TCDD contamination Bartleson, F.D., D.D. Harrison, and J.D.-Morgan. Field studies of wildlife exposed to TCDD contaminated soils. AFATL-TR-75-49, Air Force Armament Laboratory, Bglin AFB, Florida, 1975. 31 �were proposed for these birds. The first was through the process of dusting and subsequent ingestion of contaminated soil while preening. A second possible route was through the ingestion of soil-borne insects from the test grid; an analysis of a single composite insect, sample indicated a concentration of 40 ppt TCDD. Vegetative Succession Studies on TA C-52A TCDD analysis of vegetation has been limited to seed samples collected in support of the rodent diet study. No TCDD was found in four samples of seeds collected from vegetation on Grids I or II. The minimum level of detection was 1 ppt. A vegetative succession study has been conducted by Young and Hunter (18) to document the re-vegetation of an area denuded first by mechanical means and then by hundreds of applications of phenoxy herbicides. Nine months (June 1971) after the last defoliant-equipment test mission, a detailed survey of the vegetation was initiated. The area was divided into a grid of 169 sections (each 122 by 122 m), and within each section the percentage vegetative coverage was visually ranked as Class 0, 0-5 percent; I, 5-20 percent; II, 2040 percent; III, 40-60 percent; IV, 60-80 percent; and V, 80-100 percent. Three sections within each class were selected at random and surveyed for dicotyledonous plants. An unsprayed area 0.32 km northwest of the test area was also surveyed. In June 1973, each Young, A.L., and J.H. Hunter. A long-term field study of vegetative succession following repetitive application of phenoxy herbicides. Weed Sci. Sec. Amer. Abst. 1977. 32 �of these areas was again surveyed, but in addition/ a square-foot 2 (0.093m ) analysis technique was performed in 15 additional sections. These sections were randomly selected and within each 2 section, nine areas, each 0.093m , ware analyzed for species composition and ground cover density. Both methods of vegetative survey were repeated in June 1976. The number of dicotyledonous species increased from 74 in 1971 to 107 in 1973, and to 123 in 1976. In 1971, 20 percent of the test area had less than 20 percent vegetative cover, while 26 percent of the test area had more than 60 percent vegetative cover. In 1976, no sections had less than 20 percent vegetative cover, but over 73 percent of the test area had a cover of more than 60 percent. The major grass species were Panicum yirgatum and Panicum lanuginosum. The major dicotyledon was Diodia tores in 1971, but was replaced by Chrysqpsis graminifolia in 1976. These data demonstrate the rapid invasion of dicotyledonous species despite the unusually heavy applications of phenoxy herbicides. As a concluding remark, Test Area C-52A, Eglin AFB, Florida, has offered a unique opportunity to examine the effects of longterm, low-level exposure of biological systems to TCDD. Perhaps when the herbicide 2,4,5-T (contaminated by TCDD) was first applied to the test area (1962-1964), the levels of TCDD that accumulated on the soil may have been sufficiently high to be toxic, although there is no mention of animal deaths in the records of test missions for this area. It is of interest to note that in the 33 �Italian TCDD episode, an estimated 0.9 to 4.5 kg TCDD were 2 disseminated on an area of 1.4 km . This is approximately equal to 6.5 to 32 g/ha. Grid I on Test Area C-52A probably received between 0.07 and 1.86 kg TCDD on an area of 37 ha, or approximately 2 to 50 g TCDD/ha over a 2-year period. This range of values was arrived at using the arithmetic mean and maximum concentration of TCDD contamination of the herbicide Orange presently in the United States Air Force inventory. 34 �LABORATORY AND GREENHOUSE EXPERIMENTS WITH TODD Two additional studies have been conducted in support of the previous investigations of TCDD in field ecosystems. One of these studies has been conducted by Cupello and Young (19) on the potential uptake from soil of 14C-TCDD by plants. In this study, 2,240 kg active ingredient Orange herbicide/ha, containing 14 ppm 14C-TCDD, was placed beneath the soil surface in specially designed growth boxes containing 100 plants of Sorghum (Sorghum vulgare) per box. The plants were grown under controlled environmental conditions for 9 weeks; 14-hour photoperiod, diurnal temperature of 35 ± 2°C and 15 ± 1°C, and a relative humidity of 60 and 85 percent, day and night, respectively. On day 64 the plants were cut at the soil surface, ground in a Wiley Mill, and extracted with hexane in a Soxhlet Extraction apparatus for 4 hours. The TCDD in the extract was then concentrated by using the Dow Chemical Company Analytical Method ML-AM 73-97. The "TCDD concentrate" was quantitatively transferred to a scintillation vial using benzene, and 15 cc of Aquasol added to it. Analysis of the counting data from a liquid scintillation counter indicated no significant uptake of hexane extractable 14C-TCDD activity in the plant material. An analysis was also performed on the plant tissue prior to hexane extraction, and after hexane extraction for 4 hours. These plant samples were combusted in a 19Cupello, J.M., and A.L. Young. Radiochemical bioassay of TCDD uptake in plant material. Department of Chemistry and Biological Sciences, United States Air Force Academy, CO, 1976, unpublished. 35 �Packard Model 306 sample oxidizer, the OCL collected in Packard Carbo-Sorb, this solution diluted in Packard Permafluor-V, and the filler counted in a liquid scintillation counter. These data indicated the presence of sufficient C activity in the unextracted plant material to be equivalent to approximately 430 ppt TCDD in the plant tissue. This activity was not significantly reduced by hexane extraction. This relatively high 14C activity in the plant tissue could be explained by one of at least four hypotheses. It could represent the presence of (1) bound (non-hexane soluble) TCDD, (2) a soil biodegradation product of TCDD that was taken up and bound by the plant, (3) a metabolic breakdown product of the TCDD that was formed after incorporation of the TCDD into the plant/ or (4) a contaminant in the original C TCDD stock solution that eventually found its way into the plant either as the original contaminant or as a metabolic of it. A second study has been conducted by Bartleson, Harrison, and Morgan (17) on the effect of tilling TCDD contaminated soil. One cubic meter of soil was collected from Grid I, TA C-52A, and removed to the laboratory. Four samples were taken from the uniformly mixed soil, analyzed and found to contain 1,100 ppt (2 samples) and 1,300 ppt (2 samples) TCDD. The contaminated soil was placed in two groups of four pots (20 cm deep and 20 cm in diameter). The four pots in each group were treated as follows: two were left outside and exposed to natural elements, and two were placed in a greenhouse and watered with a nutrient solution. 36 �One of the two containers in each location was left undisturbed, and the other was stirred (tilled) weekly with a spatula. This stirring was not complete, and soil in the bottom of the pots was relatively undisturbed. The soil in each of the pots was emptied into a clean tray and mixed thoroughly before samples were collected and analyzed for degradation of TCDD. The data shown in Table 14 suggest that sunlight, tilling and perhaps increased temperatures (associated with the greenhouse) may promote more rapid degradation of TCDD. There also may be an additive effect from use of nutrients. 37 �TABLE 14. DEGRADATION OF TCDD (PARTS PER TRILLION) IN A GREENHOUSE EXPERIMENT, EGLIN AFB, FLORIDA LENGTH OF EXPOSURE 0 (PPT) 9 weeks (PPT) 23 weeks (PPT) Tilled 1,200 1,100 520 Untilled 1,200 1,000 530 Tilled 1,200 640 460 Untilled 1,200 810 530 TREATMENT Full Sunlight3 Greenhouse Samples placed outside of greenhouse Samples watered with a nutrient solution 38 �RECOMiyENDATIONS FOR DECONTAMmTION OF TCDD EXPOSED FIELD SITES Although there are many potential options for the decontamination of an area exposed to TCDD (see reference 4), data provided in this report would suggest that one of the most feasible options would be soil incorporation/biodegradation. The data base used in selecting this option is as follows: 1. TCDD may persist (in biotic and abiotic components) for long periods of time when initially present at extremely high concentrations on the soil surface. 2. TCDD will accumulate in the tissues of rodents, reptiles/ birds/ fish/ and insects when these organisms are exposed to TCDD contaminated soils (however, the levels of TCDD in the tissues apparently do not exceed the levels of TCDD found in the environment). 3. Organisms tolerate/ i.e./ based on no observed deleterious effects, soil levels between 10-1,500 ppt TCDD. 4. TCDD is degraded by soil microorganisms, especially when in the presence of other chlorinated hydrocarbons. 5. TCDD is degraded in the presence of sunlight. 6. Movement of TCDD in the abiotic portions of the environment can be by wind or water erosion of soil particles, but leaching by water alone does not appear to occur. 7. TCDD is probably not readily released or degraded in the environment when bound to activated coconut charcoal. 39 �Specific Re<xirntrendations In locations where accidental TCDD contamination covers Significant geographical area, e.g., many hectares, an in situ biodegradation program may be most effective in reducing levels of TCDD residues. Incorporation of organic material, lime, and fertilizer to enhance microbial activity may be advantageous. The biodegradation site should be tilled frequently so as to expose residue to sunlight. Watering of the site is recommended to reduce wind movement of contaminated particles and to enhance biodegradation. In locations where a limited area has been exposed to accidental contamination of TCDD, the top 0-15 cm of soil should be removed and taken to an isolated area where biodegradation procedures can be conducted. Similar treatments should be applied to these plots as would be for an in situ program. Protective clothing should be worn by all site personnel. The contaminated clothing should be incinerated at an approved incinerator. Following use, all equipment should be rinsed with an organic solvent (e.g., diesel fuel) to remove TCDD residue. The solvent containing TCDD residue may be collected in activated coconut charcoal and either incinerated or placed in an approved sanitary landfill, although if a sufficiently isolated land area is available, biodegradation may be feasible. It should be noted that some TCDD residue will remain in a contaminated site. However, research on the ecosystem at Test Area C-52A, Eglin AFB, Florida, indicated that organisms do have 40 �a tolerance to low levels of TCDD. Therefore, in those areas having soil residues below 1 ppb, further efforts to decontaminate the area are not practical. These areas should, however, be fenced and posted to prevent livestock and human exposure. 41 � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 017 Folder The folder containing the original item. 0193 Series The series number of the original item. Series II Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Young, Alvin L. Charles E. Thalken Eugene L. Arnold James M. Cupello Lorris G. Cockerham Description An account of the resource <strong>Corporate Author: </strong>Department of Chemistry and Biological Sciences, USAF Academy, Colorado Date A point or period of time associated with an event in the lifecycle of the resource 1976-10-01 Title A name given to the resource Fate of 2,3,7,8-Tetrachlorodibenzo-P-Dioxin (TCCD) in the Environment: Summary and Decontamination Recommendations Subject The topic of the resource biodegradation ecological fate soil decontamination Eglin AFB https://www.nal.usda.gov/exhibits/speccoll/files/original/dd4280761c30ba23ac1c8e04d3d1a0a7.pdf 72b4a89c20932245745139584e7e6195 PDF Text Text 00187 Young, Alvin L. USAF Occupational and Environmental Health Laboratory, Brooks AFB, Texas ReOOrt/ArtJCiB Tlth Herbicide Orange Site Treatment and Environmental Monitoring: Summary Report and Recommendations for Naval Construction Battalion Center, Gulfport, MS 1979 November Color n 46 Friday, January 05, 2001 Page 187 of 194 �Report OiHL HERBICIDE ORANGE SITE TREATMENT AND ENVIRONMENTAL MONITORING SUMMARY REPORT AND RECOMMENDATIONS FOR NAVAL CONSTRUCTION BATTALION CENTER GULFPORT MISSISSIPPI November 1979 Approved for public release; distribution unlimited USAF Occupational and Environmental Health Laboratory Aerospace Medical Division (AFSC) Brooks Air Force Base, Texas 78235 �S11H TREATWHf MID ENVIRQHiffililAL MQHITORIMG AND FOR NAVAL CONSTRUCTION BAOTM.ION November 1979 . Prepared for AIR FORCE IiOGISTICS COMMAND WB OH ��- .. JECURlTV Ct A»riCATiON OF THi« SEAS INSTRUCTIONS BEFORE COMPt-ETlNG FORM REPORT DOCUMENTATION PAGE 2, OOVT ACCfSflON NO. «fHT*S CATALW tttttllf• OIHL-fR-79-169 S. TYPE OF REPORT * CEHlOO COVEHIO *. TITLE Herbicide Orange Site Treatment and Environmental final Monitoring* Sawary leport and !eeoiui»ndatlons for Naval Construction Battalion Center, i, PBMPemuita ens. RSPDMT Gulfport MS I CONIHACT 9» HAIT . Alvin L. Young, Major, USAF Charlea 1. fsalkan, Lieutenant Colonel, USA?,-VC Williaa J. Gainsay, Major, QSAF, BSC onaAiiiAfiON MMII *«§ USAP Occupational and Environmental Health laboratory iroofes Mr Force Base, Itoas 78235 ^ ^ i, g^/i,jimraMis' I, ItiPQllT BAT• I H, COttT«Ot.lilN« OF^tet NAMI ANO ABPflltll USAF Occupational and Environmental Health Laboratory Brooks Mr Force Base, Texas 78235 Moveaber 197! 36 Ti, »OllrTOlHS8 AOSNCY MAMI ft AODMBSSfJl dilftt^i Irom Ooatrenini Olllef) !•• MCUWTT CUASI, f*f Unclassified It. ITATIMtNT f*l » for public release *, distribution unlimited •>, DtlTNilUTION STATSM8NT (el tfe* *fe«if*«t fnitrti in Mae* M, I lUPPLEMIMTAIiy NOTIt , I. KEY WONBI CCenltniM MI tmmtm «)<*• // n»s««»«ry «nd id«n(//y by M«eft nu»b«o aquatic studies bioaeovmulation biod»fradation of herbicides biodegradation of TCDD chlorinated phenols ecological effects 2,4-dicnlorophenoxyacetic acid {2,4-D) environmental aonitoring herbicides Herbicide Orange dloxin Orange phenos^ herbicides PACER HO 0, ABfrftACT fCenthMM on «»««• *!4t It n*a***«y »nd ia»nlHy kr Moo* mambtr) Snviroiu»ntal surveys of the soils, plants and the aquatic system in and around a 12-acre Herbicide Orange storage area at Gulfport MS were conducted from 1970 through 1979. The major objectives of the surveys were to (1) determine the magnitude of Herbicide Orange contamination on the storage area| (2) determine the fate of the phenoxy herbicides 2,4-D and 2,4,5-T, their phenolic degradation products and fCDD in soils of the storage area?{3) monitor movements of residues from the storage area into adjacent water, sediments and biological organisms! and (4) recommend managerial techniques for niniaizing the impact EDITION Of 1 NOV ft IS OMOLETE Unclassified CtAStlfICATtOM Or THIS PAOC �HCURtTy CI.»SSIFIC*"nOH OF THJkf AqgftHJMQ D»t* soil microbial studies TCDD 2,3»7,8HMtr«ehlorodibenso-p-dloxin (TCDD) 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) 20. of the herMcldes and TCDD residues on the ecology and human populations adjacent or near the storage area. High levels"of TCDD (e.g., 100-200 parts per billion [ppb]) were associated with spill sites on the herbicide storage area. Sediment samples from the storage area contained 2.7 to 3.6 ppb TCDD and biological organisms closely associated with the sediment contained 0.14 to 7.2 ppb TCDD. Water staples collected in the same area were negative £or TCDD at a detection level of 0,02 ppb. Two of five off-base samples were positive for TCDD (ft crayfish and a sediment sample both contained 0.02 ppb TCDD). The primary recommendation is that the 12-acre Herbicide Orange storage area be left undisturbed permitting the continuation of "natural" degradation of the herbicides and TCDD. It is recommended that the area be restricted and that efforts be immediately undertaken to minimize future erosion of contaminated soil into the ditches. The prevention of soil and silt movement from the area may be accomplished by stabilizing the ditch banks, constructing silt catchments within the ditches and constructing a silt retaining pond prior to the stream leaving the NCBC. Unclassified SECURITY CLASSIFICATION OF THIS PAQEfffftwi Dm* �PURPOSE The report was prepared to present senior Mr Force leaders the latest available data In the continuing environmental monitoring studies of a 12-acre storage area on the Naval Construction Battalion Center (NCBC), Gulfport MS, ftie area had been used for the long-term storage of approximately 8 0 0 0 gallons of Herbicide Orange from mid-1968 to 4,0 mid-1977, SASIC HISTORY . Since 1970,, various Air Force and contract laboratories have been conducting environmental surveys and analyses of the soils, plants, and the aquatic system in and around the Herbicide Orange storage area. As some leaking became evident and as more information became available on the toxic contaminant 2,3,7,8-tetrachlorodibenzo'~p-dioitin (TCDD) contained in the herbicide, more extensive monitoring programs were conducted, fhe entire inventory was redrummed in 1972 and checked for leaks continuously thereafter. In the summer of 1977, the herbicide was transferred to a specially equipped ship and destroyed by at-sea incineration dwinf Project PACER HO. fhe Air Force Plan and the 1PA permits for the disposal of the herbicide committed the Air Force to a follow-on storage site reclamation and environmental monitoring program, fhe major objectives of this program were to (1) determine the magnitude of Herbicide Orange contamination in the storage area; *Updated to include data received 3 Dec 1979 subsequent to report preparation, �(2) determine the soil persistence of the pheonxy herbicides 2f4-dichJ.orophenoxyacetic acid (2,4-D) and 2,4,5-T, their phenolic degradation products and TCDD in soils of the storage area; (3) monitor for potential movement of residues from the storage area into adjacent water, sediments and biological organisms; and (4) recommend managerial techniques for minimizing any impact of the herbicides and TCDD residues on the ecology and human populations adjacent or near the storage area. STORAGE SITE CWTAMIHATIOti AND FATE The monitoring approach used to determine storage site contamination consisted of analyzing soil samples selected from 42 different sites within the storage area. Sampling points were selected in groups depending upon whether a spill of the herbicide had occurred in that area or not. Previous studies had shown that residue did not appreciably move within the acid soil or significantly penetrate the impervious concrete-stabilized hardpan located approximately six inches below the soil surface. Soil samples were also analyzed for microorganisms. The results indicated that approximately 15% of the 12-acre site is significantly contaminated with Herbicide Orange and TCDD. Levels of 2,4-D and 2,4,5-1" in the samples, which were greater than 100,000 parts per million (ppu) in July 1977, have decreased to one-third that level in IS months. Data from spill sites monitored for this same time period also suggested that TCDD levels are decreasing but at a slower rate. The soil penetration of the herbicides was low while penetration of TCDD was negligible. Sterilization of the soil did not occur; rather, certain microflora proliferated under high levels of herbicides. �RESIDUE MOTEMBI1 IMTO ADJACENT AlffiAS To monitor for potential movement of residue from the storage area, soil and biological samples were collected from the drainage ditch directly adjacent to the site. A Novenbar 1978 analysis of this nearby on-base drainage ditch found positive TCDD residues [o.14-3.6 parts per billion (ppb)]. She TCDD movement was presumably caused through soil erosion from the annual (Jan-June) heavy rain season {approximately 60 in). Drainage ditches carry heavy rain from the storage site and other parts of the bas« into Ixsng Beach Canal 11» approximately 9,000 feet from the site. The canal runs from the city of Long Beach through the base carrying municipal surface drainage, and until July 1978, carried treated sewage materials. The canal eventually runs into Turkey Creek approximately 12,000 feet from the storage site. Due to the November 1978 findings, further samples were collected at varying distances from the site in January, February, and June 1979. Following extensive and difficult analyses in contract laboratories, the results were received in September, November, and December 1979, The results confirmed the November 1978 data and indicated slightly higher levels (sediment levels of 1.7-3.6 ppb and biological levels of 0.14-7.2 ppb). Water samples collected in the same area were negative for TCDD at a detection level of 0.02 ppb. TCDD appears to move only as a part of soil sediment. Sediment and biological sauries taken downstream at 3,000, 7,000, 9,000 and 12,000-feet from the site indicated that some TCDD residue was now present but at very low levels. A crayfish collected at 9,000 feet and numerous fish collected at 12,000 feet were analyzed with .032 ppb the highest level detected. This figure of .032 ppb is three times lower than the Pood and Drug iii �Administration suggested maximum permissible level of 0.1 ppb. With present "state-of-the-art" detection limits, readings as low as these in biological samples have only been considered reliable in recent months. RECOMMENDATIONS To control the now verifiable but very low levels of residue, the report recommends the following actions: - Stabilize drainage ditch banks to prevent water erosion during heavy seasonal rainstorms. - Construct siltation traps in the drainage system allowing for greater silt catchment prior to drainage water leaving the base. - Leave the storage area in its present undisturbed state and continue to limit access so that the "natural" degradation of the herbicide and its TCDD continue to occur. - Allow the continued growth of native vegetation in the contaminated storage area and drainage ditches since this plant community inhibits water erosion. - Continue sampling to ensure that preventive actions do control contamination. - Develop follow-on reserach to determine possible methods for returning the storage area to full and beneficial use. iv �PREFACE This technical report represents the culmination of a two-fear environmental monitoring program of an area previously used for the long-term storage of Herbicide Orange at the Naval Construction Battalion Center. The study was conducted by personnel of the United States Mr Force Occupational and Environmental Health Laboratory, Brooks Mr Force Base, Texas and the United States Mr Force Academy, Department of Chemistry and Biological Science, USAF Academy, Colorado. Funds for this program were provided by Air Force Logistics Command through the San totonio Mr Logistics Center, Directorate of Fuels, Kelly Air Force Base, Texas, fhe report was prepared for the Mr Force Logistics Conaand, Wright-Patterson &FB, Ohio. �Acknowledgements Analyses of herbicides, phenols, and soil TCDD were perforaed by Dr B. Mason Hughes, Mr W.H. McClennen, Mr L.H. Wojcik and Mr F,D. Hilematn, Flaranability Research Center, the University of Utah, Salt lake City Uf 84108. The analyses of ethers and isooctyl esters of trichlorophenol and herbicides were conducted by Or E.L. Arnold, formerly of the Clinical Sciences Division, USAF School of Aerospace Medicine, Brooks AFB TX 78235. High resolution GG-MS analysis of TCDD in selected biological and sediment samples was performed by Dr M.L. Gross, Mass Spectrometry Laboratory, University of Nebraska, Lincoln NE 68588. The assistance of Mr Tom Murphy, Epidemiology Division, USAF School of Aerospace Medicine, in statistically analyzing herbicide data is gratefully acknowledged, The assistance of Mrs Joyce Kidd, Secretary to the Vice Commander, USAF Occupational and Environmental Health Laboratory, in typing and editing this report is gratefully acknowledged. WILWMI E. MABSOM, Colonel, USAF, BSC Commander VI �IMTBOOUCTIOII During the sooner'of 1977 the United States Air force (0SAF) disposed of 2.22 million gallons of Herbicide Orange by high temperature incineration at sea. This operation, Project PACER HO, was accomplished under the very stringent criteria set forth in an tF.S. Environmental Protection Agency (IPA) ocean dumping permit. Among the numerous conditions of thi« UPA-approved disposal operation was the requirement for the USAF to conduct extensive environmental and occupational monitoring of the land-transfer/loading operations, shipboard incineration operations and subsequent storage site reclamation and environmental monitoring. Details of the proposed site monitoring programs were documented in April 1977 by the Air Force Logistics Command (AFLC) in a programming plan for the disposal of Herbicide Orange ( ) In this plan, AFLC proposed that 1. soil samples from the storage sites at both the Naval Construction Battalion Center (NCBC), Gulfport MS, and Johnston Island (JI), Pacific Ocean, be Qollnated and analyzed for Herbicide Orange after the completion of transfer operations, These analyses were to aid in the establishment of a •chadule for future monitoring. The site monitoring program would be flexible to requirements generated by construction of any facility on the storage site and would be concluded upon mutual agreement of all agencies involved. In July 1977, following the completion of the PACER HO dedrunming and subsequent site clean-up operations at NCBC, the USAF Occupational and Environmental Health Laboratory (USAF OEHL) initiated an extensive site monitoring program, fhe objectives of this program were: 1. To determine the magnitude of Herbicide Orange contamination on th« storage site. •. �2. To determine the soil persistence of the two phenoxy herbicides contained in Herbicide Orange and a. dioxin contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 3. To monitor for any movement of residues from the site into adjacent water, sediments and biological organisms. 4. To recommend techniques for managing the storage area with the ultimate goal of returning the area to full beneficial unrestricted use. HISTORICAL BACKGROUND (GENERAL) In April 1970, the Secretaries of Agriculture; Health, Education and Welfare; and the Interior, jointly announced the suspension of certain uses of the herbicide 2,4,5-trichlorophenoxyacetic acid ( , , - ) These 2457. suspensions resulted from published studies indicating that 2,4,5-T was a teratogen. Subsequent studies revealed that the teratogenic effects had resulted from a toxic contaminant in the 2,4,5-T, identified as 2,3,7,8-tetrachlorodibenzo-p-diojcin (TCDD). Subsequently, the Department of Defense suspended the use of Herbicide Orange [a mixture of 2,4,5-T and 2,4-diehlorophenoxyacetic acid C2,4-D)] in South Vietnam. At the time of the suspension, the Air Force had an inventory of 1.37 million gallons of Herbicide Orange in South Vietnam and 0.85 million gallons at the Haval Construction Battalion Center, Gulfport MS. In September 1971, the Department of Defense directed that the Herbicide Orange in South Vietnam be returned to the United States and that the entire 2.22 million gallons be disposed of in an environmentally safe and efficient manner. �The 1.37 million gallons were moved from South Vietnam to Johnston Island, Pacific Ocean, for storage in April 1972,' HISTORICAL BACKGROUND (NCBC) Craig (2), in a historical review of herbicides for Southeast Asia noted that the storage of Herbicide Orange became an item of significant importance with the temporary suspension placed on all uses of Herbicide Orange by the Assistant Secretary of Defense on 15 April 1970. Prior to 1970, shipments of herbicides into and out of the Mobile Outport and the Naval Construction Battalion Center were handled in a routine manner. As the herbicide inventory began to accumulate in Southeast Asia, the San Antonio Air Logistics Center, Directorate of Fuels (SA ALC/SF), Kelly AFB TX, discontinued shipments from the port of embarkation to Southeast Asia in 1963 to avoid exposing large quantities of herbicides * to possible damage by enemy action. The SA ALC then had to determine disposition of the product at the port and that scheduled for delivery. Bather than return the product to the manufacturer and suspend delivery to the port, SA ALC decided to arrange for the product to be temporarily placed in storage. Since the Mobile Outport, Mobile AL, was routinely used as the port of embarkation for herbicides, this was the logical place for the temporary storage. It was anticipated at that time that the storage period would be about six months. Herbicides were sent to the Mobile Detachment for storage between April and June 1968, and were removed from storage between September and December 1968. Except for �one shipment to Southeast Asia during September 1968, herbicides removed from this storage site were used only to fill equipment test requirements at Iflin AFB PL. On 26 June 1968 an Interservice Support Agreement was made by and between SA ALC and NCBC, to provide services related to receiving and storing approximately 50,000 18-gauge, 55-gallon drums of herbicide. The agreement was effective for the two-year period 1 July 1968 - 1 July 1970. It was to be reviewed annually by both parties. Input of herbicides to Gulfport began in July 1968. Additional Interservice Support Agreements were made in 1970 and 1972. Storage was considered a better alternative than the return to the manufacturer where storage charges would have been more expensive, lite NCBC agreed to receive and store the drums of herbicide and remove from storage quantities of drums as designated by SA ALC while SA ALC agreed to provide personnel in support of this operation. This was modified in July 1968 to reimburse NCBC for material and supervisory personnel salaries. The Gulfport outside storage area was about two miles from the docks, with convenient access to the railroads. It was fenced and isolated from public traffic. The NCBC provided surveillance personnel as well as a controlled access. It was planned and set up for long-term storage. To provide good drainage, 2 x 6-inch dunnage (creosoted lumber) was laid on a hard surface and drums, positioned horizontally with the bung closure pointing outward, were stacked in double rows, three high, in pyramidal fashion. The number of drums in each single row, bottom to top, was 55, 54, and 53. To allow inspection of the bungs, there was an 18-inch walking space between each double row. �HOC urns the only Continental Onited States (COOTS) storage facility used daring the last half of FT69 and through Pf70. The Mobile Outport intransit storage facility was not used after Deeeatoer 1968 when the last drums of herbicide were moved to NCBC. At the end of FY70 there were 833,855 gallons of Herbicide Orange in storage at NCBC. Except for a small quantity stored at iglin AFB FL for test purposes, Gulfport was the CONUS storage point. & few damaged drums were received at NCBC with leaks around the bung closures because the seals had vibrated loose. In such cases the producer was notified to supply new bung closures. NCBC personnel took the corrective action. Usually the leaks could be stopped by removing the cover and tightening the bung or replacing the bung gasket. When damaged leaking drums were spotted while in storage, they were redrumtad by the people on duty. It was discovered that a herbicide moistened area usually appeared on the drum two or three weeks before noticeable loss occurred, and the contents could be saved by transferring it to a new drum when the damp area was noted. In May 1971, during an inspection of the inventory, it was noted that deterioration of some of the drums had required HCBC personnel to redrum the product. As drums were removed from the stacks, indications of additional leaking drums became apparent. Previously, leaking had been attributed to breakdown of the bung seals used in the drum closures or an occasional seam leak. Now there were indications of leaks starting in the drum surfaces. During 1972, military personnel moved, inspected, and redrummed as required, the entire inventory of approximately 15,400 drums. Thereafter, an intensive drum surveillance program was initiated �in which all drums were routinely inspected and moved or redrummed as required. The drum surveillance program was continued until May 1977 when Project PACER HO began. The observations in 1971 and 1972 that drums were deteriorating prompted AFLC to task the USAF Environmental Health Laboratory (EHL/K) , Kelly MB TX and the Department of Chemistry and Biological Sciences (USAF/DFCBS) , USAFA CO, to undertake a cursory chemical and biological monitoring program of the storage site. & review of these efforts is provided in a subsequent section of this report. DESCRIPTION OF JHEBBICIEB Pour military herbicides were stored for various lengths of time at NCBC. These herbicides were code-named Herbicides Orange, Orange II, Blue and White. Herbicides Blue and White were intermittently stored at NCBC during 1968 and 1969. However, all stores of these materials were shipped to South Vietnam. Since these two herbicides (Blue and White) were only briefly stored at NCBC, site monitoring programs did not include these materials. The herbicide inventory that underwent long-term storage was comprised of primarily Herbicide Orange (approximately 13,855 drums) and a relatively small quantity of Orange II (1,545 drums) . Young, et al. (8) have described these herbicides. 1. Herbicide Orange Orange was a reddish-brown to tan colored liquid, soluble in die se 1 fuel and organic solvents, but insoluble in water. One gallon or Orange theoretically contained 4.21 pounds (Ib) of the active ingredient of 2,4-0 and 4.41 Ib of the active ingredient of 2,4,5-T. Orange was formulated to contain a 50s 50 mixture of the n-butyl esters of 2,4MJ and 2,4,5-T. The percentages of the formulation typically weres �n-twityl ester of 2,4-D free acid of 2,4-D n-butyl ester of 2,4,5-T free acid of 2,4,5-T 49.49 0,13 48.75 1.00 in*rt ingredients {e.g., butyl 0.63 alcohol and ester moieties) 2. Herbicide Orange II Orange II was a formulation similar to Orange with the only difference being the substitution of the iaooctyl eater of 2,4,5-T for the n-butyl e«ter of 2,4,5-T. The physical, chemical, and toxicological properties of Orange II were similar to those of Orange. Orange IX was produced solely by one chemical company. A detailed analyses of the inventory of Herbicide Orange and Orange II stored at NCBC was prepared in 1975 by Hughes, et al. (4) and Fee, et al (3) A summary of manufacturers and TCDD contents is presented in Table 1. SUMMARY Of SAKL? EJiViaOHMENTAL MONITORING PROGRAMS As early as 1970 the Air Force was expressing its concern about the possible adverse environmental impact of the storage of Herbicide Orange at NCBC, Gulfport MS. Environmental scientists from Eglin AFB visited the storage site at the request of SA ALC/SP and conducted an environmental survey of the plant and aquatic animal community in and around the herbicide storage cite. No significant environmental problems were noted at that time. In 1972, members of the OSAP Environmental Health Laboratory, Kelly AFB TX (EHL/K), conducted an environmental survey of the storage area and also found no significant environmental problems. �TJBL! 1. Identification Data on Herbicide Orange Stocks Stored at the Naval Construction Battalion Center, Gulfport MSa Manufacturer Analysis Total Number Transportation b Seepienee of Drums *TCDDC Control No. (TCN) Mo. with Same TCN (ppm) Hercules Co 9 6 8156 0 0 44 01 Hercules Co 9464 8192 001 14 Diamond Co PY9461 7165 0001AA 18 60 14. 2e Diamond Co PY9461 8156 001AA 11 421 8.62f Thompson Hayward Co 9463 8155 X032 8 1 500 2,152 <0.05 n&a 1,546 0.32 0.12 Dow Chemical Co 9463 8155 X052 10 6,976 Thompson Co 9463 7184 X011 3 46 HA Thompson Co 9463 8155 X012 5 808 0.17 Monsanto Co FY9463 7163 X0001XX 4 563 NA Monsanto Co PY9463 8183 X002XX 6 2,185 15,257 a SOURCEs 7.62 Pee, et al. (3). Each separate purchase of herbicide was designated by a separate TCN G Tetrachlorodibenzo-p-dioxin (TCDD) content. Results reported in this column are the average of six samples collected from six different barrels of Herbicide Orange having the same TCN. d Not Analysed. ^Average value of five samples: 12, 17, 12, 15, 15. Other sample value was 0 0 with recheeJcs. .7 ^Average value of four samples: 8.0, 8.1, 8.7, and 9.7. Other two samples each averaged <0.05 with rechecks. *0n the bajis of 280 samples of Herbicide Orange taken from the Gulf port inventory, the weighted mean concentration of TCDD was 2.06 ppm. �In July 1974, members from the OSAF Academy Department of Chemistry and Biological Sciences conducted an extensive survey and ecological assessment of the herbicide storage area and collected soil, water, and biological samples. There was considerable evidence of herbicide contamination within th« storage area itself (i.e., visual evidence of leaks and •pill* on the soil)i however, there was no evidence that any of the material had been carried from the storage area by the surface drainage system. Soil samples collected between the stored drums, on the banks of the drainage system and silt deposits at various points in the drainage ditches had no detectable levels of herbicide at the 1 part per million (ppm) level, One soil sample was taken only six feet from the drums where prior leakage had been detected as evidenced by discoloration of the soil surface. Hater samples from the drainage ditches had no detectable levels of herbicide at the 50 parts per billion (ppb) level. One of the water samples did, however, contain hydrocarbon residues apparently from washing operations in the area. The presence o£ the fuel in the water gave the stream an oily appearance which may have lead some people to conclude that a herbicide residue was present. The biologicals (frogs, tadpoles, minnows) that were collected were not analyzed because there was no evidence that the aquatic drainage system was contaminated at that time. Upon gross examination no abnormalities were seen in any of these aquatic specimens. A complete survey of the flora surrounding the storage area was also completed during the July 1974 visit by the USAF Academy personnel. Plant damage of a herbicidal-nature (twisting and bending of leaves and stems) was noted on two plant species as far as 85 yards west (downwind) of the drum storage site. �In December of 1974 Dow Chemical Interpretive Analytical Services reported the first known TCDD positive soil sample frent between the rows of barrels on the storage site. Two soil samples were analysed. One sample had nondetectable levels at a detection limit of 4 parts per trillion (ppt) while the second soil sample was positive for TCDD at IS ppt. During the period of August 1974 to October 1976 representatives of the EHL/K made 11 trips to the Naval Construction Battalion Center to monitor pilot plant activities, drum rinse studies and conduct environmental monitoring including the collection of water samples from the herbicide storage area drainage ditches. Water sample values for 2,4-D had a range of average mean value of 0.15 ppb to 409.4 ppb; the 2,4,5-T range of average mean values for water was 0,3 ppb to 519.4 ppb and a 1976 TCDD positive sample that had an average mean value of 7.7 ppt. Sediment samples collected from the drainage area contained 2,4-D in a range of average mean values of 0.04 ppm to 0.24 ppm; the 2,4,5-T range of average mean values for sediment was 0.04 ppm to 0.42 ppm. All sediment samples for TCDD were negative} however, the analytical laboratory could not establish a level of detection for TCDD because of interferences. In the October 1976 report it was noted that of the 26 water samples analyzed, 13 were reported as containing more than 10 ppb herbicide. However, at the base discharge sample point leading off base, there were no water samples analysed that exceeded this lower detection limit of 10 ppb. Also, of the 23 water samples that were analyzed for TCDD, there was only one that had a positive reading and that sample was collected near the storage area. TCDD. Samples collected further downstream had no detectable The detection limit in these samples was 0.01 ppb. These results indicated that although some herbicide was entering the drainage system, 10 �it was not leaving the base and most likely was being held in the bottom sediments of the drainage ditch system. Visual observations of the drainage ditch system indicated that there. were no deleterious effects being exerted on the biotic community and that fish, frogs, snakes and other normal fauna and flora seemed to flourish. Only two of the sediment samples analyzed exceeded 1 ppm herbicide. These samples were collected near- the storage area. The sediment samples collected near the base discharge point never exceeded the 1 ppa herbicide leval and no fCDB was ever detected in any of these sediment samples. However, the analytical laboratory could not establish a level of detection for TCDD because of interferences. Soil sample data in October 1976 was not sufficient to make an interpretation as to the degree of severity of the herbicide contamination of the soil. Recommendations from the October 1976 EHIi/K report weres 1. The levels of Herbicide Orange (HO) in the ambient air were not high enough to create any concern about any on- or off-base exposure. Thi« was also borne out by the biomonitoring that had been performed during the Agent Chemical Inc (ACI) operation at NCBC. If the TCDD analytical result* were viewed as upper limits, as suggested by the analytical laboratory [Wright State University {WSU)], then there was no need for concern. 2. There was no indication of any off-base discharge of TCDD in the water or sediment samples. 3. Quarterly environmental monitoring surveys should be continued. 4. There is need for a comprehensive sailing program of the soil in the HO storage area to permit a better evaluation of the degree and extent of contamination by both HO and TCDD. 11 �In January 1976, members from the USAF Academy, Department of Chemistry and Biological Sciences,conducted an extensive aquatic and soil survey of the herbicide storage area. During this survey, many soil, sediment and biological samples were collected from throughout the storage area and the surface drainage system. These samples were frozen and archived as baseline samples should the need arise to evaluate similar types of samples during or after the dedrumming operation. Selected samples frost this collection were later analyzed in 1978. Data from these samples are incorporated into the Results and Discussion Section of this report. USAF OEHL SITE MONITORING PROTOCOL Four problem areas were apparent in the design of a study: 1. Over 25 individual chemical components in Herbicide Orange had been identified [Hughes, et al. ( ) . Should or could a monitoring 4] program include all of these components? The low percentage in content of most of these components combined with their known low toxicity and/or rapid biodegradability (e.g., butanol, toluene and xylene) suggested that only the principle herbicides (acid and ester formulations of 2,4-D and 2,4,5-T), their major breakdown products (di- and trichlorophenol) and TCDD should be followed. 2. What criteria should be used to determine the number and location of sampling sites on an area of approximately 12 acres? Spills, due to handling of the drums during dedrum operations (during and prior to PACER HO) or to leakage (prior to PACE! HO), could have occurred almost anywhere on the storage area over the eight-year period. Certainly, the persistence and fate of individual herbicides, phenols or dioxin might be determined if a technique could be used to determine old spills from new spills. 12 �3. What factors associated with'the actual storage Urea at NCBC will have influenced the penetration of herbicides/TCDD into the •oil profile? This problem would certainly influence the depth of sampling that would be required, 4. In an "ideal" monitoring program, some method would be required to determine a minimum level of residue that could be considered biologically and ecologicallf acceptable, i.e., a "no significant effect" residue level. Should this no effect level be based upon soil micro- organisms, surface vegetation or some other criterion? Previous environmental studies in 1974 and 1976 by Young, 19), and Ifoung, et al. (10), showed that movement of the herbicide components of Herbicide Orange and the TCDD contaminant was low, suggesting that both lateral movement and soil penetration of the water-insoluble Herbicide Orange and TCDD would be minimal. Thus, surface sampling, e.g., the top three inches (S cm) of soil, should constitute the primary sampling depth. As noted above, the depth of routine sampling was of major concern in designing the residue monitoring program. Young, et ai. ( 0 had shown that 1} neither the herbicide components of Orange nor the TCDD had appreciably moved in the soil during biodegradation studies at Eglin AFB PL or the APLC test lange Complex, Hill AFB OT. However, these studies had involved soils treated with herbicides by using a hand sprayer and at concentrations greatly below those encountered in spills. Certainly some of the spills that had occurred at NCBC were "old" spills and the effects of time (years) on these spills was essentially unknown. Another factor in sampling depth was that the soil in the outdoor storage areas of NCBC had been treated in the 1940s with cement and compacted ( ) This treatment had created a 6-12 inch (15-30 1. en) layer of hardened stabilized soil. This "hardpan" was relatively 13 �impervious to water and presumably herbicide; however, in 1977, the hardpan was 3 to 6 inches (8-15 cm) below surface due to the addition of soil and gravel during the intervening years. This upper layer of soil was primarily sandyloam in texture. Selected sites where heavy spills had apparently occurred had also been treated with a 2 inch (5 cm) layer of oyster shells. All of these factors influenced the decision to select only one depth as the primary sampling depth which was the top three inches (8 cm). In July 1977, a preliminary sampling study was initiated. This consisted of assessing the heterogenity of the soils on the sites and the heterogenity of the herbicide concentrations. Twelve sites were selected for sampling; six were in areas of obvious spills and six in areas that showed no spill. Not only were the spills discernible by sight but also by smell. Winston and Ritty (7) had previously found that the olfactory senses can detect a butyl enter formulation of 2,4,5-T at levels of 0.4 ppb. The results of this fir»t sampling after PACER HO are shown in Table 2. Significant concentrations of herbicides, phenols and TCDD were detected in soils from spill sites. The variation in concentrations and in the portion of acids to ester* suggested that the spills were from different time periods. Accordingly, a more extensive protocol was proposed for future sampling. 197§ fROTOCQE The sites selected within the storage area for monitoring of residue were determined by whether a spill had occurred or not occurred at that specific location. The basis for determining a spill was whether a herbicide stain was discernible (heavy, light, absent) and whether a herbicide odor was detectable (strong, mild, absent). Thus, within the Storage Area numerous location* were found that had a heavy stain ajid strong odor (labeled 8/H, presumably representing a recent spill)? a light stain and 14 �2. Concentration parts per Million, of total herbicides, total phenols, and TCDD in 12 soil samples collected July 1977 from the Herbicide Orange Storage Area, Naval Construction Battalion Center, Golfport MSa Location total Herbicides (ppm) Total Phenols13 (ppm) TCDD Spill Sitesc 1 51,600 132,400 3 5 8 10 11 37,350 34,840 117,060 Mean = 95,000 78,040 42,395 87 109 166 96 303 152 (5) 90 019 .00 0.6310 »008) (.049 0.1900 0.0185 MA. 0.2371(4) 4- 0.2718 Mo Spill Sitesd 2 4 6 7 9 12 •f 12.4 0.7 0.2 0.1 0.6 0.2 0.2 0.3 + 0.2 NA NA NA MA HA NA a Analysis by the Flasmability Research Center, The university of Utah, Salt Lake City OT. Air Force Contract No. 561178C0062. Report submitted 17 May 1 7 . 99 "Total herbicides refers to concentrations of acid and all esters detected of 2,4-D and 2,4,5-f. °Total phenols refers to concentrations of dichlorophenol and trichlorophenol. %he sample consisted of a cube (3x3x3 inches) of soil removed from the center of an area designated spill or no spill. 8 HA • Mot Analyzed. ( ) refers to number of samples included in obtaining the means and standard deviation. %D • Not Detected at the detection limit specified in parenthesis. 15 �mild odor (labeled L/L, presumably representing an older spill); and no stain and no odor (labeled O/O, presumably representing an uncontaminated area). Fourteen replications of each treatment were then randomly selected to represent the storage area (thus a total of 42 permanently marked sampling locations). Twelve of these locations had been tentatively located and marked on 28 July 1977 with the remaining 30 located and marked on 17 January 1 7 with sampling being conducted on these dates, as well 98 as 6 November 1978. In collecting the soil samples, a 3-inch square was marked, 6 inches away from the site marker pin. At each sampling tine, soil was taken from a different "point of the compass" with reference to the marker pin to insure a fresh and undisturbed profile. At the designated site, a 3x3x3-inch cube of soil was removed with a ceramic spatula which was rinsed with acetone between uses to prevent carryover of residue and microorganisms. Wherever possible, sediment samples were collected from the drainage ditches in a similar manner. CHEMICAL ANALYSES Each soil sample consisted of approximately 200 grans and was placed into new glass jars ( 0 ml) appropriately labeled and transported to the 40 laboratory where they were uniformly mixed and subsampled. The subsample used for chemical analysis was immediately frozen. The remaining sample was used for microbial studies (see Microbial Analyses). All soil samples collected from NCBC in July 1977, January 1978 or November 1978 were submitted for chemical analyses to the Flantmability Research Center, University of Utah, Salt Lake City UT. Each soil sample was analyzed for the esters and acids of 2,4-D and 2,4,5-T. In addition, each sample was analyzed for diand trichlorophenols (intermediate degradation products of 2,4-D and 16 �2,4,5-7) and selected samples analyzed for TCDD. & brief description of the netted employed in the analyses has been published ( ) 5. MICROSIAL ANALYSES SubBttRf>le8 of all soils were sent to the Department of Chemistry and Biological Sciences, USAF Academy CO for microbial analyses. Ml samples were analyzed for total populations of actinomycetes, fungi and bacteria. In addition, Jcey species presumably responding to the presence of herbicides were identified. The method employed in the microbial analyses has been previously described by Young ( ) It was hoped that quantitative and 9. qualitative studies of the microorganisms from each of the treatment classes used in association with residue data would permit an establishment of a no effect level. CTSULTO AMD DISCUSSIONS, Of HERBICIDl AMP MICBQBIAI* DATA A summary of the analytical results for the 42 sites sampled in January and November 1978 is shown in Table 3. A statistically significant decrease in the levels of total herbicides and total phenols was found to occur between the two dates. There was also a downward trend in TCDD levels, but it was not statistically different {P.05), This trend'in decreasing levels of TCDD (as well as in herbicides and phenols) is even more pronounced when the July 1977 data (Table 2) are compared to the 1978 data (Table 3). Unfortunately, because of differences in site delineation between 1977 and 1978, data for spills vs no spills between the two years cannot be "paired" and statistically analyzed. Nevertheless, the data suggest that TCDD may be degrading within the time period of this study (18 months). Data on the soil penetration of the herbicides, phenols, and TCDD are shown in Table 4. This site (site 17) was a site where a herbicide spill 17 �TABLE 3. Mean concentrations, parts per million, of total phenols and TCDD in soils collected in January and November 1 7 frost selected sites on the Herbicide 98 Orange Storage Area, Naval Construction Battalion Center, Gulfport MS* Location Number of Sites Sampled*3 Total Herbicides (ppit)c Total Phenols (ppm)a 14 14 32af 36* 3.5a 04 .0 TCDD (pp«) "Ho" Spills ( / )e 00 Jan 78 78 ND(4) "Old" Spills ( / ) LL Jan 78 Kov 78 14 14 1,2020. 4920 86a 230 14 14 51,2850 30,0050 437tt 2530 O.G3641(3) 003(} .483 "New" Spills (H/B) Jan 78 Nov 78 026(0a .041) 014(1a .441) a Samples analyzed by the Flammability Research Center, The University Of Utah, Salt Lake City OT. Mr Force Contract Mo. 561178C0062. Reports submitted 17 May 1979 and 7 November 1 7 . 99 Each soil sample consisted of a cube of soil (3x3x3 inches) removed adjacent to a designated marker. °fotal herbicides refers to the concentration of acid and all esters of both 2,4-D and 2,4,5-T. %otai phenols refers to total concentration of both dichlorophenol and tr ichlorophenol . e The coding O/O, L/L and H/H are described in the text. Means within columns within subtitles followed by the same letters are not significantly different at the 0.05 probability level. For the statistical analyses, the Wilcoxon Paired-Sample Test was used. A test for a one- tailed hypothesis with paired samples was used in the procedure for nonparametric data since it could not be assumed that the levels of residue detected were from a normal distribution and it was expected that the residues would decrease with time. See Reference 11. Detected? the number of samples analyzed is in parentheses. The detection limit was generally 0.0002 ppra ( 0 ppt) . 20 n NA-Mot Analyzed. %he number within parentheses refers to number of positive samples used in calculations of the means. In L/L sites, the other 11 samples were either ND or not analyzed; in H/H sites the remaining samples were HD. 18 �TABUS 4. Penetration of herbicides, phenols and TCDD in soil collected June 1979 from a site (Nuaber 17, H/H) where a herbicide spill occurred in 1977 on the Herbicide Oranfe Storage Area, Haval Construction lattalion Center, Gulf port MSa Description of Siteb Soil Depth (Inches) Total Total Herbicides (Pl»»}c Phenols (ppa)d KDD (ppm) Surface Layer 0-3 61,650 365 0.325 Above Hardpan 3-6 34,690 95 0,340 Within Hardpan 6-9 1,620 48 0.021 Within Hardpan 9-15' 322 " 11 MDe *Sanf»les analyzed by the Flaamability Research Center, fhe Uniwrsity of Utah, Salt lake City OT. Mr Force Contract No. 561178C0062. Report submitted 7 Marorober 1979. See text for description of flardpan. C fotal herbicides refers to concentration of acid and all esters of both 2-4D and 2,4,5-T. total phenols refers to total concentration of both dichlorophenol and trichlorophenol. e ttot Detected. The detection limit was 0.00048 pp» ( 8 ppt) for this 40 sample. 19 �had occurred during the PACER HO Operation in Jane 1977. The soil core was collected in June 1979; thus, a period of at least two years had elapsed from date of spill to date of sampling, A decrease in concentration of residue occurred with depth. The hardpan (soil stabilized with cement at least 30 years earlier) was relatively impervious to any residues, despite the high annual rainfall (60 inches) received in this geographic location. These data suggest that soil penetration of residue as a route for contamination of subsurface water will be negligible. Some additional observations of the residue data that may influence future monitoring programs concern the nature of the remaining residues. Although most of the sites, where high levels of residues have been found, have been associated with a spill of Herbicide Orange, two of the sites contain significant levels of the isooctyi esters of 2,4-D and 2,4,5-T. These data suggest that Orange II was spilled at these sites rather than Orange. Whereas the butyl esters of 2,4-D and 2,4,5-T have rapidly hydrolyzed in the soil, the data from Orange II sites show little or no degradation of the isooctyi esters over the two-year period, especially the isooctyi esters of 2,4,5-T. In addition, in these two sites detailed studies of the reiidue indicate the presence of an apparently very stable isooctyi ether of 2,4,5-trichlorophenol. Unpublished data by Arnold* of the studies on soils treated with Orange II in 1972 and collected six years later, have shown negligible degradation in the isooctyi ether of 2,4,5-trichlorophenol. The stability of this ether has permitted its use in confirming the actual concentration of herbicide in the soil at the time of treatment. It may be possible to use this "marker" ether to date selected spills at NCBC, *E.L. Arnold, August 1979. Analysis of Herbicide Orange Components in Selected Soil Samples. USAPSAM/NGP, Brooks APB TX. Report submitted to USAF OEHL. 20 �Data from the micrcbial analyses of soil samples collected from the storage area in July 1977 and January and November 1978 are shown in Tables 5 and 6. Although the biological activity was high in all three treatment areas ( / , L/L, and H/H) trends in populations were discernible. The 00 July 1977 data in fable 5 indicate the impact that activities associated with Project PACER HO may have had on the storage area. During PACER HO, not only did personnel and vehicular traffic disturb the entire site, but when the operation was complete, the site was leveled and a layer of oyster shells was placed in selected sites where spills of herbicide and fuel oil had occurred. The bacteria were especially affected} note that the July 1977 levels in either no spill or new spill sites were ituch lower than the other two dates. However, these data may also reflect both an effect of PACER HO and a lag-phase effect in the adaptation of the bacteria to herbicide. The highest levels of bacteria were found in highly herbicidecontaminated sites (January 1978). Of the several bacterial genera isolated and identified, Psuedoponas spp. predominated in samples with the highest levels of herbicides. Levels of fungi decreased both with time and herbicide concentration. Only 50 percent of the H/H sites in January or November 1978 had detectable levels of fungi, and then, as noted in Table 6, they were not always of genera found in O/O or control soils. Proliferation of certain organisms could indicate their ability to metabolize or co-metabolize herbicide or herbicide degradation products or it could indicate elimination or inhibition of natural competitors. Specific metabolic activity studies using the predominant organisms would be necessary to determine their exact role (if any) in biodegradation. 21 �TABLE 5. Microbial population levels (number of organisms per gram of soil) in soils collected in July 1977, January and November 1978 from selected sites on the Herbicide Orange Storage Area, Naval Construction Battalion Center, Gulfport MSa Fungi, xlO5 Number of Sites Bacteria, xlO7 "No" Spills ( / )b 00 Jul 77 Jan 78 Nov 78 6 14 14 29.7 45.6 40.2 29.6 Old Spills (L/L) Jan 78 Nov 78 14 14 41.8 36.3 1 .2 ( ) 0 8 4.2 ( ) 8 6 14 14 15.4 49.4 34.6 28.6 (5) 7.7 ( ) ? 6.1 (7) Location tsr 7.8 6.2 New Spills (K/H) Jul 77 Jan 78 SOV 78 Control*1 Jan 78 1 38 3.0 Sov 78 I 35 3.2 a Microbial analyses conducted by Department of Chemistry and Biological Sciences, USAF Academy CO. Final report received August 1979. **fhe codling 0/0, L/L and H/H are described in text. c The number within parentheses refers to number of samples where colonies could be counted. Fungi in soils contaminated with herbicide frequently showed no growth after 7 days or growth was random. Control taken in open grassy area one mile from Storage Area. 22 �TABLE 6. Fungal genera found in soils collected from selected sites in 197? and 1978 on and off the Herbicide Orange Storage Area, Naval Construction Battalion Center, Gulfport MSa Predominant Genera Off-Site Control On Site o/o VL Aspergillus spp. Panici Ilium spp. Gunninghamella spp. Zygorhynehus sp. Alternaria sp. Mycelial Molds Candida^ spp. Rhodotorula sp. Geotrichum sp. Triehoderma spp. Muoor. spp. Rhizopus sp • Absidia sp. X X X X X X X X X X X X X X X X X X X X X A X X X X X X A X Miorobial analyses conducted by Department of Chemistry and Biological Sciences, OSAF Academy CO. Final report received August 1979. ft» ceding 9/0, L/L and H/H refer to no spill ( / ) old spill 00, (L/L) and new spill (H/H) and are further described in text. 23 *Jf / f ^ t* I /H I X �AQUATIC SYSTEM MOIilTORIHG FOR TCDD RESIDUE, 1 7 - 9 9 9717 The extreme toxicity associated with 2,3,7,8-TCDB (Reference 8) and its occurrence as a contaminant in 2,4,5-T (and hence Herbicide Orange) dictated that it must be the focus of any residue monitoring study. The location of the NCBC in relation to the major population center of Gulfport MS and to the associated aquatic system is shown in Figure 1. Previous ecological studies on the environmental fate of TCDO by Young ( ) 9 and Young, et al. ( 0 suggested that aquatic drainage systems could be 1) contaminated by water erosion of soil particles containing TCDD. The herbicide storage area is drained by a series of snail ditches that connect into a single ditch immediately adjacent to the area. This larger ditch is fed by other small ditches as it transversea the property of the NCBC. Zn an effort to obtain baseline data on TCDD in this aquatic system, archived biological samples (collected in the immediate storage area and frozen in January 1976) were analyzed in November 1978 and found positive for TCDD residue. Thereafter, additional environmental samples were collected in January, February and June 1979 at varying distances downstream from the storage area. These designated Aquatic Sampling Sites are shown in Figure 2, Aquatic Site III was located at the NCBC perimeter. Aquatic Site IV was at a culvert discharge from the drainage ditch into Long Beach Canal Number 1. Aquatic Sampling Site V was at the confluence of the canal and Turkey Creek. The analytical results from some of these environmental samples were received in September and November 1 7 . 99 A summary of all available TCDD residue data for the aquatic system draining from the storage area is shown in Table 7. It should be again noted that TCDD data in Tables 2, 3 and 4 are presented as parts per million (ppm). Aquatic monitoring studies detected residue levels in 24 �4» O O -H 3 *J C (0 g« o «o ® r-i +J 15 111 > -H 4 O 3 0 CO C S ffi 5° •P C I I tie Is H 14 (D S +J e 9 V Il l rt i & 25 �ci4e M O 4) 41 « §« •H £8 re i-t -ft C 4J •H A (0 i) 31 •H «H 0) -P .si ^ «• D» 3 n. jjj S J3 io (0 rt o * "51 §• a> «g ««4 « O « • tt a 1 tie s H M \ \ V \ 26 M 10 �TABLE 7. Summary of results (parts per billion) for TCDD residue studies in water, sediments anil biological organisms associated with drainage from the Herbicide Orange storage area, Naval Construction Battalion Center, Gulfport IB* Aquatic Sampling Site Distance from Storage Area (Feet) Water Cppb) Maximum Concentration in Sediments (ppb) I Immediate Area ND 3.6 Biologicals (ppb) 0.14-3,5fc 1.6 -7.2 II III 3,000 NAd 7,000 NA 0.01 005 .4e IV 9,000 NA 0.02 0.02f V 12,000 NA ND ND 0.2-2.2 ND9 The analyses for TCDD were conducted by the University of Nebraska, Mass Spectroroetry Laboratory, Lincoln HE, under Mr Force Contract Ho. P0561178C0063 and the Oniversity of Utah, Salt Lake City Of, under Air Force Contract No. 5S1178C0062. Reports submitted 6 September 1979 from the University of Nebraska and 17 May 1979 and 7 November 1979 from the University of Utah. m » Not Detected. Detection limit varied with the sample. All water samples were analyzed by the university of Utah and the detection limit was 0.02 ppb. Sediment samples from Sites I, II and V were analyzed by the University of Utah by low resolution GC-MS where the detection limit was 0.5 ppb. Sediment sauries from Sites III and IV were analyzed by the Dniversity of Nebraska by hifh resolution GC-MS where the detection limit was O.OOS ppb. All biological samples were analyzed by the University of Nebraska and the detection limit ranged from approximately 0.05 to 0.005 ppb, °First sample set collected in January 1976 and analyzed and reported in January 1979; second sample set collected in January 1979 and reported in September 1979. NA - Not Analyzed. This value is an average for a single biological, a crayfish, which was analyzed twice. The mean detection limit was 0.01 ppb. This value was for a single biological, a crayfish, which was analyzed twice. The mean detection limit was 0.008 ppb. A single biological sample, a composite of mosquitofish, was analyzed three times. The sample was considered negative at a mean detection limit of 0.007 ppb. 27 �parts per billion (ppb) and pacts per trillion (ppt). Thus, the average mean level of TCDD in storage site soils (spills) in July 1977 was 237 ppb (0.237 'pftt, see Table 2) j 206 ppb in January 1978 and 144 ppb in November 1978 (see Table 3). Data in Table 7 in very low parts per billion are two orders of magnitude below levels in the storage area soils. Water Samples - Surface Drainage System Herbicide storage Area h total of 61 surface drainage system water samples were collected (Aquatic Sampling Site I) during the history of the project. One sample collected in 1976 was positive at an average mean value of 7.7 ppt TCDD. All remaining samples were negative for TCDD at detection limits ranging from 5-37 ppt. Water Samples - Potable Water System and Wells on the NCBC h total of 36 potable water system and well water samples taken during th« history of the project have contained no detectable levels of TCDD at detection levels as low as 10 ppt. Sediment Samples Two of eight sediment samples collected (Aquatic Sampling Site I) in the immediate surface drainage system of the herbicide storage area in June 1979 were positive for TCDD at levels of 2.7 ppb and 3.6 ppb. Of the remaining six samples, five contained no detectable TCDD at a detection limit of 2 ppb. The sixth sample contained no TCDD at a 37 ppb detection limit. The maximum positive value for this location is shown in Table 7. Two sediment samples have been collected from Aquatic Sampling Site ZZ. These samples were collected in June 1979 and were found negative for TCDD at a detection limit of 0.5 ppb. 28 �Two sediment samples have been collected from Aquatic Sampling Site III (located at the NCBC perimeter}, One of these samples was collected in February 1979,- the other in June 1979. The June sample (data reported in November 1979) was negative for TCDD at a, detection limit analysis of 0.5 ppb [low resolution Gas Chromatography-Mass Spectroraetry (GC-MS}], while the February sample (data reported in September 1979} was positive for TCDD at a level of 0.01 ppb (high resolution GC-MS analysis). the datum from the February sample is reported in Table 7. One sediment sample collected in February 1979 off-base, 9,000 feet from the herbicide storage area (Aquatic Sampling Site IV), in the drainage system leading away from the herbicide storage area and the NCBC, was positive for fCDD at 0.02 ppb with a lower detection limit of 0.01 ppb (report received September 1979). One additional sample collected from the same area (Aquatic Sampling Site IV), in June 1979 contained no detectable TCDD, when the detection limit was 0.5 ppb (report received November 1979). A single sediment sample was collected from Aquatic Sampling Site v. The sample was collected in June 1979 and analyzed by low resolution GC-MS. The sample was found negative for TCDD at 0.5 ppb. Biological Samples Aquatic biological samples (snails, fish, tadpoles, crayfish, and insects) collected over the past three years from the drainage ditch serving the immediate herbicide storage area (Aquatic Sampling Site I)» contained TCDD levels that ranged between 0.14 ppb and 7.2 ppb (Table 7). Aquatic biological samples (snails, tadpoles, fish and crayfish) collected over the past three years from the drainage ditch 3,000 feet 29 �downstream from the herbicide storage area (Aquatic Sampling Site II), contained TCDD levels that ranged between 0.2 ppb and 2.2 ppb. A large crayfish was collected in January 1979 and the muscle tissue and intestine trace separately analyzed. The intestine was found to contain 1.1 ppb TCDD, while the muscle tissue contained 0.0? ppb TCDD. A crayfish sample collected in February 1979, 7,000 feet downstream from the herbicide storage area (Aquatic Sampling site III), just before the drainage system exited the NCBC property, contained 0.045 ppb TCDD. A crayfish sample collected in February 1979, 9,000 feet downstream from the herbicide storage area (Aquatic Sampling Site IV), offbase in the drainage system serving NC1C was found to contain 0.02 ppb TCDD. A mosquitofish sample collected in February 1979, 13,000 feet downstream from the herbicide storage area (Aquatic Sampling Site V), in the off-base drainage system, contained no detectable TCDD at a detection limit of 10 ppt. 30 �Environmental studies of an area on the Naval Construction Battalion Center, previously used for the storage of Herbicide Orange from mid-1968 through mid-1977 were conducted during the period 1970 through 1 7 . The 99 following are conclusions from those studies: ' 1, .approximately 1-2 acres of the 12-acre area are contaminated with Herbicide Orange and its associated dioxin. 2. Levels of 2,4-0 and 2,4,5-T herbicides in selected saaples from the top three inches of soil profile were greater than 100,000 ppmdaean 78,040 ppn) in 1977, bat rapidly decreased to one-third that level in 18 months. 3. No accurate estimate of TCDD persistence is possible from these studies. However,, data from spill sites monitored for 18 months suggest that TCDD levels are decreasing. 4. Soil penetration of the herbicides was low while soil penetration of TCDD was very low but measurable. 5. Soil sterilization did not occur as a result of Herbicide Orange contamination. 6. Proliferation of certain microflora occurred under high levels of herbicide (specifically members of the fungal order Mucorales, white nonsporulating mutants, soil yeasts, and Pseudomonas spp.) 7. Yeast and Pseudomonas spp. predominate in samples with highest levels of herbicide, 8. Proliferation of certain organisms could indicate: a. ability to metabolize HO or degradation products. b. Ability to co-metabolize HO or degradation products. c. Elimination/inhibition of natural competitors. 31 �9. The low solubility of TCDD in water would suggest that its solubility in water alone could not account for the levels of TCDD found in the drainage ditch sediment. 10. The movement of TCDD from the storage sites is primarily through soil erosion, especially that caused by water. 11. Organisms that come into direct and intimate contact with TCDD-contaminated soil generally become contaminated themselves, (A wide variety of organisms have been examined.) 12. TCDD was found in a crayfish collected on base 3,000 feet downstream from the storage site. Levels in the intestine were 1.1 ppb, levels in muscle tissue were only 0.07 ppb. Movement of contaminated soil from the storage area downstream may have resulted in the contamination of crayfish. However, crayfish are highly mobile and nay have migrated from the storage area to the point of capture. 13. TCDD was found in two samples (1 sediment and 1 biological) collected off-base of NCBC. Although the levels of TCDD were extremely low (20 parts per trillion in each sample), it is apparent that some contamination from the storage area has occurred. Contamination from the storage area is not yet extensive and can be controlled. RECOMMENDATIONS The principle recommendation for management of the 12-acre area at the Naval Construction Battalion Center, formerly used as a storage area for Herbicide Orange, is that the area be left undisturbed permitting the continuation of "natural" degradation of the herbicides and TCDD, Specific recommendations to prevent further movement of contaminated soil from the area include: 32 �1. Limiting access to the storage area, and preventing motor vehicle traffic froa crossing the area and potentially "tracking" TCDDcontaminated soil particles to other parts of the installation. 2. Preventing water erosion wherever possible by stabilizing the drainage ditch banks with concrete or asphalt material. The ditch banks should be slightly elevated on the contour to allow pooling of water from the storage area prior to entering the ditch creating an initial siltation catchment. The ditches should be allowed to have plant growth in them to slow the movement of water and allow for more silt catchment, In several places along the ditch drainage system concrete dams should be constructed to slow water movement and provide a wide shallow overflow {in effect creating snail siltation ponds in the ditch drainage system). 3. Constructing one or two larger siltation ponds in the drainage system prior to the drainage water leaving the base. 4. Allowing native vegetation to invade the storage area and establish a plant coaanunity to help prevent both wind and water erosion, 5. Developing a research protocol to determine possible methods for returning the storage area to full beneficial use. This protocol might include techniques to: a. decontaminate TCDD-laden soils. b. increase TCDD degradation rates. c. characterize the distribution and effects of TCDD in the aquatic environment. 33 �LITERATURE CITED 1. Anonymous. 1977. Air Force Logistics Command Programming Plan 75-19 for the Disposal of Orange Herbicide. San Antonio Mr Logistics Center, Kelly AFB TX. Annex 8, pp 2-4. 2. Craig, D.A. 1975. Use of Herbicides in Southeast Asia. Historical Report. San Antonio Air Logistic Center, Directorate of Energy Management, Kelly AFB TX. 58 p. 3. Fee, D.C., B.M. Hughes, M.L. Taylor, T.O. Tiernan and C.E. Hill. 1975. Analytical Methodology for Herbicide Orange, vol lit Determination of Origin of OSAP Stocks. Technical Report ARL-TR-75-0110. Aerospace Research Laboratories, Wright-Patterson AFB OB. 36 p. 4. Hughes, B.M., D.C. Fee, M.L. Taylor, T.O. Tiernan, C.E. Bill and R.L.C. Wu. 1975. Analytical Methodology for Herbicide Orange. Vol Xi Determination of Chemical Composition, Technical Report ARL-TR-75-0110. Aerospace Research Laboratories, Wright-Patterson AFB OH. 365 p. 5. Httfh**, B.M., F.B. Hileaan, i,H. Wbjeik and W.H. MeClennen. 1979. A rapid method for the analysis of low levels of Herbicide Orange (butyl **t*rs of 2,4-D ami 2,4,5-T), 2,4-ST 2,4,5-T, dichlorophenol, trichlorophenol and tetrachlorodibenzo-p-dioxin (TCDD) in environmental samples. Division of Analytical Chemistry, American Chemical Society. Abstract, 177th ACS Rational Meeting, Honolulu HI. 6. Hummel, R.A. 1977. Clean-up Techniques for the Determination of Parts Per Trillion Residue Levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDB). Journal of Agricultural and Food Chemistry 25(5)s1049-1053. 7. Winston, A.W. and R.M. Ritty. 1971. What Happens to Phenoxy Herbicides When Applied to a Watershed Area. Industrial vegetation Management 4(1):12-14. 8. Young, A.L., J.A. Calcagni, C.E. Thalken and J.W. Tremblay. 1978. The Toxicology, Environmental Fate and Human Risk of Herbicide Orange and its Associated Dioxins. Technical Report OEHL-78-92. USAF Occupational and Environmental Health laboratory, Brooks AFB TX. 247 p. 9. Young, A.L. (Ed). 1974. Ecological studies on a herbicide-equipment test area (TA C-52A), Eglin AFB Reservation, Florida. Technical Report AFATL-TR-74-12. Air Force Armament Laboratory, Eglin AFB FL. 141 p~. 10. Young, A.L., C.E. Thalken, E.L. Arnold, J.M. Cupello and L.G. Cockerham. 1976. Fate of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the Environment: Summary and Decontamination Recommendations. Technical Report USAFA-TR-76-18. Department of Chemistry and Biological Sciences, USAF Academy CO. 41 p. 11. Zar, J.H. 1974. Biostatistical Analysis. I»renti0e-Hall Inc., Edgewood Cliffs NJ. pp 124-126. 34 �ADDENDUM Additional residue data from selected biological samples collected June 1979 were received 3 December 1 7 . These data are shown in Table A-l. 99 Vh«M data offer additional support of the previous conclusion, that TCDD from the Herbicide Orange storage area is present in selected biological samples obtained outside the boundary of the Naval Construction Battalion Center. 35 �TABLE A-l. Summary of results (parts'per billion) for TCDD residue in biological organisms collected June 1 7 fj?o» the 99 drainage system associated with the Herbicide Orange storage area, Naval Construction Battalion Center, Gulfport MS* Aquatic Sampling Distance iron Site Storage Area Mature of Sample Concentration Detection of Limit TCDD (ppb) (ppb) 11 3,000 Composite: Crayfish/Fish 015 .7° 0.035 III 7,000 Composite: Crayfish/Fish Turtle ( a ) Ft 0081 .8* HD® 0.010 0.035 IV 9,OOO Composite: Crayfish/Fish 001 .3f 0.017 V 12,000 Composite: Crayfish/Fish Frog (whole body) 000 .2 006 ,0 008 .0 O.OOS *fhe analyses for TCDD were conducted by the University of Nebraska, Mass Spectrometry Laboratory, Lincoln HE, under Mr Force Contract No. F056118C0063. Report submitted 3 December 1 7 . 99 This composite sample and subsequent composite samples in this table consisted of mosquitofish and snail crayfish. Q Average of three analyses. dAverage of two analyses. eND * not detected. Average of two analyses. 36 � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 017 Folder The folder containing the original item. 0187 Series The series number of the original item. Series II Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Young, Alvin L. Charles E. Thalken William J. Cairney Description An account of the resource <strong>Corporate Author: </strong>USAF Occupational and Environmental Health Laboratory, Brooks AFB, Texas Date A point or period of time associated with an event in the lifecycle of the resource 1979-11-01 Title A name given to the resource Herbicide Orange Site Treatment and Environmental Monitoring: Summary Report and Recommendations for Naval Construction Battalion Center, Gulfport, MS Subject The topic of the resource biodegradation Mississippi dioxin Pacer Ho https://www.nal.usda.gov/exhibits/speccoll/files/original/373c0ef0b1de1f948ab7cf276942002a.pdf 7bdc005fa5bab510c2b0a3ddc943e2df PDF Text Text Wilson, James G. Advisory Committee on 2,4,5-T Report of the Advisory Committee on 2,4,5-T to the Administrator of the Environmental Protection Agency Journal/Hook Titlo Year 1971 Month/Day Ma Color ' v' ! 79 Alvin L. Young filed this item under the category "Human Exposure to Phenoxy Herbicides and TCDD" Thursday, April 05, 2001 Pago 1152 of 1180 �CHILDREN'S V<.-*$VJ HOSPITAL MEDICAL CENTER Y"ha Children's Hospital Research Foundation titling* & Bethesda Ave. 'Cincinnati, Ohio 45e?£?9 Department of Pediatrics College of Medicine University of Cincinnati May 7, 1971 Mr. William D. Ruckelshaus Administrator Environmental Protection Agency Washington, D.C. 20460 Dear Mr. Ruckelshaus: On behalf of the membership of the Advisory Committee on 2,4,5-T, I am pleased to submit the attached .Report. We earnestly hope the Report will prove helpful to you and your staff in establishing policy and procedures relative to future regulation of the use of the herbicide 2,4,5-T. I shall endeavor to be of further service in this connection if needed. Sincerely yours, James G. Wilson, Chairman Advisory Committee on 2,4,5-T JGW:bh ADOLESCENT CUNl'O • CHILDREN'S DENTAL CARE FOUNDATION • THE CHILDREN'S HQSP'TAL THE CHILDREN'S HOSPITAL RESEARCH FOUNDATION • CHILDREN'S NEURPMUSCLJL.AR DiAGNOE'?IC!Cl'.IIMIC _ CONVALESCENT HOSPITAL FOR CHILDREN • HAMILTON COUNTY DIAGNOSTIC CLINIC FOH THEi MENTALLY 7>kT/*PQK;'J. '' LINITGD CEREBRAL PALSY OF CINCINNATI. INC. AFFILIATED WITH THE UNIVERSITY OF CINCiN r: - �R E P O R T of the A D V I S O R Y C O M M I T T E E ON 2,4,5-T to THE A D M I N I S T R A T O R of the E N V I R O N M E N T A L P R O T E C T I O N A G E N C Y Submitted, May 7, 1971 �CONTENTS Page Membership of the Advisory Committee 1 Introduction 3 I. Factors Influencing Exposure to Man A. Patterns of use of 2,4,5-T B. Fate in soil, air, water and plants Fate of 2,4,5-T Fate of TCDD References cited in Section I A and B C. Fate in animals Fate of 2,4,5-T Fate of TCDD References cited in Section 1 C II. Toxicity of 2,4,5-T and TCDD in Animals and Man A. Nonteratogenic toxicity of 2,4,5-T of TCDD References cited in Section II A B. Teratogenic Potential of 2,4,5-T 1. Scope of embryotoxicity 2. Data from laboratory animals 2,4,5-T in rats TCDD in rats 2,4,5-T in mice TCDD in mice 2,4,5-T in hamsters TCDD in hamsters 2,.4,5-T in rabbits 2,4,5-T in sheeps 2,4,5-T in rhesus monkeys Summary of data on laboratory animals 3. Human exposure during pregnancy Vietnam Summary of Vietnam data on Human Embryotoxicity Globe, Arizona Swedish Lapland References cited in Section II B 8 8 9 9 14 18 23 23 25 26 28 28 28 33 34 37 37 39 41 45 46 47 48 49 49 49 49 50 51 51 57 58 59 60 �III. General Conclusions IV. Recommendations V. 64 66 Statement of views of Dr. Theodor D. Sterling entitled, "Objections to and Modifications of the Final Report and Recommendations of the 2,4,5-T Advisory Committee". 68 VI. List of Persons conferring with the Committee 76 �-1MEMBERSHIP of the ADVISORY COMMITTEE James G. Wilson, Ph.D., Chairman Professor of Research Pediatrics and Anatomy, Children's Hospital Research Foundation and College of Medicine, University of Cincinnati, Ohio Roswell K. Boutwell, Ph.D. Professor of Oncology, McArdle Laboratory for Cancer Research, University of Wisconsin Medical Center Madison, Wisconsin Donald E. Davis, Ph.D. Alumni Professor, Department of Botany and Microbiology, Auburn University, Auburn, Alabama Frank N. Dost, DVM Associate Professor of Veterinary Medicine, Science Research Institute, and Environmental Health Sciences Center, Oregon State University, Corvallis Wayland J. Hayes, Jr., M.D.,Ph.D. ^Professor of Biochemistry, Department of Vt Biochemistry, University School of Medicine, Nashville, Tennessee Harold Kalter, Ph.D. Professor of Research Pediatrics, Children's Hospital Research Foundation and College of Medicine, University of Cincinnati, Ohio �-2- Ted A. Loomis, M.D., Ph.D. Professor Pharmacology and State Toxicologist, Department of Pharmacology, University of Washington School of Medicine, Seattle Arthur Schulert, Ph.D. President, Environmental Science and Engineering Corp. and Associate Professor of Biochemistry, Vanderbilt University School of Medicine, Nashville, Tennessee Theodor D. Sterling* Ph.D. Professor, Dept. of Applied Mathematics and Computer Science, Washington University, St. Louis, Missouri David L. Bowen Secretariat to Advisory Committee Environmental Protection Agency �-3- INTRODUCTION On October 29, 1969, the President's Science Advisor, Dr. Lee A/. s DuBridge, announced that a series of coordinated actions was being taken by several governmental agencies to restrict the use of the herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). This was precipitated by release a few days earlier of the findings of a large-scale screening study of a number of pesticides and industrial chemicals conducted by Bionetics Research Laboratories in which it was found that mice and rats treated during early pregnancy with large doses of 2,4,5-T gave birth to defective offspring. The announcement, together with reports of an increased occurrence of birth defects by South Vietnamese newspapers during June and July 1969, elicited far-reaching reactions from governmental agencies, segments of the scientific community, various lay groups concerned with environmental problems, and from the public communications media. Government-sponsored panels of experts, special commissions set up by scientific organizations, hearings before subcommittees of the U.S. Senate, and conferences attended by representatives.from industry,, government, and universities examined available data and heard expert opinions. None of these groups, however, was able to provide a generally acceptable answer' to the central question of whether 2,4,5-T, as currently produced and'usad, constituted a risk for human pregnancy. At least one reason for failure to reach a>satisfactory resolution of the issue was the paucity of reliable, scientific evidence. Additional animal experiments performed early in 1970 confirmed that the purest available sample of 2,4,5-T, given in large doses to �-4- pregnant mice, did indeed result in the delivery of some malformed offspring. The question then becomes one of whether, or to what extent, such animal data could be extrapolated to man. On April 14, 1970, an attitude of caution was expressed by the Secretary of Health, Education and Welfare, who advised the Secretary of Agriculture that: "In spite of these uncertainties, the Surgeon General feels that a prudent course of action must be based on the decision that exposure to this herbicide may present an imminent hazard to women of child-bearing age." Accordingly, on the following day the Secretaries of Agriculture, of Health, Education, and Welfare and of Interior jointly announced the suspension of the registration of 2,4,5-T for: "I. All uses in lakes, ponds or on ditch banks. II. Liquid formulations for use around the home, recreation areas and similar sites." (USDA-PRD PR 70-1, 20 Apr. 1970) A notice for cancellation of registration was issued on May 1 for: "I. All granular 2,4,5-T formulations for use around the home, recreation areas and similar sites. II. All 2,4,5-T uses on crops intended for human consumption." (USDA-PRD PR 70-13, 1 May 1970) All registrants of 2,4,5-T were advised of these actions, and two of the registrants, Dow Chemical Company and Hercules Incorporated, exercised their right under Section 4.c. of the Federal Insecticide, Fungicide and Rodenticide Act (7 U.S.C. 135 gt seq.) to petition for referral of the matter to an Advisory Committee. The National Academy of Sciences supplied a list from which was selected a nine-member Advisory Committee of scientists with appropriate qualifications from universities and research institutes over the country. At its first meeting on February 1 and 2, 1971, the Advisory Committee was given a charge which in substance asked that it: 1) consider all �—5— relevant facts, 2) submit a report and recommendations regarding registration for certain uses of 2,4,5-T, and 3) state the reasons or bases for these recommendations. It was the concensus of the Committee that the central issue was whether use of the herbicide does in fact constitute an imminent health hazard, especially with respect to human reproduction. Accordingly, the Committee has undertaken to examine all available information and to evaluate its relevance to the potential hazard of human exposure during pregnancy. During the intervening months since restrictions were placed on the use of 2,4,5-T a number of additional studies have been carried out on several animal species and a few reports on human exposure during pregnancy have been further evaluated. Although the new data have not answered all of the questions that have been or could be raised, they have undoubtedly provided a more substantial basis for making a scientific judgment about possible effects of this herbicide on prenatal development than previously existed. In undertaking such judgment the Committee has taken into account certain considerations that seem appropriate to the issue, as follows: 1) As is frequently the case, available data are insufficient for a definitive statement of conditions under which a specified risk might occur, assuming that freedom from risk is ever attainable. 2) Since most chemicals under suitable laboratory conditions could probably be demonstrated to have teratogenic effects, and certainly all could be shown to produce some toxic effects if dosage were raised high enough, it would not be reasonable to consider the demonstration of toxic effects under conditions of greatly elevated dosage sufficient grounds for prohibiting further use of a particular chemical. 3) Benefits are to be expected from the continued use of �-6- 2,4,5-T. The necessity of making a value judgment of benefit vs. risk, therefore, must be accepted, not only for this herbicide, but for numerous valuable drugs, some natural nutrients, and many other chemicals, some of which are known to be teratogenic in laboratory animals. The risk vs. benefit judgment for a particular herbicide or drug can be evaded only if it can be shown that another compound is equally as efficient and involves less risk. This presupposes that the risk potential of a substitute herb- icide is at least as well known as that of the original (in this case 2,4,5-T), a fact that may be difficult or impossible to ascertain. The substitution of a relatively unknown pesticide for an older one with known adverse effects is not a step to be taken lightly. Even with steadily improving methods for safety evaluation of new chemicals it is impossible to anticipate all of the conditions and permutations of use that could result in undesirable effects. The task of making a judgment about the central question of hazard to human pregnancy is complicated by still other considerations. Although herbicides are of economic benefit to man, their use is not without possible hazard to the environment and to other aspects of human welfare. In various connections questions have been raised about: 1) damage to non-target plants caused by spray drift or by movement in water, 2) damage to subsequently planted sensitive crops owing to herbicide persistence in the soil, and 3) acute or chronic toxicity to man or other animals aside from that related to pregnancy. In addition, there is some concern that traces of the chemical or its contaminants in food may cause unsuspected effects in man or that minute amounts in the environment >may -adversely affect untested species in the ecosystem. �-7- It is scientifically impossible to prove that a chemical is without hazard. Pesticide regulations now require that new agents be tested for acute and chronic toxicity, mutagenicity and carcinogenicity. These tests may involve the use of two or more species of animals taken through several generations and the examination of thousands of individuals. Since it is necessary to extrapolate from effects in test animals to man and since species are known to differ in sensitivity to chemicals, the permissible residue levels in food must always be many-fold below the minimal effect level for the species tested. Concern that some unexpected detrimental occurrence may outweigh the benefit of a pesticide has doubtless been heightened by the finding that DDT residues in the environment have adversely affected reproduction in certain predatory avian species that are at the top of their food chains and, as a consequence, ingest large accumulations of this persistent compound. With these considerations in mind the Advisory Committee has examined all available information relating to factors that may influence human exposure to 2,4,5-T and the toxic reactions, nonteratogenic as well as teratogenic, such exposure of man and other animal species may entail. �-8- I. FACTORS INFLUENCING EXPOSURE TO MAN, Human exposure to an environmental chemical such as 2,4,5-T depends on 1) pattern of usage, i.e., how widely and frequently applied and in what amounts, and 2) its fate in the environment, i.e., does it accumulate or is it degraded as fast as applied. A. Patterns of use. The chloro-phenoxy herbicides 2,4-D and 2,4,5-T have been widely used to control broad-leaved weeds for over 20 years. Because 2,4,5-T is more expensive than 2,4-D (2,4-dichlorophenoxyacetic acid) it has been primarily used to control woody plants and a few herbaceous species against which it is more effective than 2,4-D, and because of the cost difference, commercial formulations containing 2,4,5-T are usually mixtures of the two herbicides. In 1964 the uses of 2,4,5-T were: rights-of-way - 49%, non-farm forests - 10%, hay, pasture, and rangelands - 7%, all other farm uses - 12%, lawns and turf - 7%, federal agencies - 6%, and other miscellaneous uses - 9%.—' The tocal domestic use at that time was about 9 million pounds and incomplete information indicates that this value may also be approximately correct for 1969.-/ Most of the 2,4,5-T used is applied as a spray to foliage. Lesser amounts are sprayed on the trunks and branches of dormant trees, injected into the bases of trees, poured or sprayed into frills around the trunks of trees, or sprayed or painted on newly cut stumps of trees. Amine salts of 2,4,5-T dissolved in water are most often used when the herbicide is applied to foliage and esters dissolved in oil are most �—9— often used when it is applied to bark. The spray concentrations usually vary between 0.1 and 2.5% and the rates of application are usually between 0.5 and 8 Ib per acre, depending on the size, and sensitivity of the plants being treated. Higher rates and concentrations have been used in Vietnam for military purposes. On domestic rice, 0.50 to 1.25 Ib per acre of 2,4,5-T is used in 3/ 5 to 7 gal of water—' , applied from the air when the rice is 7 to 9 weeks old, has emerged from the water, and is'standing erect. Directions for the use of 2,4,5-T warn against allowing it to drift onto susceptible plant species and require that the herbicide not be allowed to contaminate water used for irrigation or domestic purposes. B. Fate in soil, air, water and plants. When 2i4,5-T is applied as a spray, the great bulk of the herbicide and any contaminant it may contain, e.g., 2,3,7,8-tetrachlorodibenzo-paradioxin (TCDD), are deposited on the foliage of the plants, on the ground in the immediate vicinity or, in the case of rice, on the impounded water. Much smaller amounts may be inserted into the air or settle on streams of water and by either means be carried many miles from the site of appl'ication. After 2,4,5-T and TCDD are applied, however, each moves through the biosphere and accumulates or degrades according to its own chemical and physical properties. The fate of 2,4,5-T has been more extensively studied than that of TCDD. Fate of 2,4,5-T. Once the herbicide reaches the soil it is immediately subjected to physical and chemical actions that continually reduce the amount remaining at the site of application. These actions include degradation by soil microorganisms, leaching and surface �-10- movement in water, volatilization, movement by wind, and photochemical decomposition. The persistence of 2,4,5-T is influenced by its rate of application and by various climatic and edaphic factors, and occurs most rapidly under conditions that are optimal for the growth of soil microorganisms.— At least two bacterial isolates, Mycoplano sp. and Achro- mobacter sp.— — — — and one actinomycete, Streptomyces viridochromogenes— from soil are known to metabolize 2,4,5-T. Br.evibacterium sp. has been shown to cometabolize 2,4,5-T to a product tentatively identified as 3,5dichlorocatechol— . Morris— found that 2,4,5-T was decarboxylated in the litter of the forest floor and had a half-life of approximately 40 days. 12/ Loos— has thoroughly reviewed degradation of phenoxyalkanoic acids, including 2,4,5-T. Loss of all phytotoxicity of 2,4,5-T applied to the soil 13/ was reported to occur 3 to 6 months after application.— No chemically detectable amounts of 2,4,5-T were found in the soil 1 year after an application of 2 Ib per acre and only very small amounts were found 3 to 7 months after application.— Although the rate of disappearance varies, there have been no reports of carry-over of 2,4,5-T from one year to the next, indicating that no build-up in the soil would result from recommended rates of treatment repeated annually. When phenoxy herbicides were first introduced, highly volatile esters were available and farmers were inexperienced in their use, there were several instances in which the drift through air produced severe injury to sensitive crops, usually in adjoining fields or more rarely at some distance from the point of application. Owing to accumulated experience and the institution of regulations regarding the conditions under which applications can be made, as well as the removal of the volatile esters from the market, �-11injury to crops is now unusual. The elimination of drift sufficient to injure most crop plants, however, does not eliminate the possibility of drift that can be detected chemically. Some of the 2,4,5-T applied as spray can be transported in the atmosphere as droplets of spray, as the gaseous phase of 2,4,5-T, or adsorbed on dust or other particulate matter in the air. In a survey in the State of Washington, 2,4,5-T was detected 9 days out of 99 at Pullman, o in average concentration in positive samples of 0.045 yg/m . At Kennewick it was found 14 days out of 102 at average concentration in positive samples 3 147 of 0.012 yg/m — . In Cincinnati, Ohio, 0.04 ppm was found adsorbed on dust in a trace of rain—' presumably from applications in Texas. Photo- chemical degradation would be expected to occur in the air, particularly at high altitudes and in dry climates where ultraviolet radiation is highest. Kearney et al.—' report that exposure of 5 and 10 ppm water solutions of 2,4,5-T to ultraviolet light from a 450 watt Hanovia lamp greatly reduced the 2,4,5-T present within 5 minutes. It is not possible to extrapolate accurately from these data to the rate of decomposition in sunlight, but it is obvious that photochemical degradation could play a significant role. Probably most of the 2,4,5-T that gets into the air very soon either settles out or is washed out by rain and thereby is returned to soil and water. There is no evidence to suggest that 2,4,5-T remains in the air for more than a few weeks after insertion. Measurable quantities of 2,4,5-T could enter water iL'n several ways, e.g., by inadvertent direct spraying, from surface leaching of treated soils and plants, or in rain that falls through air containing 2,4,5-T; but undoubtedly most of it is washed from treated plants and soil. �-12- Apparently the amounts are usually quite small since only 28 of 322 water samples taken in western states, where 2,4,5-T is widely used for brush control, were shown to contain 2,4,5-T— in concentrations ranging from 0.01 to 0.07 ppb. In closely controlled watershed studies in Waynesville, North Carolina, no 2,4,5-T was found in any sample of run-off from an area one-fourth of which was treated with 2 Ib of 2,4,5-T per acre in 1968 or 18/ 1969— . When one-fourth the area was treated with 4 Ib per acre some herbicide was found in the water after the first and second rain storms, but the highest concentration found was 0.048 ppm in run-off water during a storm that occurred 8 days after application of the herbicide. No 2,4,5-T was found in the last sample collected that day or in those collected on subsequent days. Few data are available on the rate of disappearance of 2,4,5-T from water. It would be expected to be adsorbed on clay particles or adsorbed by aquatic species within a few days. The concentration of picloram, a considerably more persistent herbicide than 2,4,5-T in most situations, decreased from 0.965 ppm to 0.129 ppm in 3 weeks in a test in which it was applied at 19/ the rate of 4 Ib per acre to a pond— . All available data suggest that the amount of 2,4,5-T entering water is quite low and that it does not remain in the water very long. Absorption, translocation, and metabolism of 2,4-D and 2,4,5-T by plants have been extensively investigated. Most investigations have dealt with 2,4-D, but numerous studies have involved both and it is apparent that their behavior in plants is similar. Ready absorption of 2,4,5-T by leaves, , , 20/21/22/23/24/25/ n f stems, and roots of plants is known to occur. Once absorbed 2,4,5-T may either move upward in the xylem or bidirectionally in �-la- the phloem. Some 2,4,5-T is absorbed by the leaves, transported down the 22/ stem and into the roots, and excreted by the roots into soil solution— . Decarboxylation of 2,4,5-T has been demonstrated in a number of plant 127 species— . The varied sensitivity of different species to 2,4,5-T may be attributable in part to different rates of metabolism. 25/ Slife et al.—• found only traces of unidentified metabolites 8 days after applying C- carboxyl-labeled 2,4,5-T to wild or cultivated cucumber plants, both species susceptible to 2,4,5-T. Easier and associates—'—' applied labeled 2,4,5-T to excised blackjack oak leaves. C-carboxyl- They found no decarboxyl- ation but did find that an average of 59% of the 2,4,5-T was broken down into three major unidentified metabolites in 24 hours. 28/ Morton—' reported that 80% of 2,4,5-T applied to mesquite was metabolized in 24 hours. Fitz- 297 gerald et al.— identified 2,4,5-trichlorophenol as a common metabolic product of 2,4,5-T in sweetgum and southern red oak but found that no 2,4,503 / trichloroanisole was formed. Morton et al.— have studied the metabolism of various formulations of 2,4,5-T by beardgrass, little bluestem, and sideoats gramma and observed only moderate effect of formulation and species on the rate of metabolism. to 2.9 weeks. Half-life values in green tissues ranged from 1.6 In one experiment using radioactive 2,4,5-T ester and silver beardgrass, little bluestem, and dallis grass, alcohol extracts of green tissue taken 1 week after application contained no 2,4,5-T ester, 50% 2,4,5-T acid, and 50% unknown radioactive metabolite. Authorization to use 2,4,5-T on food crops depends on demonstrating that no residue exists in the edible product at harvest. The following studies illustrate the amounts of 2,4,5-T that may persist in food crops at various intervals after treatment. When 2,4,5-T was applied to apples as a �-14- spray concentration of 40 ppm, residue in the fruit had fallen to 0.004 ppm in 22 days.—' The application of 2,4,5-T to blueberries at 1 Ib per acre resulted in a concentration in the fruit of 0.05 to 0.33 ppm 44 days after 31 application although none was found 733 days after application.— / No detect- able 2,4,5-T (sensitivity =0.01 ppm) was found in rough rice 50 days after •JO/ applying 2.25 Ib per acre of 2,4,5-T.—' The rice straw contained 0.18 to 1.04 ppm 2,4,5-T 50 days after but none 84 days after application. Further evidence that very little 2,4,5-T gets into food is seen in results of assays of raw agricultural products and in the Market Basket Survey samples. From about 10,000 food and feed samples examined from 1964 through 1969 only 25 contained trace amounts of 2,4,5-T (less than 0.1 ppm) and only two contained measurable amounts, 0.19 ppm in a sample of milk in 33/ 1965 and 0.29 ppm in a sample of sugar beets in 1966.—' Furthermore, of the 134 total diet samples involving 1600 food composites (Market Basket Survey) analyzed from 1964 through April 1969, only 3 contained 2,4,5-T. Two were dairy products containing 8 to 13% fat with 0.008 and 0.19 ppm in the fat. A single meat, fish and poultry composite from Boston consisting 33/ of 17 to 23% of fat was found to contain 0.003 ppm 2,4,5-T on a fat basis.—' 34/3S/ It is concluded from the foregoing that: 1) The herbicide 2,4,5-T does not accumulate in any compartment of the biosphere. 2) The risk of human exposure to 2,4,5-T in food, air or water is negligible. Fate of TCDD. Under present conditions of manufacture this con- taminant is usually present in 2,4,5-T at less than 1 ppm, thus insuring that very little TCDD is inadvertently applied with 2,4,5-T. Like 2,4,5-T any contaminating TCDD would be deposited on the leaves of treated vegetation �-15- or on soil and water in the vicinity, although as indicated for 2,4,5-T, smaller amounts could enter air or water and be carried some distance from the site of application. Water transport, however, is sharply limited by 36 / the fact that the solubility of TCDD in water is only 0.2 ppb.— As a consequence it would tend to remain on the surface of plants and soil at the site of application. Photochemical decomposition of TCDD has been studied at Dow Chemical 37/ og/ Co.— and the United States Department of Agriculture.— Exposure of 1.02 mg of TCDD in 100 ml of water-saturated chloroform to ultraviolet light at 35°C caused 50 to 100% degradation in 2.5 hours. The Department of Agriculture, using a sunlamp with a peak emission at 310 nm, irradiated TCDD dissolved in methanol and found it to have a half-life of 3.5 hours. Rapid decomposition was also reported in natural sunlight when approximately 5 ml of a 24-ppm methanol solution of TCDD was sealed in glass tubes and exposed to 7,000 to 9,000 footcandles of sunlight, with a half-life of approximately 5 hours, virtual disappearance in 48 hours, and none detectable after 72 hours. Similar rates of decomposition, however, were not observed when the TCDD was placed on the surface of dry soil where irradiation for 96 hours with a sunlamp (maximum energy at 310 nm) did not cause any significant loss by either photodecomposition or volatilization. The same was true for wet soil irradiated for 6 hours. Interactions of TCDD with soil have also been studied by the United 39 States Department of Agriculture.— / When TCDD was placed on the surface of five very different soils and subjected to leaching with water, the TCDD did not move into any of the soils, probably because of its very low water solubility. Similarly, in leaching experiments using soil thin- �-16- layer chromatographic technique, no TCDD moved from the spot of origin in OQ / either a Hagerstown silty clay loam or a Norfolk sandy loam.— It would thus appear that most of f-ho chemical falling on the soil surface would remain there. The fate of TCDD mechanically incorporated into.soil has 39/ been investigated by the Department of Agriculture.— Radiolabeled TCDD was mixed into soil at the rates of 1, 10, and 100 ppm and soil extracts radio-assayed 20, 40, 80, and 160 days after application. The amount of radioactive material (probably TCDD) in the soil decreased 15 to 20% in 160 days, indicating that this compound was very slowly degraded in the soil and could persist for more than a year. The possibility that TCDD incorporated in the soil might be absorbed 39 by plants has been studied.— / Soybean and oat plants x^ere grown on Lake- land sand containing 0.06 ppm radiolabeled TCDD, which is 40,000 times the amount that would appear in soils treated with 2 Ib per acre of 2,4,5-T containing 1 ppm TCDD. Less than 0.2% of the available TCDD was absorbed by either type of plant, with radioactivity reaching a peak at 10 days at which time it measured about 0.12 ppm in oats and 0.05 ppm in soybeans on a dry weight basis, then it declined to an insignificant level at 40 days. The most likely source of plant contamination by the TCDD present as a contaminant in commercial 2,4,5-T is by way of foliar application. 39/ When radioactive TCDD was applied to the surface of leaves— no material was translocated from the site of application on the plant; but about 40 percent of the applied TCDD could be leached from the surface of the leaves by water, probably because the TCDD was added with a surfactant. This suggests that surface contamination could be the source of a very small TCDD residue in leafy food plants, but 2,4,5-T is not used on such �-17- plants. Even if 2,4,5-T containing 1 ppm TCDD were applied to such plants at the rate of 2 Ib per acre, the resultant TCDD contamination would be at 2 the extremely low level of 0.224 yg per m on the exposed surface. It is concluded from the foregoing that: 1) There is no indication that TCDD accumulates in air, water or plants, although it fyught accumulate in soils after heavy application of a highly contaminated sample of 2,4,5-T. 2) Direct application of 2,4,5-T containing TCDD could result in minute quantities of the latter remaining on the surface of foliage. than 0.2% of TCDD in soil is known to be absorbed into plants. 3) Less �-18- References Cited in Section I A and B 1. USDA, 1970. and 1966. Report and tables on domestic use of 2,4,5-T, 1964 Supplied by Production Resources Branch, Farm Production Economics Division, April, 1970. 2. Byerly, T.C., 1970. Use of 2,4,5-T in the United States. Letter from Dr. Byerly to Senators Magnuson and Hart. 3. Dow, 1970. 245. Petition, Part III, Item 3. Specimen labels for VEON The Dow Chemical Co. 4. De Rose, H.R. and A.S. Newman, 1947. The comparison of the persistence of certain plant growth-regulators when applied to soil. Soil Sci. Soc. Amer. Proc., 12;222-226. 5. Bell, G.R., 1957. Some morphological and biochemical characteristics of a soil bacterium which decomposes 2,4-dichlorophenoxyacetic acid. Canad. J. Microbiol., 3_:82l-8^0. 6. Bell, G.R., 1960. Studies on a soil Achromobjicter which degrades 2,4-dichlorophenoxyacetic acid. Canad, J. Microbiol., j$:325-337. 7. Steenson, T.I. and M. Walker, 1958. Adaptive patterns in the bacterial oxidation of 2,4-dichloro- and 4-chloro-2-methylphenoxyacetic acid. J. Gen. Microbiol., 18;692r-697. 8. Walker, R.L. and A.S. Newman, 1956. Microbial decomposition of 2,4-dichlorophenoxyacetic acid. Appl. Microbiol., 4_:201-206. 9. Bounds, H.C. and A.R. Colmer, 1965. Detoxification of some herbicides by Stre^tomyces. Weed Sci., 13:249-252. 10. Horvath, R.S., 1971. Microbial cometabolism of 2,4,5-trichloro- phenoxyacetic acid. Bulletin of Environmental Contamination and Toxicology, _5:537-541. �-1911. Norrls, L.A., 1970. Degradation of herbicides in the forest floor, p. 397-411. In; Youngberg, C.T. and C.B. Davey. Tree Growth and Forest Soils. Oregon State Univ. Press, Corvallis. 12. Loos, M.A., 1969. Phenoxyalkanoic acids, p. 1-49. Kearney and D.D Kaufman. Dekker, Inc., New York. 527 p. In; P.C. Degradation of Herbicides. Marcel 394 p. 13. Kearney, P.C., R»G. Nash and A.R. Isensee, 1969. pesticide residues in soils, p. 54-67. In; Persistence of Chemical Fallout; Current Research in Persistent Pesticides, ed. M.W. Miller and George G. Berg, Chas. C. Thomas, Ft. Lauderdale, Florida. 14. Bamesberger, W.L. and D.R. Adams, 1966. the environment. Organic pesticides in Adv. Chem. Ser., 60. ACS Publ. Wash., D.C. 15. Weibel, S.R., R.B. Weidner, J.M Cohen and A.G. Christiansen, 1966. Pesticides and other contaminants in rainfall and runoff. J. Amer. Water Works Assn., 58;1075-1084. 16. Kearney, P.C., E.A. Woolson, J.R.. Plimmer and A.R. Isensee, 1969. Decontamination of pesticides in soils. Residue Reviews, 29;137-149. Edited by F. Gunther. Springer-Verlag, New York. 17. Manigold, D.B. and J.A. Schulze, 1969. Pesticides in Water - Pesticides in Selected Western Streams. A Progress Report. Pesticide Monit. J., _3:124-135. 18. Sheets, T.J., 1970. picloram. Watershed studies with 2,4-D, 2,4,5-T and Communication from George Irving, Jr., to T.C. Byerly, April 3, 1970. (ARS Contract 12-14-100-893 ( 4 ) 3). 19. Hoffman, G.O., E.D. Robinson and M.G. Merkle, 1969. Loss of picloram into surface and ground waters. Weed Science Soc. of Amer., Abstract 75. Supplemented by personal communcation from M.G. Merkle. �-20- 20. Easier, E., 1962. Penetration, movement, and behavior of herbicides in plants. Proc. Southern Weed Conf., 15;8-15. 21. Fisher, C.E., C.H. Headers and R. Behrens, 1956. Some factors that influence the effectiveness of trichlorophenoxyacetic acid in killing mesquite. Weed Sci., JK139-147. 22. Hurtt, W., W.A. Wells and C.P.P. Reid, 1970. Foliar uptake and root exudation of picloram and 2,4,5-T by selected woody species. Weed Sci. Soc. Amer., Abstract 145. 23. Morton, H.L., E.D. Robinson and R.E. Meyer, 1967. Persistence of 2,4-D, 2,4,5-T and dicamba in range forage grasses. 24. Perry, P.W. and R.P. Upchurch, 1968. Weeds 15;268-271. Growth analysis of red maple and white ash seedlings treated with eight herbicides. Weed Sci., 16:32-37. 25. Slife, F.W., J.L. Key, S. Yamaguchi and A.S. Crafts, 1962. Penetration, translocation and metabolism of 2,4-D and 2,4,5-T in wild and cultivated cucumber plants. 26. Easier, E., 1964. Weed Sci., 10:29-35. The decarboxylation of phenoxyacetic acid herbicides by excised leaves of woody plants. Weed Sci., 12:14-16. 27. Easier, E., C.C. King, A.A. Badiei, and P.W. Santelmann, 1964. breakdown of phenoxy herbicides in blackjack oak. The Proc, Southern Weed Conf., 1J:351-355. 28. Morton, H.L., 1966. Influence of temperature and humidity on foliar absorption, translocation, and metabolism of 2,4,5-T by mesquite seedlings. Weed Sci., 14:136-141. �-2129. Fitzgerald, C.H., C.L. Brown and E.G. Beck, 1967. Degradation of 2,4,5-trichlorophenoxyacetic acid in woody plants. Plant Physiol. j42:459-460. 30. Edgerton, L.J. and D.J. Lesk, 1963. Determination of residues of 2,4,5-trichlorophenoxyacetic acid in apples by radioisotopes and gas chromatographic methods. Proc. Am. Soc. Hort. Sci., 83;120-125. 31. Trevett, M.F., 1964. A request for approval of a contact method of applying 2,4-D and 2,4,5-T for control of woody weeds in Maine lowbush blueberry fields. Unpublished data. Cited in Dow communication dated Jan. 19, 1971. 32. Syracuse University Research Corporation, 1970. 2,4,5-T residues in rough rice and straw. Unpublished data. Cited in Dow communication dated January 19, 1971. 33. Duggan., R.E., 1971. Memorandum to Way land J. Hayes. Unpublished. March 12, 1971. 34. Corneliussen, P.E., 1969. Pesticide residues in total diet samples. Pesticide Monit. J., .2:140-152. 35. Duggan, R.E., H.C. Barry, and L.Y. Johnson, 1967. Pesticide residues in total diet samples. Pesticide Monit. J., JL:2-12. 35a. Martin, P.J. and R.E. Duggan, 1968. Pesticide residues in total diet samples. Pestiicde Monit. J., JL:11-20. 36. Dow, 1970. Petitions, Part III, Item 20. Solubilities of 2,4,7,8tetrachlorodibenzo-p-dioxin. The Dow Chemical Co., December 8, 1964 (Revised April 1970). 37. Dow, 1970. Petitions, Part III, Item 19. The degradation of 2,3,7,8-tetrachlorodibenzo-p-dioxin by ultraviolet light. The Dow Chemical Co., May 1970. �-22- 37a. Lynn, G.E., 1971. p-dioxin. Photodegradation of 2,3,7,8-tetrachlorodibenzo- Unpublished work by Dow Chemical. Letter dated February 1, 1971. 38. USDA, 1970. Progress report on dioxin research. IV. Unpublished report dated March 25, 1970. 39. Kearney, Philip C., 1970. Chlorinated dioxin research. Presented before a Joint Meeting on Pesticides, United Kingdom, Canada, United States. November 5. �-23- C. Fate in Animals Fate of 2,4,5-T. Information on absorption, distribution, and metabolism of 2,4,5-T is not extensive. The most thorough studies are 1/2/ those reported by Erne — — who demonstrated that the triethanolamine and alkaline salts of 2,4,5-T and 2,4-D were readily absorbed, distributed and eliminated from the body. Rats and pigs given single doses of 100 mg/kg of the amine salt showed plasma half-life values of 3 and 10 hours respectively. Residues in kidney, liver, lungs and spleen sometimes exceeded plasma levels, but there was little indication of penetration into brain or adipose tissues. via the kidney. The compounds were excreted mainly With repeated administration plasma levels decreased and excretion rates increased. Up to 20% of the material in blood was in erythrocytes. As with single doses, little was found in adipose tissue or in the central nervous system. Placental transfer was found to be rapid in swine. Tissue half-times ranged from 5 to 30 hours and,were lowest in rats. There was no apparent retention of either 2,4-D or of; 2,4,5-T after repeated administration. 3/ According to St. John et al.,— when a cow was given 450 mg of 2,4,5-T acid divided among four daily doses, all of the administered material was excreted in the urine as the salt within 6 days. Zlelinski and Fishbein- found that a dose of 100 mg/kg of 2,4,5-T in mice was lost from the body more slowly than were several other herbicides, with disappearance rates ranging between 1 and 4% of the original dose per hour. The rate of excretion of 2,4,5-T in man is unknown, but it seems to be slower than that of 2,4-D. A man who committed suicide with a mixture of the two compounds had substantial concentrations of 2,4,5-T in all organs analyzed but no 2,4-D in any organ?-'. �-24- Using massive doses it is possible experimentally to exceed the ability of domestic animals to eliminate 2,4,5-T and thereby to produce measurable residues in their tissues. Four or more 250 mg doses of 2,4,5-T given to sheep produced levels of 33 to 113 ppm in fat and 40 to 100 ppm in muscle. The residues were 99% or more in the acid form regardless of whether the acid form or an ester was fed SJ. The Chemical form of the agent, however, may influence its deposition. Oral administration of the propylene glycol or butyl ether esters of 2,4,5-T to yearling cattle for 32 weeks at rates of 0.15 and 0.75 mg/kg/day produced no residues greater than those occasionally found in untreated controls. Subsequently Clark et al., — fed 2,4,5-T, 2,4-D and Silvex (2,4,5-trichlorophenoxy propionic acid) to sheep and cattle at several dietary concentrations for 28 days. Sheep receiving 2000 ppm 2,4,5-T in the diet were found to have muscle tissue residues of 1.0 ppm when treatment was terminated, and no detectable residue o/ 7 days later. Newton and Norris —' analyzed tissues from deer that had ranged over reforested land treated with 2,4,5-T and found essentially no residues. Several factors limit the intake of 2,4,5-T by domestic animals and man following recommended use of the compound, namely, low rate of application and breakdown by plants, animals, photochemical degradation and soil microorganisms. Owing to both the limited nature of prescribed use and the decomposition that occurs in the environment, 2,4,5-T almost never reaches a detectable level in human drinking water or food (see Section I B, pp. 11 and 14). Examination of approximately 11,600 samples of food offered for retail sale in the United States revealed only five �-25- with measurable residues, the highest concentration being 0.29 ppm. The highest level in potable water was 0.00007 ppm . 12 / Fate of TCDD. Piper and Rose —' have reported a preliminary study of the tissue distribution and disposition of C-labeled TCDD administered as a single oral dose of 0.05 mg/kg to male rats. The biological half-time for this dose was approximately 20 days, and fecal excretion accounted for the greater part of the TCDD removal. Three days after administration 3.1% of the total dose per gram was recovered from liver and 3.0% of the total dose per gram was contained in fat. The residual radioactivity in these tissues was not identified and therefore cannot be assumed to be TCDD. The fact that 8.3% of the dose was recovered from 14C02 in expired air indicated that some of the TCDD was completely metabolized. The Dow Chemical Co. has recently provided comparative solubility data on TCDD and p.p'DDT at 24°C, as follows: corn oil lard oil water TCDD 28 44 PPM of Solvent p.p'DDT 86,000 86,000 0.0002 0.001 Although suggesting a petitioning toward fat, these data clearly indicate that, unlike DDT, TCDD is so insoluble in fat that it would not be expected to accumulate in body fat depots in appreciable amounts. It is concluded from the foregoing that: 1) 2,4,5-T is rapidly excreted in all animals studied using doses in the range of those likely to be encountered in the environment; 2) 2,4,5-T is not known to be accumulated in any animal tissues or product used for human food; �-26- 3) 2,4,5-T has been detected in animal tissues or products used for human food very infrequently and then only in minute quantities; 4) limited data indicate that TCDD is also eliminated, at least some by metabolic breakdown, with a half-life of 20 days; and 5) the solubility of TCDD in fat is limited which would preclude appreciable accumulation in body fat. References Cited in Section I C 1. Erne, K., 1966. Distribution and elimination of chlorinated phenoxyacetic acids in animals. 2. Erne, K., 1966. Acta. Vet. Scand., 7:240-256. Animal metabolism of phenoxyaeetic herbicides. Acta. Vet. Scand., _7:264-271. 3. St. John, L.E., D.G. Wagner and D.J. Lisk, 1964. Kuron, Silvex and 2,4,5-T in the dairy cow. Fate of atrazine, J. Dairy Sci., j47:1267-1270. 4. Zielinski, W.L., Jr. and L. Fishbein, 1967. Gas chromatographic measurement of disappearance rates of 2,4-D and 2,4,5-T acids and 2,4-D esters in mice. J. Agr. Food Chem., 15;841-844. 5. Curley, A., 1971. Personal communication to Wayland J. Hayes. 6. Clark, D.E., J.S. Palmer and C.H. Ayala, 1970. Residual and toxicological aspects of 2,4,5-T and an ester in sheep and cattle. Presented at the meeting of the Pesticide Division, American Chemical Society and Chemical Institute of Canada, Toronto, May 28, 1970. 7. Clark, D.E., H.R. Crookshank, R.D. Radeleff and J.S. Palmer, 1971, Tissue residues of chlorophenoxy acid herbicides in cattle and sheep. Am. Chem. Soc. Meeting, April 2, 1971. �-278. Newton, M. and L.A. Norris, 1968. Herbicide residues in blacktail deer from forests treated with 2,4,5-T and atrazine. Western Soc.. Weed Sci., Proceedings pp. 32-34. 9. Corneliussen, P.E., 1969. Pesticide residues in total diet samples. Pest. Monit. J., j2:140-152. (Mar.) 10. Duggan, R.E., H.C. Barry and L.Y. Johnson, 1967. Pesticide residues in total diet samples. Pest. Monit. J., JL:2-12. (Sept.) 11. Martin, R,J. and R.E. Duggan, 1968. Pesticide residues in total die-t samples. Pest. Monit. J.,. JL:11-20. (Mar.) 12. Piper, W.N. and J.Q. Rose, 1971. The excretion and tissue distribution of 2,3,7,8-tetrachlorodibenzo-p-dioxin in the rat. Unpublished report from Dow Chemical Co. dated March 18, 1971. �-28- II. TOXICITY OF 2,4,5-T AND TCDD IN ANIMALS AND MAN Currently available commercial preparations of 2,4,5-T can be characterized as having at least 95% 2,4,5-T with less than 0.5 ppm TCDD and no other toxicologically significant compound. Many earlier studies on the adverse effects of 2,4,5-T employed preparations containing considerably greater concentrations of TCDD than this, and others used 2,4,5-T samples of unspecified purity. Toxicological studies utilizing 2,4,5-T preparations which were not known to conform to the standards suggested above, nevertheless, have some value because any error attributable to larger amounts of TCDD would have been toward the conservative side, that is, would have suggested greater toxicity than if a purer 2,4,5-T had been used. A. Nonteratogenic Toxicity. Of 2,4,5-T. Among the earlier reports of 2,4,5-T toxicity that did not fully identify the composition of the product under investigation were the studies of Drill and Hiratzka— in which oral LD5Q for dogs was estimated to be in excess of 100 rag/kg, and of Rowe 2/ and Hymas— in which the oral LD,-n to various rodents was found to be greater than 350 mg/kg. Drill and Hiratzka found no adverse effects in dogs which were fed 2,4,5-T five times a week for 90 days at dosage levels of 2.5 and 10 mg/kg. Four dogs were treated at a level of 20 mg/kg 2,4,5-T and died at 11, 49, 59 and 75 days after the first dose, Rowe and Hymas reviewed the toxicologic information available on 2,4,5-T at that time, and concluded that the acute lethal oral toxicity, in terms �-29- of LDcQ and-19/20 confidence limits, of 2,4,5-T was for male rats 500 (391-640) mg/kg; for male mice, 389 (245-619); guinea pigs, male and female, 381 (307-472); chicks, male and female, 310, (211-456). The latter authors also used various commercial formulations of the butyl, isopropyl and amyl esters of 2,4,5-T in single oral-dose animal-feeding experiments in rats, chickens and guinea pigs and reported LDc0 levels with 19/20 confidence limits which were all greater than those listed above. They concluded that oral administration of 2,4,5-T could be tolerated without adverse effects in doses only slightly smaller than those which caused toxic effects and stated that this fact demonstrates o/ that 2,4,5-T has a low degree of chronicity. Palmer and Radeleff—' found that the propyl glycol butyl ether ester of 2,4,5-T was lethal to one sheep after 369 daily oral doses of 100 mg/kg and to another sheep after seven doses of 250 mg/kg. A single cow also succumbed to the latter dose. The triethylamine salt of 2,4,5-T caused no observed effect (sheep) after 481 doses of 100 mg/kg/day. The propionic acid butyl ether ester of 2,4,5-T was lethal to a sheep after 11 daily doses of 100 mg/kg orally and lethal to a cow after 29 such doses. Five daily 250 mg/kg oral doses also killed a cow. Fifty mg/kg/day orally had no effect after 73 days. In 1969 an investigation of the carcinogenicity in mice of 120 pesticides and herbicides— ; 2,4,5-T was among the compounds tested which did not cause significant increase in tumors after oral administration. The purity or dioxin content of the sample was not described. This represents the only report of long-term treatment with 2,4,5-T other than the few farm animals mentioned above. The dose was the maximum �-30- tolerated dose (zero mortality) determined with single doses, 6 daily doses, and finally 19 daily doses. The dosage was given by stomach tube at 21.5 rag/kg from the end of the first through the fourth weeks and thereafter it was mixed in the diet at 60 ppm of food and continued until 18 months of age. It is presumed that all animals survived the 18 month test period although this was not stated in the publication. Johnson— has reported acute oral, single dose toxicity studies on commercial 2,4,5-T in which the LD5Q for 2,4,5-T was 500 mg/kg in the rat and 380 mg/kg in the guinea pig. Ninety-day feeding studies with 2,4,5-T containing 0,5 ppm TCDD were recently reported by McCollister and Kociba.— The acid form was administered to groups of 10 male and 10 female rats at 100, 30, 103 and 0 mg/kg/day. No significant adverse effects were observed in the groups receiving doses at or below 30 mg/kg/day, but those receiving 100 mg/kg/day showed a depression of body weight gain, a decrease in food intake and elevated alkaline phosphatase levels. The males showed slightly increased serum .glutamic-pyruvic transaminase levels and slight decreases in red blood cell counts and hemoglobin levels. Histological evidence of toxicity were minor and inconsistant. In an earlier experiment at Dow Chemical Co.—', the mono-, di-, and tripropylene glycol butyl ether esters of 2,4,5-T were administered orally to rats over a similar 90-day period at doses as high as 186 mg of 2,4,5-T acid equivalent per kg per day. At the highest dose and at 62 mg/kg/day of acid equivalent various evidences of toxicity developed, but no adverse manifestations attributable to the agent were detected at dosages of 18.6 or 6.2 mg/kg/day. Q / The Dow Chemical Co.— has prepared an extensive health inventory of 126 manufacturing personnel in an effort to identify adverse effects �-31- of inhaled 2,4,5-T. The inhalation rate of the agent was estimated to be 1.6 to 8.1 rag/day per worker, depending on the work assignment, for periods of up to three years and at total career exposures in excess of 10,000 mg. The survey indicates that no illness was associated with 2,4,5-T intake. Specifically there was no increase in skin ailments or of alkaline phosphatase or SGPT levels as compared with controls having no exposure to 2,4,5-T. The result was entirely different in a plant where the 2,4,5-T produced contained a high proportion of dioxin. The latter plant was 9/ studied by Bleiberg— in 1964 and again six years later by Poland et al.— who also reviewed earlier studies in factories in other countries where TCDD had been a problem. Poland and associates reported on 73 employees whose health was found to be improved compared to that of workers in the plant six years earlier. Eighteen percent of the men had suffered moderate to severe chloracne, the intensity of which correlated significantly with the presence of residual hyperpigmentation, hirsutism, and eye irritation and with a high score on a test indicating a manic reaction. The chloracne did not correlate with job location or duration of employment at the plant or with coproporphrin excretion. One of the men had uroporphyrinuria but, unlike the situation six years earlier, no porphyria could be found. Systemic illness such as may be produced by TCDD was markedly less than that reported in previous studies of 2,4,5-T plants and probably no greater than expected in unexposed men of the same age. Dogs and rats tolerate oral intake of 2,4,5-T at a rate of 10 mg/kg/day or higher without detectable clinical, biochemical, or pathological change. The tolerance limit of people is not known but �-32- no injury was detected in workers with the highest recorded, prolonged exposure in a factory making low-dioxin 2,4,5-T, i.e., 8.1 mg/man/day or about 0.11 mg/kg/day°/. In view of the small and highly infrequent occurrence of residues of 2,4,5-T in human food (see Section IB), it is clear that exposure from this source is too small to measure accurately. Thus, although it is impossible to estimate how much greater the 2,4,5-T exposure of workers is than the exposure of the general population, it is clearly much greater than the corresponding one for DDT—. In fact, exposure to 2,4,5-T is trivial even for persons who daily eat unpolished rice. The very small number of cases in which human irigestion of 2,4,5-T led to clinical illness offer no information on the minimal dosage of the compound that is toxic to man. In animals, however, the toxicity of 2,4,5-T is similar to that of 2,4-D, consequently some information on 2,4-D is of interest. When 2,4-D was investigated as a possible treatment for disseminated coccidiodomycosis, the patient had no sideeffects from 18 intravenous doses during 33 days; each of the last 12 doses in this series was 800 mg (about 15 mg/kg) or more, the last being 2000 mg (about 37 mg/kg). A 19th and final dose of 3600 mg (67 mg/kg) produced mild symptoms—/. Suicidal ingestion of a quantity of 2,4-D as a single dose known to be greater than 6500 mg 13/ (in excess of 90 mg/kg) was fatal— • Butler —' —' has reviewed Fish and Wildlife Service studies of pesticide and herbicide effects on marine organisms. Several 2,4,5-T derivatives were examined (TCDD content was not known). A 96-hour exposure of oysters to the polyglycol butyl ether esters of 2,4,5-T at a concentration of 0.14 ppm in the water caused a 50% decrease in shell �-33- growth rate, with recovery in one week. The 24-hour LD^Q of this ester to juvenile esta"3<jine fish was 0.32 ppm. A concentration of 2,4,5-T acid at 2 ppm caused no decrease in growth after 96 hours. A level of 50 ppm 2,4,5-T was not lethal to juvenile mullet and killifish in 48 hours, and 1 ppm was without effect on shrimp in 48 hours. It is thus apparent that aquatic species tolerate higher concentrations of 2,4,5-T than have been reported in water samples taken from heavily sprayed areas (see Section I B, pp. 11-12). It is concluded from the foregoing that: 1) most species tested can survive a single oral dose in excess of 100 mg/kg and several, excepting the dog, can survive daily treatment for a number of days at this level or higher; 2) dogs die after 11 to 75 doses at the rate of 20 mg/kg/day and rats show toxic signs at repeated daily doses of 100 mg/kg; both species tolerate 10 mg/kg/day without detectable effect; 3) no proven instance of toxicity associated with 2,4,5-T intake in man has been found in industrial or agricultural workers known to have had repeated, relatively high levels of exposure to 2,4,5-T of low dioxin content; and 4) the safety factor for the general population is estimated to be several orders of magnitude greater than that of 2,4,5-T factory workers. Of TCDD. TCDD has been recognized as a contaminant of commercial preparations of 2,4,5-T for several years; however, there has been no extensive study of its toxicity. According to JohnsonM' the acute LDtjQ for TCDD is 0.022-0.045 mg/kg in the rat and 0.0006 mg/kg in the guinea pig. Because of the high potency of this compound in the guinea pig, these experiments were repeated and confirmed by �-34- Dow Chemical Co. Some information on the toxicity of TCDD is available from a study of TCDD teratogenic effect in the rat (see Section II B, p. 44). No evidence of clinical effect on the dams was found at doses of 0.0005 mg/kg/day, although embryotoxicity appeared in litters of females given 0.000125 mg/kg/day. Some vaginal hemorrhage was caused by 0.002 mg/kg/day and 0.008 mg/kg/day caused pallor and debilitation. As far as occupational exposure is concerned, it is clear that any danger of 2,4,5-T formulations resides in their TCDD content. The primary manifestation of industrial TCDD intoxication is chloracne, an easily detected, in fact highly disfiguring, dermatitis. It is significant that this condition has not been a problem in factories producing 2,4,5-T with a low content of TCDD, nor among persons who apply the herbicide as a part of their regular occupation. It is therefore highly unlikely that exposure to traces of TCDD will have any effect on persons who use 2,4,5-T formulations occasionally or who merely encounter possible traces of it in the environment. Data are too limited for a firm conclusion but there is no evidence to suggest that TCDD as a contaminant in 2,4,5-T is likely to be encountered by animal or man in. sufficient dosage to cause toxic reactions. References Cited in Section II A 1. Drill, V. A. and T. Hiratzka, 1953. Toxicity of 2,4-dichlorophenoxyacetic acid and 2,4,5-trichlorophenoxyacetic acid. A Report on Their Acute and Chronic Toxicity in Dogs. AMA Arch. Indust. Hyg. Occup. Med., ^:61-67. �-35- 2. Rowe, V,.K. and T.A. Hymas, 1954. Summary of toxicological Information on 2,4~D and 2,4,5-T type herbicides and an evaluation of the hazards to livestock associated with their use. 3. Palmer, J.S. and R.D. Radeleff, 1964. Am. ,J. Vet. Res., 15:622-629. The toxicologic effects of certain fungicides and herbicides on sheep and cattle. Ann. N.'Y. Acad. Sci., 111:729-736. 4. Innes, J.R.M., B.M. Ulland, M.G. Valeric, L. Petrucelli, L. Fishbein, E.R. Hart, A.J. Pallotta, R.R. Bates, H.L. Falk, J.J. Gart, M. Klein, I. Mitchell and J. Peters, 1969. Bioassay of pesticides and industrial chemicals for tumorigenicity in mice: A preliminary note., J. Nat'l Cancer Inst., .42:1101-1114. 5. McCollister, Susan, B. and R.J. Kociba, Sept. 18, 1970. Results of 90-day dietary feeding study on 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in rats. Dow Chemical Co. Internal report. 6. Johnson, J.E. Paper presented at Symposium of A«*,issaucan Institute of Biological Sciences, Bloomington, Indiana, August 26, 1970. 7. Dow Chemical Co., Internal communication, Nov. 27, 1961. Results of 90-day dietary feeding studies on Dowanol 97B ester 2,4,5-T in rats. 8. Dow Chemical Co., letter with attachment from C.G. Kramer to J.E. Johnson, April 7, 1970 (see Dow Petition). 9. Bleiberg, J., M. Wallen, R. Brodkin and I. Applebaum, 1964. Industrially acquired porphyria. Arch. Derm., 89:793-797. 10. Poland, A.P., D. Smith, G. Metter and P. Fossick, 1971. A health survey of workers in 2,4-D and 2,4,5-T plant, with special attention to chloracne, porphyria cutanea tarda, and psychologic parameters. Arch, Environ. Health, 22:317-327. �-36- 11. Laws, E.R., Jr., A, Curley and F.J. Biros, 1967. Men with intensive occupational exposure to DDT. Arch. Environ. Health, 15:766-775. 12. Seabury, J.H., 1963. Toxicity of 2,4-dichlorophenoxyacetic acid for man and dog. Arch. Environ. Health, 2.:202-2°9- 13. Nielsen, K., B. Kaempe and J. Jensen-Holm, 1965. Fatal poisoning in man by 2,4-dichlorophenoxyacetic acid (2,4-D): of the agent in forensic materials. Determination Acta Pharmacol. Toxicol., j22:224-234. 14. Johnson J.E., 1970. Symposium on Possible Public Health Implications of Widespread use of Herbicides, AIBS Meeting, August 26, 1970. 15. Butler, P.A., 1963. Pesticide-Wildlife studies; A review of fish and wildlife service investigations; Circular 167. Commercial Fisheries Investigations. 16. Butler, P.A., 1964. Pesticide-wildlife studies, 1963; A review of Fish and Wildlife Service investigations during the calendar year, circular 199. Commercial Fisheries Investigations. �-37- B. The Teratogenic Potential of 2,4,5-T 1. Scope of embryotoxicity. Teratology is the science dealing with the causes, mechanisms, and manifestations of deviant structural or functional development. Such deviation can be the result of mutation in which case the defect may be transmitted by heredity, or it may be induced by unfavorable environmental conditons during the developmental period: usually during the formative stages of the embryo, less often during functional maturation of the fetus, and possibly even during the final stages of development postnatally. Many types of adverse factors in the environment have been shown to initiate abnormal development when applied during pregnancy in laboratory animals, including: certain dietary deficiencies (mostly of vitamins); many classes of chemicals, including some drugs; various physical factors such as ionizing radiation, drastic temperature changes, and alterations in atmospheric gases; a few viral infections; some maternal endocrine and metabolic imbalances; and undoubtedly some combinations of these. Relatively few of these experimentally demonstrated teratogenic agents have been shown to be effective in man. High doses of ionizing radiation such as are used in therapy for cancer or emanate from nuclear explosions are well known to be teratogenic when applied during early human pregnancy. Two infectious agents, rubella and cytomegalic viruses, have been clearly implicated. Three types of drugs - thalidomide, folic acid antagonists, and androgenic hormones - have been established as causes of malformations in man and a few others are suspected but are not at this time proven to be teratogenic. Maternal metabolic diseases �-38- such as endemic cretinism, diabetes, phenylketonuria, and adrenal hyperplasia account for a small percentage of human developmental disease. One environmental pollutant, methylmercury, proved to be teratogenic for man when it reacned high concentrations in certain watet in Japan from which fish were eaten as a large part of the diet. Adverse effects on development are difficult to evaluate because they vary greatly in degree and type. Collectively these effects can be designated as embryotoxic because they most often have their inception in the embryo and include such manifestations of toxicity as lethality, teratogenicity, prenatal growth retardation, and postnatal functional deficiencies. Few attempts are made to evaluate functional deficiency except as it may be reflected in postnatal survival data. On the other hand embryolethality, teratogenicity, and growth retardation can under laboratory conditions be readily detected and quantitated. Difficulty is often encountered, however, when all three toxic manifestations are simultaneously evaluated, since the phenomena involved are rarely affected to the same degree by a given embryotoxic agent. Although most chemical substances probably could be shown to be teratogenic under suitable experimental conditions and all could be shown to have some toxic effects when dosage is sufficiently high, some would be more strongly teratogenic, others would be predominantly embryolethal, whereas still others would tend mainly to cause intrauterine growth retardation. While these toxic manifestations vary directly with dosage, they may not show parallel dose-response effects. Any one of the three may begin to appear at a somewhat lower dose than either of the others. Lethality is probably the most variable from one agent to another, sometimes appearing at low doses and increasing slowly as dosage is increased, sometimes �-39- ''appearing abruptly at doses already causing considerable teratogenicity and growth retardation. Teratogenicity is probably the most predictable of the three in' that it usually has an easily demonstrable no-effect range of dosage and a steep dose-response curve once teratogenicity begins. These variations in embryotoxic manifestations are particularly troublesome when it is necessary to establish the highest no-detectableeffect or the lowest effect level of dosage. A level that has no detec- table teratogenic effect may already be in the effect range for lethality or growth retardation. The solution to this dilemma requires either that one form of embryotoxicity be selected as the criterion of interest or that the one showing the lowest effect level arbitrarily be accepted in setting tolerance limits. Such complications have been encountered in attempting to evaluate 2,4,5-T results, particularly in those experiments in which data on all embryotoxic manifestations were not reported. In some experiments only results pertaining to teratogenicity were given and in these cases dose-response evaluation had to be limited accordingly. For others, the Advisory Committee has tried to extrapolate the data in such a way as to approximate a no-effect level, i.e.,, the largest dose at which no increased lethality, teratogenicity, or growth retardation occurred. 2. Data from laboratory animals. In 1964, the National Cancer Institute contracted with Bionetics Research Laboratories to perform screening studies for carcinogenicity and teratogenicity on a number of pesticides and industrial chemicals. The results, released in October 1969, indicated that of the 53 compounds examined, 2,4,5-T in particular showed embryotoxicity in two stocks of mice at a dose of 113 mg/kg/day �-40- when given for several days during organogenesis. Cleft palate, cystic kidneys, intestinal hemorrhage and fetal mortality occurred in higher percentages of treated than of control animals although a clear doseresponse relation was not evident at lower doses. The results have been reviewed elsewhere =J±J and published in summary form _' and therefore require no extensive discussion here. Certain inconsistencies in the data —/—- likewise need no comment because the sample 2,4,5-T used in the Bionetics study is known to have been contaminated with 27 * 8 ppm of TCDD and the results can no longer be considered a valid indication of the teratogenicity of the herbicide. This contaminant itself has since been shown to have teratogenic and embryolethal properties, as will be discussed later. Despite the limitations of the original Bionetics study, it served two useful functions, in: 1) highlighting the possibility that herbicides may cause previously unknown adverse effects on nontarget organisms, including mammals, and 2) emphasizing the need for more thorough safety evaluation of such compounds before they are approved for widespread use. The discovery that the contaminant TCDD was present in the herbicide used in the Bionetics study made it necessary to determine whether the reported teratogenicity was caused by 2,4,5~T or TCDD. Additional studies relating to this question have been completed at the Dow Chemical Company, the Food and Drug Administration, the National Institute for Dental Research, the National Institute of Environmental Health Sciences, the Department of Agriculture Animal Disease and Parasite Research Division, the Food and Drug Directorate of Canada, Bionetics Research Laboratories, and �-41- the Children's Hospital Research Foundation of Cincinnati, on rats, mice, hamsters, rabbits, sheep and rhesus monkeys using samples of 2,4,5-T containing known concentrations of TCDD as well as relatively pure samples of TCDD, These studies are summarized below, species by species and separately for 2,4,5-T and TCDD. Insofar as the original reports permits, data are summarized on maternal toxicity, e.g., death or failure to show normal weight gain during pregnancy; as well as on embryotoxicity and fetal toxicity, e.g., prenatal death teratogenesis, intrauterine growth retardation, and perinatal signs of other toxicity. It is recognized that fetal death, either individual or as whole litters may also reflect maternal toxicity, and therefore may be difficult to interpret. 2,4,5-T in rats. Sprague-Dawley rats at Dow Chemical Co. were fed 1, 3, 6, 12, or 24 mg/kg/day of 2,4,5-T containing 0.5 ppm of TCDD on days 6 through 15 of pregnancy —'—'U . No maternal death or reduced maternal weight gain during pregnancy was noted. There was also no increase in prenatal mortality, only slight impairment of fetal growth in a few cases at the 24 mg/kg dosage, and no malformations. The poor ossification of the 5th sternebra noted in some cases was probably a sign of mild transient retardation of skeletal development and of no known significance. Pregnant rats of the same stock were fed 50 or 100 mg/kg/day of "commercial production grade" 2,4,5-T containing 0.5 ppm TCDD on days 6 through 15 of gestation, or 100 mg/kg/day on days 6 through 10 _/OL/, The only effects observed after the lower dose were intestinal hemorrhage in one of 203 offspring and a slight increase in �-42- frequency of delayed ossification of skull bones. The larger dose produced 83% maternal death and early death (resorption) of the entire litters in most of the surviving pregnant animals. Surviving offspring were reduced in size but had no anomalies except delayed ossification of skull bones, and this retardation was overcome within three weeks after birth, Sprague-Dawley rats at the National Institute of Dental Research —' —' were given orally 60, 80, 100, or 120 mg/kg/day of 2,4,5-T containing 0.4 ppm TCDD over various periods of consecutive days during the middle third of gestation. Maternal toxicity data were not reported. No treatment greatly increased the intrauterine mortality rate and many had no effect. growth retardation was not mentioned, Prenatal Apparently the offspring were examined only for external malformations and those of the oral cavity. Very few with such defects were found (7 of 1500 at susceptible periods). of cleft palate. from females treated A mixture of 2,4,5-T and 2,4-D produced one case To rule out the possibility that the chemical might not be reaching the fetus, millipore filters soaked with 0.05, 0.1, 0.11, or 0.125 mg 2,4,5-T were applied to amniotic sacs on day 12, 13, 14, 15, or 16 of gestation. Of 68 fetuses surviving to the time of examination two had cleft palate, one had a tail defect, four had limb defects, and others were small or edematous. A second study of this type yeilded one possible limb defect and four possible tail defects in 68 survivors. Rats of the FW-49 stock in Germany recently were given 25, 50, 100, or 150 mg/kg/day of 2,4,5-T (containing <C0.02 ppm TCDD) on days 6 through 15 of gestation (cited by Tschirley 12/ —• ) . Macro-and Microscopic examination revealed no signs of teratogenicity even with the highest �-43- dosages. There was an increase in the prenatal mortality beginning at the 50 mg/kg dose and a reduction in the mean fetal weight beginning at the 100 mg/kg dose. Complete details of the study were not given. Charles River rats at the National Institute of Environmental Health 13/14/15/ Sciences — — — received samples of 2,4,5-T CO.5 and 30 ppm TCDD) at the rate of 10 to 80 mg/kg/day orally or subcutaneously on days 6 through 15 of gestation, or 2,4,5-T C^ 0.05 ppm TCDD) at the rate of 150 mg/kg/day subcutaneously on days 14 and 15 of gestation. The 80 mg/kg dose was stated to be the maternal LD, dose but data were not presented. The 80 and 150 mg/kg doses caused a reduction in maternal weight gain and increased prenatal mortality, but fetal weight was unaffected. A low incidence of fetal kidney anomalies was noted, but could not be attributed with .confidence to the treatment. In addition, pregnant females were fed 50 mg/kg of 2,4,5-T (< 0.05 ppm TCDD) and allowed to deliver. The offspring examined periodically for 3 weeks postnatally during which time mortality, weight gain, and general development did not differ from those of control animals, Wistar rats at the Food and Drug Directorate of Canada ~ were fed dosages of 25, 50, 100, and 150 mg/kg/day of 2,4,5-T acid or of 2,4,5-T butyl ester containing <0.5 ppm TCDD on days 6 through 15 of gestation. No apparent adverse effects on pregnant females were noted, but fetal weight was reduced. At the largest dosage there was an apparent increase in the frequency of "spontaneously occurring" skeletal anomalies. The largest dose of the acid form killed 3 of 8 pregnant females and reduced maternal weight gain but lower do'ses were without maternal toxicity. Intrauterine death was increased at 50 mg/kg and was pronounced at larger dosages, at which levels weight of surviving �-44- fetuses was reduced. At the higher doses there was also increased skeletal variations some of which did not occur spontaneously in controls. Postnatal survival of young was not adversely affected by maternal dosage with 100 rag/kg. The 2,4,5-T butyl ester was without effect. The foregoing rat experiments all involved repeated daily treatment of pregnant females with 2,4,5-T. The possibility exists, that owing to maternal homeostatic mechanisms, e.g., inducation or inhibition of metabolic enzymes, the most sensitive teratological test would be one involving a single treatment during early organogenesis. To test this possibility rat experiments were carried out at the Institute of Developmental Research, Children's Hospital Research Foundation of Cincinnati ^-'. Using a sample of 2,4,5-T containing 0.5 ppm of TCDD, groups of pregnant Wistar rats were treated by gavage on day 9 of gestation with doses of 100, 200 or 400 mg/kg in 0.2% carboxymethylcellulose. Day 9 is generally regarded as the time at which the rat embryo is teratogenically most susceptible. Dose Days of mg/kg treatment Control Control 20 100 200 400 none 9 7-13 9 9 9 Whole litters res orbed 0/40 0/45 0/11 0/11 0/11 2/10 Litters continuing to day 20 Total % dead or mean wt.of % survivors implants resorbed survivors malformed 509 558 170 170 156 122 5.4 7.2 8.8 9.0 11.5 25.4 3 . 7 gin 3.8 3.7 3.7 3.8 3.2 1.9 0.8 0.7 1.9 5.1 11.0 Cumulative untreated control over past 4 years. Cumulative vehicle treated control (per gavage) over past 4 years. ^Types of malformations; anophthalmia, microphthalmia, curly or short tail, hydronephrosis, ectopic testes, agnathia. �-45- The data in the accompanying table indicate that a single dose of 100 rag/kg at a highly sensitive time in rat emhryogenesis did not cause an increase in abnormal development or a decrease in intrauterine growth but did cause a slight increase in intrauterine death. This effect was accentuated at higher doses and a moderate increase in malformations above control levels was also noted. Intrauterine growth was affected only at 400 mg/kg, a dose sufficient to cause severe embryotoxicity as evidenced by complete resorption of 2 of the 10 whole lititers. In summary, it appears that rat strains vary considerably in their susceptibility to the embryotoxic effects of 2,4,5-T. A low level of teratogenicity may appear in some strains when repeated dosage exceeds 100 mg/kg/day, or single dosage on day 9 is at 200 to 400 mg/kg of maternal weight. Some increase in intrauterine death and decrease in intrauterine growth, as well as maternal toxicity, was sometimes noted at lower daily dosage, e.g., 50 mg/kg. TCDD in rats. Rats have been treated during pregnancy with TCDD in 18/ appreciable dosage in only two laboratories. At the Dow Chemical Co. ~ pregnant Sprague-Dawley rats received 0.00003, 0.000125, 0.0005, 0.002, or 0.008 mg/kg/day of dioxin (91% TCDD) orally on days 6 through 15 of gestation. Only one maternal death occurred and maternal weight gain was depressed only by the largest doses. Prenatal mortality was greatly increased at the 0.002 mg/kg dosage and all fetuses were killed at the 0.008 mg/kg level. Fetal weight was greatly reduced at 0.002 mg/kg and somewhat reduced at lower doses. tions of the tail and limbs. Only two offspring had possible malforma- Edema and intestinal hemorrhage were observed in some offspring of females treated with 0.000125, 0.0005, or 0.002 mg/kg. 9/ In a second Dow study — pregnant rats of a stock of unstated origin received �-46- by an unstated route 50 mg/kg/day of "pure" 2,4,5-T Cprobably containing 0.05 ppm TCDD) to which was added 0.00001, 0,00003, 0.00006, 0.000125, 0,0005, or 0.001 mg/kg/day of TCDD on days 6 through 15 of gestation. Cleft palate occurred in ten litters, mostly in those receiving the 2,4,5-T plus 0.0005 or 0.001 mg TCDD. The frequency of offspring with cleft palate, as well as procedural details and toxicity were not described. Charles River rats at the National Institute of Environmental Health Sciences — received TCDD subcutaneously 0.0005 mg/kg/day on days 6 through 10 of gestation, or 0.002 mg/kg/day on days 9 and 10 or 13 and 14 of gestation. No malformations or excessive fetal mortality were noted; but various possible kidney anomalies and several instances of intestinal hemorrhage occurred. Thus, TCDD given to pregnant rats caused embryolethality and occasional teratogenicity at doses below the maternal toxic level. 2,4,5-T in mice. Mice of GDI, C57BL/6J and DBA/2J strains received, subscutaneously, 50, 100, 113, 125, or 150 mg/kg/day of 2,4,5-T containing <L, 0.5, or<0.05 ppm TCDD on days 6 through 15 of pregnancy at the 14/ National Institute of Environmental Health Sciences — . No maternal death occurred and maternal weight was depressed only in C57BL mice at the 100 mg/kg dosage. Fetal mortality was increased only in GDI mice at the 150 mg/kg level. Fetal weight was reduced in all three lines of mice at dosages of 100 mg/kg and greater. Cleft palate occurred in low but consistent frequencies in all three lines of mice at doses of 100 mg/kg and more with all three samples of 2,4,5-T. Where sufficient data were available, a dose-response relation for fetal mortality and growth retardation was noted. Paradoxically the frequency of kidney �-47- anomalies, types unspecified, was increased above the low level of background occurrence by the 2,4,5-T containing 0,05 ppm TCDD, but not by the 2,4,5-T containing 0.5 ppm TCDD. In general, these mice showed a low level of teratogenicity at 100 mg/kg/day during embryogenesis, and some embryolethality and decreased fetal weight at lesser doses. Moore 197 found no appreciable difference in teratogenic and embryolethal —' potential between 2,4,5-T as free acid and its butyl, isooctyl and butyl ether esters at approximately molar equivalent dosage in...jnice. Mice of the NIH all-purpose albino stock were given subcutaneously 113 mg/kg/day of 2,4,5-T containing 0.4 ppm TCDD or 113 mg/kg/day of a mixture containing 50% 2,4,5-T and 40% 2,4-D ("Orange") usually on days 6 through 14 of gestation at the National Institute of Dental Research —• . Cleft palate occurred in 9 of 141 offspring, but no data regarding maternal toxicity and other fetal effects were reported. In a recent study made by the Bionetics Research Laboratories, commissioned by Hercules Incorporated, GDI mice were injected subcutaneously on days 6 through 15 of gestation with 100 mg/kg/day of 2,4,5-T supplied by the Dow Chemical Co. and Hercules Inc. No maternal death seems to have occurred and maternal weight gain was unaffected. Intra- uterine mortality was not increased but mean fetal weight was slightly reduced. The only malformation that occurred was cleft palate and its frequency was 11.1% (27/243) with the Dow sample and 1.3% (3/235) with the Hercules sample. Both products had<0.5 ppm TCDD. TCDD in mice. TCDD given to mice at 0.001 or 0.003 mg/kg/day subcutaneously on days 6 through 15 of gestation did not affect fetal mortality, maternal weight gain, or fetal weight, but did produce low frequencies of cleft palate in the three mouse lines used in the �-48- National Institute of Environmental Health Sciences study In one experiment 2,4,5-T (100 rag/kg) and TCDD ( . 0 mg/kg) given 001 together apparently produced no greater frequency of cleft palate than when each was given alone. TCDD greatly increased the background rate S'f. kidney anomalies, especially in C57BL mice. Thus the limited data indicate that TCDD has some teratogenic potential in mice at doses even lower than those causing appreciable intrauterine death. 2,4,5-T in hamsters. Golden hamsters of a commercially obtained stock were treated orally on days 6 through 10 of gestation with 20-100 mg/kg/day of 2,4,5-T from seven sources, at the Food and Drug Administration 20/21/ Four of the samples contained 45, 2.9, 0.5 and 0.1 ppm TCDD, respectively, and three contained no detectable TCDD. on maternal toxicity was not given. Information Fetal mortality was greatly increased by the TCDD-containing 2,4,5-T samples and its frequency was usually directly related to both 2,4,5-T dosage and dioxin content; but it was also moderately high and dose-related after 2,4,5-T containing no detectable dioxin. The mean weight of surviving fetuses was unaffected or only mildly so for the different samples. A low to moderate incidence of gastrointestinal hemorrhage was observed, but this was probably not developmental in origin. Malformations were noted in offspring exposed to 2,4,5-T containing TCDD or not, but their frequency was usually higher after 2,4,5-T containing dioxin than after 2,4,5-T that did not. No malformations were produced by 2,4,5-T alone below the 100 mg/kg dose, whereas all dosages of dioxin-containing 2,4,5-T produced malformations. Very few malformations (cleft palate, 2 cases, and ectopic heart, 1 case) resulted from use of dioxin-containing 2,4,5-T, and only at 100 mg/kg. �-49- The most frequent defects, poorly characterized as "bulging eyes" and "poor head fusion", occurred in low percentage (15.8% and 11.4%, respectively) after 2,4,5-T with or without TCDD. Some apparent discrepancies were present in the calculations of the malformation rates. In addition 150 mg/kg/day of a recrystalized and extracted 2,4,5-T was used 22J and produced a high fetal mortality rate but no malformations. TCDD in hamsters. Hamsters were given dioxin (21% tri, 53% tetra CDD) orally at 0.00013, 0.002 or 0.0091 mg/kg/day on days 6 oo/ through 10 of gestation at the Food and Drug Administration — . Maternal toxicity was not mentioned. Mean fetal weight was reduced only at the two highest dosages. Eye anomalies and prenatal mortality were most frequent at the highest dose. Gastrointestinal hemorrhage was noted at the 0.0005 and 0.002 mg/kg doses. 2,4,5-T in rabbits. New Zealand white rabbits were treated orally with 10, 20, or 40 mg/kg/day of 2,4,5-T containing 1 ppm TCDD on days 6 through 18 of gestation at Dow Chemical Co. — —'• No deaths of pregnant females occurred, and maternal weight gain and fetal mortality and weight were unaffected. No congenital malformations were noted and developmental variations were not increased in frequency. 2,4,5-T in sheep. Sheep were fed 100 mg/kg/day of Dow production 2,4,5-T or of Dow production 2,4,5-T propyleneglycolbutylether ester on days 14 through 36 of pregnancy at the Department of Agriculture Animal 9/ Disease and Parasite Research Division ~ . Two of 19 ewes died on days 35 and 36 of pregnancy, but their fetuses were normal. The other 17 delivered normal offspring at term. 2,4,5-T in rhesus monkeys_. No further details were provided. The Poisons and Pesticides Board of �-50- 23/ Sweden has commissioned a study in pregnant rhesus monkeys — a t doses of 5, 10, 20 and 40 tng/kg given three times per week for 4 weeks between days 20 and 48 of gestation. The sample of 2,4,5-T contained 0.5 ppm of TCDD. Twelve fetuses removed by hysterotomy at 100 days of gestation from females treated with one of the three lower doses (4 pregnancies each dose), were developmentally normal and fell within the range, of weight for untreated fetuses of this age. Two of 4 pregnant females treated with the highest dose yielded normal fetuses and the other 2 have not been hysterotorn!zed at this writing but are still pregnant. One- f emajL treated at this level aborted on day 61 of gestation and the conceptus was too macerated for examination. Abortion rate among untreated females in this colony is about 7% prior to day 100 of gestation. Summarizing available data on exposure of pregnant laboratory animals, it is notable that rats were used most often and under the widest variety of conditions. Pregnant females of several stocks received orally administered low-dioxin-content 2,4,5-T in doses up to 400 mg/kg for durations varying from single treatment to periods including much of embryonic development. In the studies in which dosage was kept below the toxic level for the pregnant females malformed offspring rarely occurred, and at higher dosages only a low teratogenic potential was revealed. Results of rat studies with TCDD were variable. In two of three experiments very few malformed young occurred, but in the third an appreciable incidence of cleft palate was reported. Mice proved to be more susceptible than the other species to the embryotoxic effects of both 2,4,5-T and TCDD. Both compounds produced low to moderate frequencies of cleft palate in all stocks tested but �-51- they did not appear to be more teratogenic when given together than when given separately. Hamster studies with large doses of 2,4,5-T containing no detectable or low concentrations of dioxin (0.1 and 0.5 ppm) produced significant fetal mortality but relatively few instances (14/760 = 1.8%) of maldevelopment. Trials with high-dioxin-content 2,4,5-T (2.9 and 45 ppm) also caused appreciable fetal mortality but moderate frequencies of anomalies (16/209 = 7.6%). Based on these data jL_t can be concluded that: 1) doses of low- dioxin-content 2,4,5-T and of TCDD below the level producing maternal toxlcity were without significant effect on prenatal development, producing little or no embryotoxicity in, rats, rabbits, hamsters, sheep, and rhesus monkeys, and 2) these chemicals were more embryotoxic in mice, producing a low to moderate frequency of a specific malformation, cleft palate. The significance of the finding that TCDD in mice increased certain anomalies of the kidney, which occurred in low frequency in controls, can only be resolved by further investigation. 3. Human exposure during pregnancy. Reports have appeared in the news media that the use of 2,4,5-T was associated with an increased occurrence of congenital malformations and/or stillbirths in human beings in Vietnam; Globe, Arizona; and Sweden. Vietnam. Because of the increased use of several defoliating chemicals by the United States Military in South Vietnam during the past several years, particular concern was aroused by the reports in Vietnamese newspapers between June 26 and July 5, 1969 of human birth defects attributed to these chemicals. Two surveys have been undertaken to evaluate the situation. One was conducted by Dr. R. T. Cutting, U. S. �-52- Army Medical Research Team (Walter Reed Army Institute of Research), Dr. Tran Hun Phuoc, Ministry of Health, Government of the Republic of Vietnam, and three collaborators from the Military Assistance Command, 24/ Vietnam. A report was issued in December 1970 — and will be referred to here as the Army report. A second survey was recently made by the Herbicide Assessment Commission (HAG) of the American Association for the Advancement of Science, consisting of Drs. M. S. Meselson, A. H. O c IO£ / Lesting and J. D. Constable The Army study surveyed obstetrical records mostly for the years 1960-69 of 22 provincial, district, and maternity hospitals in 18 cities and other areas in various geographical localities. In most hospitals the records consisted of daily summary ledgers, prepared by the chief midwives, and contained such relevant information as the age and parity of the mothers and the sex, weight, and general condition at birth of the babies. Space was provided for additional remarks concerning maternal or infant complications. In three hospitals such ledgers were not kept but instead individual records were available. In the hospital yielding the largest number of births, the Tu-Du Maternity Hospital in Saigon, as system of automatic data processing existed, which provided for separate recording of numerous categories of malformations. Almost half a million births were included in cumulative records, and the overall recorded stillbirth and congenital malformation rates for the entire period were found to be 33.7 and 4.9 per 1000 livebirths, respectively. Attempts were made to analyze the information by geograph- ical area, by year, and by intensity of herbicide spraying. can be summarized as follows. The findings (1) In four geographical regions - capital, �-53- coastal, interior, and delta - the rates per 1000 livebirths of stillbirth and congenital malformation were 32.5 and 5.8, respectively, in the capital area, and 36.7 and 2.9 in the three remaining areas. The differences in these rates may be attributable to better maternal and neonatal care, or to more competent or thorough examination for congenital malformations in the capital area. (2) The rates for stillbirths de- clined and for congenital malformations remained unchanged during this 10-year period. (3) The only differences in these rates between the years 1960-65 and 1966-69, periods of relatively light and heavy defoliant spraying, respectively, was a downward trend (from 36.1 to 32.0 for stillbirths, and from 5.5 to 4.5 for congenital malformations). (4) There were no consistent differences between heavily and lightly defoliantsprayed areas. For the most part, however, the possibility of meaningful interpretations of the results of the Army study were precluded by their several limitations. First, it is obvious that only a fraction of the total births that occurred during these years were included in the records examined by the survey team. The report states that "RVN [Republic of Vietnam] officials estimate that currently only 70% of all births are reported to the MOH [Ministry of Health]" (emphasis added). The«New York Times Encyclopedic Almanac for 1971 (p. 877) gives the estimated population of South Vietnam for 1970 at 18 million and the birth rate as 3542 per 1000 population, which would yield between 630,000 and 750,000 27/ births in 1970 — . The last complete year for which records were examined by the Army survey, 1969, yielded a total of 87,153 births. Also the births that were included in the Army survey were far �-54- from evenly distributed throughout the country, the three capital-area hospitals contributing over 67% of the total. In addition, the Chinese, 211 who comprise a significant fraction of the population (over one million)—- , were probably completely omitted since, as was stated by the Army report, they did not attend the hospitals surveyed. Finally, any hope of relating the results to variations in the degree or geographical region of herbicide spraying was frustrated by a number of factors. For example, changes in the local practices of referring difficult obstetrical cases to provincial hospitals, determined by availability of trained personnel in the centers, and increasing with gradual improvement in transportation and security, probably greatly influenced stillbirth and malformation rates in •specific hospitals. Probably most significant was the fact that populations most heavily exposed to 2,4,5-T were those most likely to be underrepresented in the Army survey or to be inadequately dealt with when recorded. Thus, as the HAG report stated, the bulk of 2,4,5-T used in Vietnam was sprayed in relatively remote and sparsely populated areas; the population directly exposed to 2,4,5-T probably did not exceed 5% and may have been 1% or less of the total population of Vietnam; and very likely a significant proportion of the exposed population consisted of Montagnard people, whose births usually did not occur in hospitals and rarely were included in medical records or statistics. It is equally probable that other remote and lightly populated areas were similarly underrepresented and incompletely recorded. The Army survey noted that during 1960-69 there was a countrywide downward trend in the stillbirth rate. But, as was pointed out in the �-55- HAC report, this was heavily influenced by data from the capital area, in which 67.8% of all the surveyed livebirths occurred, and which generally experienced little or no exposure to 2,4,5-T. Deducting the capital area data and considering only data from the other parts of the country apparently reverses the trend, giving stillbirth and malformation rates for 1960-65 (years of no or light spraying) and 1966-69 (years of heavy spraying) of 31.9 and 2.3, and 38.4 and 3.1, respectively. This would seem to indicate that in the remoter areas, where exposure could have been intense, stillbirth and malformation rates increased during years when spraying was heavy. A possible explanation for these apparent differences was provided by the HAC report, in noting that more complete recording and increased referral of difficult pregnancies from the countryside to the provincial hospitals occurred in these years. A more likely explanation, however, is that in recent years, as a larger and larger proportion of births was registered (e.g., number recorded in noncapital areas in 1960-65 was 37,951; in 1966-69, 113,358) a larger proportion of stillbirths was ascertained and a more complete examination for and/or recording of congenital malformations was made. Particular attention was directed by the HAC reports &o the records for the Tay Ninh Provincial Hospital, because although "the total number of directly exposed Vietnamese to 2,4,5-T is* probably low, the northern portion of Tay Ninh has been heavily defoliated and the rivers draining the areas of defoliation run through the remainder of the province and are a source of fish for some of the population." Examining records that were apparently not available to the. Army survey, the HAC found that �-56- in 1968-69 the stillbirth rate recorded at the Tay Ninh City Provincial Hospital was 68.5, which they believed to be a higher rate than that found anywhere else by the Army survey. Although this is true, it should be noted that in two provincial hospitals, Qui Nhon, for which records only for 1966-69 were available, and Da Lat (nonpaying patients) during 1960-65, the stillbirth rates were not far below this, being 62.7 and 61.4, respectively. The HAG also discovered how unreliable the records were regarding congenital malformations, since they noted that not a single malformation was recorded for the 2551 births in 1969 in the Tay Ninh Provincial Hospital, and on questioning the midwives it was learned that although a fair number of deformities had been seen none were reported. Another hospital, at Vung Tau, during most of 1968-70 reported no congenital malformations in 6198 births and a much lower stillbirth rate than did the Tay Ninh Hospital, yet it closely bordered and included in its referral area a zone of intense defoliation. A further point needing critical scrutiny is the finding by the HAG of an apparent increased prevalence of children with spina bifida and isolated cleft palate among admissions to the Saigon Children's Hospital, the former increasing from 0.7% in 1959-66 to 2.1% in 1967-68, and the latter from 0.5% in 1959-65 to 2.6% in 1966-68. It should be emphasized that the figures do not pertain to- incidence at birth, but to the percentage of malformed children admitted to this Hospital some time after birth for operative care. It should also be stated that at least 77.5% of all the admissions in 1959-69 came from Saigon or nearby areas in which defoliation was not practiced. Again the most lilcely explanation �-57- of the apparent sudden rise in prevalence of these two malformations is more thorough examination and increased referral for surgical repair. Supporting this probability is the fact, noted by the Army Report, that the frequency of congenital malformations recorded in the capital area hospitals was much higher (although it varied greatly among the three hospitals) than in the remainder of the country, a fact in turn attributable to availability of more complete and competent medical services and personnel in the former than in the latter. • Summarizing the Vietnam data on human embryotoxicity, it can be said that (1) the sample of births surveyed was from year to year a variable but usually very small fraction of the total number, (2) it was quite unrepresentative of the geographic and ethnic distributions, (3) the heavily sprayed and otherwise exposed areas were greatly underrepresented, and (4) the birth records were not trustworthy and, therefore, the rates of stillbirth, and especially of congenital malformation, derived from them were equally unreliable. For example, the overall congenital malformation rate found in South Vietnam, 4.91 per 1000 livebirths, is about half of what was reported in other studies in various 24/ parts of Asia — , and possibly a quarter of what might actually exist at term. A further indication that the newborn children were not carefully examined is tlie absence of Down's syndrome in the list of specific malformations compiled by the Army survey, despite the fact- that some Oriental populations have been reported to have an incidence of this condition not 28/ unlike that in Western populations — . Finally there is, and can be, no precise knowledge or reasonable approximation of the exposure to 2,4,5-T experienced by pregnant �-58- Vietnaraese women, Including what amounts they ingested or absorbed and when this may have occurred during pregnancey. Thus, any attempt to relate birth defects or stillbirths to herbicide exposure is predestined to failure. It can only be concluded that the birth records that have been surveyed, and probably any that will be surveyed in the future, for South Vietnam for the period 1960-1970 cannot answer positively the questions about possible adverse prenatal effects following human exposure to 2,4,5-T. It must be emphasized, however, that the searches that have been made almost certainly would have revealed any marked increase in the incidence of birth defects or the introduction of a striking defect such as that produced by thalidomide. In spite of considerable effort, no such occurrences were found. 29/ Globe, Arizona was another site of human exposure — . The herb- icides used in the Kellner Canyon-Russell Gulch spray project near Globe were, in 1965 and 1966 the isooctyl esters of 2,4-D and 2,4,5-T, in 1968 an ester of Silvex (2,4,5-TP), and in 1969 about 97% Silvex (3680 Ib) and almost 3% 2,4,5-T esters (Hercules Co., 30 gal.). The reports of harmful effects to animals and people from the spraying began during and after the 1969 spraying. Those concerning possible reproductive and embryonic effects consisted of two miscarriages by a woman, one in April and the other in December 1969; a number of stillbirths of kids; and one miscarriage in a goat. Two other alleged cases consisted of a deformed goat approximately 5 years old, and therefore born before any herbicide spraying in the area (incidentally the defects were not of developmental origin), and a chicken with a slipped tendon which was incubated 4 miles from the sprayed area and after the spraying occurred in 1969. In all likelihood none of these reported effects was due to the sprayings. Competent �-59- medical and agricultural experts have been unable to find evidence of adverse effects on either human or animal reproduction that could be attributed to the defoliants applied during the Kellner Canyon-Russell Gulch spray project. Swedish Lapland. Swedish government defoliation projects to improve the quality of forests in Lapland have been associated in the public press with the occurrence of human malformations and abortion among reindeer. The chlorophenoxy acids 2,4-D and 2,4,5-T were used in routine fashion for a number of years without reports of untoward effects until the spring of 1970 when several instances of unexplained death and abortion among reindeer were attributed to use of these compounds. A group of scientific experts has investigated these claims 30 / for the National Poisons and Pesticides Board — and has failed to find a substantial basis for relating the toxic manifestations in these animals to ingestion of herbicides. Subsequently two instances of con- genital malformations in human infants have been attributed to alleged exposure of pregnant women during application of the herbicides. Highly competent medical scientists at the Institute of Hygiene and the Teratological Laboratories of the Karolinska Institute of Stockholm and at the Institute of Human Genetics at Mllnster, Germany have beeh unable to find temporal or clinical evidence to suggest that the occurrence of these human birth defects was more than coincidentally related to defoliating operations in Sweden. �-60- References Cited in Section II B 1. Report of the Secretary's Commission on Pesticides and their Relationship to Environmental Health. U.S. Department of Health, Education, and Welfare, Washington, D.C. 2. 1969. Report on 2,4,5-T of the Panel on Herbicides of the Office of Science and Technology, April 1971. 3. Courtney, K.D., D.W. Gaylor, M.D. Hogan, H.L. Falk, R. R. Bates, and I. Mitchell, 1970. Teratogenic evaluation of 2,4,5-T. Science 168;864-866. 4. Klingman letter to DuBridge, December 22, 1969. 2,4,5-T Advisory Committee Exhibit 5. 5. Emerson, J.L., D.J. Thompson, C.G. Gerbig and V.B« Robinson, 1970. Teratogenic study of 2,4,5-trichlorophenoxyacetic acid in the rat. Toxic. Appl. Pharmacol., JL7:317 (abstract). 6. Emerson, J.L., D.J, Thompson, R.J. Strebing, C.G. Gerbig and V.B. Robinson, 1971. Teratogenic studies of 2,4,5-trichloro- phenoxyacetic acid in the rat and rabbit. Food Cosmet. Toxicol., in press. 7. Thompson, D.J., J.L. Emerson and G.L. Sparchu, 1971. Study of the effects of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) on rat and rabbit fetal development. Teratology, in press. 8. Sparschu, G.L., F.L. Dunn, R.W. Lisowe and V.K. Rowe, 1971. Study of the effects of high levels of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) on rat fetal development. Unpublished study. �-619. Johnson, J. E., 1970. The public health implications of widespread use of the phenoxy herbicides and picloram. Presented at the Symposium on Possible Public Health Implications of Widespread Use of Pesticides, American Institute of Biological Sciences, Bloomington, Indiana, August 26, 1970. 10. King, C. T. G., 1971. Teratogenicity studies of 2,4,5-T and 2,4-D. Unpublished report, February 25, 1971. 11. King, C. T. G., E. A. Horigan, and A. L. Wilk, 1971. Screening of the herbicides 2,4,5-T and 2,4-D for cleft palate production. Teratology, in press. 12. Tschirley, F. H., 1971. 2,4,5-T. Report on status of knowledge regarding Submitted by the USDA to the EPA, March 5, 1971. 2,4,5-T Advisory Committee AE-20. 13. 2,4,5-T Advisory Committee Exhibits I-13a, 1-14, and 1-15. 14. Courtney, K. D. and J. A. Moore, 1971. 2,4,5-T and tetrachlorodioxin. Teratology studies with Submitted to Toxic. Appl. Pharmacol. 15. Moore, J. A. and K. D. Courtney, 1971. Teratology studies with the trichlorophenoxyacid herbicides 2,4,5-T and Silvex. Teratology, in press. 16. Khera, K. S., B. L. Huston and W. P. McKinley, 1971. Pre- and postnatal studies on 2,4,5-T, 2,4-D, and derivatives in Wistar rats. Toxic. Appl. Pharmacol., in press. 17. Wilson, J. G., 1971. Unpublished data. 18. Sparschu, G. L., F. L. Dunn and V. K. Rowe, 1970. Teratogenic study of 2,3,7,8~tetrachlorodibenzo-p~dioxin in the rat. Toxic. Appl. Pharmacol., 17:317 (abst.). �-62- 19. Moore, J. A., 1971. Personal communication to 2,4,5-T Advisory Committee. 20. Collins, T. F. X., and C. H. Williams, 1971. with 2,4,5-T and 2,4-D in the hamster. Teratology, in press. 21. Collins, T. F. X., and C. H. Williams, 1971. with 2,4,5-T and 2,4-D in the hamster. Teratogenic studies Teratogenic studies Unpublished studies. 2,4,5-T Advisory Committee AE-16. 22. Effects of 2,4,5-T on Man and the Environment. Hearings before the Subcommittee on Energy, National Resources, and the Environment of the Committee on Commerce, U. S. Senate, April 7 and 15, 1970. Serial 91-60, p. 354. 23. Wilson, J. G. Preliminary report submitted to Swedish Poisons and Pesticides Board, April 19, 1971. 24. Cutting, R. T., T. H. Phuoc, J. M. Ballo, M. W. Benenson, and C. H. Evans. 1970. Congenital malformations, hydatidiform moles, and stillbirths in the Republic of Vietnam 1960-1969. Govt. Printing Office, Washington, D. C. 25. Meselson, M. S., A. H. Westing and J. D. Constable, 1970. Background Material Relevant to Presentations at the 1970 Annual Meeting of the AAAS. Herbicide Assessment Commission of the American Association for the Advancement of Science. Revised January 14, 1971. 26. Summary of presentations by the Herbicide Assessment Commission of the American Association for the Advancement of Science, Chicago, Illinois, December 29, 1970. 27. Foster, L., and M. Harth, eds., 1971. The New York Times Encyclo- pedic Almanac 1971. New York Times, New York. �-63- 28. Kikuchi, Y., H. Oishi, A. Tonomura, K. Yamada, Y. Tanaka, T. Jurita and E. Matsunaga, 1969. Translocation Down's syndrome in Japan: age. 29. its frequency, mutation rate of translocations and parental Jap. J. Human Genet., 14:93-106. Binns, W., C. Cueto, B. C. Eliason, H. E. Heggestad, G. H. Hepting, P. F. Sand, R. F. Stephes, and F. H. Tschirley, 1970. of Spray Project near Globe, Arizona. February 1970. Investigation Investigation Conducted 2,4,5-T Advisory Committee AE-15. 30. Rapport frlm en expertgrupp, 1971. Fenoxisyror, granskuing av aktuell information, Giftnamnden, Stockholm. �-64- GENERAL CONCLUSIONS The Advisory Committee on 2,4,5-T has accepted as its primary objective the evaluation of hazards to human reproduction of continued use, under appropriate regulations, of the herbicide 2,4,5-T. Toward this end it has examined all available information pertinent to a scientific consideration of the subject. The level of human exposure depends on rate of application of the herbicide, balanced against the rate at which it is removed from the environment. Current patterns of usage of 2,4,5-T and its known fate in various compartments of the environment, including the plant and animal foods of man, are such that any accumulation that might constitute a hazard to any aspect of human health is highly unlikely. Special note has been taken of the toxic contaminant TCDD. .The limited data now available indicate that this dioxin is not as rapidly degraded in the environment as is 2,4,5-T, but modern methods for the manufacture of the herbicide are capable of routinely producing a product with such a low level of contamination as to eliminate the likelihood of human toxicity from exposure to TCDD. Manufacturing standards must, however, be subject to continued monitoring. Much of the general toxicity attributed to 2,4,5~T in the past now appears to have been caused by the contaminant TCDD. The herbicide when essentially free of this contaminant, e.g. 1 ppm, has relatively low toxicity for all animal forms in which it has been tested. Particular attention was given to the teratogenic potential of �-65- both 2,4,5-T and TCDD. Acceptable data are now available on the embryotoxicity of 2,4,5-T in 6 mammalian species, mouse, rat, hamster, rabbit, sheep and rhesus monkey. None of these showed adverse effects at dosage of 40 mg/kg/day of maternal weight. The mouse appears to be more sensitive than the other forms studied in that it shows a low level of teratogenicity (cleft palate) at 100 mg/kg/day given throughout organogenesis, whereas hamster and rat required higher dosage to obtain comparable effects. It is likely that all species could be caused to show some embryotoxicity if 2,4,5-T dosage were raised high enough, a fact already well known for many prevalent environmental chemicals such as aspirin, caffein, nicotine and organic mercury. The dioxin contaminant TCDD also has been shown to have a low teratogenic potential at doses in excess of 0.001 mg/kg, but this dosage level is virtually impossible with currently produced 2,4,5-T. No evidence has been found of significant potentiative interaction between 2,4,5-T and TCDD. No evidence has been found of adverse effects on human reproduction in three separate locations, namely Vietnam; Globe, Arizona; and Sweden, where pregnant women have allegedly been exposed to high levels of 2,4,5-T. On the basis of these observations, it is concluded that, as presently produced and as applied according to regulations in force prior to April 1970, 2,4,5-T represents no hazard to human reproduction. �-66RECOMMENDATIONS The Advisory Committee on 2,4,5-T after careful consideration of available information on potential hazards to man, -particularly as regards reproductive functions, of continued, regulated use of 2,4,5-T, recommends the following: 1. That registration for use of 2,4,5-trichlorophenoxyacetic acid and its esters be restored to the status existing prior to April 1970, with the following 2. exceptions. That certain specific limitations and qualifications be added to the previously existing registration, as follows: a. A permissible residue or not more than 0.1 ppm of 2,4,5-T on the edible parts of food products and in potable water for human consumption be accepted. It is recognized that very few foods tested to date have contained this level of residue, but it is probable that some of the reports of no residue in the past were due to limited sensitivity of the analytical method. In view of recent and future advances in methodology, which tend to make zero residues of anything increasingly unlikely, a more realistic policy would be the setting of safe tolerance limits at this time. b. A limit of 0.5 ppm of contamination with 2,3,7,8- tetrachlorodibenzo-p-dioxin be set for existing inventories of 2,4,5-T, except as specified in item c. below, and a limit of 0.1 ppm of contamination with this dioxin be established in all future production of 2,4,5-T. Surveillance should be maintained by requiring that a manufacturer submit a reference sample and a certified analysis of each future production lot to the Environmental Protection Agency. �•67- c. All formulations to be used around the home and in recreational areas as of present date should be limited to 0.1 ppm of the dioxin, TCDD, and also should bear a conspicuous warning, e.g., "This compound may be dangerous to pregnant women and animals and its use must be such as to reduce the possibility of exposure to an absolute minimum". 3. That existing deficiencies in information relative to possible accumulation in the soil and possible magnification in the food chain of the dioxin TCDD be rectified by specific research directed to this end, with these questions to be subjected to scientific review within three years of the present date and yearly thereafter until these questions are resolved. 4. That additional post-registration monitoring for adverse effects of agricultural chemicals be established, to include both surveillance for such effects in man and domestic and wild animals, as well as consideration of the applicability of new methodology that may be evolved for specialized testing, e.g., for carcinogenesis, mutagenesis or teratogenesis. Date: May 7, 1971 Respectfully / submitted, James G. Wilson, Ph.D. �-68- Objections to and Modification of the Final Report and Recommendations of the 2,^,5-T Advisory Committee The report by the 2,U,5-T Advisory Committee is basically an accurate statement of the present state of information; however, it falls short of being completely fair in its evaluation of the evidence on which conclusions are based. It is true that considerable uncertainty exists about the tera- togenic potential of 2,^,5-T (and of its impurities) especially for the small doses at which man may make effective contact with this suostance. On the other hand, the report is overoptimistic in assessing the implications of data so that it may well underestimate what dangers may lurk in the unrestricted use of 2,H,5-T. Particularly: The data do not necessarily justify a conclusion that there is a level at which TCDD is not teratogenic. There is an unjustified certainty that Vietnam birth records do not show teratogenic effects. The report fails to consider the consequences of the (admitted) uncertainty about the fate of TCDD in the food chain and in tissue. The report does not weigh risk vs. benefits, as it was charged to do. The report presumes to lecture the scientific community on the wisdom of instituting a "permissible residue" of substances thought to be teratogenic. The report is overoptimistic in believing that recommendations for needed research will be followed by industry or by public agencies once a decision has been rendered to restore 2,lt,5-T to unrestricted use. �-69We can only conclude that the Surgeon General was justified in feeling that a prudent course of action must be based on the decision that exposure to this herbicide may present an imminent hazard to women of childbearing age. Hence, we can only recommend that the registration of 2,l|,5-T be suspended and/or cancelled for use around the home, recreation areas, and similar sites and on all crops intended for human consumption. However, the use of 2,U,5-T may be permitted under certain conditions for uses in forestration and rights-of-way providing: 1. That the limit be set of 0.1 ppm of contamination with 2,3,7,8tetrachlorodibenzo-p-dioxin for all future production of 2,lj,5-T. (However, the use of present inventories may be permitted until used up providing the amount of contaminant in them does not exceed .5 ppm of the dioxin TCDD.) 2. That 2,^,5-T be applied no more often than once a year at any one site. 3. That 2,lj,5-T be applied with proper caution so that it will not contaminate other areas where it may come into human contact. We also recommend that this action be reviewed again when the existing deficiencies in information relative to possible accumulation in the soil and possible magnification in the food chain of the dioxin TCDD have been rectified by specific research directed toward that end. It is always difficult to make decisions in the face of uncertainty. insufficient data makes the work of the committee very difficult. The The fact that ours is the view of the minority ought to strengthen the impression that the committee labored honestly and conscientiously to deduce the best recommendations from a confused aggregate of observations. c- /) sv us-~ 5/5/71 l^s i—? i Theodor D. Sterling �-70Additional Comments It Is- Hot _Quite Certain .at What Dpje TCDD Has Mo Effect The report gives the impression that 2,^,5-T shows a teratogerxic effect uniformly at high doses only. One reason for that impression is that most investigations concentrate on doses of 100 mg/kg or more so that data are lacking to a large extent on how much of teratogenic effects could show up at smaller doses. Yet, there are a number of studies that do show definite effects for doses of less than 100 mg/kg of weight.* Also, the dose effect of 2,H,5-T depends largely on its impurities, especially on TCDD. The experiments which provide the basic animal data and the analysis of these data unfortunately were not done with the sophistication necessary to throw light on the effect of 2,H,5-T and TCDD at very low doses. Many of the reports presented no more than tables of group means, and some even presented pages and pages of undigested numbers on individual observations. It is difficult to draw any final and firm conclusion from data such as these. Nevertheless, there are sufficient instances where teratogenic * For example, on rabbits increased resorption and diminished fetal weight reported by Emerson, J. L., Thompson, D. J,, Gerbig, C. G., and Robinson, V. B.: Teratogenic Study of 2,^,5-Trichlorpphenpxyacetie Acid in the Rabbit, The Dow Chemical Co., Zionsville, Indiana. A number of instances are cited by Epstein, S. S., of the Children's Cancer Research Foundation, Inc. and Harvard Medical School, Boston, Mass., lt/lV70, Subject: Teratogenic effects of 2,^,5-T formulations. Another example is the study on hamsters by Courtney, K. D. , Moore, J. A., Gaylor, D. W., Hogen, M, D., Falk, H. L.: Summary Teratogen Study NIEHS. �-71properties have been observed at lower doses than 100 rag/kg so that the question whether there is a zero effect for some dose is not easily answered. A case in point is the data included in this report by the chairman of the committee. The experiment provides for doses of 100, 200, and ^00 mg/kg but only tests at one single low dose, that of 20 mg/kg, although the effect of a dose at this low level is of utmost importance. Also, there are no control animals. Cumulative experience with untreated controls over the past four years and cumulative vehicle treated controls (per gavage) over the past four years are used as controls. Given oxir knowledge of variation in experiments, it is difficult to understand why this important experiment was performed without a concurrent control. Yet, per cent dead or resorbed fetuses show a trend toward lower dose which is still detectable at 20 mg/kg. (Whether or not we think of this effect as large or small will depend on whether or not we are willing to accept Control 1. or Control 2. of that Study.) Taking these factors into consideration, it becomes difficult to see how the report can conclude that "doses of low-dioxin-content 2,H,5-T and of TCDD below the level producing maternal toxicity were without significant effect on prenatal development producing little or no embryo-toxicity in rats, rabbits, hamsters, sheep, and rhesus monkeys" (page 50, Final Draft). If anything, the conclusion ought to have read that, despite the small amount of data present, some of it does point to teratogenicity at lower doses. The Uncertainty About the Vietnam Human Data Does Mot Mean These Data Show No Effects pf___2,U',5-T on Stillbirth and Malformation 2,^,5-T was used extensively in Vietnam for defoliation. Unfortunately, birth records show a confused and confusing picture of what happened to malformation in Vietnam during the years in which defoliation efforts increased �-72- and how stillbirth rates compare between regions that are heavily defoliated and regions that are not. The Army survey notes that during 1966 to 1969 there was a countrywide downward trend in the stillbirth rate. But the HAC report points out that this conclusion was heavily influenced by data from the capitol area in which 67.8 per cent of all live births surveyed occurred and which, in addition, generally experienced little or no exposure to 2,1*,5-T. Deducting the capitol area data and considering only that from other parts of the country, reverses the trend and results in lower stillbirth and malformation rates for 1960-65 (years of no or light spray) than for 1966-69 (years of heavy spraying). Also, HAC found that the 1968-69 stillbirth rates recorded at Tay Ninh City Provincial Hospital, a hospital which was in a region heavily defoliated and through which rivers draining areas of defoliation run, had a recorded stillbirth rate of 68.5, which they believe to be higher than that found anywhere else. The 2,U,5-T Advisory Committee report goes into the unreliability of all the human data that comes from Vietnam in great detail. It is true that the instances cited might easily have created a spurious impression of an increased stillbirth rate for the defoliated regions or periods. the opposite might be just as true. However, Factors could just as easily have worked to hide a large stillbirth rate than to spuriously create one. If we already speculate, we might just as easily speculate the other way. Thus, the best we can say is that these data do not definitely show an effect of defoliation. However, they do show an effect which has to be explained away. It is up to the committee to register our doubts, but it is unseemly to spend page after page denying the reality of the Vietnam observation in the face of the careful report by a select committee of the American Association for the Advancement of Science. �_73~ The Report Fails to Consider the Uncertainty About the Fate of TGDP It is not possible to produce 2,H,5-T without impurities, especially the dioxin TCDD. These impurities have been shown to be toxic and teratogenic in the extreme. (In fact, the recommendations of the report to restrict the permissible level of TCDD in 2,lj,5-T and to monitor this restriction is in recognition of its hazard.) While 2,if,5-T is quickly eliminated from the soil by biological and other actions, the same cannot be said of TCDD. The report notes that TCDD might accumulate in the soil from one year to the next. There is also evidence that a small amount of the soil's TCDD is absorbed by plants. But there is no information on the concentration of TCDD in the food chain at this level, nor is there information as to what extent TCDD may be stored by animal tissues. Again, the report speculates that TCDD is not stored to a significant extent because it is not easily soluble in oils. However, may it not be stored by other tissues besides fat, and, in fact, may it not be stored more by animal fatty cells than in oils? (There is some evidence that TCDD, when digested, finds its way to every tissue in the body.) There is no question but that some doubts exist in the minds of the committee on this point. The recommendations acknowledge these doubts and ask that the deficiency in information relative to possible accumulation in the soil and possible magnification in the food chain of the dioxin TCDD be rectified by specific research directed to this end, with this question to be subjected to scientific review within three years of the present date and yearly thereafter until these questions are resolved (Section 3 of Final Draft Recommendations). �-74We find it difficult to go along with this reasoning. After recent experience with DDT and with mercury, it would be reckless to leave such questions in abeyance while approving the unrestricted use of 2,U,5-T. Nothing would be lost by waiting two or three years while this question can be settled. On the other hand, a great deal of damage may be created if the committee restores 2,H,5-T to its normal use while hoping that further research will justify our confidence in having made a correct guess. Moreover, the restriction of 2,^,5-T from regular use would work as a powerful motive, spurring industry and concerned government agencies to seek to settle this important question by initiating appropriate studies. Yet, at the same time, the use of 2,lf,5-T could be maintained in all those instances where contamination of food or people would be unlikely. Considering the Risk/Benefit Equation A curious situation emerges in evaluating the benefit of 2,^,5-T. It is apparently of major value in its nonfarm uses, especially for forestry and road clearance, where it can be applied sparingly and with a great deal of expertise. Also, in forestration 2,U,5-T may be reapplied only every few years. The other uses in or near food crops and around the home represent less frequent areas of application but may expose very large numbers of individuals to 2,^,5-T, to its impurities, and to its residues. Thus, it is not true that all uses of 2,lt,5-T are equivalently beneficial. Many of the nonfarm uses of 2,1*,5~T clearly have national benefit. On the other hand, the use of 2,H,5-T for the growing of crops, especially rice, is basically of benefit to a few farm industries because it increases the yield per acre of cultivated ground. Since there are available many acres that are not now cultivated, there does not appear to be a national �-75urgency to support that limited use of 2,U,5-T until important questions about buildup of TCDD have been settled. Similarly, the use of 2,U,5-T for grazing land is of relatively small benefit for a small number of people. Finally, although the use of 2,lj,5-T around the house may be thought of as of national importance, adequate alternate means for home gardening do exist, so that it may be best to avoid for the moment the possible risk of direct contact with man. Theodor D. Sterling 5/5/71 �-76- LIST OF PERSONS CONFERRING WITH THE COMMITTEE Mr. Harold G. Alford, PRO Dr. Theodore Byerly, USDA Mr. Robert L. Caswell, PRB Dr. Cipriano Cueto, PRD Dr. K. D. Courtney, NIEIIS Mr. Charles Dunn, Hercules Incorporated Mr. Elaine Fielding, OGC Dr. John Frawley, Hercules Incorporated Dr. Dan Gaylor, NIEHS Dr. R. E. Johnson, EPA, OP Mrs. Joan Katz, Attorney representing Harrison Wellford, et al. Dr. Albert Kolbye, FDA Mr. John Kuniholm, Hercules Incorporated Mr. D. D. McCollister, Dow Chemical Company Dr. I. A. Mitchell, Office of Surgeon General Dr. J. A. Moore, NIEHS Dr. David P. Rail, National Cancer Institute Mr. George Robertson, OGC Dr. Virgil Robinson, Dow Chemical Company Mr. V. K. Rowe, Dow Chemical Company Dr. Jessie Steinfeld, Surgeon General Mr. Paul Whiteaker, PRD � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 046 Folder The folder containing the original item. 1152 Series The series number of the original item. Series III Subseries I Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Wilson, James G. Description An account of the resource <strong>Corporate Author: </strong>Advisory Committee on 2,4,5-T Date A point or period of time associated with an event in the lifecycle of the resource May 7 1971 Title A name given to the resource Report of the Advisory Committee on 2,4,5-T to the Administrator of the Environmental Protection Agency Subject The topic of the resource dioxin herbicide toxicology animal testing biodegradation ao_seriesIII Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 055 Folder The folder containing the original item. 1447 Series The series number of the original item. Series III Subseries II Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Travis, Curtis C. Holly A Hattemer-Frey Source A related resource from which the described resource is derived Chemosphere Date A point or period of time associated with an event in the lifecycle of the resource 1978 Title A name given to the resource Human Exposure to 2,3,7,8-TCDD Subject The topic of the resource dioxin biodegradation ao_seriesIII https://www.nal.usda.gov/exhibits/speccoll/files/original/9aa3c7403d775662daeff3c3b2db666c.pdf b9edb2dc9b63d6208296861a49a4d9d4 PDF Text Text Item ID Number: Author CorpOratB Author 00102 Rosenberg, Arthur Department of Agronomy, Cornell University, Ithica, New York Roport/Artldo TltlO Microbial Degradation of Pesticides Journal/Book Title Year 197S Month/Day November 17 Color Number of Images 30 DOSCrlptOn Notes Contract No. N00014-78-C-0044; Task No. NR 205-032: Annual Report Friday, December 08, 2000 Page 102 of 106 �Annual Report October 1, 1977-Sept.30,'78 Micrcbial Degradation of Pesticides • . MMOMMINO OH«. Nft»O«t N T CONTRACT OH «NMT MOU«IIV«j N00014-78-C-0044 . ^.^ Arthur toaenberg aixi Martin Alexander ORGANISATION NAMI AND -X 00 of Agronomy Cornell tluvwrsity , Now York 14853 II NR 205-032 II. MPOMT O*r« CONTMOLLINO OFPtCl NAMI AND ADDMIII 17 NowtMr 1978 Office of Naval Research Department of the Navy, Code 200 ITONlNQ AOCNCV NAMI 4 A I* •If" «lff*r«nr ta* ConN«IIHi« OHIcij OtltmtuTlON ITATCMlNT f*f Ml* Jt*»o/O Distribution of this report is unlimited., »; DEC 7 IT CMITMIIUTION ITATIMKNT (•/ Hi* »78 *l*o* >0. 8 NOTII U. ». KIV WOIIOI fCoiltaM «n rtrcrM «M* </ n«o««MTr MM (4wi(lf|> k? M*«k i.iaikw) Kbcrcblal degradation, Herbicides, Pesticides, Pollutants, 2,4-D, 2,4,5-T M AMTMACT fCmlfniM «n «•»•»•• •«• If Ma«M«r •»* an next page n •WTJOH OP I NOV •• IB OMIOLITI t/H 0101-014-IWI i lifted ••nu II �{. \. HBSTWSCT ^ ^ Fitt:y-two bactati.<i isolated frxin twiwaqt?, tai^>ci.itr soil, and var Tropical aoils were tested foi their «bility to attack 2,4-D and 2,4, V'r F Mirteen caused the disappearance of JO to 100% of the 2,4-0, and nine bixxight about the deatmction of 20 to 100% of the 2,4,5-T. None of t.h»orqaaiww oould uae 2,4-D or 2,4,5-T aa a sole source of carhun. Degradation of 2,4-D and phanoxyacetic acid in nonaterile aowaqo and a tropical soil was greatly <u>hanoed by pretreatincj the sewage and soil with these coipounda, suggesting the selection for organisms capable of attacking 2,4-D and phenoxyaoetic acid. Cell yields of the three most active 2,4,5-T degradera in a madi.um with glucose, glycerol, and sodium succinate and in a banzoate-supplement. medium with and without 2,4,5-T did not differ, suggesting oometabolic attack. Resting dell suspensions of nine of the isolates cleaved chlorine from the 2,4,5-T molecule while metabolizing more than 40% of the 2,4,5-T, suggesting ring cleavage of the herbicide. Eight isolates produced chlorinated phenol from 2,4,5-T. Studies of the respiratory activity of three isolates also suggested ring cleavage of 2,4,5-T, By use of (^Q-ring-UL) 2,4,5-T, it was found that the herbicide was readily metabolized in a tropical son. MCUWTV ci.Mwric*rieM OP AOK(lNll|BJ 197 �•f NAVAL RESEARCH Task No. NR 205-032 A;I.HIM, AU'JKT JJICRCBIAL gBGRADATION OF J>ESnCIDEB Ay'Stoaonborg 4£ M./Alexander Cornell University Department of Agronomy Ithaca, New York 14853 7 /^ 7 3tf Reproduction in whole or in part is permitted for any purpose of the United States Government Thin document has been approved for public release; its distrilution is unlimited ±>2ij �WriUUUCTlGN herbicides such as 2,4-D and 2,4,'j-T ^ro .imnny the mnet ocrnnrmly usecl horbicidaa foi selective weed control and for defoliation. The metabolic fates of 2,4-0 and 2,4,5-T are of obvious concern because of the potential toxicity of the herbicides and their metabolites to nontarget organisms. Although considerable work has been done on the persistence of 2,4-D in the soils characteristic of agricultural lands of continental United States, little attention has been given to the persistence and fate of this herbicide or 2,4,5-T in tropical soils of the Pacific Ocean area. The research in this report was designed to determine the persistence and fate of 2,4-D and the persistence, fate, ard role of ccmetabolism in the biodegradation of 2,4,5-T in such soils. MATERIALS AND METHODS »^ Materials. 2,4-Dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyaoetic acid (2,4,5-T) were obtained from Dow Chemical Co., Midland, Mich.; phenoxyacetic acid (PA.), 2,4-dichlorophenol (OCP), 2,4,5-trichlorophenol [TCP), and catechol fron Eastman Organic Chemicals, Rochester, N.Y.; and phenol and sodium benzoate fron Mallinckrodt Chemical Works, New York, N.Y. Uniformly ring-labeled (14C] 2,4,5-T (sp act 1.61 nCi/ranol) was purchased from California Bionuclear Corp., Sun Valley, Calif. The purity of the C~labeled compound was 98% as determined by thin-layer chrcmatography. Unlabeled 2,4,5-T and 2,4-D were purified by recrystallizing them twice in benzene. The purity of the oonpounds was greater than 99% as determined by thin-layer chronatography and melting point determinations. The compounds were prepared at 10,000 ppm in either 95% ethanol (Mallinckrodt) or as the ilium salt in distilled water. �(jJMWware. Glassware was cltMied by .1 24-h immersion in 20» (vol/vol) Nitric acid was removed by multiple washings in tap water followed by distilled water. Isolation of sewage and soil microorganisms. Bacteria capable of degrading 2.4-D and 2,4,5-T were isolated by the enrichment culture technique usinq the following sewage and soils at A concentration of 10% as initial sources of inocula: sewage collected at the primary effluent of the Ithaca, N.Y. sewage treatment facility (used within 30 min after collection), a temperate-zone soils mixture, Philippine soil (pll 6.8), Puerto Rico soil (pH 5.8), Nigerian soil (pH 5.9), and Trinidad soil (pll 6.1). Ttw; enrichment medium was an inorganic salts medium (3) and contained (per liter): (NH.)-SO., 0.5 g; NCI, 0.2 g; NaCl, 0.1 g; CaCl0.2H20, 50 mg; MgS04-7H2O, 0.2 g; PeCl.j.6H2O, 20 mg; and bufr fered with 12 mM potassium phosphate buffer, pH 7.2. When used as the source of carbon, the compounds were added to final concentrations of 250 and 1000 ppn. When used as a substrate for cometabolism, the compounds were added to a final concentration of 100 ppm in the inorganic salts medium containing 0.3 g/liuu: each of glucose, glycerol, and sodium succinate (basal medium). The medium was sterilized by filtration through sterile 0.2 urn membrane filters (Millipore Corp., Bedford, Mass.). The enrichment cultural (10 ml total volume) were incubated statically in screw-cap tubes at 29°C. 2,4-D, 2,4,5-T and PA disappearance were determined by UV absorbance. Once significant loss and visible turbidity occurred, 1.0 ml of the enrichment culture was transferred to fresh medium. After two successive transfers, the enrichments were streaked on plates containing either the inorganic salts medium with 15 g/liter agar (Difco) and amended with 250 or 1000 ppm of the compound if used as carbon source or basal medium with 15 g/liter agar and amended wii.: 100 ppn of the test compound. Isolates able to attack 2,4-D and 2,4,5-T were subsequently recognized by their ability to degrade the compound in liquid medium. Growth �4 . curvei and kinetics of 2,4,5-T disappoarancx' were mudted by tjrowinq selected ^ organisms ui basal median amended with r>0 ppm 2,4, VT or mineral uclu medium with 300 ppm 2,4,5-T at 29°C and 150 rpm. Periodically, portions won; remtjved, and either- the optical density determined or the samples were oenlrifuged at 10,000 X a at 4°C for 15 mui and the supernatant fluid assayed for 2,4,5-T disappearance. Nonbiological disappearance of 2,4,5-T was assessed using sterile incubation medium. Resting cell preparations. To prepare resting cells, cultures were grown in 1-liter Erlenmeyer flasks containing 500 ml of basal median amended and uriamended with 25 ppm 2,4,5-T and incubated at 29°C and 150 rpm for 36 h. The cells were harvested by centrifugation for 15 nvin at 10,000 X ^ at 4°C and washed three times with and resuspended in 10 ml of 10 nM phosphate buffer, pH 7.2 to an optical density of 1.5 at *20 nm. lt> 10 ml of the resting cell sus.„_, pens.Lon was added 25 ppm 2,4,5-T, and the suspensions were incubated for 24 h at 29°C and 150 rpm. The reaction mixtures were centrifuged, and the supernatant fluid was used for the analytical and chemical procedures. Nonbiological degradation of 2,4,5-T was assessed with sterile medium. Manometry. Standard manonetcic procedures were used (20). Each flask received either 0.33 ml of a solution with 1.1 pinoles of substrate as 2,4,5-T (sodium salt) in distilled water or inorganic salts medium with glucose or sodium benzoate as sole carbon source. The endogenous flask contained 0.33 ml of 10 nM phosphate buffer, pH 7.2, in the side arm. The main compartment contained 2.67 ml of cell suspension in the phosphate buffer, and the center well received 0.2 ml of 20% KGH. The cells were grown in the sane median as used for respiration studies. Degradation of (14C-ring-UL) 2,4,5-T. To determine the persistence anil ^_ degradation of 2,4,5-T in soil, 25 and 75 vq 2,4,5-T (14Oring-UL)/g aoil wire add<2d to 5.0 g of Philippine soil (pH 6.8, organic matter about 3%) in 50 ml �Erlanneyeu flaska. The screw C»UH weio mxlititxl n> aouomnudare \.atlun-ailieone discs (Pierce Chemical Co., Rxrkford, Til.). The herbicide was dissolved in 95% ethanol, And the uolvent was allowed to evaporate before mixing with the soil. The soil was wetted to 70% of field capacity with dist.'lled water. One flaak with each chemical concentration contained a sanple of soil irradiated with a tot*I dosage of 6 megarads; this dosage was sufficient to totally inactivate the soil microflora. Periodically, the soil was acidified with) 10 N HjSO., and air was passed into the soil for 90 min. The air passing out of each soil was bubbled through filter sticks (Ace Glass, Inc., Vineland, N.J.,) into disposable scintillation vials (Kimble, Toledo, Ohio) containing 2.0 ml of carbon dioxide-trapping agent ( 0 mMet, Amer sham/Searle Corp., Arlington 0. "oights, 111.) and 13 ml of aqueous counting scintillant (ACS, Amarsham/Searle ^^rp.). Anadytical methods. Turbidity was measured at 420 ran in a Bausch and Lamb spectrojihotaneter, model Electronic 20. 2,4,5-T, 2,4-D, and PA disappearance were monitored by ultraviolet (UV) absorbanoe measurements at 292, 280, and 268 ran, rea{iective.Lyf in 1-on quartz cuvcittes in a Beckman grating spectrophotaneter, model DO-G. Chloride release was determined by the technique of Bergmann and SaniK () 6. Ph<anol production was determined by the method of Chrastil (10). Catecnol production was determined by the method of Arnow ( ) 4. Carbon dioxide-14C activity in the scintillation vials was determined by counting in a Beckman liquid scintillation counter, model LS-100C. All counts corrected for quenching and background. �RKSU1.TS Isolationofj»jjjj>Jja. Km ichmont oultuu\>; Abl<- to dogr.ide 2,4-D 2,4,5-T ware isolated I" run se*«*ie and soils. IXii irxj the course of the onrichnwnt studies, the par*1 is tenet? of 2,4-0, 2,4,5-T and phannxyacet ic acid (PA) was dotenr.med for sewage and Philippine soil. Sewatjo .ind soil was amended with 100 ppm of the compound, and the degradation was followed by a decrease in UV absorbancy. vtian cxn|Mred to au toe laved sowaqe (cxintnil), qi-oater than 90% of the 2,4-D and PA disappeared after 7 and 12 days, respectively; however, 2,4,5-T was not attacked after 60 days (Pig. 1). Subsequent additions of 2,4-D and PA to thct sewage showed greater than 75% disappearance after 2 and .1 days, respectively, suggesting the selection for organisms capable of attacking the ccn|xxmds. Similar results wore obtained with Philippine soil, except that the time needed 'to obfwrve 90% disappearance of 2,4-D and PA was 14 and 16 days, respectively,, while 3 and 4 days were required for 75% disappearance of subsequently added 2,4-D and PA, respectively (Pig. 2}. 'To determine the number of isolates f ran each inoculum t' at could degrade 2,4-D and 2,4,5-T, the bacteria were grown in basal medium amended with 50 ppm 2,4-D or 2,4,5-T. Disappearance of the compounds was monitored periodically by recording the UV absorbancy of the culture's supernatant fluid, and these data were ocnpared to the disappearance of the confounds in sterile medium (control). A sximnary of the study to show the number of isolates from each inoculum capable of degrading 2,4-D and 2,4,5-T is given in Table I. Sewage and Philippine soil provided the most 2,4-D-metabo.lizing isolates, whereas the numbnr of 2,4,5-T-metabolizlng isolates, although highest from sewage, were fairly evenly distributed among the various soils. All enrichments yielded organisms capable of natabolizing 2,4-D and 2,4,S-T. Phenoxyacetic acid, Malt, �245-T 100 SE 2,4-D ADDITION COND PA DlTiON 75 UJ !5 (T 25 8 12 16 60 DAYS Fig. 1. Disappearance of 2,4-D, 2,4,5-T, and phenoxyaoetic acid in sewage amended with 100 ugAnl of each compound. �SECOND (SECOND PA ADDITION 20 60 Fig. 2. Disappearance of 2,4-D, 2,4,5-T, and phenoxyaoetic acia in Philippine soil amended w. th 100 Mg/ftg of each ccnpound. �1. Nuifcar of 2,4-D and 2,4,5-T •tihnUttnrj bactaria Uolatad fro* ',4-0 taldwnt atdjau-ataS- Soil Sewage Tenpera*a Philippina Puerto Rloo Nigeria and •oil 2,4,W Trinidad Soil SCMMje Tenperate Philippine Puerto Rico Nigeria Trinidad 2.4-Dfe 25 1 3 1 0 0 1 1 1 1 0 0 2,4-D£ 0 0 0 0 0 0 0 0 0 0 0 0 2,4,5^lfe 4 1 2 0 0 0 2 1 1 1 1 1 2,4,W£ 0 0 0 0 0 0 0 0 0 0 0 0 P)£ 23 0 3 2 2 0 2 1 1 1 * n£ 2 2 1 1 0 1 0 1 3 3 1 1 1 0 2 0 - N*£ 2 2 1 0 0 1 1 1 1 1 ••£ 1 1 1 1 1 0 i. 1 0 1 Ph»£ 3 0 2 1 0 1 2 1 1 0 1 PhamlS 1 0 1 1 0 0 1 1 0 0 1 1 1 KP* 2 1 1 0 1 1 0 0 0 0 0 0 DCT£ 0 0 0 0 0 0 0 0 0 0 0 0 *P^yB» 1 1 1 1 0 0 1 1 1 0 1 1 H^pCL 0 0 0 0 0 0 0 0 0 0 0 0 MA. 4tt»ri•tiona 2,4-D, ! • • t A. *• * * -* i . *m t A <_<•.•< for 2,4, 5-T *- * e>.*tic acid; PA, pharocyacatic acid; NaB. oodiia txruB- �8 p- .and phenol were used as a carbon source unci as a substrate for crme'-abolism, whereas 2,4-D, 2,4,5-T, DCP, and TCP were used as a substrate for cometabol ion only. The isolates were studied further to ascertain their morphological and biochemical characteristics. The bacteria exhibited the following diversity: 88* 'nere Grant-negative, 78% wore .xd-shaped, 58% were motile, 32% were pigmenbad and/or fluorescent, 68% were oxidase positive, and 94% were catalase positive (liable 2) . A breakdown of the characteristics of the isolates by inoculum indicated that the inocula contained a high percentage of Gram-negative, rod-shaped, catalase-positive bacteria, while the remaining characteristics fluctuated from a low of 5% pigmented and/or fluorescent bacteria fron the temperate soil to 88% oxidase-positive bacteria from the Philippine soil. Metabolism of 2,4-D and 2,4,5-T. Nineteen isolates were capable of metabolizing 2,4-D and 2,4,5-T. Resting-oeli suspensions of these bacteria were prepared, and 2,4,5-T disappearance, phenol and catechol production, and chloride release were determined. When compared to sterile controls, eight isolates caused the disappearance of greater than 50% of the 2,4,5-T. Extensive metabolism occurred with isolates 2A3 (88%), 4C3 (88%), and 5DJ (92%) (Table 3). Twelve isolates released chloride! in the medium, with isolates 2A3, 4C3, and. 5D3 liberating 90% or more. Eight isolates produced phenol from 2,4,5-T. to catochol was detected in the medium after a 36-h incubation period. The loss of tJV abaorbancy, release of chloride, and absence of phenol and catechol indicated that certain isolates were metabolizing 2,4,5-T by destroying the aromatic ring. The production of phenol with and without chloride release suggested that some of the isolates were converting 2,4,5-T to 2,4,5-trichlorophonol and mono- and dichlorophenol. �9 • ^ TABTE 2. Morphological and biochemical characteristics of bacteria isolated fran sewage and soil Percentage of isolates showing characteristic Gram Rod Pigmantad/ Qxidaae Catalase negative shaped Mobility fluorescent positive positive Source Sewage 90 95 69 50 87 100 Taiperate soil 92 60 60 5 40 97 Philippine soil 88 86 71 43 88 91 Puerto Rico soil 73 76 49 28 67 100 Nigeria soil 91 75 50 29 57 85 Trinidad soil 94 76 49 37 69 91 _ 88 78 58 32 68 94 Mean �10 tf K 3. M^tahnLiant of ^,4, VI', lolwnHo of i-Jiloi idu, and pmducHon of i>hejv by reatmi-ooll Phunol 2.4.S-T ,£> ,» (as'*) LAI 0 24 60 2AI 8 0 60 2AJ 0 40 •JO 2AJ 88 «M 0 4AJ 0 0 35 4A5 44 24 0 -, % 0 0 itr; 44 40 0 6B2 24 0 10 2C1 52 0 0 2C2 0 0 75 2C4 64 30 0 4C1 44 50 0 4C3 88 90 0 4C5 8 0 30 403 4 24 25 503 92 90 0 3E3 72 40 0 5F4 68 50 0 -Initial concentration: 25 of chlcvldft in 25 ugAil 2,4,5-Tj 10.5 �•^ " Tho throe most active J^.VT-iloii.uli!*) iHol.iti»H (2A\, 4C1, .uvl MM) wutt- grown in basal medium .inundud w i t h '>() \\>\\ ot .>,4,'>-T 01 iimnjamr H . i l t s int-tlium unanded with JOO ppm 2,4 f r >-T. cubatod v/ith the isolate. I'onlrol t Links (.xaUaiiumj bnaal mud tun weir in- C.rowth. monsumi by *iptical density, W«H with 2,4,T>-T disappearancx: rtH uiLvisured L~v lk>8S ol tlV nbsorlxuK^. of the presence 01 Absence ot 2,4,S-T in the bns-il medun\, isolate 2A.J .1 sigmoidal qruwth cutvt^ with nvotinwl qniwtJi .iftor JO h (Fiq. J) . iance ot" 2,4,5-T at^irttxl dbout 8 h after inoculation, .\iid .tfter 90 h, greater than 90* of the herbicide had disappeared. Sterile controls had leas than 2* disappearajice after 90 h. No qrc*rt± occurred in the inoixjanic salts medixm after 90 h. The inability of 2,4,5-T to serve as sole carbon source, *he disappearance of the ccropound in the presence of an external carbon source, ^^J the lack of significant differences in growth between amonded and unamended bas.il medium indicated that the loss of the herbicide resulted from cumetabolism. Conetabcilism ot" 2,4,5-T was also indicated for isolates 4CJ (Kig. 4) and 5D3 (Fiq. 5). The rate and extent of O uptake was measured with resting-cell suspensions ot 2A3, 4C3, and 5D3 prepared from cultures grown on glucose-uxarganic salts madium with and without 2,4,5-T (30 ppm) or inorganic salts medium with sodium benzoate as sole carbon source. The oxyqen o.>iisumption values are the means of two replicates corrected for endogenous respiration (less than 3 nmol of O- in 1 h) and are determiivad for sodium benzoate or glucose as sole carbon source and 2,4,5-T in the glucose-inorganic salts medium. The oxidation of 2,4,5-T, glucose and sodium bonzoate is presented in Fig. 6. Oxyqen consumption was high for sodium benzonto (5 »imol of O ' -nol of Jium benzoate). Glucose was completely oxidized (6 iinol of O_/nnol of qlucoae) by 2A3. Although O2 consumption for 2,4,5-T was negligible by 2A3 when grown �IOC) PTICAL DENSITY o- Q75 75 e> gO.50 ti 50 in « csf 0.25 - 25 2,4,5-T 30 60 HOURS 90 Pig. 3. Growth of isolate 2A3 in the presence (closed circles) and absence (open circles) of 50 ug 2,4,5-T/tal and 2,4,J-T disappearance. �TICAL DENSITY 100 8" 75 in cvf ^ 25 30 60 HOURS 90 Ficj. 4. Growth of isolate 4C3 in the presence (closed circles) and absence (open circles) of 50 ug 2,4,5-T/tal arid 2,4,5-T disappearance. �100 .OPTICAL DENSITY '8- 75 50 I in + CM* .4.5-T 30 60 HOURS 90 Fig. 5. Growth of isolate 5D3 in the presence (closed circles) and (open circles) of 50 ug 2,4,5-T/taU, and 2,4,5-T disappearance. �6- 120 160 MINUTES Fig. 6. Metaboliaro of glucoM, •odiun bwwoat*, and 2,4,5^ by cell* of 2*3 grown in 0.5% gluooM (cloMd oirclw) or 0.5% auditm cirolM) inorganic Mlts broth. iting �12 with glucose, the cells consumed «l»xit 1.7 iimul of oy'iimul of 2,4,'i-T whan grown with sodium benzoate, suggesting a subatrate-anahxj at initiation of respiration. The amount of 0^ ixjnsumed was about 2b» of the theoretical amount needed to oxidize the 2,4,5-T completely. Resting cells of 4C3 were prepared frun cultures qrown in qluooae-inorganicsalts medium with aivi without 2,4,5-T. The cells cutpletely oxidized qlucosc (Fig. 7) . Oxygen consumption in the presence of 2,4,5-T by cells not grown in the presence of 2,4,5-T was 2 umol of OVumol of substrate. However, cells exposed to 2,4,5-T in the growth medium consumed nearly 4 umol of OVionol of 2,4,5-T, suggesting that the presence of 2,4,5-T stimulated metabolism and ring cleavage of the herbicide. Resting cells of isolate 5D3 were prepared similar to 4C3, and these cells o oxidized all the glucose (Fig. 8). Cells not exposed to 2,4,5-T in the •v ^ growth medium consumed nearly 2 umol of O^umol of 2,4,5-T while "pre-exposed" cells consumed 3 umol of 0_/umol of substrate. The enhanced 0_ consumption (about 40% of the theoretical amount for complete oxidation of 2,4,5-T) suggests, similar to 4C3, that the presence of the herbicide during growth stimulated subsequent 2,4,5-T oxidation. To determine further the persistence and degradation of 2,4,5-T in soil, the Philippine soil was amended with 5 and 15 ppm of 2,4,5-T ( V-ring-UL). The CO2 evolved was measured periodically by acidifying the soil and trapping the CD- i"a trapping solution. Compared to gamma-irradiated controls, CD- evolution was detected in the soil with 5 ppm 2,4,5-T (Table 4). The amount of 1 4 (X>2 detected was 16% of the initial radioactivity added after 2 wceka and 23% after 3 weeks. No significant CO- evolution occurred in the soil with 15 ppm 1,'>T-14C in a 3-week period. Evolution of mf ditional evidence of ring cleavage. GC*2 from the soil provided ad- �60 120 180 MIMJTES Fig. 7. itetAbolism of glucose and 2,4f5-T by resting cells of 4C3 grown in 0.5% glucose-inoxqanic salts broth (cloned circles) and broth amended with 30 u<-j 2,4,5-T/ml (open circles). �GLUCOSE cr CO CD CO I 3 O _l O 2,4,5-T 120 180 MINUTES Fig. 8. Metabolism of glucose and 2,4,5-T by resting cells of 5D3 grown 60 in 0.5% glucose-inorganic sa.lts broth (closed circles) and broth amended with 30 ug 2,4,5-T/ml (open circles). �13 TABLE 4. Degradation of 2,4,5-T( C-ring-lJL) by Philippine 9011 Degradation (*)Vteeks 5 ptm 15 pptn 1 0 0 2 16.3 < 1.0 3 22.6 1.8 ^Measured as % of 2,4,5-TC C-ring-UL) evolved as CO,. �IHHIUSMCN Enrichment-culture techniques using 2,4-1), 2,4,0-T, «nd irv»loquen indicated that the inocula fran natural ocosystuns contained many bacteria cai**M'.of destroying 2,4-D and 2,4,5-T but only by crmetabol ism. Studies with resting cell suspensions of the bacteria showed that 74% of the isolates deatioyad ficm 8 to 92% of the 2,4,5-T in the medium, 63% released chloride from 2,4,5-T, arid 42% produced phenol. In addition, 64% of the bacteria that degraded 2,4,5-T also released chloride. The liberation of chloride with loss of UV absorbancy indicated ring cleavage of the herbicide. Further, the data from manometric studies suggested ring cleavage of 2,4,5-T by two "induced" bacterial isolates, 4C3 .and 503. The cleavage of the herbicide agrees with the findings of Ou and Sikka (17), who found extensive degradation of the aromatic ring of a structurally similar molecule, 2-(2,4,5-trichlorophenoxy)propionic acid by aquatic bacteria. In contrast, other workers (2,9) have reported that phenoxy herbicides with a chlorine in the meta position of the aromatic ring were resistant to microbial degradation in soil. The failure to show microbial degradation of these chemicals may have resulted from soil inocula in which the appropriate microorganisms were- either absent or not present in sufficient numbers to produce degradation of the compound in the time of the experiment. In addition to organisms degrading 2,4,5-T, bacteria were also isolated that could produce a phenolic compound from the herbicide. In some cases, phenol production was accompanied by chloride release, suggesting the conversion of 2,4,5-T to the mono- or dichlorophenol. In other instances, phenol was produced without a loss of UV absorbancy and chloride release, suggesting the production of 2,4,5-trichlorophenol. Sharpee (18) showed also the production of 2,4,5-trichlorophenol from 2,4,5-T. The appearance of the chlorinated phenols in the culture medium suggests that 2,4,5-T degradation proceeds via the cleavage; �of the acetate moiety as described for 2,4-1) doqr.idcit ion ( 1 , 7.8, \'>, I')) . If the trxohloroiphenoj. is dehaloyenaturt, then the molecule rr»y Ix? decomposed l»y »hu pathways described for 2,4-D degradation (18,19) . The pathway of deqrdd.it;on of the trichlorophenol, however, remains unknown (1). Alternately, 2,4,5-Tmay be converted to a hydroxylated, dehaloguvated organic product such as 3,rj-dichlorocatechol as described by Horvath (12) . If so, then the catechol may be deoorvosod as described for 2,4-D since the catechol as also produced during the bacterial degradation of this herbicide (14,18,19) . The data frxm the enrichment cultures indicated that 100 ppm of 2,4,5-T persisted in sewage and Philippine soil for 60 days. However, a subsequent experiment using a larger sample of Philippine soil amended with only 5 14 2,4,5-T ( C-ring-UL) indicated ring cleavage and evolution of 140 , within 0, <eeks. Inasmuch as 2,4,5-T does indeed disappear fron soil (1,11) and evidence exists that microorganisms are involved (12) , one might expect that microorganisms could be obtained which use it as a source of carbon and energy. However, such an organism had yet to be found. In this stud", the three most active bacteria attacked 2,4,5-T by cometabolism. Come tabol ism is the metabolism by a microorganism of a conpound that will not supply that organism with energy or an essential nutrient. The species thus does not replicate at the expense of the compound; hence, should the initial cell number be small, there will be no increase in cells with the requisite enzymes so that the rate of decorposition will ranain low and also will not show the typical increase with time that is characteristic of substrates supporting growth (13) . This long persistence coinciding with an apparent microbial transformation (5) is typical of the behavior of 2,4,5-T in soil. The persistence, however, of 2,4-0 ard 1,5-1 is dependent on many factors, not the least of which is abundance of ^v •* 2,4-D aixJ 2,4,5-T-metabolizing bacteria (1,14). Thus, a small soil sample may �1ft not ix>nt -tin i 'v Ixsciei la in sutl iciei.l number to dogiticlu ^,4-L; .ind (\specMlJy 2,4,5-T w i t h i n U>e teat, per ml. ^ dependency of 2,4-D and 2,4,'i-T metiib'jlian on size >n ; v > i l sarples has be«ui shtjwn (16,21) . research w i l l be di.rect.ed t o (^; determining the fdte <irvd pcraisteiv?e ot 2,4,5-T in Pacific Island soils utilizing gas-liquid chrcmat'xjraphy and 14 C-tagged herbicide, (b) determining tho role of cunetabolian in the bioof 2,4,5-T and 3eeking means to enhance the process and (c) assessing the effect of selected pesticides 01 the function of microbial cotitunities of sewage. CREDIT Ti.i.s research was supported in part by the Office of Naval Research, Microbiology Program, Naval Biology Project, under contract N00014-78-C-O044. �J/ MIHMOCHAI'IfY 1. Aii'-xandei, M. 1974. Miciubuil format ion <>l (jnvironmcntal i»)l lutanta. Advan. Appl. Microbiol. 18:1-71. 2. Alexander, M. and M. r. II. Akwni. L961. Effect of chunical structure an microbial decunposition ci miTHtic herbicides. J. Agric. Food. Chein. 9:44-47. .}. Alexander, M. .and B. K. Lust iqnvm. 1966. Effect jf chemical structure on microbial degradation of substituted benzenes. J. Agric. Food Chem. 14:410-413. 4. Arnow, L. E. 1937. Colorimetric determiiiation of the ccnvjnents of 3,4diJiydroxyphenylalaniije-tyrosine mixtvres. J. Biol. Chan. 11Q-531-537. 5. Audus, L. J. 1951. The biological detoxication of hormone herbicides in soil. Plant Soil 3:170-192. 6. Bergman, J. G., and J. Sanik. 1957. Determination of trace amounts of chlorine in naphtha. Anal. Chem. 29:241-245. 7. Bollag, J.-M., C. S. Helling, and M. Alexander. 1968a. 2,4-D metabolism: enzymatic hydroxylation of chlorinated phenols. J. Agric. Food Chem. 16:826-828. 8. Bollag, J.-M., G. G. Briggs, J. E. Dawson, and M. Alexander. 1968b. 2,4-D matabolism: enzymatic degradation of chlorocatechols. J. Agric. Food Chem. 16:829-833. 9. Burger, K., I. C. MacRae, and M. Alexander. 1962. Decomposition of pnenoxyalkyl carboxylic acids. Soil Sci. Soc. An. Proc. 26:243-246. ].0. Chraatil, J. 1975. Colorimetric estimation of phenols and tyrosine. Anal. Chan. 47:2293-2296. 11. De Rose, H. R., and A. S. Newnan. 1947. The comparison of the persistence of certain plant growth regulators when applied to soil. Soil Sci. Soc. Am. Proc. 12:222-226. �IB 12T"Horv»tli, R. S. 1970. Microbial acnDtabol ism of 2,4,5-LrichloroiJJ»noxyaoetic acid. Bull. Environ. Content. Tcwicol. 5:537-541. 13. Hotvath, R. S. 1972. MicrobiaL oan*>tsLoIism and the degradation of organic cun»unds in nature. Bacteriol. Rev. 36:146-155. 14. Loos, M. A. 1975. Phanoxyalkanoic acids, p. 1-128. In P. C. Kearney and 0. D. Kaufman (od.), Herbicides: Chemistry, degradation, and mode of action, vol. 1, 2nd ed. Marcel Dekker, New York. 15. Loos, M. A., R. N. Roberts, and M. Alexander. 1967. Formation of 2,4-dichlorophenol and 2,4-dichloroanisole from 2,4-dichlorophenoxyacetate by an Arthrobacter sp. Can. J. Microbiol. 13:691-699. 16. Ou, L.-T., D. F. Rothwell, W. B. Wheeler, and J. M. Davidson. 1978. The effect of high 2,4-D concentrations on degradation and carbon dioxide evolution in soil. J. Environ. Qual. 9:241-246. iTTcu, L.-T., and H. C. Sikka. 1977. Extensive degradation of silvex by synergistic action of aquatic microorganisms. J. Agric. Food Chem. 25:1336-1339. 18. Sharpee, K. W. 1973. Microbial degradation of phenoxy herbicides in culture, soil, and aquatic ecosystems. Ph.D. Dissertation. Cornell Univ., Ithaca, N.Y., 94 pp. 19. Tied'ie, J. rt., and M. Alexander. 1969. Enzymatic cleavage of the ether bond of 2,4-dichlorophenoxyacetate. J. Agric. Food Chen. 17:1080-1084. 20. Umbreit, W. W., R. H. Burris, and J. F. Stauffer. 1964. Manonetric techniques, 4th ed. Burgess, Minneapolis. 305 pp. 21. Yoshida, T., and T. F. Castro. 1975. Degradation of 2,4-D, 2,4,5-T, and picloram in two Philippine soils. Soil Sci. 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Naval Ntedical Research Unit #5 APO, New York 09319 ( 1) Officer in Charge Submarine Medical Research Laboratory U. S. Naval Subnarine Base, New London Groton, CT 06342 ( 1) Scientific Library Naval Bioscienoes Laboratory Naval Supply Center Oakland, CA 94625 ( 1) Scientific Library Naval Aerospace Medical Research Institute Naval Aerospace Medical Center Pensacola, FL 32512 ( 1) Commanding Officer U. S. Naval Air Development Center ATTN: Aerospace Medical Research Department Johnsville, Warminster, PA 18974 ( 1) Commanding General U. S. Army Medical Research and Development Command Porrestal Building Washington, DC 20314 ATTN: MEDDH-Sr ( 1) Director of Life Sciences Air Force Office of Scientific Research Boiling Air Force Base Washington, DC 20032 ( 1) STIC-22 4301 Suitland Road Washington, DC 20390 ( l) Director Walter Reed Army Institute of Research Walter Reed Army Medical Center Washington, DC 20012 � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 012 Folder The folder containing the original item. 0102 Series The series number of the original item. Series II Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Rosenberg, Arthur Martin Alexander Description An account of the resource <strong>Corporate Author: </strong>Department of Agronomy, Cornell University, Ithica, New York Date A point or period of time associated with an event in the lifecycle of the resource November 17 1978 Title A name given to the resource Microbial Degradation of Pesticides Subject The topic of the resource biodegradation soil decontamination https://www.nal.usda.gov/exhibits/speccoll/files/original/9346e6068481f593b699f8853bda813b.pdf 553b9c533e1e82c5b45c3ef79964b2ae PDF Text Text Item ID Number Author CorpOratB Author 00184 Patrick, Michael A. Environics and Human Factors Office, Air Force Armament Laboratory, Armament Development and Test Center, Eglin AFB, Florida Toxicological and Recalcitrant Properties of a Proposed Propellant Ingredient, Triaminoguanidine Nitrate (TAGN). I. Microbiological Study Journal/Book Title Year 1976 November Wnr Number of Images Project No. 5066; Task No. 01 ; Work Unit No. 001 Friday, January 05, 2001 Page 184 of 194 �AFATL-TR-76-139 TOXtCOLOGICAL AND RECALCITRANT PROPERTIES OF A PROPOSED PROPELLANT INGREDIENT, TRIAMINOGUANIDINE NITRATE (TAGN) I. MICROBIOLOGICAL STUDY ENVIRONICS AND HUMAN FACTORS OFFICE NOVEMBER 1976 FINAL REPORT: APRIL - NOVEMBER 1976 Approved for public release; distribution unlimited AIR FORCE ARMAMENT LABORATORY AIR F O R C E S Y S T E M S COMMAND • UNITED S T A T E S AIR F O R C E EGLIN AIR F O R C E B A S E , F L O R I D A �UNCLASSIFIED SECURITY CLASS'FICATION OF THIS =>AG€ (When Rate Entered) READ INSTRUCTIONS BEFORE COMPLETING FORM 2. GOVT ACCESSION NO, 3. RECI^'FWT'S CATALOG NUMBER REPORT DOCUMENTATION PAGE 1, REPORT NUMDER AFATL-TR-76-139 4. TITLE (and Subtitle) 5. TVFE OP REPORT * PERIOD COVERED Final Report - April to November 1976 TOXICOLOGICAL AND RECALCITRANT PROPERTIES OF A PROPOSED PROPELLANT INGREDIENT, TRIAMINOGUANIDINE NITRATE (TAGN). I. MICROBIOLOGICAL STUDY 6. PERFORMING ORG. REPORT NUMBER 7. AUTHORfs) 8. CONTRACT OR GRANT NUMBERfa) Michael A. Patrick, Lt, USAF 10. PROGRAM ELEMENT. PROJECT, TASK APE* ft WORK UNIT NUMBERS 9. PERFORMING ORGANIZATION NAME AND ADDRESS Environics and Human Factors Office Air Force Armament Laboratory Eglin Air Force Base, Florida 32S42 Project No. 5066 Task No. 01 Work Unit No. 001 tl. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE Air Force Armament Laboratory Armament Development and Test Center Eglin Air Force Base, Florida 32542 November 1976 14. MONITORING AGENCY NAME ft AODRESSfff different from Controlling Office) 15. SECURITY CLASS, (at thlt report) 13. NUMBER OF PAGES 72 UNCLASSIFIED 15«. OECLASSIFtC ATI ON/ DOWNGRADING SCHEDULE 16. DISTRIBUTION STATEMENT (of this Report) Approved for public release; distribution unlimited. 17. DISTRIBUTION STATEMENT (of th» abttroct entered in Block 20, If different tram Report) 18. S U P P L E M E N T A R Y NOTES Available in DDC. 9. K E Y WORDS (Continue on reverse side It necessary and identify by block number) Toxicological Properties Recalcitrant Properties Triaminoguanidine Nitrate Microbial Populations 20. ABSTRACT (Continue on reverse mid* If necessary end Identity by block number) The toxicological and recalcitrant properties of a proposed propellant ingredient, triaminoguanidine nitrate (TAGN), were investigated. Pure cultures of microorganisms isolated from Eglin Air Force Base, Florida, as well as cultures obtained from US Army Natick Laboratories, Natick, Massachusetts were exposed to TAGN and evaluated. During the course of this investigation, it was determined that microbial populations were not adversely affected by short-term exposure to TAGN. The following parameters were not significantly DD 1473 EDITION OF 1 NOV 65 IS OBSOLETE UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE (When Dmtu Entm-nS) �UNCLASSIFIED SCCURITY CLASSIFICATION OF THIS FAG£fiMj«n Da** Entered) (Item 20 concluded) altered by TAGN concentrations up to 50 ppm: ' growth rate, respiratory activity, and viability. At concentrations greater than 100 ppm, TAGN was bacteriostatic but not bacteriocidal. Of the two bacteria tested, Pseudoaonas aerugi.nosa and Escherichia coli, both were capable of removing (degrading) TAGN from aqueous solution. UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGEfflfmn D*>* �PREFACE This technical report is the result of research conducted by the Air Force Armament Laboratory, Armament Development and Test Center, Eglin Air Force Base, Florida, from April 1976 to November 1976 under Air Force Exploratory Development Project 50660101. Reference to specific manufacturers or suppliers of scientific equipment used in this study is for the sole purpose of identification and does not constitute endorsement of these products by the United States Air Force. The assistance of Cadet Ron Alford, USAF Academy, in the bacteriocidal portion of this study is gratefully acknowledged. This report has been reviewed by the Information Office (01) and is releasable to the National Technical Information Service (NTIS). At NTIS, it will be available to the general public, including foreign nations. This technical report has been reviewed and is approved for publication. FOR THE COMMANDER: A. FARMER Chief, Environics and Human Factors Office i (The reverse of this page is blank) ��TABLE OF CONTENTS Section I II III IV Title Page 1 INTRODUCTION MATERIALS AND METHODS, . . . Cultures . . . . . Inhibitory Studies . . Bacteriocidal Effects Oxygen Uptake. . . . . . . . TAGN Degradation . . . . . . . . ..... ... RESULTS AND DISCUSSION CONCLUSIONS. . . . . . . . ill 3 3 3 3 3 4 5 . . 7 �LIST OF FIGURES Figure 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Title Page Standard Growth Curves of (A) Pseudoaonas aeruginosa QMB 1468 and (B) Bacillus megaterium QMB 1605 Exposed to TAGN . . 8 Standard Growth Curves of (A) Staphyj.ococcus aureus QMB 1458 and TO Bacillus cereus QMB 1597 Exposed to TAGN. . 10 Standard Growth Curves of (A) Escherichia. coli QMB 1557 and (B) SR 401 Exposed to TAGN , 12 Standard Growth Curves of (A) SR 403 and (B) SR 404 Exposed to TAGN , 14 Standard Growth Curves of (A) SR 405 and (B) SR 407 Exposed to TAGN 16 Standard Growth Curves of (A) SR 408 and (B) SR 409 Exposed to TAGN . 18 Standard Growth Curves of (A) C 1 and (B) C 4 Exposed to TAGN . . . . . . . . . . . . . . . . . . . . 20 Standard Growth Curves of (A) T 6 and (B) Arthrobacter sp. QMB 1631 Exposed to TAGN. 22 Standard Growth Curves of (A) Bacillus subtilis QMB 1611 and (B) Serratia marcescens QMB 1466 Exposed to TAGN 24 Standard Growth Curves of (A) SR 402 and (B) SR 406 Exposed to TAGN . . . . . . . . . . . . . . . . 26 Standard Growth Curves of (A) T 4 and (B) T 100 Exposed to TAGN ............ 28 Endogenous (A) and Exogenous (B) Oxygen Uptake by Pseudomonas aeruginpsa QMB 1468 Exposed to 500 ppm TAGN . 30 Endogenous (A) and Exogenous (B) Oxygen Uptake by Bacillus megaterium QMB 1605 Exposed to 500 ppm TAGN 32 Endogenous (A) and Exogenous (B) Oxygen Uptake by Staphylococcus aureus QMB 1458 Exposed to 500 ppm TAGN. . . . . . 34 Endogenous (A) and Exogenous (B) Oxygen Uptake by Serratia_ marcescens QMB 1466 Exposed to 500 ppm TAGN 36 Endogenous (A) and Exogenous (B) Oxygen Uptake by Escherichia coli QMB 1557 Exposed to 500 ppm TAGN . . . . . . . . 38 Endogenous (A) and Exogenous (B) Oxygen Uptake by Arthrobacter sp. QMB 1631 Exposed to 500 ppm TAGN . . . . . . . . 40 Endogenous (A) and Exogenous (B) Oxygen Uptake by Bacillus cereus QMB 1597 Exposed to 500 ppin TAGN 42 IV �LIST OF FIGURES (CONCLUDED) Figure 19 20 Title Page Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 402 Exposed to 500 ppm TAGN 44 Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 404 Exposed to 500 ppm TAGN 21 22 23 24 46 Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 406 Exposed to 500 ppm TAGN . 48 Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 407 Exposed to 500 ppm TAGN 50 Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 408 Exposed to 500 ppm TAGN. 52 Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 410 Exposed to 500 ppm TAGN 25 54 Endogenous (A) and Exogenous (B) Oxygen Uptake by C 4 Exposed to 500 ppm TAGN 26 27 56 Disappearance of TAGN from Cultures of (A) Pseudomonas aeruginosa QMB 1468 and (B) Escherichia coli QMB 1557 as a Function of Cell Density (O.D.) Thin-Layer Chromatogram Depicting the Disappearance of TAGN from the Cell-Free Supernatant of a Growing Culture of Pseudomonas aeruginosa as a Function of Time 58 . 60 LIST OF TABLES Table 1 2 Title Page Exposure of Bacterial Cultures Obtained from US Array Natick Laboratories to TAGN 61 Exposure of Bacterial Cultures Indigenous to Eglin AFB, Florida, to TAGN. . 63 v (The reverse of this page is blank) ��SECTION I INTRODUCTION An experimental propellant consisting of approximately 45 percent triaminoguanidine nitrate (TAGN), 19 percent nitrocellulose (NC), 30 percent cyclotetramethylene tetranitramine (HMX), 5 percent isodecyl pelargonate, and I percent resorcinol is being considered by the Air Force for use in gun ammunition employing high-density, armor-piercing penetrators. It is a matter of environmental policy to determine toxicity and evaluate methods for disposal of new propellant constituents before inventory acquisitions. Prior to this study, no information was available concerning the biodegradation or toxicity of the major component, TAGN. The objectives of this initial study were to investigate whether TAGN is degradable by microorganisms and to determine if TAGN adversely affects microbial populations indigenous to soil and water habitats where appreciable amounts of TAGN may accumulate during propellant testing and disposal. 1 (The reverse of this page is blank) ��SECTION II MATERIALS AND METHODS CULTURES Bacterial strains used in this study were obtained either from US Army Natick Laboratories, Natick, Massachusetts, or isolated from soil or water samples collected at Eglin Air Force Base, Florida. Original cultures were preserved under liquid nitrogen. Subcultures were maintained on Trypticase soy agar (TSA) at 4°C and were transferred monthly. INHIBITORY STUDIES Starter cultures were grown overnight in Trypticase soy broth (TSB) with agitation at 20°C and were diluted 1:10 in 15-mM phosphate buffer (pH 6.6) prior to use. Experiments were initiated by inoculating 0,1-aJt cells into S.Q-m£ filter-sterilized (0.45-um Millipore filters) TSB containing TAGN at concentrations of 500, 100, 50, or 10 ppm. Control samples contained no TAGN. All experiments were performed in triplicate at 20°C with agitation on a gyratory shaker (120 rpm). Growth was monitored periodically by recording the optical density (O.D.) of each sample with a Bausch and Lomb Spectronic 20 Spectrophotometer at 520 nm.1 All sanples were corrected for O.D. discrepancies due to tube variations and TAGNinduced absorption. BACTERIOCIDAL EFFECTS Cultures were grown overnight in 50-mH TSB at 25°C with agitation and were harvested at late log or stationary phase by centrifugation at 6,000 rpm for 15 minutes in an IEC/B20 refrigerated centrifuge. Following resuspension in sterile phosphate buffer, the cells were diluted to give a final O.D. reading of 0.2 at 520 nm. Diluted samples (5.0 mi) were added in duplicate to 5.0-m£ phosphate buffer containing TAGN at final concentrations of 0, 500, and 2,000 ppm. Samples were shaken in sterile 15-m£ centrifuge tubes at 25°C for 1-hour or 5-hour time periods. Afterwards, the exposed cells were centrifuged at 6,000 rpm for 15 minutes to remove TAGN and were resuspended in equal amounts of phosphate buffer. Samples were subsequently diluted with buffer to a final titer of 3.0 x 10a 3.0 x 10s colony-forming units/mi (CFU/m£) and were spread plated in triplicate. Following incubation overnight at 34°C, the plates were counted with the aid of a Quebec Colony Counter. OXYGEN UPTAKE Cultures were grown at 25°C, harvested, and resuspended in phosphate buffer as previously described. Endogenous preparations contained 1.5-ntfc �cells, 1.5-ml phosphate buffer, and a final TAGN concentration of 500 ppm, Exogenous preparations contained 1.5-mi cells, 0.5-mH phosphate buffer, 1.0-m£ TSB, and a final TAGN concentration of 500 ppm. Exogenous samples were pre-incubated 30 minutes at 30°C prior to data collection. All control samples were identically prepared but contained no TAGN, Oxygen uptake measurements were performed with a YSI 5331 Oxygen Probe at 30°C with airsaturated solutions. TAGN DEGRADATION Twelve liter fermentors (Virtis Research Equipment, Gardiner, New York) containing 10 £ of a mineral salts medium consisting of 1,79 g/Ji KH2POi», 1.65 g/£ Na2HPO% • 7H20, 0.12 g/£ MgSQK, 0,03 g/£ CaCl2, and 5.0 g/£ glucose were inoculated with 25 m£ of an actively growing culture of either Pseudomonas aerujinosa or Escherichia coli.2 Immediately following inoculation, filter-sterilized TAGN was added to give a final concentration of 61 ppm for the P. aeruginosa culture and 75 ppm for the E_, coli culture. NaNOs (0.7 g/£) was added to each fermentor at a designated time following inoculation. Periodically, samples were aseptically withdrawn, centrifuged at 6,000 rpm for 15 minutes, and analyzed for TAGN by a modification of the ninhydrin assay.3 Freshly prepared ninhydrin reagent (3.0 m£3 was added to l.Q-mJl sample and heated for 5 minutes in a boiling water bath. The sample was cooled, and the resulting optical density was determined at 570 nm against a blank containing no TAGN. Culture densities were aeasured prior to centrifugation at 520 nm. In order to rule out the effects of other ninhydrin reacting substances, 50 u£ supernatant samples were spotted on silica gel GF thin-layer plates (Analtech, Inc., Pittsburgh, Pennsylvania) and were developed against a solvent system of methanol-water-methyl sulfoxide (40:30:30). Plates were sprayed with 0.2 percent ninhydrin in watersaturated butanol. �SECTION III RESULTS AND DISCUSSION Growth of the majority of the bacterial isolets examined was not adversely affected by TAGN concentrations up to 50 ppm. However, at 100 ppm and above, 16 of the 22 bacterial cultures tested were markedly inhibited (Figures 1 to 8). Since continued incubation of these cultures for up to seven days did not result in further growth initiations, it must be assumed that the inhibitory effects of TAGN were absolute and not merely the result of greatly extended lag periods. Of the 6 remaining bacterial cultures capable of growth in the presence of 100 ppm TAGN (Figures 9 to 11), all exhibited prolonged lag phases prior to logarithmic growth. Although the overall growth rates of these cultures were considerably retarded, the ultimate cell densities attained, when compared to controls, were not significantly affected by exposure to TAGN. At the present time, inadequate evidence is available to explain the inhibitory actions of TAGN on bacterial cultures. However, it is clear that the inhibitory effects were not due to TAGN-induced pH changes, since the addition of this substance had no pronounced influence on initial hydrogen ion concentration of the media. To determine whether TAGN was bacteriocidal, cells were suspended in buffered solutions of TAGN at concentrations of 500 or 2,000 ppm for up to 5 hours. These concentrations were high enough to prevent cell proliferation in a suitable medium such as TSB, but as shown in Tables 1 and 2, viability of the cultures was unaffected. In every case the bacteria were capable of renewed growth following TAGN removal by centrifugation. Therefore, while TAGN was bacteriostatic under the specified conditions of this test, it was neither bacteriocidal nor significantly toxic to the microbial cultures examined . Oxygen uptake, a method of evaluating cellular oxidative capabilities, was investigated at a constant TAGN concentration of 500 ppm (Figures 12 to 25). In several instances oxygen uptake was markedly depressed by 500 ppm TAGN, as in the case of the common soil inhabitants Arthrobacter sp. (Figure 17) and Bacillus cereus (Figure 18). But the majority of the bacteria tested were not significantly influenced by exposure to TAGN. In most cases, the bacteria assimilated oxygen at nearly identical rates to those determined for the controls. A few isolets, such as StaphylocQccus^ aureus (Figure 14) and SR 406 (Figure 21), were even stimulated by exposure to TAGN. Both Pseudomonas aeruginosa and Escherichia coli were examined for their ability to degrade TAGN under batch fermenter conditions (Figure 26), In each case the bacteria significantly reduced the quantity of TAGN available in solution, persumably through degradation, although no methods were �available to determine active bioaccumulation or adsorption. Thin-layer chromatography of the resulting cell-free supernatants of the Pseudpmonas aeruginosa culture (Figure 27) failed to show the presence of any soluble TAGN byproducts, but did provide an additional method to verify the reduction of TAGN in aqueous solutions under these culture conditions. �SECTION IV CONCLUSIONS The results of this study indicate that, while TAGN was generally bacteriostatic at concentrations of 100 ppm and above, the bacteria tested were not otherwise adversely affected by concentrations as high as 2,000 ppm for contact periods up to 5 hours. Under the experimental conditions of this study, TAGN was neither bacteriocidal nor did it appreciably affect the respiratory activity of the cells. Following exposure and subsequent removal of TAGN from solution, all bacteria tested were capable of normal growth resumption. Moreover, some bacteria were capable of degrading or at least removing TAGN from solution, thereby effectively reducing the aqueous concentration of this compound as might result from testing and disposal of this proposed propellant. �1.6 1 (A) PseydoMonas aeruginosa 1,4 X 1.2 •M •H in (3 4> O 1.0 <D u o O.f <M 1/5 (fl c 0.6 (U Q en u p. o 0.4 0.2 10 Time (hours) 12 �1.6 -.1 (B) Bacillus megaterlum 1.4 , . X *J 1.2 •H t/> Q 2 1.0 SC O 0.8 - - X •M •H tfi g 0.6 Q Q •H 0.4 0.2 -- 8 10 12 14 16 18 20 Time (hours) Figure 1. Standard Growth Curves of (A) Pseudoiaonas aerugino sa QMB 1468 and (B) Bacillus megaterium QMB 1605 Exposed to TAGN �1.6 -r 2 (A) Staphylococcus aureus 1.4 - o 10 n Time (hours) 14 16 20 �l.fi-r 2 (B) Bacillus cereus 1,4- - X 1.2 • H tn c i.o- - O C. S to X g C.6 Q o • r4 10 12 14 16 18 Time (hours) Figure 2. Standard Growth Curves of (A) Staphylococcus aureus QMB 1458 and (B) Bacillus cereus QMB 1597 Exposed to TAGN �1.6 — 3 (A) Escherlchia coll 1.4- X 1.2. tn (3 O Q 1.0 - fl> U 3E C 0.8 - - CM LTS X +-> •H w C (U Q 0.6 - - tfl o •r-l *J 0.4 . . 0.2 . . Time (hours) �1.6 T 3 (B) SR 401 1.4 - - X1.2-- c Q -« 1.0 - i—i u 35 o o.e + LO X +J g 0-6 + Q ,0,4 - - 0.2 - - 50 ppm 100 ppm 500 ppm I Time (hours) Figure 3. Standard Growth Curves of (A) Escherichia coli QMB 1557 and (B) SR 401 Exposed to TAGN �4 (A) SR 403 1.4. . X 1.2. _ w C tt» o l.C o CJ s: O 0.8-- LD X 4-1 •—! £ 0.6. - ctt o .-4 a. 0.4 . _ o 0.2 - - Time (hours) 20 �1.6 -r Time (hours) Figure 4. Standard Growth Curves of (A) SR 403 and (B) SR 404 Exposed to TAGN �1.6 _ 1.4 - X 1.2 to 1.0 4» U s^/ as O 0.8 CM tn X 4-1 Pi 4> 0.6 Q O 0.2 -- 10 Time (hours) 12 14 16 18 20 �1,6-*5 (B) SR 407 1.4-- 1.2-0> o 1.0- 0) u O 0.8- CM LO W g 0.6' O n) U •H a, 0.4 O 0.2 -- 10 12 14 16 Time (hours) Figure S. Standard Growth Curves of (A) SR 405 and (B) SR 407 Exposed to TAGN 18 20 �1.6 10 Time (hours) 12 14 16 18 20 �<£> 10 Time (hours) 12 u Figure 6. Standard Growth Curves of (A) SR 408 and (B) SR 409 Exposed to TAGN 18 �7 (A) C 1 K) o Time (hours) �1.6 —. 8 10 12 14 U Time (hours) Figure 7. Standard Growth Curves of (A) C 1 and (B) C 4 Exposed to TAGN �N) K> 10 Time (hours) 12 14 16 18 �8 (B) Arthrobacter sp. 1.4. . X 1.2. . o> cs 2 i.o4- o 0.84- CN U^ •Jl g 0.6-JQ td o •H cL 0.4- . 0.2 - - 10 12 14 Time (hours) Figure 8. Standard Growth Curves of (A) T 6 and (B) Arthrobacter sp. QMB 1631 Exposed to TAGN 16 18 20 �1.6 — 9 (A) Bacillus subtilis 1.4. . X 1.2 •H c OJ a 1-0 tt» u 2 0 0.8 r-4 tn X g 0.6 o 03 O 0.2 20 Time fhours) �9 (B) Serratia marcescens a> Q •-< 1.0 - - u v_/ z O 0.8 r-j NJ cn tn g 0.6- - a 0.4-- 0.2- - 10 12 16 18 Time (hours) Figure 9. Standard Growth Curves of (A) Bacillus subtilis QMB 1611 and Serratia marcescens QMB 1466 Exposed to TAGN �1.6 -_. 20 Time (hours) �1.6 10 (B) SR 406 1.4 - - X 1.2 - . <D Q 1.0 - 0) u 3E O 0.8 fM LA tn C 0.6 o Q 0.2. . 16 Time (hours) Figure 10. Standard Growth Curves of (A) SR 402 and (B) SR 406 Exposed to TAGH IB 20 �1.6 ro 00 8 W Time (hours) 12 14 16 18 �1.6 -r 11 (B) T 100 Time (hours) Figure 11. Standard Growth Curves of (A) T 4 and (B) T 100 Exposed to TAGN �100 T 12 (A) PseudoiBonas aeruginosa (Endogenous) ( N O fti O CO 80- - o (U o TAGN (U O. Relative Rates: .Control (100 %) .500 ppm TAGN (86"r) 70- - 60 i I 10 Time (min") 12 14 16 18 �100 T 12 (B) Pseudoroonas aeruginosa (Exogenous) ^ Control \ D . 40 J_ Relative Rates -Control (100?) 500 ppm TAGN 20 10 14 16 Time (min) Figure 12. Endogenous (A) and Exogenous (B) Oxygen Uptake by Pseudomonas aeruginosa (^ffi 1468 Exposed to 500 ppm TAGN 18 20 �100 T 13 (A) Bacillus rnegaterium (Endogenous) Control 70 - - Relative Rates: V .Control (1002) .500 ppm TAGN (lOOt) I 60 10 Time (min) 12 14 I 16 18 20 �13 (B) Bacillus megateriurn (Exogenous) Relative Rates: Control (IOCS) 500 ppm TAGN (114%) 20 8 10 12 14 16 Time (rain) Figure 13. Endogenous (A) and Exogenous (B) Oxygen Uptake by Bacillus megaterium QMB 1605 Exposed to 500 ppm TAGN 18 �100 - . 14 (A) Staphilococcus aureus (Endogenous) 70 Relative Rates: .Control (100%) ,500 ppm TAGN (142%) 60 10 Time (min) 12 14 16 18 20 �100 T 14 (B) Staphylococcus aureus {Exogenous) Control 90 . _ o 3 r—i O 80. . D U SH 0> \ 500 ppm \ TAGM V \ \ N a. 70 . _ Relative Rates: .Control (100$) ,500 ppm TAGN (200%) f 60 S 10 12 a 14 16 Time (min) Figure 14. Endogenous (A) and Exogenous (B) Oxygen Uptake by Staphylococcus aureus QMB 1458 Exposed to 500 ppm TAGN 18 20 �100 . 15 (A) Serratla marcescens (Endogenous) 90 - - 500 ppm TARN <M o CD *—I o 80 - - c d> u o> ^ a. 70 . _ Relative Rates: .Control (100°*) ,500 ppm TAGN (112%) 60 10 Time 12 14 +— 16 f 18 20 �100 15 (B) Serratla inarcescens (Exogenous) 90 - - CM O ppm TAGN JO 3 80 - - c 4) o H 4) Q. 70 - - Relative Rates: .Control (100%) — -.-.—500 ppm TAGN (93%) 60 10 iz 14 Time (min) Figure 15. Endogenous (A) and Exogenous (B) Oxygen Uptake by Serratia inarcescens QMB 1466 Exposed to 500 ppm TAGN IB �100 -r- 16 (A) EscheH.chla colj (Endogenous) 90 - - . Control ( M O 0 ) 500 ppm TAGN •s r-t i—i O in 80 - CM 00 4) u 70 . . Relative Rates: .Control (100X) .500 ppm TASN (103%) 60 10 Time (min) 12 14 16 is 20 �100 16 (B) Escherichia coll (Exogenous) to OJ ( X 40 4- Relative Rates: .Control (100%) .500 ppm TAGN (118S) 20 10 12 14 16 Time (min) Figure 16, Endogenous (A) and Exogenous (B) Oxygen Uptake by Escherichia cpli QMB 1557 Exposed to 500 ppm TAGN 18 20 �100 .*17 (A) Arthrotuctar sp. (Endofenous) 500 ppir, ' v. TAGN CM O Control 3 i—i O 80. *-> 4> U f-i 70 Relative Rates: .Control (100%) ,500 ppm TA6N (56%) 60 10 Time (min) 12 14 16 18 20 �100 TT 17 (B) Arthrobacter sp. (Exogenous) 80 4- (M O 4> ! >. 500 ppm v TAGN V—* . 0 O CO 60-4- -(-I Q> CJ ^H 0) a. 404Relative Rates: .Control (1005:) .500 ppm TAGN (90?.) 20 10 Time (rain") Figure 17. Endogenous ( ) and Exogenous (B) Oxygen Uptake by A Arthrobacter sp. QMB 1631 Exposed to 500 ppm TAGN �100 T 18 (A) BacjVTus cereus (Endogenous) O C <£> O (H (U a, Relative Rates: .Control (10OT) _ _ _ _ _ _ 500 ppm TA6N (103'* 80 10 Time (min) 12 14 16 18 �100-t- 18 (B) Bacillus cereus (Exogenous) 500 ppm TAGN 90- - Control O 0> rH £3 •—t O CO 80- . c <u u CD ^ D, 70. - Relative Rates: Control (1005) 500 ppm TAGN (69°",) 60 10 14 16 Time (rain) Figure 18. Endogenous (A) and Exogenous (B) Oxygen Uptake by Bacillus cereus QMB 1597 Exposed to 500 ppm TAGN 18 20 �100 19 (A) SR 402 (Endogenous) 500 ppm TAGN 90- - Control o 0> i-H • § t-H O !) / 80- - <o o f-l 0) .. 0 70. _ Relative Rates: .Control (100%) ,500 ppm TAGN (72%) 60 10 Time (min) 1.2 14 16 18 20 �100 __- 19 (B) SR 402 (Exogenous) 90- 500 ppm TAGN (M o 3 i—t O 80 _ _ O> o !-. 03 O. 70 _ . Relative Rates: .Control (100%) 500 ppm TAGN (99*) 60 10 12 14 16 Time (min) Figure 19, Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 402 Exposed to 500 ppm TAGN 18 20 �100 _ 20 (A) SR 404 (Endogenous) 90- - O tu r-1 , 0 3 c 0 U 500 ppm TAGN Control 70- . Re1atl¥e Rates: , Control (100*) 500 ppm TAGN (84%) 60 10 Time (rain) 12 34 16 18 20 �100 _ 20 (B) SR 404 (Exogenous) 80- - CM o , 0 <—I O CO 60- - c <o u ft Relative Rates: 40- - .Control (100?) 500 ppm TAGN (1125) 20 H \ 8 10 12 16 Time (min) Figure 20. Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 404 Exposed to 500 ppm TAGN 18 20 �100, 21 (A) SR 406 (Endogenous) 4:1. oo 70. . Relative Rates: Control (100%) 500 ppm TASN (140%) 60 10 Time (min) 14 16 18 20 �100--. 21 (B) SR 406 (Exogenous) 90 - - o 0> I—I 3 O r—I 80-- -ft10 0) o (H 0) a. Control 70 Relative Rates: ..Control (100*) — _ — _. 500 ppm TAGN (87% 60 8 Figure 21, ^ 10 Time (rain) 12 14 16 Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 406 Exposed to 500 ppm TAGN 18 �100 T 22 (ft,) SR 407 (Endogenous) 90- - CM O <u 1—I , 0 3 80- VI O 4J CD O N S> £L, V 500 ppm TAGN S Control 70. Relative Rates: .Control (100*) .500 ppm TAGN (91%) 60 I I 10 Time (min) 12 14 16 18 20 �1CW T 22 (B) SR 407 (Exogenous) 80 . . r-j O 3 i-H O 60 - - O !~i 0> a. 500 ppm\ TAGN \ 40 - - Relative Rates: Control (100%) 500 ppm TAGN (134%) 20 10 14 16 Time (min) Figure 22. Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 407 Exposed to 500 ppm TAGN 18 20 �100-_ 23 (A) SR 408 (Endogenous) in r-o 70 Relative Rates: .Control (lOOt) 500 ppm TASN (107%) 60 10 Time (min) 12 14 16 18 20 �90-_23 (B) SR 408 (Exogenous) 70. - CN o O en 50- - 500 ppra TAGN o UJ F-t <u Cu 30. Relative Rates: .Control (100%) 500 ppm TAGN (77%) 8 10 12 14 16 Time (min) Figure 23, Endogenous (A) and Exogenous (B) Oxygen Uptake by SR 408 Exposed to 500 ppm TAGN 18 �100 T 24 (A) SR 410 (Endogenous) 90 . > o w TAGN GJ F-H •§ o I—I t/3 80 . _ Control C CO u f-l 70 _ . Relative Rates: .Control (10021) .500 ppm TAGN (102%) 60 10 Time (min) 12 16 18 �100 T 24 (B) SR 410 (Exogenous) CM O 0) f—t O 60 •M C 0) u 40 - - Relative Rates: .Control (1001) ,500 ppm TAGN (77° 20 8 10 12 14 16 Time (roin) Figure 24. Endogenous (A) and Exogenous (B) Oxygen Uptake by SR410 Exposed to 500 ppm TAGN 18 20 �100 25 (A) C 4 (Endogenous) 90 CM O 4) O to 80 c <u O 0) CL, 500 ppm TAGN 70- - Relative Rates: .Control (100%) __ _ _ _ 500 ppm TAGN (94%) 60 1*4 Time (min) re �100 T 25 (B) C 4 (Exogenous) \ 90 . . \ \ \ \ Cvl O t-t \ f> t-t O 01 500 ppm TAGN 80 __ 0) u \ N 0) o. 70 __ — Relative Rates: .Control (100S) 500 ppm TAGN (92%) 60 8 10 12 16 Time (min) Figure 25. Endogenous (A) and Exogenous (B) Oxygen Uptake by C 4 Exposed to 500 ppm TAGN �—.0,16 80 __ 26 (A) Pseudowonas aeruglnosa 70. . & O, ui z 'J DO Culture Density (O.D.; pp« TAGN 80 100 Time (hour) 120 140 160 180 �0.16 26 (B) Escherich^ia coil * en 20 40 60 80 100 1?0 140 160 Time (hour) Figure 26. Disappearance of TAGN from Cultures of (A) Pseudomonas aeruginosa QMS 1468 and Escherichia coli QMB 1557 as a Function of Cell Density ( . . 0D) �Solvent Front R f 0.11 Origin 0 hr 48 hr Mobile Phase: 72 hr 96 hr 120 hr 140 hr Standard TAGn Methane1 - Water - Dimethyl Sulfoxide (40:30:30) Figure 27. Thin-Layer Chroaatogram Depicting the Disappearance of TAGN from the Cell-Free Supernatant of a Growing Culture of Pseudomonas aeruginosa as a Function of Time 60 �TABLE 1. EXPOSURE OF BACTERIAL CULTURES OBTAINED FROM US ARMY NATICK LABORATORIES TO TAGN (N is the number of replicate samples; a is the observed significance level) Sample Incubation (hr) TAGN (ppm) N Standard Deviation Mean a 1 0 6 2.2xlO? 0.6xl07 .. . 1 500 5 l.SxlO7 0.9x10 0.114 1 2000 6 1.4x10 5 Pseudomonas aeruginosa 0 5 6.3x10 7 7 7 0.4x10 7 1.1x10 7 5 500 6 3.8x10 5 2000 4 3.2x10 1 0 6 11x10 7 1.0x10 7 7 0.2x10 6 Bacillus megaterium 6 1 500 6 5.8xl0 2.7xl0 1 2000 6 6 6.7x10 1.2x10 5 0 6 2.0x10 6 — 0.004 0.002 6 2.0x10 6 0.011 6 — 0.003 0.002 6 0.7x10 5 5 l.OxlO 0.3xl0 5 Bacillus cereus 500 — 0.007 2000 6 2.8xl06 0.6xl06 0.022 1 0 6 2.1x10 0.6x10 1 500 6 2.6xl06 2.0xl06 1 2000 6 2.9x10 5 0 6 2.7x10 5 500 6 1.2x10 5 2000 6 2.6x10 61 6 6 6 6 6 6 2.0x10 5 6 6 0.147 0.103 6 0.7x10 6 0.5x10 1.4x10 6 0.002 >0.2 �TABLE 1. EXPOSURE OF BACTERIAL CULTURES OBTAINED FROM US ARMY NATICK LABORATORIES TO TAGN (CONCLUDED) /v (N is the number of replicate samples; a is the observed significance level) Sample Incubation (hr) TAGN (ppm) N Mean Standard Deviation A- a 6 7,3xl07 I.SxlO7 500 6 7.9xlO? I.SxlO7 0.13 2000 6 6.6xlO? 1.9xl07 0.128 5 0 6 7.7xi07 O.SxlO7 5 500 6 S.lxlO7 2.1xl07 0.169 5 2000 6 7.9xlO? 1.2xl07 0.182 1 0 6 7.0xlO? 0.4xlO? 1 500 6 8.2xl07 3.3xlO? 0.109 1 2000 6 llxlO7 2,0xl07 0.002 5 0 6 8.2xlO? 2.0xl07 5 500 6 7.2xlO? 1.4xl07 5 Eseherichia coli 0 1 Serratia marcescens 1 1 Staphylococcus aureus 2000 6 8.2xl07 I.SxlO7 1 0 6 l,3xlO? 0.7xlO? 1 500 6 1.6xlO? 0.9xl07 0.138 1 2000 6 i.SxlO7 O.SxlO7 0.002 5 0 3 6,9xl07 3.1xl07 5 500 6 2.8xlO? I.SxlO7 0.042 5 2000 6 2,lxlO? 0.7xlO? 0.031 62 0.097 �TABLE 2. EXPOSURE OF BACTERIAL CULTURES INDIGENOUS TO EGLIN AFB, FLORIDA, TO TAGN A (N is the number of replicate samples; a is the observed significance level) N Mean Standard Deviation 0 6 l.SxlO7 0.2xlO? 1 500 5 l.SxlO7 0.3xl07 1 2000 6 l.SxlO7 5.6xlO? 5 0 4 2.8xl07 6.3xlO? 7 7 Sample Incubation (hr) SR 409 1 TAGN (ppm) 5 6 l.SxlO O.lxlO 5 SR 404 500 2000 6 2.3xl07 O.SxlO7 1 0 5 O.SxlO6 0.4x10 6 f\ a ___ 0.033 >0.2 — 0.194 >0.2 1 500 6 l.SxlO O.lxlO — 0.013 1 2000 5 l.lxlO6 0.2xl06 0.100 5 0 4 7.0xl06 0.6xl06 6 6 6 — <0. 00025 5 6 3.9xl0 l.lxlO 5 SR 406 500 2000 4 J.OxlO6 2.4xl06 1 0 6 5.6xl07 l.OxlO7 _ — 1 500 6 5.7xlO? 0.9xlO? >0.20 1 2000 6 S.OxlO7 0.6xlO? 5 0 5 8.7xl07 l.OxlO7 7 7 — 0.001 5 500 5 8.4xl0 l.SxlO — 0.191 5 2000 6 7.6xl07 1.9xlO? 0.076 63 �TABLE 2. EXPOSURE OF BACTERIAL CULTURES INDIGENOUS TO EGLIN AFB, FLORIDA, TO TAGN (CONTINUED) (N is the number of replicate samples; a is the observed significance level) Sample Incubation (hr) SR 402 1 TAGN (pprn) Standard Deviation a 0 6 4.3xl07 l.OxlO7 — «.— 500 6 4.8xl07 2.0xl07 0.154 1 2000 6 5.8xl07 l.SxlO7 0.024 5 0 6 5.9xl07 0.9xlO? --- 5 500 6 lOxlO7 l.OxlO7 <0. 00025 5 2000 6 S.SxlO7 0.9x10 0.002 1 0 6 4.8x10 1.9xlO? 1 500 6 4.1xl07 O.SxlO7 0.114 I 2000 6 7.4xl07 l.lxlO7 0.009 S 0 6 3.7xlQ7 l.SxlO7 -__ 5 500 6 5.2xl07 2.1xl07 0.061 S SR 408 Mean 1 SR 407 N 2000 6 2.9X107 O.SxlO7 0,092 1 0 6 2.4xl07 0.6xlO? 1 500 6 1.9xlO? 0.2xl07 0.028 1 2000 6 S.lxlO7 0.6xlO? 0.029 5 0 6 3.2xl07 0.7xlO? 7 7 A. _ __ 5 500 6 2.8xl0 0.4xl0 — 0.083 5 2000 6 3.0xl07 O.SxlO7 0.150 64 �TABLE 2. EXPOSURE OF BACTERIAL CULTURES INDIGENOUS TO EGLIN AFB, FLORIDA, TO TAGN (CONCLUDED) (N is the number of replicate samples; a is the observed significance level) Sample Incubation (hr) SR 405 1 TAGN (ppm) Standard Deviation N Mean 0 5 1.0x10 1 500 6 1 2000 6 5 0 6 5 500 6 1.2xlO? 7 1.0x10 7 1.6x10 7 1.0x10 0.4xlO? 7 0.2x10 7 0.3x10 7 0.4x10 5 2000 6 0.3xlO? 0.2xl07 7 0.1x10 65 (The reverse of this page is blank) /•>• a 7 — 0.080 — — 0.009 <0. 00025 ��REFERENCES 1. Oster, G., and A.W. Pollister, (eds.). Physical Techniques in Biological Research, New York: Academic Press, 1955, Vol I, pp. 51-76. 2. Norris, J.R., and D.W. Ribbons, (eds.), Methods in Microbiology, New York: Academic Press, 1969, Vol I, pp. 473-504. 3. Housewright, R.D., and C.B. Thorne, "Synthesis of Glutamic Acid and Glutamyl Polypeptide by Bacillus anthracis; I. Formation of Glutamic Acid by Transamination," Journal of Bacteriology, 1955, 60:89. 67 (The reverse of this page is blank) ��INITIAL DISTRIBUTION DDC 12 AUL (AUL/LSE-70-239) 1 ASD/ENFEA USAF (AF/SAMI) 1 1 Ogden ALC/MMWM AFIS/INTA Veg Con Div (SAREA-CL-V) DDR§E (Tech Lib) 2 1 1 1 USAFA/DFCBS 1 AFLC (DS) Deseret Test Cen (Tech Lib} 1 1 AFLC/MMNO SAAMA/SFOT 1 1 NWC (Tech Lib) NWL (Tech Lib) USDA/Pesticide Coordinator USDA/Agr Env Qual Inst AFSC/SDW DDR§E (Env § Life Sci) Edgewood Arsenal (SAMUEA-SA) AFSC/DEV AEDC/DEE Edgewood Arsenal (SAREA-TS-L) 1 1 1 1 1 1 1 1 1 1 Edgewood Arsenal (SAREA-CL-V) 1 CINCPAC(JSAl) USAF Env Health Lab NASA Miss Test Facility NWC Env Eng AMD (RD) 1 1 1 1 1 USA Natick Lab 1 AMRL/THE AFCEC/EQ AMRL/THT Eglin AFB: ADTC/DEN ADTC/SGPE TAWC/TRADOCLO 1 1 1 1 1 1 AFATL/DL 1 AFATL/DLOSL 9 AFATL/DLV 10 ADTC/CSV 1 69 (The reverse of this page is blank) �� Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 017 Folder The folder containing the original item. 0184 Series The series number of the original item. Series II Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Patrick, Michael A. Description An account of the resource <strong>Corporate Author: </strong>Environics and Human Factors Office, Air Force Armament Laboratory, Armament Development and Test Center, Eglin AFB, Florida Date A point or period of time associated with an event in the lifecycle of the resource 1976-11-01 Title A name given to the resource Toxicological and Recalcitrant Properties of a Proposed Propellant Ingredient, Triaminoguanidine Nitrate (TAGN). I. Microbiological Study Subject The topic of the resource microbial populations biodegradation Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 049 Folder The folder containing the original item. 1264 Series The series number of the original item. Series III Subseries II Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Matsumura, Fumio Herman J. Benezet Source A related resource from which the described resource is derived Environmental Health Perspectives Date A point or period of time associated with an event in the lifecycle of the resource 1973-09-01 Title A name given to the resource Studies on the Bioaccumulation and Microbial Degradation of 2,3,7,8-Tetrachlorodibenzo-p-dioxin Subject The topic of the resource dioxin biodegradation ecological fate ao_seriesIII Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 038 Folder The folder containing the original item. 0827 Series The series number of the original item. Series III Subseries I Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Klopffer, W. G. Rippen R. Frische Source A related resource from which the described resource is derived Ecotoxicology and Environmental Safety Date A point or period of time associated with an event in the lifecycle of the resource 1982 Title A name given to the resource Physiochemical Properties as Useful Tools for Predicting the Environmental Fate of Organic Chemicals Subject The topic of the resource biodegradation ao_seriesIII