1 15 1 https://www.nal.usda.gov/exhibits/speccoll/files/original/b29b54a15edda14ac6493b0c79bcf958.pdf 7aeb403cf849e31e37aa9c0d15379e01 PDF Text Text Item ID Number: AllthOT Corporate Author 00103 Harrison, Don D. Environics Office, Air Force Armament Laboratory, Eglin AFB, Florida Report/Article Tltlfl Residual Levels of 2,3,7,8-Tctrachlorodibenzo-p-Dioxin (TCDD) Near Herbicide Storage and Loading Areas at Eglin AFB, Florida Journal/Book Title Year wn Month/Day February Color Number of Images 33 DeSCrlptOD NOtOS Report No. AFATL-TR-79-20; PE: 62602F; JON: 06CD0101; 3 partial duplicateserrata for document. Full document has already had errata pages replaced. Friday, December 08. 2000 Page 103 of 106 �AF ATL-TR- 79-2O Residual Levels of 2,3,7,8-Tetrachlorodibenzo-p-Dioxin (TCDD)Near Herbicide Storage and Loading Areas at Eglin AFB, Florida MMJ. HARRISON RICHARD C. CREWS FEBRUARY 1979 FINAL REPORT FOR PERIOD JANUARY 1976-DECEMBER 1978 Approved for public release; distribution unlimited Air Force Armament Laboratory AIR FORCE SYSTEMS COMMAND*UNITED STATES AIR FORCE+EGLIN AIR FORCE BASE, FLORIDA �UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE (When READ INSTRUCTIONS BEFORE COMPLETING FORM REPORT DOCUMENTATION PAGE 1. REPORT NUMBER 7. OOVT ACCESSION NO 3. RECIPIENT'S C A T A L O G NUMBER AFATL-TR-79-20 4. TITLE (md Subtitle) 5. TYPE OF REPORT ft PERIOD COVERED RESIDUAL LEVELS OF 2,3,7,8-TETRACHLORODIBENZO-pDIOXIN (TCDD) NEAR HERBICIDE STORAGE AND LOADING AREAS AT EGLIN AFB. FLORIDA Final Report: December 1978 January 1976 6. PERFORMING 0=»O. REPORT NUMBER e.~"C*GNTRACT OR <3RANT"NUMBER(«J 7. AUTHORS Don D. Harrison Charles I. Miller Richard C. Crews 9. PERFORMING O R G A N I Z A T I O N NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT. T A S K AREA ft WORK UNIT NUMBERS Environics Office Air Force Armament Laboratory Eglin Air Force Base, Florida 32542 PE: 62602F JON: 06CD0101 12. REPORT DATE II. C O N T R O L L I N G OFFICE N A M E AND ADDRESS Air Force Armament Laboratory Armament Development and Test Center Eglin Air Force Base, Florida 32542 February 1979 13. NUMBER OF PAGES 32 14. MONITORING AGENCY NAME fi ADDRESSfl/ dlllerent from Contr<-l!tng Ottice) 15. SECURITY CLASS, (ol this report) UNCLASSIFIED I5«. DECLASSIFI CATION''DOWN GRADING SCHEDULE 16. DISTRIBUTION STATEMENT fof ffif* Report) Approved for public release; distribution unlimited. 17. DISTRIBUTION STATEMENT (ol lha abstract entered In Block 30, II different from Report) IB. SUPPLEMENTARY NOTES 19. KEY WORDS (Continue an reverse aide It necessary and Identity by black number) Hards band 7 2,4-dlchlorophenoxyacet1c add (2,4-D) 2,4,5-tr1chlorophenoxyacet1c add (2.4,5-T) 2,3,7,8-tetrachlorodibenzo-p-d1ox1n (TCDD) Herbicide Orange »0 (Agent Orange) Herbicide Blue Herbicide White Herbicide Purple D1ox1n A B S T R A C T fC'onllriuv nr- reverse side II necessary mud Identify by blorh number) A study was made of the residual levels of 2,3,7,8-tetrachlorodibenzo-pdioxin (TCDD) in the areas surrounding three hardstands on Eglin AFB, Florida, that had been previously used for storing end loading military herbicides. The study deals only with areas in the immediate vicinity of these hardstands and their associated drainage systems. Massive quantities of herbicides, including Herbicide Orange, were loaded at these hardstands between 1962 and 1970. Only one of the three storage and loading areas was found to be contarninatec wich TCDD. Hardstand 8 and the East End of Taxiway 9 were relatively free of FORM I JAN 73 1473 EDITION OF I NOV 65 IS OBSOLETE UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE (When Data Entered) �UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGErH'hsrt Data Entered) 19. CONCLUDED Chlorinated phenols Environmental Monitoring Phenoxy Herbicides Defoliant Environment Contamination 20. CONCLUDED TCDD residues in the soil. Soil from around Hardstand 7, the most intensively used hardstand, still has concentrations of TCDD as high as 275 parts per b i l l i o n (ppb), however. Concentrations of one-third that amount were present to a depth of one meter at two sampling sites. Soil contamination around Hardstand 7 is confined to a small area immediately surrounding the concrete pad. A map of TCDD soil concentrations is presented. "•"CDD was found to be present in biological organisms in the immediate vicinity of Hardstand 7 and the Hardstand Pond. However, no TCDD was found in any of the environmental samples collected in a bayou immediately downstream from the Hardstand 7 area. UNCLASSIFIED ',t< . i K i r y Ci • ','iiFH.ArioN O' '• "• r>>"'-' " ' " ' ' " »'" " " �PREPACK This report is the result of research conducted by the Air Force Armament Laboratory, ADTC from January "1976 to December 1978 under Air Force Exploratory Development Project 06CD0101. The Brehm Laboratory and Department of Chemistry at Wright State University (WSU), Dayton, Ohio, performed all tetrachlorodibenzo-p-dioxin (TCDD) analyses in this study except where noted. Most soil samples analyzed under this study employed Gas Chromatography-Quadrupole Mass Spcctrometry (GC-QMS) at the 100 - 1000 picogram/gram (parts per trillion) detection limit. Some soil samples and all biological sajnples analyzed by WSU were analyzed employing Gas Chroma tography - High Resolution Mass Spcctrometry (GC-HRMS) at the 30 picograrns/gram detection limit. The primary reason for the predominant use of the low resolution method was the lower cost of analysis. The reduced cost per sample permitted more samples to be taken. For the purposes of this study, a more intensive sampling effort was considered more important than a low detection limit. This report has been reviewed by the Information Officer (01) and is re leasable to the National Technical Information Service (NTIS). At NTTS 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 Thief, Environics Office (The reverse of this page is blank) ��TABLE OF CONTENTS Section Title Page I INTRODUCTION 1 II BACKGROUND 2 1. Description of Monitoring Areas 2 a. East End of Taxi way Number 9 2 b. Hardstand 8 4 c. Hardstand 7 5 2. Herbicides Used on Eglin 9 a. Herbicide Orange 9 b. Herbicide White 10 c. Herbicide Blue 10 d. Herbicide Orange II 11 e. Herbicide Purple 11 3. Chemical Properties and Effects of TCDD. . 12 III TCDD Analysis 14 1. East End of Taxiway Number 9 14 2. Hardstand 8 14 3. Hardstand 7 17 a. Sediment Samples b. Soil Samples 17 c. Biological Samples IV 17 21 CONCLUSIONS 25 REFERENCES 26 �LIST OF FIGURES Figure ' Title Page 1 East End of Taxiway Number 9, Eqlin AFB, Florida 2 2 Eglin AFB Herbicide Storage and Loading Sites with Associated Aquatic Drainage Areas 3 3 Hardstand 8, Eglin AFB, Florida 4 4 Aerial View of Hardstand 7, Eglin AFB, Florida 5 5 Hardstand Pond Located Behind Hardstand 7 6 6 Beaver Pond Located Downstream From Hardstand 7 6 7 Typical Storage of Herbicide on Hardstand 7 7 8 Locations of Known Herbicide Storage Sites and Disposal ?it on Hardstand 7 8 Total Herbicide Application on Test. Area C-52A, Eglin AFB, Florida, 1962 Through 1970 9 9 10 Soil Sampling Sites at East End of Taxiway Number 9, Eglin AFB, Florida 15 11 Soil Sampling Sites at Hardstand 8.. Eglin AFB, Florida . . . 16 12 Sampling Sites at Hardstand 7, Eglin AFB, Florida 19 13 Tom's Pond, Eglin AFB, Florida 22 14 Snapping Turtle (Male) Collected 1978 from Hardstand Pond, Eglin AFB, Florida 24 IV �LIST OF TAULES Table Title Page 1 Approximate Total Volume of Herbicides Applied to Test Area C-52A, Eglin AFB Reservation, Florida, 1962 Through 1970 11 Total Pounds of Active Ingredients of Herbicides Disseminated on Test Area C-52A, Eglin AFB Reservation, Florida, 1962 Through 1970 12 Results of TCDD Determinations in Soil Samples Collected January 1976, from East End of Taxi way Number 9, Eglin AFB, Florida 14 Results of TCDD Determinations in Soil Samples Collected January 1976, from Hardstand 8, Eglin AFB, Florida 17 Results of TCDD Determinations in Sediment and Soil Samples Collected for TCDD Analysis in 1977 18 Results of TCDD Determinations in Soil Samples Collected January 1978 from Hardstand 7, Eglin AFB, Florida 20 TCDD Analysis of Organisms Collected on Eg'lin AFB, Florida 23 2 3 4 5 6 7 (The reverse of this page is blank) ��SECTION I INTRODUCTION Reported here are the results of a study made of the residual levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the areas surrounding three hardstands that had been previously used for storing and loading military herbicides at Eglin Air Force 3ase, Florida. TCDD is an extremely toxic material that has been reported to be mutagenic, teratogenic, and carcinogenic in some organisms, although those effects are unconfirmed in man (References 1, 2, and 3). It was shown to be a contaminant in several herbicide formulations which were used extensively on Cglin test ranges from 1962 through 1970 (Reference 4). The objective of this effort was to determine concentrations and distribution of contamination detected during work reported in AFATL-TR75-49 (Reference 5). The study was designed so that data obtained from it could be used to map TCDD soil concentrations in the immediate vicinity of three hardstands and to determine range boundaries of the contamination emanating frorr the hardstands. The hardstand areas were subjected to massive amounts of herbicides due to spills, leaking drums, purging of aircraft spray systems, and malfunctions of aircraft spray nozzles. For lack of exact information on the time, amount, and type of herbicide released to the environment at each specific site, precise degradation rates for the TCDD could not be calculated at the completion of this study. As more samples are analyzed in the future, using data in this report as a baseline, valuable conclusions on degradation rates may be established. Because of the dynamic nature of the areas studied for this report and the many factors that can influence movement and degradation of any contaminant, caution should be used in applying these data to other situations. �SECTION II BACKGROUND 1. DESCRIPTION OF MONITORING AREAS a. East End of Taxiway Number 9 This area is the end of a taxiway that was used briefly during the beginning of the defoliation test program at Eglin (Figure 1). The quantity of herbicide previously stored or loaded at this location is unknown but is suspected to be small. However, at the time that this location was used, the herbicides involved were predominantly Purple and Orange, both of which contained TCDD as a contaminant.' The concrete runway area is bordered by an asphalt strip and is approximately 55 feet (17 meters) above sea level. The soil surrounding the area is sandy with excellent drainage potential. Excess water is drained by a storm sewer into a bayhead to the east of the runway. This bayhead forms a stream which empties into Tom's Bayou approximately 1000 meters downstream {Figure 2). Figure 1. East End of Taxiway Number 9, Eglin AFB, Florida �Figure 2. Eglin AFB Herbicide Storage and Loading Sites with Associated Aquatic Drainage Areas �b. Hardstand 8 Hardstand 8 (Figure 3) is an asphalt and concrete aircraft parking area located west of the north-south runway on the main Eglin airdrome (Figure 2), approximately 65 feet (20 meters) above sea level. The hardstand is connected to the airdrome by an asphalt taxiway. This hardstand was used for limited herbicide storage and loading during the latter portion of the spray program. The area surrounding Hardstand 8 is level with very little runoff occurring. The soil of this area is sandy with excellent drainage potential. Figure 3. Hardstand 8, Eglin AFB, Florida �c. Hardstand 7 Hardstand 7 (Figure 4) is -ar asphalt and concrete aircraft parking area located west of the north-south runway on the main Eglin airdrome, approximately 65 feet (20 meters) above sea level. The hardstand is connected to the airdrome by an asphalt taxiway. This hardstand was the most extensively used site for herbicide storage and loading during the 1962 through 1970 spray test program. The soil of this area is sandy with good drainage properties. Directly behind the hardstand is a ravine that drops off approximately 15 meters to a small pond (Figure 5). Because of the packing caused by vehicular traffic and the water-repellent nature of the oil-based herbicide contamination, runoff of excess water caused an erosion problem in some spcts which led to the frequent use of fill dirt. Eventually, a dike covered with asphalt was constructed on the rim of the ravine for soil stabilization. A storm drain was alse installed to help control erosion. The pond behind Hardstand 7 drains into a small stream which flows north until it enters a man-made reservoir named Beaver Pond (Figure 6). The drainage system eventually flows into Tom's Bayou and Choctawhatchee Bav. " *'*•* , •''• '*''•."?«. " Figure 4. Aerial View of Hardstand 7, Eglin AFB, Florida 5 i *', ;b * �.1' Figure 5. Hardstand Pond Located Behind Hardstand 7 Figure 6. Beaver Pond Located Downstream From Hardstand 7 �Several hundred 55-gallon drums of various types of herbicide were stored around Hardstand 7 for later transfer of their contents into tanks aboard spray aircraft (Figure 7). Known storage locations are shown in Figure 8. Much of the area immediately surrounding this hardstand was contaminated with herbicide due to accidental spills during loading operations and transfer procedures, leaking drums, and purging of spray systems before and after missions. A pit was dug in 1969 (according to the best available information) to the southwest of the hardstand as a temporary means of preventing the excess herbicides from entering the stream back of the hardstand (Figure 8). After several months of use, the pit was filled with soil. —r . ™—™: - "•" •* •.' ' ' Figure 7. Typical Storage of Herbicide on Hardstand 7 �' FIVE FOOT A S P H A L T COVERED DIRT MOUND W \ ASPHALT N \ Pit DIRT MOUND HERBICIDE DRUMS igure R. Locations of Known Herbicide Storage Sites and Disposal Pit on Hardstand 7 �2. HERBICIDES USED ON. EGLIN Several herbicides and/or mixtures of herbicides were tested at Eg!in during the period 1962 through 1970. These herbicides were loaded into aircraft spray tanks at the previously described storage areas. Spray equipment and planes were also washed down at bhese sites after the spray missions. Characteristics of these herbicides are listed below (Reference 6), Although other formulations of 2,4,5-T were also used (e.g., Pink, Green), the formulations listed below were the predominant ones used in Eglin test programs. As seen in Tables 1 and 2 and Figure 9, massive quantities of these herbicides were stored and disseminated on Eglin test ranges during the period 1962 through 1970 (Reference 7). 5 ^ PURPLE 55 C ORANGE ^ H WHITE a z > I } BLUF z 62 63 64 65 66 67 68 f VEAR OF APPLICATION 70 Figure 9. Total Herbicide Application on Test Area C-52A, Eglin AFB, Florida, ]962 Through 1970 The names Orange, White, Blue, and Purple used below were code names and unrelated to the color of the materials. a. Herbicide Orange Orange was a reddish-brown to tan colored liquid soluble in diesel fuel and organic solvents but insoluble in water. One gallon of Orange contained about 4.21 pounds of the active ingredient of 2,4-dichlorophenoxyacetic acid (2,4-D) and about 4.41 pounds of the active ingredient of 2,4,5-trichlorophenoxyacetic acid (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 49.49 free acid of 2,4-D 0.13 n-but;yl ester of 2,4,5-T free acid of 2,4,5-T 48.75 1.00 inert ingredients (e.g., butyl alcohol and ester moieties) 0.63 b. Herbicide White White was a dark brown, viscous liquid that was soluble in water bit insoluble in organic solvents and diesel fuel. One gallon of White contained 0.54 pound of the active ingredient of 4-amino-3,5,6-trichloropicolinic acid (picloram) and 2.00 pounds of the active ingredient of 2,4-D. White was formulated to contain a "!:4 mixture of the triisopropanolamine salts of picloram and 2,4-D. The percentages of the formulation were: triisopropanolamine salt of picloram 10.2 triisopropanolamine salt of 2,4-D inert ingredient (primarily the solvent triisopropanolamine) c. 39.6 50.2 Herbicide Blue Blue was a clear yellowish-tan liquid that was soluble in water but insoluble in organic solvents and diesel fuel. One gallon of Blue contained 3.10 pounds of the active ingredient hydroxydimethlarsine oxide (cacodylic acid). Blue was formulated to contain both cacodylic acid (as the free acid) and the sodium salt of cadodylic acid (sodium cacodylate). The percentages cf the formulation were: cacodylic acid 4.7 sodium cacodylate 26.4 surfactant 3.4 sodium chloride / water 5.5 59.5 antifoam agent 0.5 10 �It should be noted that cacodylic acid and sodium cacodylate contained arsenic in the form of the pentavalent, organic arsenical. This form of arsenic has a low mammaliam toxicity. Of the total formulation, 15.4 percent was arsenic in the organic form, and only trace quantities were present in the inorganic form. The term Herbicide Blue was applied to powdered cacodylic acid in 1961 through 1964. This herbicide contained 65 percent active ingredient cacodylic acid and 30 percent sodium chloride and was mixed in the field with water. d. Herbicide Orange II Orange II was the military designation of a formulation similar to Orange with the difference being ths substitution of the isooctyl ester of 2,4,5-T for the n-butyl ester of 2,4,5-T. The physical, chemical, ana toxicological properties of Orange II were similar to those of Orange. e. Herbicide Purple The first record of the use of Purple in large quantities was in the Camp Drum, New York defoliation test in 1959. The formulation was a brown liquid, soluble in diesel fuel aid organic solvents but insoluble in water. One gallon of Purple contained 8.6 pounds of the active ingredients 2,4-D and 2,4,5-T. The percentages of the formulation were: r-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. TABLE 1. APPROXIMATE TOTAL VOLUME OF HERBICIDES APPLIED TO TEST AREA C-52A, EGLIN AFB RESERVATION, FLORIDA, 1962 THROUGH 1970 Herbicide Gallons Disseminated Orange 19,807 Purple 16,164 White 4,172 Blue 4,395 11 �TABLE 2. TOTAL POUNDS OF ACTIVE INGREDIENTS OF HERBICIDES DISSEMINATED ON TEST AREA C-52A, EGLIN AFB RESERVATION, FLORIDA, 1962 THROUGH 1970 Pounds Active Ingredient Chemical 2,4-D 169,292 • 2,4,5-T 160,948 Piclorain 2,253 - Cacodylic Acid and Sodium Cacodylate 3. 13,624 CHEMICAL PROPERTIES AND EFFECTS OF TCDD 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is molecule that has received a great deal of public since 1970 because of its highly toxic properties its being a contaminant in the environment by the from trichlorophenols. a heterocyclic organic and scientific attention and the possibility of use of products made TCDC is a synthetic, chlorinated hydrocarbon produced from trichlorophenol at high reaction temperatures. Trichlorophenols are used in the production of several chemicals. Since trichlorophenol is a precursor of 2,4,5-T, TCDC was present in varying quantities as an impurity in herbicides that contained 2,4,5-T (e.g., Orange and Purple). TCDD is a solid which is very insoluble in water (0.2 parts per billion (ppb) at 25° C); very slightly soluble in fats (44 parts per million (ppm) in lard oil); slightly soluble in hydrocarbons (570 ppm in benzene); and somewhat more soluble, but still not very highly so, in chlorinated organic solvents (1400 ppm in ortho-dichlorobenzene)., Its solubility in Orange is 580 ppm. Like other chlorodioxins, TCDD is relatively stable when subjected to heat, acid, and alkali. For thermal decomposition, a temperature of about 800° C is required (Reference 3). 12 �iCDD is an extremely toxic material that is aloo reported to cause hirth defects and embryo mortality (Reference 2). It is an extremely stable compound which has a relatively long half-life (References 8 and 9). U(!(,dir;r! of it.1, insolubility in water, TCDD is considered to be relatively immobile in the environment. It is impossible to state the exact concentrations of TCDD in herbicides Orange and Purple that were used on Eglin, but analyses of samples from herbicide Orange left over from ~;he Vietnam conflict can be used to estimate the probable concentrations. The mean TCDD concentration range in Herbicide Orange was <0.02 to 15 ppm with an overall mean of 1.98 ppm. The mean TCDD concentration range in Herbicide Purple was 17 to 47 ppm with an overall mean of 32.8 ppm (Reference 6). Herbicides used at Eglin from 1962 throuph 1970 probably contained concentrations of TCDD similar to those analyzed from Johnston Island and Gulfport, Mississippi. 13 �SECTION III TCDD ANALYSIS 1. EAST END OF TAX IWAY NUMBER 9 In January 1976, five soil samples were taken from the east end of Taxiway Number 9 and one sediment sample from the exit of the storm sewer drain (Figure 10). The soil samples were taken from the top 10 cm at sites considered to be likely areas for herbicide contamination. No TCDD was found in any of the samples (Table 3). TABLE 3. RESULTS OF TCDD DETERMINATIONS IN SOIL SAMPLES COLLECTED JANUARY 1976, FROM EAST END OF TAXIWAY NUMBER 9, EGLIN AFB, FLORIDA TCDD Concentration Sample TCDD (ppb) Detection Limit (ppb) 6 0.045 7 NDa 0.030 8 NDa 0.030 9 NDa 0.030 10 NDa 0.032 11 a NDa NDa 0.040 Not Detected 2. HARDSTAND-8 Five soil samples from the top 10 cm were also collected in January 1976, from Hardstand 8 (Figure 11). Site Number 5, with 0.034 ppb, was the only sampling point around this hardstand that contained a detectable quantity of TCDD (Table 4). 14 �Stream 6 concrete 10 5Om Figure 10. Soil Sampling Sites at East End of Taxiway Number 9, Eglin AFB, Florida 15 �Concrete N i 15m I igure 11. Soil Sampling Sites at, Hardstand 8, Eglin AFB, Florida 15 �TABLE 4. RESULTS OF TCDD DETERMINATIONS IN SOIL SAMPLES COLLECTED JANUARY 1976, FROM HARDSTAND 8, EGLIN AFB, FLORIDA TCDD Concentration Sample TCDD (ppb) Detection Limit (ppb) 1 0.030 2 NDa 0.030 3 NDa 0.030 4 NDa 5 a NDa 0.034 0.030 _b Not Detected Not Applicable 3. MAROSTAND 7 Because of the potential for TCDD contamination of the aquatic system draining Hardstand 7 and the previous data obtained from that area (Reference 5), sediment and soil samples, as well as biological organisms, were collected from several locations at this area in February 1977. a. Sediment Samples. Two sediment samples were collected from the hardstand pond directly behind Hardstand 7. Silt sample 1 consisted of organic dctritis, and silt sample 2 was taken from below that layer and was predominantly sand. Silt sample 3 was from Tom's Pond taken downstream from the man-made Beaver Pond dam (Figjre 2), which in turn was approximately 15 meters below a natural beaver dam. Silt sample 4 was taken from the head of Tom's Bayou at the creek entrance. This sample was taken from the surface to a depth of 15 cm and consisted almost entirely of detritis. Results from these samples are listed in Table 5. b. Soil Samples. In addition to bhe sediment samples, soil samples were taken ir February 1977from two locations at Hardstand 7 where herbicide con Lamination was known to exist (Figure 12). These samples were designated sample 5 and sample 6 and were taken from 0 through 10 cm and 40 throuch 50 cm, rcspecLively, ?. meters northeast of the concrete edge of the hardstand. Samples 7 and 8 were taken from 0 through 10 cm arid 40 throuch 50 cm, respectively, 2 meters southwest of the concrete edge of the hardstand. Results from these soil samples are given in Table 5. 17 �TABLE 5. RESULTS OF TCDD DETERMINATIONS IN SEDIMENT AND SOIL SAMPLES COLLECTED FOR TCDD ANALYSIS IN 1977 TCDD Concentration TCDD Date Collected (ppb) Sample Location Collected Detection Limit (ppb) 1 Hardstand 7 Pond (Detritis) Feb 77 NDa 0.370 2 Hardstand 7 Pond (Sand) Feb 77 NDa 0.037 3 Tom's Pond May 77 4 Tom's Bayou Mar 77 5 2 Meters N of Concrete (0-10cm) Feb 77 6 2 Meters N of Concrete (40-50 cm) Feb 77 7 2 Meters S of Concrete (0-10 cm) Feb 77 8 2 Meters S of Concrete (40-50 cm) Feb 77 a 0.65 NDa 37.8 0.69 275 37.1 -b 0.031 -_b _b _b _b Not Detected Not Applicable Since relatively high levels of TCDD were found in soils around Hardstand 7, it was decided to conduct a more thorough monitoring effort at this hardstend. A grid system was established around Hardstand 7 (Figure 12) in order to facilitate the monitoring effort. Beginning at the center of the hardstand pad, 14 radians were established at 22.5 degree intervals, designated A through N, with A being the south southeast radian and proceeding clockwise. Sampling points on each radian were established at 20, 25, 30, am1 40 meters from the center point. These sampling points were designated by the numbers 1, 2, 3, or 4, respectively, following the letter designating the radian. The third designation for each sample identification indicates the depth at which the sample was taken: 1 = 0 through 10 cm, 2 = 20 through 30 cm, 3 = 55 through 70 cm, and 4 = 95 through 110 cm. Soil samples were collected using this grid system during January 1978. All designated sairpling sites were not actually sampled since asphalt covered some areas, and other areas had been covered with overfill to the extent that the sanple would have been meaningless. Those sites used and the TCDD concentrations found at those sites are presented in Table 6 and Figure 12. 18 �FIVE FOOT A S P H A L T COVERED DIRT MOUND N D4 DIRT MOUND C4. 20m Note: Soil concentrations of TCDD in ppb are given at each site by depth from top to bottom. Depths sampled were 0-10 cm, 20-30 cm, 55-70 cm, and 95-110 cm. £11 depths were not sampled at each site, however. Figure 12. Sampling Sites at Handstand 7, Eglin AFB, Florida 19 �TABLE 6. RESULTS OF TCDD DETERMINATIONS IN SOIL SAMPLES COLLECTED JANUARY 1978 FROM HARDSTAND 7, EGLIN AFB, FLORIDA TCDD Concentration Sample TCDD (ppb) TCDD Concentration Detection Limit {ppb) Sample b A21 1.5 A22 NDa NDS A31 4.2 NDa A41 NDa Bll 198.9* B12 53.6 B13 20.4 ND d 1 .0 F41 1.0 b A32 Detection Limit (ppb) F33 1.0 A23 TCDD (ppb) NDa 1 .0 G31 NDa 1.0 632 NDa 1.0 1 .0 G33 NDa 1.0 b H31 0.2 1.0 b H32 ND3 1.0 H33 NDa 131 0.5 1.0 b b _b B21 NDd 1.0 132 NDa 1.0 B22 NDa 1.0 133 ND3 823 NDa 1.0 021 0.8 1.0 b B31 NDa 1.0 J22 NDa 1.0 B41 NDa ND3 cn 3.0 1.0 _b 023 J31 0.5 1.0 b C12 1.0* J32 NDa i.n 03 5.9* 041 NDa C14 0.7* 1.0 b b b b Kll 70.2* C21 NO 3 1 .0 K12 20.2* C22 NDS 1.0 K13 16.6* C23 NDd 1.0 K14 19.0 C31 a ND 1.0 K21 3.9 C32 N0a 1.0 K22 0.8 C33 a ND 1.0 K23 0.030** C41 NO3 1.0 b K31 0.4 Dll D12 D13 D14 77.7* K32 127.4 97.1* 4.5 L12 0.133** LI 3 b _b NDa 111 b 0.5* K41 _b 121.4 HDa b b b b b b b b 1.0 b b D21 0.079** L21 0.4 023 NDa 1.0 L22 NDd 1.0 D31 NDa 1.0 L23 NDa 1.0 032 N0a 1.0 L31 ND8 1.0 033 NDS 1.0 L41 ND3 D41 NO3 Mil 0.8 1.5* 1.0 b 1.0 b Ell Ml 2 NO3 1.0 E12 NO3 1.0 M21 NDa 1 .0 E13 NDa ND3 1 .0 Q.I 1.0 b M22 E14 H31 NDa 1.0 E21 0.5 M41 NDa E22 NDa 1.0 Nil 1.0 b E23 NDa 1.0 N12 N0a 1.0 E31 NO 3 1.0 N13 NDa 1 .0 E32 NDa 1.0 N21 NDa 1.0 E33 a ND 1.0 N22 NDa 1.0 E41 NDa 1 .0 N23 NDa F31 NDa 1.0 N31 3.0 1.0 t> F32 a 0.7 D22 NDa 1.0 N41 NDa b _b 18.9 1.0 _b 1.0 Not Detected riot Appl icable 'samples contained varyi ig quantities of red dye. Red dye was used as an indicator for test purposes during the 1962 through 1970 spray m i s s i o n s . A slightly different extraction technique was used for these samples. "samples were subjected to high resolution mass spectrometry (GC-HRMS). 20 �The highest concentration of TCDD found in the soil surrounding Hardstand 7 from this set of samples was 198.9 ppb. This was found in the surface sample at site 81. Several other sampling sites nearest the concrete pad were also heavily contamirated. This was expected, however, since drainage of spills from the concrete pad woulc migrate to those areas and also because of leakage from drums that had been stored at those areas. The presence of TCDD at depths down to 100 cm at site Dl was also expected because of the pit which had been dug in that area to restrain herbicide runoff. The high concentrations in the deeper samples at sites Bl and Kl, however, are not as easily explained. Probably several factors are involved. The most obvious explanation is the probable saturation of the soil with herbicide to a considerable depth when the hardstand was being used for loading operations. TCDD could have been transported to those depths via the herbicide solvent. After the degradation of the herbicide, the TCDD remained at the lower depths. The vertical movement of TCDD in the soil probably decreased greatly at that time, however. Although it is recognized that TCDD has little vertical mobility in soil, some vertical movement probably has occurred around Hardstand 7 because of the high concentrations. It should be pointed out that the detection limit for the samples from Hardstand 7 was 1 ppb except where noted in Table 6, Therefore, TCDD in concentrations less than 1 ppb could have been present in samples reported as "not detected" in this study. An important finding in this study was that soils containing high levels of TCDD contamination around Hardstand 7 were in a very confined area. TCDD contamination above 1 ppb was found predominantly in an area 3 to 4 meters wide surrounding the perimeter of the concrete pad. Soils outside this area were largely below the detection limit of 1 ppb. Although soil levels of TCDD below 1 ppb cannot be dismissed as insignificant, the magnitude of concern is obviously different from soils with much higher levels. c. Biological Samples. Biological organisms were collected from Hardstand 7, the Hardstand Pond, Beaver Pond, Tom's Pond (Figure 13) and Tom's Bayou (Table 7). No TCDD was detected in any of the samples collected from Tom's Bayou., Tom's Pond, or Beaver Pond. However a large snapping turtle (Figure 14) collected from the Hardstand Pond contained 1.5 ppb TCDD in fat tissue. TCDD was not detected in muscle, liver, or testes of the turtle, although it should be remembered that the detection limit in the liver tissue was high (0.260 ppb) due to high levels of interfering compounds. The turtle was not subjected to pathological examination, but no gross abnormal pathological findings were noted during visual observations. It is interesting and perhaps of some significance to note that the turtle was collected immediately after having been observed in the act of copulation. The fact that TCDD was found in fat tissue yet absent 21 �(at the admittedly high detection limit) in the liver might point toward species dependence not only for biological effects, but also for sites of bioaccumulation. Snapping turtles are near the top of the food chain in the aquatic system draining the contaminated hardstand. Therefore, the potential for TCDD accumulation from both the environment and contaminated food existed. Because of this, the TCDD concentration found in this specimen may be high compared to other organisms existing at this area. This specimen was old enough to have been living during the 1962 through 1970 spray orogram, although it cannot be determined if he actually lived in the Hardstand Pond/Beaver Pond area all that time. Figure 13. Tom's Pond, Eglin AFB, Florida 22 �TABLE 7. TCDD ANALYSIS OF ORGANISMS COLLECTED ON EGLIN AFB, FLORIDA TCDD Concentration Location Collected Date Collected Snails (NerUina _recl_avala) Tom's Bayou Mar 77 Alcwlfc (Ppnnlohus pseudoharongus) livor Tom' 1 ) Bayou Mar 77 TCDD (ppb) Detection Limit (ppb) NDa (l.(!ll NDa ND Sample 0.015 0.109 ND3 0.0l r i NDd 0.026 0.030 d muscle Cldins (4) (Pnlymp.soda carol irn ana and Rangia cuneata) Tom's Bayou Mar 77 Crab (4) ( C a l l incctus sapidus) muscle Tom's Bayou Mar 77 viscera ND° Bass (Micrpptprus salinoirles! 1 1 ve'i Tom1'. Pond May 77 ND3 NDfl *Turtle (Cnelydr.) serpent ina) fat llardstcind Pond 0.017 0.010 1.5 IIIUSClL' _b Mar 78 3 livor ND iiusi.le NDa 0.009 lestes NDa 0.011 *Beach Mice ('!) (Poromyscus polionotus) 1 i vcr lldrdstand 7 Mar 70 0.5SO 0.053 skin 0 f) *Sunfish (Lc'.P ."!J:'. l ' - ) muscle Beaver Pond _b o.oon NDa 0.007 Nof Delected b _b Nl)° viscera a Mar 78 0.2f>() Not A|)pliu)blc Samples were analyzed by !.ne Dcparlmcnt of Chemistry, University of Nebraska, under contract from the Department of Chc-ir.isr.ry and Biological Sciences, 1,'SAFA, Colorado (Contract *F056117RC0063). Funds provided by ACLC.'LO in support of studies on the Environmental rate of Herbicide Orange. 23 �Figure 14. Snapping Turtle (Male) Collected 1978 from Hardstand Pond, Eglin AFB, Florida A pooled sample of one female arid two male beach mice collected from Hardstand 7 contained 0.550 and 0.053 ppb TCDD in liver and skin samples, respectively. Weights of the mice were 6.96, 12.24, and 13.18 grams with liver weights of 0.44, 0.77, and 0.76 grams, respectively. Total weight of the three skins was 4.25 grams. Liver tissue was examined grossly and histologically for congenital and teratogenic defects by the Armed Forces Institute of Pathology (AFIP), Washington, DC. Microscopic examination of tissue showed no abnormal characteristics. 24 �SECTION IV CONCLUSIONS Analyses from this study revealed that only one of the three storage and loading areas included in the monitoring effort was appreciably contaminated with TCDD. Samples from near the surface around Hardstand 7 had concentrations of TCDD as high as 275 ppb with one-third that amount to a depth of 1 meter. However, this contamination was largely confined to an area approximately 3 meters wide around the perimeter of the concrete pad (a total area of about 350 square meters). At Hardstand 8, only one sample was found to be contaminated, and it contained only 0.034 ppb TCDD. No TCDD was found at the east end of Taxiway 9. The minimal contamination at Hardstand 8 and its absence at the east end of Taxiway. 9 was not surprising since these two hardstands were not used nearly as much as was Hardstand 7. TCDD has apparently migrated from Hardstand 7 as far downstream as Tom's Pond. The presence of TCDD downstream, however, does not necessarily mean that the material is spreading at this time. Much of the downstream TCDD contamination probably occurred during the actual loading operations and before the dike was built in back of the hardstand. Soil erosion and water runoff were obvious during that time but are well controlled currently. TCDD has been picked up by biological organisms in some contaminated areas, but the paucity of analyses makes it impossible to draw any conclusions concerning the extent of bioaccumulation at this time. The absence of TCDD in the fish collected from Beaver Pond during this sampling program could indicate that TCDD is degrading in that ecosystem. Whole body samples of sunfish from Beaver Pond in 1974 contained 0.014 ppb TCDD although muscle and liver tissue were free of contamination. Additional sampling of biological organisms is required in Beaver Pond and Tom's Pond to further define the extent of contamination in the biota. The final conclusion from this monitoring effort is drawn from the fact that no TCDD could be detected in either the silt or a wide range of biological organisms collected from Tom's Bayou. That no contamination occurs in Tom's Bayou is significant because it is the first place contamination would occur off the Eglin AFB Reservation. Therefore, data obtained from this study indicate that TCDD migration from Hardstand 7 is minimal and currently limited to a small area on Eglin AFB. 25 �REFERENCES 1. 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: 864866, 1970. 2. Schwetz, B. A., J. M. Norris, G. L. Sparschu, V. K. Rowe, P. J. Gehring, J. L. Emerson, and C. G. Gerbig. Toxicology of chlorinated dibenzo-p-dioxins, Environ. Health Perspectives Experimental Issue No. 5: 87-100, September 1973. 3. Lang, Anton, et. al. The Effects of Herbicides in South Vietnam. National Academy of Sciences, Washington, D.C. 1974. 4. Biever, Helen. Defoliant History of Test Area C-52A, Working Papers, Vitro Corporation of America and Armament Development and Test Center, Eglin AFB, Florida, December 1969. 5. Bartleson, Fred D., Jr., Don D. Harrison and John D. Morgan. Field Studies of Wildlife Exposed to TCDD Contaminated Soils. AFATL-TR-75-49. Air Force Armament Laboratory, Eglin AFB, Florida, 1975. 6. Young, Alvin L., John A. Calcagni, Charles E. Thalken, and James W. Tremblay. The Toxicology, Environmental Fate, and Human Risk of Herbicide Orange and Its Associated Dioxin. OEHL TR-78-92. USAF Occupational and Environmental Health Laboratory, AMD, Brooks AFB, Texas, 1978. 7. Young, Alvin 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. 8. Young, Alvin L., Charles E. Thalken, Eugene L. Arnold, James C. Cupcllo, and Lorris G. Cockerham. Fate of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the Environment: Summary and Decontamination Recommendations. USAFA-TR76-18. United States Air Force Academy, Colorado, 1976. 9. the the Air Young, Alvip L., Charles E. Thalken and Milliam E. Ward. Studies of Ecological Impact of Repetitive Aerial Applications oF Herbicides on Ecosystem of Test Area C-52A, Eglin AFB, Florida. AFATL-TR-75-142. Force Armament Laboratory, Eglin AFB, Florida, 1975. 26 �INITIAL DISTRIBUTION AUL/LSE 71-249 ASD/ENFEA IK) USAF/SAMI AIIVINT IKJ lAC/DRA FAG/1 NAT ASU/ENESII/S. Johns US Army TRADOC ATTN: ATAA-SL 1 1 1 1 1 1 1 (Tech Lib) 1 HQ USAFE/DOQ HQ PACAF/DOOFQ ASD/XRP COMIPAC/I-232 AFATL/DLODL DDR&E (Tech L'-b) USAFA/DFCBS AFLC/MMNO SAAMA/SFQT HQ USAF/RDP AFSC/DEV 1 3 1 1 2 1 1 1 1 1 1 DDR&E (Env & Life Sciences) Chemical Systems Lab DRDAR-CLJ-L (Tech Lib) USAF (OEHL/Capt Young) NWC Env Eng (Mr Ouimette) 1 1 10 1 AMD/RD AMRL/THE (Dr London) AMRL/THT (Dr Back) ADTC/CSV ADTC/SGPE AFESC/EC AFLC/DC ADTC/DEN US Army Natick Lab AFATL/DLV 1 1 1 1 1 1 1 1 1 25 Accessions Div DDC-DDA Deseret Test Center/Tech Lib Naval Weapons Ctr/Tech Lib US EPA (Dr Edwin L. Johnson) Dow Chemical Company US EPA (Dr Jack Moore) The Brehm Lab & Dept of Chemistry 12 1 1 AFCEC/EO AFATL/DL 1 1 USDA/ARS IJSDA Forest Insect & Disease Mgt US EPA (Office of Research & Monitoring) EPA (Dr Ralph Ross) Naval Const Battalion Center 2 1 1 1 1 27 (The reverse of this page is blank) 1 2 1 2 ��AD EGLIN AFB. FLA. 32542 OFFICIAL BUSINESS PENALTY FOR PRIVATE USE S3OO THIRD CLASS � 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. 0103 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 Harrison, Don D. Charles I Miller Richard C. Crews Description An account of the resource <strong>Corporate Author: </strong>Environics Office, Air Force Armament Laboratory, Eglin AFB, Florida Date A point or period of time associated with an event in the lifecycle of the resource 1979-02-01 Title A name given to the resource Residual Levels of 2,3,7,8-Tetrachlorodibenzo-p-Dioxin (TCDD) Near Herbicide Storage and Loading Areas at Eglin AFB, Florida Subject The topic of the resource biodegradation herbicide blue herbicide white herbicide purple