4 15 672 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. 193 Folder The folder containing the original item. 5449 Series The series number of the original item. Series VIII 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 Cooper, George Title A name given to the resource Letter from George Cooper to "Colleague", December 12, 1983 ao_seriesVIII https://www.nal.usda.gov/exhibits/speccoll/files/original/9fb3db86d5bc7d4267471cb6ea35f6ce.pdf 3c8832d6604c55e424c73dc491f693fa PDF Text Text ItemD Number °5257 AuthOT Costle, Douglas M. Corporate Author Report/Article TItto Typescript: Decision and Emergency Order Suspending Registrations for the Forest, Rights-of-way, and Pasture Uses of 2,4,5-Trichlorophenoxyacetic Acid (2,4,5-T) Journal/Book Title Year Month/Day February 28 Color D Number of Imagos 95 Descrlpton Notes Friday, March 01, 2002 Page 5257 of 5263 �I. Decision and Emergency Order Suspending Registrations for the Forest, Rights-of-way, and Pasture Uses of 2,4,5-Trichlorophenoxyacetic Acid C2,4,5--n INTRODUCTION During the past ten months, the Agency has been gathering information about 2,4,5-T through its Rebuttable Presumption Against Registration I RPAR) process in order to decide whether registration of this pesticide should be continued-l 43 FR 17116, April 21, 1978) . This review was prompted by studies showing that 2,4,5-T and/or its dioxin */ contaminant, 2 , 3 , 7 , 8-tetrachlorodibenzo-p-dioxin f f "{ TCDD) — , caused reproductive and oncogenic effects in test animals. During the public debate initiated by the 2,4,5-T RPAR, the Agency received reports that women living in the vicinity of Alsea, Oregon, had miscarriages shortly after 2,4,5-T was sprayed in the forest areas where they reside. The Agency investigated the circumstances surrounding these reported ^/ Current methods for manufacturing 2,4,5-T produce TCDD as a by-product of the manufacturing process. Although 2,4,5-T manufacturers attempt to remove this contaminant, TCDD cannot be completely removed. An EPA contract laboratory has measured the TCDD content in 16 recently produced commercial samples of technical grade 2,4,5-T from five different manufacturers. The contractor reported that the TCDD content in these samples ranged from not detectable to 0.025 ppm=(J'limit of detection: 0.01 ppm) [excluding higher values that the contractor reported as doubtful]. Therefore, because TCDD is present as a low-level contaminant in commercial samples of 2,4,5-T, references in this document to "2,4,5-T" or the "pesticide product" mean 2,4,5-T that is contaminated with TCDD. -1- �miscarriages and compared the frequency of miscarriage in the Alsea area with comparable data from a control area. The Agency has concluded that the use of 2,4,5-T over a six-year period in the Alsea area was related to a statistically significant increase in the frequency of miscarriages by women residents of the area, and that these miscarriages occurred shortly after the use of 2,4,5-T in the area where these women lived. Based on this and other information detailed below, I am ordering several emergency suspensions under FIFRA Section 6(c). These emergency suspensions immediately halt the distribution, sale/ and use of 2,4,5-T for forestry, rights-of-way, and pastures until the completion of further **/ administrative proceedings.— I am ordering emergency suspen- sion of these uses because I find that they pose an "imminent hazard" to humans and because I also find that an "emergency" exists because there is not enough time to complete a suspension hearing before the next spraying season. **/ Pasture is defined as land producing forage for animal consumption, harvested by grazing, which has annual or more frequent cultivation, seeding, fertilization, irrigation, pesticide application and other similar practices applied to it. Fencerows enclosing pastures are included as part of the pasture. -2- �II. LEGAL AUTHORITY A. Standards for Maintaining a Registration In order to obtain a registration for a pesticide under the Federal Insecticide, Fungicide, and Rodenticide Act£FIFRA) [7. U.S.C. 136 et seq.], a manufacturer must demonstrate that the pesticide satisfies the statutory standard for registration* That standard requires 1 among other things) that the pesticide perform its intended function without "unreasonable adverse effects" on the environment [FIFRA Section 3( c) f 5) ] . "Unreasonable adverse effect on the environment" means "any unreasonable risk to man or the environment/ taking into account the economic, social and environmental costs and benefits of the use of any pesticide" [FIFRA Section < bb) ] . In effect, this standard requires a finding that the benefits of each use of the pesticide exceed the risks of the use* The burden of proving that a pesticide satisfies the registration standard rests with the registrant and continues for as long as the registration remains in effect [Environmental Defense Fund v. Environmental Protection Agency, 510 F.2d 1292.1297 [ CADC, 1975) ; Environmental Defense Fund v. Environmental Protection Agency, 465 F.2d 528, 532 I CADC, 1972)]. Under Section 6 of FIFRA, the Administrator is required to cancel the registration, or change the classification, of a pesticide whenever he determines that the pesticide no longer satisfies the statutory standard for registration. -3- �B. Purpose and Standard for Suspending a Pesticide The suspension provisions in Section 61(c) of the statute give the Administrator authority to take interim action until completion of the time-consuming procedures required to reach final cancellation decisions. Under this Section/ the Administrator may suspend the registrations of a product and prohibit its distribution, sale, or use during cancellation proceedings upon a finding that the pesticide poses an "imminent hazard" to humans or the environment. "Imminent hazard" is defined by the statute to mean that: The continued use of a pesticide during the time required for cancellation proceedings would be likely to result in unreasonable adverse effects on the environment or will involve unreasonable hazard to the survival of a species declared endangered by the Secretary of the Interior under Public Law 94-135. As discussed above, "unreasonable adverse effects on the environment" means that the risks from use of a pesticide outweigh the benefits of its use. Thus, in order to find an imminent hazard, it is necessary to find that the risks of use during the period likely to be required for cancellation proceedings appear to outweigh the benefits. The Administrator may not suspend a pesticide without -4- �having issued a notice of his intention to cancel the registration/ or to change the classification, of the pesticide• Suspension is the Administrator's tool for quickly correcting a situation which endangers public health. The courts have repeatedly held that "the function of a suspension decision is to make a preliminary assessment of evidence/ and probabilities/ not an ultimate resolution of difficult issues" [Environmental Defense Fund v. Environmental Protection Agency, supra, 510 F2d at 1298]. "It is enough if there is a substantial likelihood [emphasis in original] that serious harm will be experienced during the year or two required in any realistic proj ection of the administrative '*• cancellation) process" [Environmental Defense Fund, Inc. v. Environmental Protection Agency/ 510 F2d 1292, 1297, I D . C . Cir. 1975) quoting from Environmental Defense Fund, Inc. v. Environmental Protection Agency, supra, 465 F2d 540< D.C. Cir. 1972)]. Moreover/ the registrant bears the burden of proof during a suspension proceeding because, as indicated above, the burden of proof under FIFRA always resides with the proponent of registration throughout the life of a registration, t See, e.g., Environmental Defense Fund v. Environmental Protection Agency, 510 F2d at 1297; Environmental Defense Fund v. Environmental Protection Agency/ supra, 465 F2d at 532.) -5- �C. Types of Suspension Proceedings In this order, I have begun emergency suspension proceedings. This is not the only type of suspension provided in FIFRA. Section 6(c) provides for two kinds of suspension proceedings: ordinary suspensions [FIFRA Section 6(c)(2)] and emergency suspensions 6(c)(3)]. [FIFRA Section I have chosen to discuss both kinds of suspension because the procedures applicable to each action are intertwined and because of the complexity of the suspension provision as a whole. (1) Ordinary Suspensions The Administrator may begin an ordinary suspension when he finds that action is required to prevent an "imminent hazard." An ordinary suspension is not effective immediately; instead, the Administrator is required to give registrants notice of his intent to suspend and to allow five days for them to request a hearing. hearing. Only a registrant may request a If a hearing is not requested within five days, the suspension order becomes final and is not reviewable by a court. If a hearing is requested, the Administrator is required to convene an expedited proceeding at which other interested persons can intervene. The sole issue at a hearing is whether an imminent hazard in fact exists. The procedures for conducting the hearing, with limited exceptions -6- �discussed below/ parallel the hearing procedures for an emergency suspension. The Administrator decides whether to affirm his imminent hazard determination at the conclusion of the hearing; if he does, he issues a suspension order. This order is accompanied by a notice of intent to cancel the registration, or to change the classification, of a j pesticide (if one has not previously been issued). A final order on suspension following a hearing is reviewable in the Court of Appeals. (2) Emergency Suspensions Before issuing an emergency suspension order, the Administrator is required to make two findings: (1) that the pesticide poses an "imminent hazard" and (2) that an "emergency" exists. An "emergency" exists when the situation "does not permit [the Administrator] to hold a hearing before suspending" [FIFRA Section 6(c)(3), 7 U.S.C. 136d(c)(3)]. The Agency interprets this statutory provision to mean that, if the threat of harm to humans and to the environment is so immediate that the continuation of a pesticide use is likely to result in unreasonable adverse effects - i.e. the risks outweigh the benefits - during a suspension hearing, the registration of any product for that use may be suspended -7- �*/ immediately— . An emergency suspension order is issued without prior notice to registrants and takes effect immediately; it remains in effect until the cancellation decision if no expedited hearing is requested. If an expedited hearing is requested on the issue of imminent hazard, the emergency order continues in effect until the issuance of a final suspension order. Registrants are given five days to request an expedited hearing. The hearing stage is to begin within five days of the Agency's receipt of the hearing request. Unlike the ordinary suspension situation, no party other than the registrant and the Agency may participate in the expedited hearing on the emergency order, except to file briefs. The procedures for conducting the hearing are otherwise the same as in an ordinary suspension. For both types of suspension, the hearing is to be conducted in accordance with 5 U.S.C. Sections 554,.556, and 557 except that ^/ The term "emergency" is not defined by FIFRA, and the statute in the emergency suspension section does not specifically require the Agency to balance benefits against health and environmental risk of pesticide use. An alternative reading would be that an emergency should issue whenever a risk could result from pesticide use during the time for conducting a suspension hearing. However, for the purpose of this proceeding I have decided to consider the risks and benefits in ordering an emergency suspension, just as I balance risks and benefits in deciding whether to register a pesticide or to take the pesticide off the market through a cancellation or ordinary suspension order. FIFRA is a risk/benefit statute, and I see no reason to depart from this balancing test in issuing emergency suspension orders. -8- �the presiding officer need not be a certified hearing examiner. For both types of suspension, the presiding officer shall have ten days from the conclusion of the presentation of evidence to submit recommended findings and conclusions to the Administrator• The Administrator shall then have seven days to issue a final order on the issue of suspension. FIFRA provides for a special appeal of an emergency suspension order to the District Court. If an administrative hearing is requested, an emergency suspension order is subject to immediate review in District Court by the registrant or by other interested persons with the registrant's consent. On the other hand, if no request for a hearing before the Agency is made, the emergency order becomes final and is not reviewable by any court [FIFRA Section 6(c)(2), 6(c)(3)]> The District Court action may occur simultaneously with the suspension proceeding before the Administrator. The District Court reviews only whether the emergency finding is supported. The standard for review by the District Court is very narrow--whether the order of suspension is "arbitrary, capricious, or an abuse of discretion, or whether the order was issued in accordance with the procedures established by law" [FIFRA Section 6(c)(4)]. -9- If the District �Court finds against the Agency, it may stay the suspension order until completion of the expedited suspension hearing. The District Court order may be appealed to the Appellate Court by either the Agency or the registrant, depending on the outcome. A final order on suspension, after a hearing before the Agency, may be reviewed in the Court of Appeals on an expedited basis even though related cancellation proceedings may not have been completed. III. SUMMARY OF FINDINGS A. Summary of Findings on Risks Numerous studies have clearly demonstrated that TCDD and/or 2,4,5-T contaminated with TCDDD can produce fetotoxic, teratogenic, and carcinogenic effects in experimental animals which have been exposed to these chemicals. I find that the occurrence of these effects in test animals indicates that humans who are exposed to TCDD and/or 2,4,5-T may experience comparable effects. A recent epidemiological study reported that women living in the vicinity of Alsea, Oregon ( an area where 2,4,5-T is used for forest management) , have a statistically significant higher incidence of spontaneous abortions (miscarriages) than women living in a control area. Specifically, the study shows that: -10- �( 1) The spontaneous abortion index for the Alsea study area where 2,4,5-T is used is significiantly higher than the index for urban or rural control areas where there is no known use of 2,4,5-T. () 2 There is a significant increase in the sponta- neous abortion index in the study area relative to the control area in the months of June and July: this increase follows by approximately two months a period in March and April when 2,4,5-T was used to control vegetation in the forested areas in which these women live. C 3) Statistical analyses of these data indicate that there is a significant correlation between the amounts of 2,4,5-T used in the study area during the spraying season and the subsequent increase in the spontaneous abortion index in the study area. This relationship between exposure to 2,4,5-T spraying and an increased incidence of miscarriages in humans is not surprising. This is the same relationship that has been demonstrated to exist in test animals through numerous animal studies. While there are uncertainties concerning the amount of 2,4,5-T and/or TCDO to which the study area women may have been exposed and concerning the precise route I or routes) of human exposure, the statistically significant incidence of miscarriages described above makes -1 1- �it reasonable for the Agency to conclude that these women in the Alsea Study area were exposed to 2,4,5-T. The Agency concludes that it is also reasonable to assume that individuals may be exposed to 2,4,5-T and/or TCDD who frequent or live in areas where 2,4,5-T is used in ways and under conditions which may cause them to experience exposure opportunities qualitatively similar to that experienced by the Study area women. The Agency has concluded that 2,4,5-T use patterns involving exposure opportunities qualitatively similar to those experienced by the Study area women are the forestry, rights-of-way, and pasture uses of 2,4,5-T. The Agency has identified pesticide applicators and persons involved in pesticide application support activities, and persons living in or frequenting areas of 2,4,5-T use as the principal groups of individuals who may be exposed as a result of the forestry, rights-of-way, and pasture uses of 2,4,5-T. Based upon the animal test data and other information, including the Alsea study, the Agency has concluded that individuals exposed to 2,4,5-T and/or TCDD may experience adverse reproductive effects and cancer. Accordingly, the Agency concludes that it is prudent to regard individuals who may experience exposures qualitatively similar to those experienced by the Study area women as a result of the forestry, rights-of-way, and pasture uses, as -12- �individuals who may suffer adverse reproductive effects or cancer as a result of these uses of 2,4,5-T. B. Benefits of 2,4,5-T Use During the Cancellation Proceedings The suspended uses J forestry/ rights-of-way, and pastures) comprise about 74% of the estimated 9.3 million pounds of 2,4,5-T used annually in the United States. 2,4,5-T controls a wide variety of weeds at relatively low cost • I estimate that the economic impact of this suspension action will be small* considerations* This finding is based on several The inherent flexibility in the treatment schedules permits delays in treatment during an estimated two-year suspension period. Alternative chemical, mechanical, and manual control treatments are available and are being used. The availability of these alternatives will minimize the impacts of suspension on those acres which require treatment during the suspension period. ^ 1) The Forestry Use The forestry use comprises 28% of 2,4,5-T use. 2,4,5-T's advantage is its ability to control a wide sprectrum of weeds without damaging the treated trees. -13- �Forest managers take measures to control weeds on softwood forests on two maj or occasions during the approximately 50-year life of a commercial forest: ( 1) the preparation stage designed to clear a site of potentially damaging vegetation prior to planting, and 1 2) the release stage designed to free young trees I 3 to 10 years old) from weed and hardwood competition in order to promote extensive growth. I have found that the use of 2,4,5-T is not necessary for site preparation* time. 2,4,5-T is used only 20% of the Other chemicals, mechanical or manual, clearing methods, or burning can be equally effective in giving newly-planted trees the opportunity to grow. The alternatives are more expensive. A two-year suspension of 2,4,5-T use for release treatments would have no serious effect because the treatments could be delayed for two years without impairing tree growth. Alternatives are generally available where weed growth makes treatment necessary. Finally, the impact on consumers of wood products is likely to be small. t 3) The Rights-of-Way Use 2,4,5-T is used to control woody and herbaceous plants on railroads, highways, electric transmission lines, and pipelines. The rights-of-way use covers 41% of total 2,4,5-T usage. -14- �Chemical, mechanical, and manual methods of control are also used on righta-of-way acreage. more than one method is common practice. Use of The cost of 2,4,5-T is less than chemical alternatives for some methods of application, more expensive for others. Many rights-of-way managers who have scheduled 2,4,5-T use during the suspension period are likely to postpone treatment entirely. Managers will likely use alternatives when plant growth is rapid. Even if all acres were treated with alternatives, I estimate that the additional cost of treatment on rights-of-way during suspension would not have a significant impact on users' revenues or operating costs. -•£ 4) The Pasture Use Weed control in pastures is now practiced on only about 1.0 million out of about 101 million acres of pastureland. There are effective chemical and/or mechanical control alternatives for all weed species in all regions. The maj or result of suspension on pastureland would be a delay in treatment on much of the acreage scheduled for treatment due to the inherent flexibility of decisions whether to treat. The economic impacts of a two-year suspension would be of little or no consequence. -15- �C. Summary of Findings on Imminent Hazard =Q 1) The Forestry Use In order to find an imminent hazard, I must find that the risks of use during the period likely to be required for cancellation proceedings appear to outweigh the benefits* The Alsea study, establishing a correla- tion between use of 2,4,5-T in forest management and miscarriages in humans, coupled with animal studies showing similar effects, indicates that there is a substantial likelihood that serious harm could result to persons with qualitatively similar exposures from the forestry use of 2,4,5-T. Aerial application, a major forest treatment method, may result in drift and increased exposure potential* This hazard to human health clearly outweighs the benefits of 2,4,5-T use during the cancellation period. The economic impacts of suspension are small because of the flexibility of treatment schedules and the availability of alternatives. Hence, I find that an imminent hazard exists for the forestry use of 2,4,5-T. 1 2) The Rights-of-Way Use For the reasons discussed below, the use patterns of the rights-of-way use create the same, or greater, potential for human exposure as the forestry use. In broad terms, considerable exposure potential exists due to the -16- �large numbers of persons living near rights-of-way and the likelihood of drift from the widespread use of aerial application. Hence/ the rights-of-way use results in a hazard to human health which in my j udgment outweighs the corresponding benefits. Although rights-of-way is the biggest 2,4,5-T use, a use moratorium during the cancellation proceedings would not have a significant economic impact because many rights-of-way managers are likely to postpone treatment entirely during the suspension proceedings; if they do treat/ alternatives are available. Therefore, I find that an imminent hazard exists for the rights-of-way use during the cancellation proceedings. I 3) The Pasture Use For the reasons discussed below, the application of 2,4,5-T on pastures presents exposures qualitatively similar to the forestry use, and hence the risk posed by 2,4,5-T use to human health is of concern. The exposure risk may be lower than for forests and rights-of-way. The principal application technique is spot spraying with knapsack equipment, which has less drift potential than aerial application. The benefits, however, are marginal at most. Weed control is practiced on less than 2% of pasture acreage, showing the relative unimportance of chemical or other treatments. Treatment can ordinarily be delayed or -17- �dispensed with entirely. In any case, there are effective chemical and/or mechanical control alternatives for all species in all regions of the United States. Thus, while the risks to human health from the pasture use appear to be lower than from the rights-of-way and forest uses, the economic impact of two-year suspension of the pasture use is of little or no consequence. I find that an imminent hazard exists for 2,4,5-T usage on pastures because the risks outweigh the benefits of use during the cancellation proceedings. D. Summary of Findings on Emergency As previously discussed, I have interpreted the statutory provision on emergency suspensions [FIFRA Section 6( c)( 3) ] to require a preliminary balancing of risks against benefits of use during the time for holding a suspension hearing. Hence, an emergency finding involves two issues: ( 1) immediate intervention is required because there is no time to hold a suspension hearing before the next period of pesticide use; and I 2) the risks outweigh the benefits during the time for holding the suspension hearing. At the end of the suspension proceeding, I have discretion to affirm, modify, or reverse my suspension order. -18- �C 1) The Forestry Use There is not enough time to hold a hearing before the next forest spraying season. Much of the year's treatment generally occurs between March and May. I am advised that in some parts of the Pacific Northwest, spraying is about to begin or has already begun. Hence, assuming 2,4,5-T use on forests poses unreasonable adverse effects, immediate action is required to stop 2,4,5-T use. The risks posed by 2,4,5-T forestry use clearly outweigh the benefits of use during the suspension proceeding. The Alsea epidemiological study suggests that persons in the vicinity of forest spray are being exposed to the potential dangers of 2,4,5-T use. These people are about to be exposed to almost one year's dose of 2,4,5-T applications in the next two months. The emergency suspen- sion proceeding is anticipated to run from March through June I see discussion in Section V) . Hence, by the time the suspension hearing is over, it will be too late to halt much of this year's spraying. Considering benefits, the economic consequences from a three-month delay for the completion of suspension proceedings are very small. Much of the scheduled treatment can readily be deferred for this short a period of time. -19- �In any case, alternatives are generally available to prevent reductions in tree growth where treatment is considered essential. Accordingly, I find that an emergency exists for the forestry uses of 2,4,5-T. Therefore, I am ordering immediate suspension of all 2,4,5-T registrations for these uses of 2,4,5-T. ( 2) Rights-of-Way Use 2,4,5-T is applied on rights-of-way I railways, highways, electric transmission lines, and pipelines) during the spring growing season, which starts in March in some parts of the country. Additionally, some methods of application on rights-of-way may be year-round. Hence, there is not enough time to hold a hearing before humans are exposed to the risks to their health presented by this chemical. The risks of 2,4,5-T use far outweigh the benefits during the time for holding a suspension hearing. The potential for human exposure from the rights-of-way use during this period is not inconsiderable even though the use season is not limited to the March-June suspension proceeding period. Large numbers of people live near rights-of-way areas, and aerial application is an important application method. On the other hand, little economic -20- �harm will result from a three-month use moratorium. Use on rights-of-way can generally be deferred for this short period of time* At any rate/ alternatives are available* Chemical alternatives are cheaper than 2,4,5-T for some application methods, including aerial application. Accordingly, I find that an emergency exists for the rights-of-way use of 2,4,5-T. Therefore, I am ordering an immediate suspension of all 2,4,5-T registrations for the use of 2,4,5-T on rights-of-way. C 3) Pasture Use The application of 2,4,5-T to restrict weed growth on pastures is expected to occur in March in some parts of the country and in even more areas before the anticipated completion of the suspension proceeding in June. Hence, emergency measures are required since I believe that the pasture use poses the risk of unreasonable adverse effects to human health during the suspension hearing. The pasture use presents the risk of exposing innocent bystanders because residences are scattered pastureland areas. throughout The risk to humans from 2,4,5-T use on pastures may be lower than from use on forests and rights-of-way, because aerial application is used on forests and rights-ofway and not on pastureland. On the other hand, the benefits -21- �of use during the 3 to virtually nil. 4 month suspension period are Treatment can most certainly be postponed during this short period. In any case, there are effective chemical and/or mechanical control alternatives for all weed species in all regions of the country. Accordingly, I find that an emergency exists for the pasture use of 2,4,5-T. I am therefore ordering an immediate suspension of all 2,4,5-T registrations for the use of 2,4,5-T on pastures. IV. BASIS FOR FINDINGS CONCERNING IMMINENT HAZARD AND EMERGENCY In Section III of this notice, I have presented a summary of my findings that an imminent hazard and emergency exist for the forestry, pasture, and rights-of-way uses of 2,4,5-T. The data, information, and analyses upon which these findings are based are detailed below. A. Findings Relating to Adverse Effects in Test Animals (1) Adverse Reproductive Effects in Test Animals This section presents the test animal data upon which I relied in finding that exposure to TCDD and/or 2,4,5-T is likely to result in adverse reproductive effects in humans. Except as specified below, these data were derived from studies in which pregnant rodents were orally exposed to -22- �TCDD and 2,4,5-T during the second trimester of gestation by daily gavage or in which primates were chronically exposed before mating. The pregnant rodents were sacrificed shortly before the scheduled birth of the offspring, and the fetuses were examined for abnormalities. The Agency has extracted key data for presentation in this report of findings. Experimental details and descriptions of the underlying data are presented in the 2,4,5-T RPAR notice and in the published literature. C *0 Exposure of Test Animals to TCDD TCDD produces fetotoxic effects such as death and reduced fetal size; skeletal deformities such as cleft palate and clubfoot; injury to internal organs such as intestinal bleeding, intestinal lesions, and abnormal kidneys; and post-partum effects such as reduced survival. These effects appear in several different rodent strains and species, occur in all of the litters in some dose groups, and occur at doses at least as low as 0.01 ug TCDD/kg. The repeated and regular appearance of several different forms of damage to test animals of several different strains and species -23- �indicates that TCDD is a teratogenic and fetotoxic agent in mammals. (A) Fetotoxic and Embryolethal Effects Fetotoxic and embryolethal effects have been reported for at least three different mouse strains, two different rat strains, and one strain of subhuman primates exposed to TCDD during gestation. For example, in studies using generally low-dose regimens of TCDD, Neubert and Dillmann reported that resorption sites (resorbed or dead embryos) occurred in 54% (7/13) of the litters at 0.3 ug/kg and in 100% (3/3) of the litters at 9.0 ug/kg for NMRI mice, compared to 24-32% (23/95 and 24/65) of litters exhibiting resorptions in control animals which had not been exposed to TCDD. Sparschu et al. reported resorption of 100% (110/110) of the fetuses in Sprague-Dawley rats exposed to 8 ug TCDD/kg, compared to 20% resorption (63/309) of the fetuses from the control animals. Khera and Ruddick reported 100% (77/77) resorption of fetuses at 4 ug/kg and 36% (56/153) at exposures of 1 ug/kg in Wistar rats, compared to 2-7% (3/152 and 10/127) in the control animals. Smith et al. reported resorptions in 95% (18/19) of the litters of CF-1 mice exposed to 1.0 ug/kg, compared to 74% (25/34) in the control animals; despite the high control incidence of resorptions in this study, the increased incidence in the experimental -24- �animals was statistically significant. In an abstract of a current study, Schantz et al. 1979) reported 57% ( 4/7) of pregnant monkeys aborted and one delivered a stillbirth. Two others on the 50-ppt diet failed to conceive, and two delivered normally. control animals all delivered normal infants. The eight Maternal toxicity was observed in some dose groups in some of these studies. Similar effects have been reported at higher dose levels of TCDD. Neubert and Dillmann reported that a single dose of 45 ug/kg to NMRI mice on day 6 produced resorptions in 100% ( 3/3) of the viable litters, compared to resorptions in 24% ( 23/95) of the control litters. Courtney reported an average of 87% mortality in 6 litters of CD-1 mice orally exposed to 200 ug/kg, compared to an average mortality of 6% in 15 vehicle control litters. This investigator also reported an average of 76% mortality in 6 litters of CD-1 mice exposed subcutaneously to 200 ug TCDD, compared to 14% in the six litters of control animals. Some of these studies also describe statistically significant weight depression in the surviving embryos I e.g., Sparschu et al.) . These and other studies also report that TCDD had no measureable adverse effects at some dose levels in some strains* For example, Khera and Ruddick report no fetotoxic effects at 0.125 ug/kg in Wistar rats, and Neubert and -25- �Dillmann report no teratogenic effects at 0.3 ug/kg in NMRI mice. Courtney and Moore reported that TCDD had no effect on fetal weight or embryonic mortality at 0.5 ug/kg in CD rats, and Sparschu et al. reported no effect at 0.03 ug/kg in Sprague-Dawley rats. Dow Chemical Company, a 2,4,5-T registrant, has recently completed a study of the effects of TCDD on reproduction in Sprague-Dawley rats exposed to low dose-levels of this chemical for three generations. The registrant concluded that "impairment of reproduction was clearly evident among rats ingesting 0.01 or 0.1 ug TCDD/kg per day. Significant decreases were observed in fertility, litter size, gestation survival, post-natal survival, and postnatal body weight." In addition, exposure to 0.001 ug TCDD/kg per day, the lowest level tested in this study, resulted in statistically significant increases in the percentage of pups dead at birth and/or dying before the */ end of three weeks of life in some generations.— ±/ Dow Chemical Company has claimed that the results of this study are "trade secret" or "confidential." An injunction issued on April 4, 1978, in the case of Dow Chemical Co. v. Costle, Civil Action No. 76-10087, U.S. District Court for the Eastern District of Michigan =•". Northern Division) , arguably precludes EPA from disclosing the data from this study at the present time. Although the relevant provisions of FIFRA have since been amended to allow disclosure of data such as this [see, e.g., FIFRA Sections 1GC(d) and 10( g) ] , the injunction has not yet been modified. EPA intends to promptly request the Court to modify the injunction, but until this has been done the Agency will not publicly disclose the data from the study. The summary presented in the text of this Order does not, in EPA's opinion, constitute disclosure of the allegedly "trade secret" data submitted by Dow and would not cause any harm to Dow 1 s legitimate competitive interests. The data from the study may be made available to any party in a suspension or cancellation proceeding under an appropriate protective arrangement. -26- �Although the experimental protocols and strains differ for the several studies cited, in each case TCDD significantly increased the incidence of resorbed embryos or stillborn animals relative to the rate observed in control animals not exposed to TCDD. The regular occurrence of embryonic death in studies by different investigators in primates and in different rodent strains indicates that exposure to TCDD during mammalian gestation may result in the death of the embryos and related maternal reproductive failure• { ii) Skeletal Anomalies Skeletal defects appear in six studies involving four different mouse strains. Courtney and Moore report the following incidences of cleft palate in the indicated strains exposed to 3 ug/kg TCDD: 71% ( 5/7) C57BL/6 mice, compared to none I 0/23) ( 2/9) in litters of in the controls; 22% in litters of DBA/2 mice compared to none ( 0/23) in the controls; and 30% ( 3/10) for CD-1 mice, compared to none (0/9) in the controls. Neubert and Dillmann, also using 3 ug TCDD/kg, reported 29% ( 7/24) of the viable litters had fetuses with cleft palate for NMRI mice compared to 6% ( 10/160) of the control litters. Smith et al. reported cleft palate in 71% I 10/14) of CF-1 mouse litters at 3 ug/kg, compared to none (0/34) in the controls. -27- �In exposures of shorter duration, Moore et al. reported cleft palate in 86% (12/14) of C57BL/6 mouse litters exposed on days 10-13 to 3 ug/kg, compared to none (0/27) in the control litters. Neubert and Dillmann reported cleft palate in 71% (10/14) of litters of NMRI mice exposed to a single 45 ug/kg dose on day 11, compared to 6% (6/95) of litters in the controls. Courtney and Moore reported no cleft palate in any of the litters in CD rats exposed to 0.5 ug/kg. Similarly, Khera and Ruddick, using Wistar rats, reported that the occurrence of the skeletal anomalies in the fetuses exposed to 2.0 ug/kg was comparable to the rate for the untreated animals. (iii) Injury to Internal Organs Exposure to TCDD produced injury to the kidneys and intestinal tracts of at least five different mouse and rat strains. Smith et al. reported 28% (4/14) of litters with kidney anomalies at 3 ug/kg in CF-1 mice, compared to none (0/34) in the controls. Moore et al. reported 100% (14/14) of litters with kidney anomalies in C57BL/6 mice exposed to 3 ug/kg on days 10-13, compared to none (0/27) in the control litters. Courtney and Moore reported kidney anomalies in 100% (10/10) of the litters of CD-1 mice at 3 ug/kg, compared to 33% (3/9) in the controls, and 67% (4/6) -28- litters �with abnormal kidneys in the CD rat at 0.5 ug/kg as compared to none (0/9) in the control litters* Sparschu et al. reported hemorrhages or lesions of the intestine of 36% (36/99) of the fetuses of Sprague-Dawley rats exposed to 0.5 ug/kg, compared to none (0/246) in the control fetuses. (b) Exposure of Test Animals to 2,4,5-T Cleft palate, high incidences of fetal mortality, reduced fetal weight, and other indicators of injury to the developing fetus have been reported in several studies in which test animals were exposed to 2,4,5-T contaminated with varying levels of dioxin. Some of these effects have been reported in test rodents at maternal doses as low as 10 mg/kg 2,4,5-T containing no detectable TCDD (limit of detection: 0.5 ppb). For example, Neubert and Dillman (1972) studied the effects of 2,4,5-T contaminated with dioxin in NMRI mice. Using 2,4,5-T with 0.05 ppm TCDD, these investigators reported resorptions in 57% of the litters and cleft palate in 71% of the litters at 60 mg 2,4,5-T/kg, compared to 24-32% resporptions and 6% cleft palate in the controls. -29- �Similarly/ Courtney and Moore t 1971) reported that oral exposure of CD rats to 80 mg/kg 2,4,5-T containing 0.5 ppm TCDD led to 52% fetal mortality per litter, compared to 3.4% in the controls. At this dose, kidney anomalies were observed in 50% of the litters, compared to none in the controls, but none of the fetuses had cleft palate at any dose. However, subcutaneous injection of 100 mg/kg 2,4,5-T containing 0.05 ppm TCDD led to cleft palate in 40% of the litters of CD-1 mice, compared to none in the controls. The Dow Chemical Company, a 2,4,5-T registrant, has recently completed a study I Smith et al. 1978) of the effects of 2,4,5-T {.containing less than 0.5 ppb TCDD) on reproduction in Sprague-Dawley rats exposed to 2,4,5-T for three generations. The registrant reports that exposure of these animals to 10 and/or 30 mg 2,4,5-T/kg per day resulted in statistically significant increases in the frequency of stillborn rat pups, and/or decreased */ survival of the pups that were born alive.— ^/ Dow Chemical Co. has also requested confidentiality for the results of this study. The discussion in the footnote in Section IV. A fX1 XXa) J i) also applies to these data. -30- �(c) Other Effects in Test Animals Recently/ Highman et al. showed that impaired fetal kidney development followed maternal treatment with 120 mg/kg of 2,4,5-T on days 6-14 of gestation. The im- paired development was associated with a significant reduction in cellular alkaline phosphatase. TCDD has been found to induce delta aminolevulenic acid synthetase (ALA) in chick embryos with as little as 1.5 ng/egg, and Goldstein et al. found a two-fold induction of ALA in C57BL/6 mice as a significant 2,000-fold accumulation of porphyrins in the liver occurred when compared to controls after treatment with 25 ug/kg of TCDD. Abnormal porphyrin synthesis occurred in female rats when treated in a chronic study at 0.01 ug TCDD/kg per day (Kociba et al. 1977). Alkaline phosphatase and gamma glutamyl transferase levels in female rats on 0.1 ug/kg significantly increased when compared to controls. (2) Oncogenic Effects in Test Animals (a) Exposure of Test Animals to TCDD The Carcinogen Assessment Group (CAG) has concluded that TCDD induces carcinogenic responses in mice and rats at exceedingly low dose levels and that these effects, together with data showing that TCDD is mutagenic, constitute substantial evidence that TCDD is likely to be a human carcinogen. -31- �Oow Chemical Company, a 2,4,5-T registrant, studied the effects of TCDD on male and female Sprague-Dawley rats exposed to 0.022, 0.220, or 2.2 ppb TCDD. CAG agrees with the registrant's conclusion that there is a statistically significant increase in the incidence of heapatocellular carcinoma in female rats exposed to 2.2 ppb TCDD. In another study using Sprague-Dawley rats, Van Miller reported that 1 ppb and 5 ppb TCDD produced a carcinogenic response in the livers of male Sprague-Dawley rats. These observations tend to confirm the registrant's observations that TCDD produces an oncogenic response in the livers */ of male Sprague-Dawley rats.— Further, a preliminary report of a not-yet-completed National C.ancer Institute study tends to confirm these observations of a carcinogenic response in rats. A contractor for the National Cancer Institute has reported that TCDD is carcinogenic in the rats and mice used in that study. CAG also emphasized that, at low levels, TCDD is a potent inducer of arylhydrocarbon hydroxylase, an enzyme system that contains an enzyme that is known to mediate the formation of epoxides, compounds which are potentially active carcinogenic metabolites. V The CAG and an EPA audit found that this study had major shortcomings in design and conduct that limited the reliability of the data developed at dose levels lower than 1 ppb. -32- �GAG also reported that TCDD is mutagenic in the Ames test without the metabolic activation system. Its mutagenic activity is exhibited by frameshift mutations caused by intercalation between base-pairs of DNA. (b) Exposure of Test Animals to 2,4,5-T On the basis of its review of 10 chronic toxicity studies, eight using mice and two using rats, CAG has concluded that there is no significant evidence in the completed studies that 2,4,5-T is carcinogenic in these species* Specifically, CAG reported that exposure to 3, 10, or 30 mg 2,4,5-T/kg (TCDD not detectable at detection limits ranging from 0.12 to 0.33 ppb) does not have carcinogenic effects in Sprague-Dawley rats. Preliminary data from a rat study in progress are also negative. Nonetheless, these findings do not negate the cancer-causing potential of 2,4,5-T as commercially produced since it contains the TCDD contaminant. CAG's review of the design and conduct of other studies disclosed that testing in mice is inadequate because the maximum tolerated dose may not have been used in some of the studies in which mice showed no carcinogenic response, and because there were significant defects in the design and execution of a study for which the authors -33- �initially reported a statistically significant increase in tumors in female mice. B. Findings Relating to Risk to Humans (1) (a) Study of Miscarriages in Alsea, Oregon General Discussion In response to the 2,4,5-T RPAR notice, a group of eight women informed the Agency that they lived within 12 miles of Alsea, Oregon, where 2,4,5-T is used in forest management and that they had experienced a total' of 13 miscarriages between 1972 to 1977. In their letter, the women presented information showing that most of their miscarriages occurred eight to ten weeks after conception and followed by four or six weeks the date of the spring application of 2,4,5-T in the forest areas in which these women reside. The women indicated their belief that this information suggested that the unusually high number of miscarriages in their group was related to the use of 2,4,5-T. The effects which these women reported were comparable to the embryolethal and fetotoxic effects observed in test animals that have been exposed to 2,4,5-T and/or TCDD. Moreover, because embryos are particularly susceptible to the harmful or lethal effects of fetotoxic or teratogenic agents during the early stages of pregnancy, the occurrence of these miscarriages within approximately two months of the use -34- �of 2,4,5-T in the Alsea area suggested a possible relationship between the use of the pesticide and the miscarriages reported for this group of women. For these reasons/ the Agency began an epidemiological study to determine if the occurrence of the spontaneous abortions in the entire Alsea area1', parts of three counties comprising about 1/600 square miles) bore any relation to the use of 2,4,5-T in the area. To answer this question, the Agency gathered informa- tion and data from hospitals on the occurrence of spontaneous abortions in the Alsea Study area and compared these data to comparable data from a rural area where there was little or no known use of 2,4,5-T or other dioxin-contaminated phenoxy herbicides 1 Control area) • Data on spontaneous abortions from an Urban area near Alsea were also reviewed for the study. The Agency1 s preliminary analysis of the data generated through this study indicates that: */ ( 1) The spontaneous abortion index— \ hospitalized miscarriages per 1,000 births) for the Alsea Study area where 2,4,5-T was used was significantly greater than the index for the Urban and Control areas where there was little or no known use of 2,4,5-T; ^/ The investigators determined the spontaneous abortion index by relating the number of hospitalized spontaneous abortions to the number of live births, corresponding to month of conception. The ratio derived in this way is expressed as abortions/1,000 births, related to month of conception, and permits comparison between areas of different total population size. The index is based on a five-month moving average for births to correspond with monthly miscarriages for terms up to 20 weeks £ about five months) . -35- �(2) There was a dramatic increase in the spontaneous abortion index for the Study area relative to the Urban and Control areas in the months of June and July; this increase followed, by approximately two months, a period in March and April when 2,4,5-T was used to control vegetation in the forested Study area; and (3) Statistical anlyses of these data indicate that there was a significant correlation between the amounts of 2,4,5-T used in the Study area during the spraying season and the subsequent increase in the spontaneous abortion index in the Study area. In conclusion, the Agency's systematic survey of the occurrence of spontaneous abortions in an area of 2,4,5-T use indicates that there was an unusually high number of spontaneous abortions in the area, and that the incidence of spontaneous abortions may reasonably be related to the use of 2,4,5-T in the area. The data further indicate that the miscarriage experiences which the eight Alsea women reported to the Agency were representative of the experiences of the larger population of women living in the Study area. The data and information which provide the basis for these conclusions are summarized below. (b) Results and Analysis Comparison of the spontaneous abortion indices for the Study, Urban, and Control areas for the period from -36- �1972 through 1977 shows that women living in the Study area where 2,4,5-T is used were more likely to experience spontaneous abortions than women living in either the Urban or Control areas (Table 1). abortion index averaged 80.8 The six-year spontaneous for the Study area, compared to averages of 43*8 and 65.4 for the Urban and Control areas/ respectively. In addition to this general elevation in the Study area spontaneous abortion index, there was a striking increase in the Study area index for the months of June and July. During June, the index in the Study area was 130.4, compared to 44.9 respectively. and 46.0 in the Urban and Control areas, For July, the indices were 105.4 for the Study area, compared to 14.6 and 55.3 for the Urban and Control areas, respectively. These data are presented graphically in Figure A. The increased spontaneous abortion indices in the Study area during June and July are particularly significant when viewed in terms of data on the use of 2,4,5-T in the -37- �*/ Study area.— Spraying records for the Alsea area for the study period indicate that 2,4,5-T use occurs primarily between March 1 and April 30; substantially lower amounts of the pesticide are used during May and still lower amounts are used during July and August ^Figure B) . Examination of this information on the use of 2,4,5-T in light of data on the increased incidence of spontaneous abortions reveals ^/ The preliminary report inadvertently included 3,530 pounds of silvex as 2,4,5-T in the estimates of usage in the Study area. Conceptually, this flaw is not significant: 1) since its effect would merely modify slightly the very significant correlation coefficient between herbicide use and miscarriages; 2) the nature of the relationship between time of application and the miscarriages is expected to remain unchanged; and silvex contains TCDD and could be expected to result in the same effect. Nonetheless, the Agency immediately had the analysis rerun to determine whether specific change in numerical estimates result. Corrected 2,4,5-T use remained significantly correlated with miscarriages occurring 2-3 months laterC r».72; p<.01) . Combined silvex and 2,4,5-T spray data were also correlated with miscarriages since both compounds could be hypothesized to cause the observed effect due to a common TCDD contaminant. This analysis also showed strong correlation.between use of herbicides containing TCDD and miscarriages as would be expected on the basis of animal studies f r-.69; p<.02) . The relative insensitivity of the correlation to changes in quantity further demonstrates the inherent strength of the relationship between the basic use pattern and miscarriages occurring approximately 2 months later. -38- �Table 1. Monthly Spontaneous Abortion Index for the Study, , anAJTpirETo-i^Areas (Oregon, 1972-1977) Month ^StuoTy AreaS"' Lerban~ffr^a CorftrUl Are"^, Average 1 148.1 13^9 &2.Q 68.0 January February 82.2— March 93.8 April ' -"28. 1 53.2 43.9 48.1 61.9 61.9 47.0 97.5 68.8 89.9 50.8 63.2 68.0 130.4 44.9 46.0 73.8 .£0574} 14.6 55.3 58.4 August 88.1 31.8 79.8 66.6 September 46.0 49.6 85.3 60.3 October 76.2 54.8 50.5 60.5 November 76.7 19.6 54.3 50.2 December 70.3 45.6 94 . 5x 70.1 <130^1} 43.8 (6574) --^ 63.3 JteY fJune 1 1 July (Average -—49.3 -39- | 1 | 1 �Figure A. Plot of Monthly Spontaneous Abortion Index for the Study, Urban, and Control Areas Study Area Urban Area 130 . Control Area 120 110 100 . 90 x £ 80 . c H s 70 J o u 60 4 o J3 * 50 40 30 - 20 . 10 - o> 6. a. < « c 9 ••< 9 JC Month -40- a o (A o o > o o o O �Figure B. Pounds of 2,4,5-T Sprayed in Alsea Basin Accumulated by Respective Month, 1972 through 1977, Compared with Abortion Index for the Same Period Pounds Sprayed 9- — -* Abortion index 130 . 120 / A\ \ / \ / 110 - xA X £ c 80 f - H t! 60 . o A < 50 - 1-1 \ i \ \ \ 1 t \ 1 V •H \ Ift (J \ 1 \ . 4 x -u c \ 1 I e 70 o o o \ / 90 . 0 \ / 100 . - 5 1 0) M \ D> / \ N - 3 / \ I ^ •H -U U f^ / \/ I « a) \ V f Q CO 40 - C 3 O 30 - cu - 1 20 -f" 10 1 i ' e 1 .a M M i >i i C ^ O» 14 ^ h X * X >0 fa « «n Month -41- o o o z S o �that this increase occurs approximately two months after the period of annual application of 2,4,5-T in the Alsea area. More refined analysis of these data on total abortions and total 2,4,5-T use by month during the period from 1972 to 1977 indicates that there was a statistically significant correlation between the abortion index in the Study area and the amount of 2,4,5-T used there* That is, when the increased spontaneous abortion index was compared to the amount of 2,4,5-T used each month in the areas where the women resided, the peak in the abortion index followed the peak in the spray pattern by approximately two months. This two-month lag time corresponds to the time predicted on the basis of the initial reports from the eight Alsea women. Because this correlation is statistically significant (p<0.01), there is strong reason to suspect that the spontaneous abortion increase was related to the use of 2,4,5-T. In view of the laboratory data establishing that 2,4,5-T and its contaminant TCDD have embryolethal effects in test animals and the susceptibility of the young embryo to fetotoxic and teratogenic agents, the increased spontaneous abortion index in an area of 2,4,5-T use may reasonably be interpreted to be a consequence of the exposure of women residents of the area to the 2,4,5-T used for forest -42- �*/ management.—' (2) (a) Seveso (Italy) and Vietnam Seveso, Italy On July 10, 1976, an accident at the ICMESA chemical plant in the Seveso region of Italy released 2 to 10 pounds of TCDD over a wide area. Hundreds of animals died, many area residents reported skin disorders, and an area of 110 hectares was evacuated. The most pertinent reports on this incident are provided by Reggiani (1977), Tuchman-Duplessis (1977), and Whiteside (1977; 1978). There is an apparent consensus that the reproductive epidemiology of Seveso, as presented, does not provide firm evidence of increased risk of spontaneous abortions or congenital malformations following the explosion. The ^/ The Alsea experience may not be an isolated incident. Reports of people adversely affected by exposure to phenoxy herbicides and/or TCDD have frequently appeared in medical and scientific journals. Recent summaries appear in IARC, NRCC, and U.S. Air Force documents on phenoxy herbicides and dioxins. Further, as a result of the 2,4,5-T RPAR, the Agency recently received numerous accounts of human health effects attributed to phenoxy herbicides and/or TCDD. These have been summarized in a document included in the record. The cumulative effect of these reported incidents suggests that people who live and/or work in areas of 2,4,5-T use may experience adverse health effects. -43- �Agency does not believe, however, that those investigations provide sufficient evidence of the absence of increased teratogenic risk in humans, either for dioxin in general or among the women of Seveso in particular. reasons for this conclusion: There are three (1) deficiencies in the available data; (2) methodologic deficiencies in the treatment and interpretation of the data which are available; and (3) suggestive indications in the available data that there may actually have been an increase in teratogenic risk in the area after the incident. Major points which illustrate deficiencies in the available data include: reproductive data in the area "either do not exist or are deliberately underreported" (Reggiani 1977); baseline rates for spontaneous abortions and congenital malformations in the area prior to the incident are not available; less than complete cooperation was obtained from local physcians and less than complete registration of pregnant women was attained (623 pregnant women were registered, but 2,513 deliveries were recorded in the area for July 1976 to May 1977; registration was thus about 25%); while 34 women obtained therapeutic abortions in the area, it is estimated that more than 2 times that number obtained them legally or illegally elsewhere (Whiteside estimates the number to be 4 times as many); and the conventional pitfalls of reproductive epidemiology could not -44- �be avoided 1 e.g., dependence on hospitalized spontaneous abortions for numerators and hospitalized births for denominators and different gestational cohorts for spontaneous abortions and births occurring in the same calendar period) . Maj or points which illustrate methodologic deficiencies in the treatment and interpretation of the available data include: estimates of the total amount of dioxin released ranged from 650 g^Reggiani 1977) to 11 kg tWhiteside) , to 130 kg;> Nature 11/28/76) ; estimates of exposure per person 2 2 varied from 29 ug/m ( Tuchman-Duplessis) to 5,620 ug/m ( Reggiani 1977); exposure was characterized by geographic zones, but reproductive data were gathered by geographic districts raising questions whether the zones were contiguous with the districts; spontaneous abortion rates were grouped in 6-month intervals, but congenital malformation rates for 1976 were grouped in 12-month intervals which could have masked an effect expected to be relatively acute or with a 2-3 month lag period; and the rates listed as "totals" for the two groups of districts in Table 13 ( in Reggiani 1977) appear to be averages of the district rates and as such are invalid and cannot be interpreted; the lack of chromosomal abnormalities in the products of therapeutic abortions is overemphasized since dioxin could conceivably produce a teratogenic effect without producing a concomitant mutagenic -45- �effect; and the wide interspecies variation seen in lethality studies should not automatically be applied to teratoqenic effects because it is known that very low doses are teratogenic in the rat I e.g., 0.01 ug/kg) and dioxin doses which caused teratogenic effects in rhesus monkeys were apparently as low as 2.5, 50, and 500 nanograms/kg. Suggestive indications of a possible teratogenic effect in humans, from the available data, includes the congenital malformation rate increased by 570% ( about 7-fold) between 1976 and the first five months of 1977 I Table 14, 0.13 to 0.87 per 100 live births) I in Reggiani 1977). The birth rate dropped "sharply" following the explosion and cows aborted and produced malformed offspring following the explosion. ! Whiteside) . A local doctor noted a "marked increase" in convulsions among infants. I convulsions could be delayed effects of neurotoxicity j.n utero) . [Whiteside]) . Cb) Vietnam A large amount of TCDD- contaminated herbicides were used in Vietnam during 1962-1971. Possible health effects have been reported upon retrospectively by groups entering Vietnam. Tung et al. charged that 2,4,5-T was responsible for much of the Down's Syndrome seen in -46- �[South] Vietnam. Crummer was quoted by Honoroff as having observed high incidences of children with Down's Syndrome. Tung et al. also noted a very significant increase in the Hanoi hospitals in hepatic carcinomas in the period 1962-1968 [1790/7911 cancer cases (10%), compared to 159/5492 (2.9%) for the period 1955-1961], It should be remembered that most of the accidents reported here were retrospective accounts. In the cases of Seveso and Vietnam, reporting was (and still is) at best piecemeal. The exposed populations contained numbers of highly mobile persons who could not be accounted for adequately. ( 3) (a) Exposure Analysis General Considerations There are two components to any pesticide-related risk: (1) the toxicological properties of a chemical, and (2) exposure to the chemical. The risk assessment is a summation of the conclusions in each of these areas. A highly toxic chemical may pose high risk even if exposure is low; conversely, a compound of low to moderate toxicity may pose high risks if exposure is high. Estimating probable exposure is difficult for a -47- �number of reasons. While it would be inappropriate to attempt a definitive discussion of these problems here, it is useful to note a few examples. First/ empirical data on exposure is less available than is toxicology data. Second, there are a number of exposure pathways which require consideration (e.g., inhalation, dermal absorption, ingestion of food residues, and ingestion of water residues). Third, the inherent complexities of the dynamics of a chemical's movement through the environment create formidable obstacles to describing any given exposure pathway. For example, the chemical may behave differently in various media depending upon a number of environmental factors which can vary at any one application site. Thus, even when some empirical data on a given route of exposure is available, there are often uncertainties concerning the applicability of the data to situations involving conditions which vary from those which obtained at the study site. The inherent difficulties of exposure assessment always create a troublesome problem for decision makers. These problems are of great concern in situations involving chemicals which appear to pose risks even at very low levels of exposure. As discussed above, the TCOD contaminant in 2,4,5-T is clearly such a chemical. For example, TCDD is carcinogenic in rats at doses as low as 1 ppb and fetotoxic in mice at doses as low as 0.01 ug/kg/day. -48- �Moreover, the complexities of exposure assessment are also amplified in situations involving persistent chemicals. This is because the length of time a chemical persists in the environment can increase the opportunities for movement of the chemical and confound attempts to eliminate pathways as pathways of concern. Time increases the possibilities of variation in enviromental factors affecting chemical mobility. The environmental persistence of 2,4,5-T is relatively short due to physical, chemical, and biological degradation processes. On the other hand, the contaminant TCDD has a much longer persistence in soil and is known to bioaccumulate in fish (Hatsumura and Benezet, 1973; Kearney et al., 1973). Generally, exposure assessments involve attempts at modeling the likely exposure potential through several pathways which are identified as pathways of principal concern. The exposure assessment typically will involve attempts to describe the movement of the chemical from the site of application to persons potentially at risk, using such empirical data as are available on the presence of the chemical at various intermediate points in the critical path. conservative assumptions based upon such things as knowledge about the behavior of similar chemicals, typical environmental conditions affecting the use site, and -49- �the like, are used to bridge inevitable gaps in the empirical data. The objective, however, is a simple one: to obtain a qualitative and (if possible) quantitative description of the likelihood that a given chemical will move from where it is applied to a given group of potentially exposed individuals• Since 2,4,5-T first surfaced as a subject of regulatory concern, determining potential exposure has been the critical issue on the risk side of the regulatory equation. Uncertainties about exposure resulted in suspension of regulatory action in 1974, and the launching of an ambitious project to generate exposure data (the "Dioxin Implementation Plan" or "DIP"). Primarily because of great difficulties encountered in developing analytical methodologies with sufficient sensitivity to measure the extremely low levels of TCDD which are of biological concern, the progress of the DIP has been disappointing. To date, it has yielded only fragmentary information. In my judgment, the information which has recently come to my attention as a result of the Alsea study constitutes a dramatic and troubling new point of departure for analysis of TCDD exposure concerns. As indicated above, these data show a striking relationship between 2,4,5-T use and increased incidences of spontaneous abortions among -50- �women residing in the use area. As further developed above, this effect is an effect which one would have predicted as a likely outcome of human exposure, based upon a body of animal data of almost unprecedented conclusiveness* The Alsea study, to be sure, contained no data showing actual exposure. However, concern for the health of humans who may be exposed to 2,4,5-T and its contaminant, TCDD, is heightened because scientists have not demonstrated that there is a level of exposure that has no adverse effects in */ humans.— Thus, in the face of the highly significant relationship which the study showed, and the animal data, I conclude it is reasonable and in the public interest to assume ** / that the women in the Alsea study were exposed to TCDD.—' ^/ A committe of the National Research Council of Canada recently agreed with the authors of the World Health Organization's monograph on TCDD that "for TCDD a no-effect level for man could not be established" (NRCC 1978). **/ I have found it prudent to suspend because data from the Alsea Epidemiological Study indicates that women experiencing adverse reproductive effects may have been exposed to 2,4,5-T. Information of this kind concerning a chemical's effects on human populations is rarely available. Before the Alsea Study was completed, Agency scientists developed preliminary exposure analyses for 2,4,5-T based on use information, assumptions, and modeling. Since I have information of adverse human effects correlating with the use of 2,4,5-T, I have chosen to rely on this correlation as a basis for regulatory action, rather than on exposure analyses based exclusively on use information and modeling. -51- �Moreover/ I also conclude that it is prudent to assume that individuals who frequent or live in areas where 2,4,5-T is used may be exposed to TCDD in ways and under conditions which may cause these individuals to be exposed in ways qualitatively similar to those experienced by the Study area women. As developed below, I find that 2,4,5-T use patterns likely to cause exposure opportunities similar to the exposure experienced by the Study area women are the forestry, rights-of-way, and pasture uses of 2,4,5-T. The Agency has identified pesticide applicators and persons involved in pesticide application support activities, and persons living in or frequenting areas of 2,4,5-T use as the principal groups of individuals who may be exposed as a result of the forestry, rights.-of-way, and pasture uses of 2,4,5-T. (b) The Alsea Study Area (i) Description of Area The Alsea Study Area comprises approximately 1,600 square miles of Oregon's forested Coastal Range centered around the "Alsea basin," an area of approximately 400 square miles. It is bounded on the west by approximately 70 miles of the Pacific Coast and extends inland for distances ranging from 10 to 35 miles. The Study area includes all but -52- �the northern and southern reaches of the Suislaw National Forest. Numerous commercially owned and Bureau of Land Management forested acreages are interspersed throughout this region. Mountain elevations of approximately 1,000 feet are not uncommon; peak elevation is slightly more than 4,000 feet. The principal rivers are the Siletz, Alsa, Yaquina and the Suislaw. Eastern fringes of the area drain eastward into the Willamette Valley. Maximum runoff is reached generally during the winter months as the result of storms off the Pacific occurring usually as rain. The Study area is predominantly rural. The four largest towns have a total population of 14,450. All other towns/villages have populations of less than 1,700. Alsea has a population of 400 (1970 census). In addition, many residences are scattered througout the forest areas. All of the nine women who were identified in the first phase of the investigation resided, at the time of pregnancy, in rural residences located within 12 miles of Alsea. (ii) Use Pattern 2,4,5-T is applied to the forests in the Alsea area almost exclusively by helicopter for control of undesirable vegetation such as red alder, vine maple, salmonberry, and thimbleberry. In general, the compound is used in the -53- �spring fMarch, April, or May) with a second application made, if needed, in middle to late summer ( July or August) . Over the six-year study period, 10,000 pounds of 2,4,5-T was distributed over a total area of approximately 7,000 acres. The usual practice was to treat any particular site approximately once every five years. However, contiguous stands could be treated in succeeding years. The spray program spans only a few days' time, with the duration depending on the number of acres to be treated and the weather conditions. To avoid contamination of water sources prior to 1978, the general application policy was to avoid spraying near homes and to provide for a single swath of 30 to 60 feet on each side of any maj or stream. In September 1978, the Oregon Forest Practices Act created guidelines which prohibited spraying within 500 feet of an inhabited residence or within 200 feet on either side of streams with fish and/or ones that are used for domestic water supplies. However, drift and runoff could contaminate surface waters. f iii) Population Exposed to the Herbicide Population of the Alsea Region is clustered in several small towns; there are also isolated homes and farmsteads in the forest area. Groups which may be traversing the forests of the Alsea Region include residents, workers engaged in forest management, incidental travelers, hikers, students, surveyors, and delivery persons. -54- �£ iv) Modes of Exposure The major method of dispensing 2,4,5-T in the Alsea Forest Region is by helicopters. Although the Oregon Forest Practices Act prohibits spraying near homes or streams, there appears a likelihood that residents and travelers of the Alsea Region might be directly exposed to 2,4,5-T during periods of application as a result of drift* Drift from a helicopter flying over a forest canopy can produce drift of the herbicide spray at significant distances from the path of the aircraft* Residents or travelers in the path of the spray might be doused with the pesticide spray. Exposure to the population from drift and direct contact is by the dermal'( exposed skin) and inhalation routes* Resident populations may also incur exposure to 2,4,5-T and TCDD subsequent to application. Waterborne residues are a possible route of exposure; other possible exposure routes include fish, wildlife, and other foods produced or found in the area* The fact that TCDD is somewhat persistent and bioaccumulative may enhance exposure possibilities. Furthermore, pesticide mixers, loaders, applicators, and other workers may be exposed to the pesticide -55- �\c () Comparison Between Presumed Exposure in The Alsea Study Area and Possible Exposure in Other Use Situations The Alsea Study shows a significant correlation between the use of 2,4,5-T in the Alsea area and increased incidence of spontaneous abortions within approximately two months after application* The Agency believes that it is prudent to assume that the women studied were exposed to 2,4,5-T. While the Agency cannot determine the actual routes of exposure, information about how 2,4,5-T is applied, population densities, and proximity of Study area residents to spray areas provides a basis for making assumptions about possible chances for exposure. That 2,4,5-T was applied by helicopter rather than by ground application methods in Alsea, enhanced the potential for exposure to 2,4,5-T from drift. Aerial application is a principal method for applying 2,4,5-T. A substantial amount of the 2,4,5-T applied in forests and on rights-of-way is applied aerially. In contrast, in pastures, application of 2,4,5-T usually is by spot treatment with knapsack spraying equipment. This method, causing less spray distribution than aerial application, lessens potential exposure from drift. -56- �Alsea inhabitants Live in towns and residences scattered throughout forests in which 2,4,5-T was applied* Effects occurred even though application near residences and streams was prohibited. The Study area women who experienced spontaneous abortions were residents of the area. Their exposure to 2,4,5-T may have occurred either while they were at home or while they were in nearby forest areas. Bystanders, workers engaged in forest management, people visiting the forests for recreational purposes, and others would have exposure potential similar to the exposure potential of the Study area women away from their homes. Because TCDD persists in the environment, such non-residents may have been exposed to 2,4,5-T and TCDD during or for some unknown length of time after application had occurred. The Study area women may have been exposed to 2,4,5-T or TCDD through ingestion of drinking water, fish, and wildlife. Residents are more likely to be exposed through this route than infrequent visitors to the spray area. Frequent visitors or workers in the area would have exposure potential similar to that of residents. All other forest areas in which 2,4,5-T is used are most obviously */ similar to the Study area.— ^/ Commercial forests are defined as those lands not withdrawn for non-timber purposes which are capable of growing 20 cubic feet of wood per year of desirable species. -57- �The use of 2,4,5-T to maintain rights-of-way involves exposure potential similar to the exposure potential of the Study area women: residents of the application area and workers and visitors who frequent the area may be exposed. The Agency estimates that a considerable number of people may be exposed to 2,4,5-T and TCDD as a result of the use of 2,4,5-T in non-urban areas to maintain rights-of-way. Rights-of-way uses include highways, railway lines, electric power lines, and pipelines. A principal method of applying 2,4,5-T is by aircraft, which was the method of application in the Alsea, Oregon area. The population that is most likely to be exposed are people who live in the path of the spray or in the area of */ drift.— A large potential exposure group would be comprised of people living along railroad tracks and along _V Factors which affect drift include wind direction and velocity, turbulence, relative humidity and air temperature, atmospheric stability, pesticide formulation, application equipment, and spray volume. For purposes of this analysis, the Agency conservatively estimated possible pesticide drift at 1/2 mile. The Agency notes, however, that pesticides could drift farther depending on the variables listed above. Some pesticide drift has been reported as far as 22 miles from target (EPA DRAFT: "Report to Congress/Study - ULV," p. 95). In addition, this same draft report estimates that percent of pesticide drift over 1,000 feet from the target variously ranges from a low of 10% to a high of 90%. -58- �highways* Other groups that may be exposed are those that live in forests or plains along power lines and pipelines. The residents may be exposed to TCDD through the diet for longer periods of time due to low levels of TCDD contamination in water and food. An additional potentially exposed group are people working in, or traveling through, the treated area. Exposure from the use of 2,4,5-T in pastures is **/ likely to be lower than the Study area*— Pastures are likely to be near farmhouses and small towns. The populations which may be exposed to 2,4,5-T include farm families, other rural residents, and workers in rural occupations. The predominant method of application for controlling brush in pastures is spot treatment with knapsack spraying equipment. The distribution of 2,4,5-T from this technique is lower than that from forestry and rights-of-way use, because this technique produces only short-range drift. Indirect exposure due to residues in food is possible. Generally, persons involved in applying pesticides have greater exposure to the chemicals than do residents of **/ Pasture is defined as land producing forage for animal consumption, harvested by grazing, which has annual or more frequent cultivation, seeding, fertilization, irrigation, pesticide application, and other similar practices applied to it. Fencerows enclosing pastures are included as part of the pasture. -59- �the area in which the pesticides are used. There is no reason to believe that this would not be true of 2,4,5-T. Therefore, the Agency is concerned about potential exposure to pilots, ground spray crews, mixers and loaders, and flaggers, all of whom are exposed to 2,4,5-T in the applica*/ tion process." For aerial application, the ground crew, including mixers and loaders of the aircraft, is the group with the highest potential for exposure by both dermal and inhalation routes, because they handle the concentrated formulations up to 41% of 2,4,5-T acid by weight) . The flaggers on the ground are exposed mainly by drift of the diluted spray deposited on their exposed skin, and to a lesser degree by inhalation. The pilots are expected to be exposed to smaller amounts of 2,4,5-T by dermal and inhalation routes because they sit in the enclosed cabin of the helicopter while applying the diluted herbicide spray. For the ground application techniques, the applicators and mixers are the workers running exposure risk. Inhalation exposure may be more significant when fine mist sprayers^ for example, ^/ In response to the 2,4,5-T RPAR, the American Paper Institute and the National Forest Products Association recently submitted a detailed study of aplicator exposure to 2,4,5-T during both areial and ground applications ; {2,4,5-T RPAR submission #1023H - 30000/26) . The results of this study indicate that workers who handled the pesticide concentrate had the highest exposure, followed by knapsack sprayer applicators, mist blower drivers, helicopter pilots, supervisors, and flagmen* -60- �spraying with a coarse spray. The reason for this is that smaller spray droplets are more readily absorbed through the lungs. C. Determination of Benefits The Agency has evaluated the potential economic impacts of suspending the forestry, pasture/ and rights-of-way */ uses of 2,4,5-T during 1979 and 1980.— The consideration of economic impacts stemming from a suspension is limited to a two-year period because the maximum proj ected length of a cancellation proceeding would be two years. A suspension order remains in effect only during a cancellation proceeding. Thus, only the impacts which would arise during this period would be at issue in a suspension. Any impacts which would be caused by a suspension, but which would be felt after **/ this period, are also considered.— ^/ The emergency suspension order will take effect immediately upon issuance of this Notice and remain in effect during any subsequent emergency suspension hearings. At the conclusion of the hearings, a decision will be made whether to continue or remove the suspension order during the ensuing cancellation proceedings. Ecomonic impacts are therefore separately evaluated for the 3 1/2 month period allocated for an emergency suspension proceeding as well as for the two years which may be required for a cancellation proceeding. **/ The Agency's analysis is based on information from a number of sources including RPAR rebuttal comments received by the Agency from registrants, users and other parties during the RPAR process; and the USDA-States-EPA 2,4,5-T RPAR Assessment Report^February 15, 19791 as well as other relevant data. Although the 2,4,5-T Report attributes a role to EPA, the final report has neither been completely reviewed nor approved by EPA. Therefore, although the Agency has relied on some portions of the report, it cannot and does not wish to adopt all portions of the report as reflecting the Agency position on matters discussed therein. -61- �2,4,5-T is registered for control of woody and herbaceous plants on rights-of-way, forestry, range, pasture/ and rice. The suspended uses ( rights-of-way, forestry, and pasture) comprise about 74% of the estimated 9.3 million pounds of 2,4,5-T active ingredient used annually in the U.S. Rights-of-way usage f3.8 million pounds) is the single largest use, comprising an estimated 41% of total annual usage; forestry f2.6 million pounds) and pasture usage t" 500,000 pounds) account for about 28 and 5%, respectively, of annual 2,4,5-T usage. Economic impacts of suspending forestry, pasture, and rights-of-way usage of 2,4,5-T during 1979 and 1980 were evaluated assuming all registered alternatives are available, except silvex which is also subject to suspension. The analysis often provides qualitative estimates of impacts due to a lack of data to support precise quantitative estimates. Economic impacts during 1979 and 1980 would depend upon the treatment options actually selected by users. For many, use of alternatives to 2,4,5-T during 1979 and 1980 would be optional ="{ i. e., could be delayed to a later year) • Other users might choose to use alternatives immediately. It is not possible to predict with precision which option may be selected by the many potential users of -62- �2,4,5-T during the suspension period. The Agency's analysis indicates that the suspension of 2,4,5-T (and silvex) for forestry, rights-of-way, and pasture uses during 1979/80 would not signficantly affect U.S. production or prices of major commodities and services from these sectors. Impacts on productivity and costs during the two years would generally be regional in nature but insignificant on the national level. Industry impacts would be nominal within the context of year-to-year variations in economic activity due to interaction of normal supply and demand forces, as affected by weather, general monetary and fiscal policies, international economic developments, etc . Economic impacts during the 3 1/2 month emergency suspension proceeding would negligible. The only noteworthy impact would involve the forestry use in which spring applications predominate in the Northwest. Even then, the impacts are nominal during the 3 1/2 month suspension proceeding. -63- �The minimal nature of the overall economic impacts follows from: ( a) the inherent flexibility of treatment schedules, permitting delays in treatment to ameliorate negative economic impacts of suspension; ( b) the existence of chemical, mechanical, or manual alternatives { or combinations) which are currently being used on these sites, even though they are not generally as cost-effective as 2,4,5-T; andr( c) the 2,4,5-T usage which normally would have occurred on the suspended sites represents a small fraction of the overall industry acreage { e.g., 0.2 percent of forestry acreage in the U.S.) ; concentrated acreages needing treatment with alternatives during the suspension period would occur only at the regional and local level. Each of the suspended uses is examined in detail in the following discussion. "( 1) Forestry Use There are about 500,000,000 acres of commercial -64- �*/ - in the U.S. of which 1.16 million acres (0.23%) are forests treated annually with 2,4,5-T. This herbicide can be used * */ at either or both of two stages in the p r o d u c t i o n — o f conifers (softwoods): (1) preparing sites for reforestation and (2) releasing young trees from hardwood competition. Each operation is undertaken once in the 50 year cycle of a softwood stand. 2,4,5-T as well as other chemical and non-chemical control methods may be used individually or in combination for site preparation and release. Use of 2,4,5-T for site preparation is not critical although it is cost effective. Several other chemical as well as non-chemical methods are also effective for site preparation. Picloram and 2,4-D, sometimes combined, are the most effective substitute chemicals. 2,4-D costs less than 2,4,5-T but controls a more limited spectrum of weeds. Because the release (weeding) operation is conducted after the seedling trees are in place, a selective herbicide which will not harm the seedlings is preferred. This is particularly true for pine; only 2,4,5-T provides control of ^/ Commercial forests are defined as those lands not withdrawn for non-timber purposes which are capable of growing 20 cubic feet of wood per year of desirable species. 5*V 2,4,5-T is sometimes used for other forestry herbicide operations, including rehabilitation or species conversion, fuel break maintenance, and timber stand improvement. The major forestry uses of 2,4,5-T are site preparation and release, which are the focus of this analysis. -65- �the wide variety of competing hardwoods without damaging the sensitive seedling pine. This often critical operation is most effective when performed two to ten years after establishment of the stand. If competing hardwoods are not suppressed, the seedlings may be overtopped, and stand growth and density may be decreased. The benefits of weed control for release and site preparation of conifer crops are increased yields at harvest time. For stands receiving no weed control for site preparation or release, annual growth can be substantially reduced on the most productive sites. Approximately 2 million acres of forests currently receive site preparation while approximately 1.5 million acres receive release treatments. 2,4,5-T is used for about 20% of the site preparation (1.16 million pounds on 414,370 acres) and about 51% of release treatments (1.48 million pounds on 749,320 acres). Other chemicals are often used for both practices, as well as hand, mechanical, and prescribed burning treatment. Herbicides are applied by broadcast foliage spray (aerial and ground) and by individual stem applications. Because it is selective and does not injure conifers, 2,4,5-T is the only herbicide widely applied by broadcast methods. Broadcast foliar applications account for 89%, and -66- �the remainding 11% are individual stem treatments* Other registered chemicals are applied almost entirely by stem treatments since they are damaging to conifers. Site preparation with other chemicals generally costs $20-50/acre, which is somewhat more than with 2,4,5-T treatment. Mechanical methods may range from $45-$200/acre. Prescribed burning is effective at $3-$14/acre in the East. In the Pacific Northwest/ burning costs $85-$225/acre, is very risky and hard to control/ and may be restricted because of smoke management regulations. Severe sprouting after fires requires 1-2 release treatments in nearly all cases. Mechanical or combination methods provide the best sites for reforestation. They are limited, however, to gentle terrain and may cause erosion on sloping lands. They can sometimes be incorporated with logging slash cleanup on western forests, reducing the costs of new stand establishment. Release of young conifer stands from hardwood competition can be accomplished only by chemical or hand methods. Chemicals, principally 2,4,5-T, provide some control of sprouting which manual methods do not. Thus, manual weeding may require two or more treatments in severe cases. Only two other chemicals, fosamine and glyphosate (registered only in Washington and Oregon), provide this -67- �selective control. Their costs are $30-$250/acre. Aerial applications of 2,4,5-T cost $ 10-$20/acre in the South and $10-$75 in the West* Hand methods may be used to a limited extent where labor is available, at costs of $30-$200/acre or more depending on density and size of hardwoods* No chemical other than 2,4,5-T is presently available in the eastern U.S. where 67% of the acreage of the 2,4,5-T for release work is accomplished. Intensive management of young confier stands is practiced primarily by public agency managers or timber companies, rarely by small owners. Site preparation is normally tied to harvest cutting which in turn is dependent upon marketing commitments (e.g., U.S. Forest Service) or company raw material needs (industry). Where current site preparation plans include 2,4,5-T, some alternative method will likely be used. Costs may increase from 20-200% for most alternatives now available. If budgets are inflexible, harvest cutting may be reduced (USFS or state agencies) in order not to accumulate acres */ needing site preparation.— Industry owners are more likely to continue planned harvests and absorb the increased site preparation costs. ^ / The U.S Forest Service is required to reforest havested [ acres within three years under the National Forest Management Act of 1976. -68- �Release activities are less dependent on other activities and can ordinarily be postponed for a few years, at the increasing sacrifice of some future production. If budgets are relatively fixed, some of the more productive acres will be treated in 1979-80 where alternatives are not too costly. Because of the lack of a selective herbicide other than 2,4,5-1 for use on pine stands (especially in the South and North), it is anticipated that approximately 60-70% of these stands in need of release will go without treatment during 1979-80. In the West, about 3/4 of needed release will be scheduled using other herbicides, although full adjustments may be delayed to the second year. Immediate impacts on users would occur in two forms: increased costs and reduced future productivity. Cost increases for site preparation would range from $20-$200/acre depending on the method chosen. For the first year, release costs would go up in the West by $ 10-$200/acre on those acres where young stands are threatened with imminent loss to weeds, possibly 20% of the 246,000 acres currently released with 2,4,5-T. The second year could see the use of substi- tutes on the entire 1/4 million acres, as budgets are adjusted to new costs. Current total release costs in the South would drop as many acres (65%) are left without treatment. However, there would be increased release costs -69- �as release is attempted at a later time, as well as productivity losses in the future. Reduced future productivity may be reflected in harvest cut adjustments where budgets cannot accomodate the increased costs of alternate methods. The U.S. Forest Service is presently considering proposals for about 34,000 acres of 2,4,5-T applications on National Forests for 1979 (USFS 1979a). Because of recent policies on the use of 2,4,5-T, these proposals are to cover situations where no alternative weed control appears feasible. The loss of 2,4,5-T for these situations could conceivably cause a reduction of FY 79/80 timber sale offerings to avoid accumulations of future problem areas. However, it is not likely to do so, as discussed below. Since weed control occurs early in the life of forest stands, the economic consequences of reduced control are delayed until harvest time 30-125 years in the future. However, substained yield management (as required on National Forests by the Multiple Use-Sustained Yield Act of 1960) requires a matching of harvest to anticipated growth of the entire forest. Any loss in productivity due to decreased weed control would, on National Forests, be reflected in reduced harvests. Obviously this effect would accumulate for each succeeding year of reduced weed control. -70- These adjust- �ments are normally made at 10-year intervals for most National Forests, and may not be reflected in immediate harvest reductions during a one or two year suspension. Private industry would likely accept the losses in ultimate harvest as they occur in the future, with no immediate reduction in harvest schedules (API/NFPA rebuttal to the RPAR on 2,4,5-T, 1978). Suspension would increase annual control costs by $13.5 million if all 1.16 million acres now treated with 2,4,5-T were treated with alternatives (USDA/States/EPA, Feb. 15, 1979). acre. This is an increase of $11.64 per treatment For site preparation, the increase in cost would average less than this, e.g., $5-$10 per acre; for release, it would be generally much higher due to increased use of the more costly manual methods, e.g., $30-$200 per acre in many cases. No overall average cost impact can be computed on a percentage basis with current information. It is unlikely that alternative control plans would be in full effect until the second year of suspension. The first year effects would likely be 50 to 70% of these costs($7-$10 million), with added spending in later years to make up for operations postponed the first year. These added control costs due to suspension would be -71- �in addition to the value of any actual growth losses associated with delayed or less effective site preparation and/or release treatments. A minor yield loss is projected for loss the first year of suspension ( less than 0.2 percent of U.S. softwood production) . This would increase in the second year to about 0.5 percent. These losses in yield, if realized would have an estimated reduction on forestry income of $9.6 million the first year of suspension and about three times this amount the second year ($29 million) under the assumptions of the USDA/ State/EPA 2,4,5-T Assessment Team Report [USDA/States/EPA, Feb. 15, 1979]. The total impact, including both increased control cost ( $7 to $10 million) and yield losses, if realized (up to $9.6 million) would be in the range of $10 to $17 million, (if all 2,4,5-T acres were treated with alternatives, which is unlikely, the total impact would be about $21.3 million the first year.) For the second year, the combined impact would be more, totalling $36 to $39 million ($7-$10 million plus $29 million in eventual yield losses) . While significant, these impacts are rather nominal within the context of overall forestry industry of the U.S. Effects on wood product prices would only occur if a decision were made by the U.S. Forest Service to curtail timber sales in the near future. -72- The limited �impacts of suspension on production would not necessitate a significant increase in wood product prices. The economic impacts of suspension of the forestry use for 3 1/2 months during emergency proceedings would be nominal even though conifer release treatments in the Pacific Northwest, are generally applied in the spring, before bud break which occurs by March. Some such treatments may have already been made and delay of others for two to four months during a suspension proceeding is of little significance. (2) Rights-of-Way 2,4,5-T is used to control woody and herbaceous plants on rights-of-way (railroad, highway, electric transmission, and pipeline) which could interfere with the functioning of the system (e.g., weed encroachment on highways), threaten the system's equipment, and/or interfere with inspection and maintenance of the system. 2,4,5-T is considered to provide longer control of pest plants than other control methods without harming grass and other vegetation desirable for erosion control, wildlife shelter, and aesthetics. Chemical, manual, and mechanical methods of control are used in various combinations on rights-of-way acres, depending on the terrain, availability of labor, type of -73- �equipment and species type and density. Combining control methods is a common practice on rights-of-way acreage. A relatively large number of acres apparently receive no vegetation management. Only about one-fourth of electric utilities, railroads, pipelines, and highway departments have all acres in management programs. For highways and pipelines, mechanical methods are used on more acres than any other method. Manual is used on most acres of electric acreage and is frequently employed as follow-up treatment to supplement chemical control. Somewhat less than 1/3 of all rights-of-way acreage are estimated to be treated by manual methods. Chemicals other than 2,4,5-T are more common on railroad acreage. Acres treated with chemicals are most likely to be acres where mechanical control is difficult and where other alternatives are expensive or relatively ineffective. About 683,000 rights-of-way acres are treated with 2,4,5-T on the average of once every four years, or 2.7 million acres total. An estimated 3.8 million pounds a.e. are used annually. Only a small percentage of rights-of-way vegetated acres are treated: 6.6% of railroad (127,000 acres), 9.4% of electric (465,000 acres), 4% of pipeline (22,000 acres), and 0.8% of highway (68,000 acres). Usage is believed to be mainly in the eastern and far northwestern parts of the continental U.S. -74- �Other chemicals are also currently used on many rights-of-way acres/ including dicamba, 2,4-D, dichlorprop, and picloram. Almost 13% of the highway, 25% of electric utilities/ 45% of railroad, and 5% of pipeline acreage is treated annually with other chemicals (which may include some non-herbicides). 2,4,5-T is $1.00 to $3.00 more expensive per application than other chemicals, for aerial, selective basal, and stump spray, which account for about 65% of annual acreage treated. For ground broadcast or selective foliar treatment, 2,4,5-T is cheaper ($2.00 to $19.00 in one case). The major economic advantage of 2,4,5-T is in the longer period of control it is said to provide. Generally, mechanical and manual methods are much more expensive than chemical methods. With use of 2,4,5-T suspended, rights-of-way managers would be faced with two main choices: (1) use alternative chemicals on acres scheduled for treatment or (2) postpone any treatment to see if 2,4,5-T would be available the next year. They would most likely use alternatives on at least some acres, in the Southeast and Pacific Northwest, where plant growth is rapid. The percentage of acres treated with alternatives would vary by right-of-way type and would probably be lower for railroads and highways, since they appear to be more flexible in treatment schedules. -75- �If some acres are not treated during the first year following suspension, they would probably be added to scheduled treatments in the second or third year. It can be assumed that many managers would continue treating acres each year as scheduled with alternative herbicides because of increases in size and density of pest plants. If so, annual costs for vegetation management for highways and railroads would increase by about $133,000 and $1,845,000, respectively, if they treat all acres with alternative herbicides. Costs for electric and pipeline rights-of-way would temporarily decrease by an estimated $680,000 and $28,000, respectively, each year during suspension, mainly because of the high proportion of aerial and selective basal applications• These applications are lower in cost than 2,4,5-T but must be repeated more often. There would be a net cost increase over time due to suspension only if 2,4,5-T is not available after the suspension period, i.e., if it is cancelled. The overall net cost increase for all rights-of-way types due to suspension only would be about $1.3 million per year during the 1979-1980 period. These changes in vegetation management costs are not expected to impact industry net revenue or operating costs significantly. Increased vegeta- tion management costs due to suspension would be less than 0.1 percent of operating expenditures for highways and railroads. -76- �Impacts at the consumer level due to suspension of highway and railroad uses are estimated at less than $0.03 per household per year* This is based upon the annual cost impacts noted above ($2*0 million) and the number of households in affected regions* No significant macro-economic impacts would be expected from suspension of 2,4,5-T on rights-of-way. In view of the limited economic impacts from a two-year suspension period, economic impacts during the 3 1/2 months required for a suspension proceeding would be of no economic significance on rights-of-way. (3) Pasture 2,4,5-T is used to control a wide variety of wood */ and herbaceous weeds in pastures— throughout the U.S. Weed control in pastures is economically sound where the cost of control is exceeded by the value of increased forage yield due to suppression of competitive non-forage vegetation. It is also practiced for reasons of long-term pasture maintenance and cheaper fence maintenance. Weed */ Pasture is defined as land producing forage for animal consumption, harvested by grazing, which has annual or more frequent cultivation, seeding, fertilization, irrigation, pesticide application and other similar practices applied to it. Fencerows enclosing pastures are included as part of the pasture. -77- �control by means of 2,4,5-T is now practiced annually on about 1% of U.S. pasture acreage (1.0 million of the estimated 101 million acres of pastureland in the U.S (48 states)). This use includes approximately ingredient of 2,4,5-T annually. 500,000 pounds of active Generally, 2,4,5-T is applied in pastures as a spot treatment with backpack or hand-held sprayers, although some broadcast treatments are also used. ** / In contrast to range—, little 2,4,5-T is aerially applied to pastures because landowners rarely allow weed infestations to become sufficiently dense to justify aerial application. There appear to be effective chemical, manual, and/or mechanical control alternatives for all species in all regions, although no single set of alternatives can be used on all weed species or in all parts of the country. Thus, alternatives such as picloram, dicamba, undiluted 2,4-D, and hand labor can generally provide the same level of control as 2,4,5-T, although at higher rates of application and/or higher expense. Since equally effective alternatives are available, no yield impacts are expected during the 2-year **/ Range is non-pasture grazing land on which forage is produced through native species, or on which introduced species are managed as native species. This precludes land on which regular cultural practices of the nature contained in the pasture definition. -78- �suspension period. On those acres where the conditions and type of weed permit use of an alternative which is not more expensive than 2,4,5-T, it is likely that these alternatives will be fully employed. Here no negative economic impact would be experienced. On those acres where the use of alternatives will cost more than scheduled 2,4,5-T treatments, treatment may be delayed, dispensed with entirely, or the more expensive alternative employed. Since treatments with 2,4,5-T are generally effective for 5 to 10 years, the timing of control is largely voluntary. Therefore, delay during the suspension period may be practical on much of the acreage scheduled for treatment. Treatment may be entirely dispensed with on acres scheduled for 2,4,5-T treatment which only marginally require such treatments. Presently the chemical costs of 2,4,5-T treatments are about $2.00 per acre (or about $2.0 million on 1.0 million acres). The chemical cost of alternatives is estimated at about $6.00 per acre. Thus, for each acre treated with alternatives during suspension, the cost impact would be $4.00. If all 1.0 million acres were treated, the cost impact would be $4.0 million. Since treatment is a given year is quite optional during the 5 to 10 year treatment cycle on pasture, as many as one-half to one-fourth might defer treatment in 1979/1980. This would reduce the impact to $2.0 to $3.0 million per year during suspension. -79- �The economic impacts of a two-year suspension of the pasture use of 2,4,5-T would be of no consequence on a national basis. It would be of significance to the individual owners or operators whose pastures are due for immediate treatment and on which more expensive alternatives must be used. These impacts would be of limited local/regional concern. In view of the limited economic impacts of a two-year suspension, the economic impacts during the 3 1/2 months required for a suspension proceeding would be of no economic significance. V. PROCEDURAL MATTERS This order directs the emergency suspension of the forestry, rights-of-way, and pasture uses of 2,4,5-T. Registrants affected by emergency suspension actions may request an expedited hearing before the Agency. This section explains how to request an expedited hearing, the consequences of requesting or not requesting an expedited hearing, and the procedures which govern an expedited hearing in the event one is requested. -80- �A « Procedures for Requesting a Hearing (1) Who May Request a Hearing and When the Request Should Be Made Registrants of 2,4,5-T products registered for the forestry, pasture/ or rights-of-way uses of 2,4,5-T may request a hearing on these specific registered uses of 2,4,5-T within five days after receipt of this opinion and order. (2) How to Request a Hearing Registrants who request a hearing must follow the Agency's Rules of Practice Governing Hearings (40 CFR, Part 164)• These procedures specify, among other things: (1) that all requests for a hearing must be accompanied by objections that are specific for each use for which a hearing is requested [40 CFR 164.121(a) and 164.123(b)] and (2) that all requests must be filed with the Office of the Hearing Clerk within the applicable five (5) days [40 CFR 164.121(a)]. Failure to comply with these requirements will automatically result in denial of the request for a hearing. Requests for hearings must be submitted to: Hearing Clerk (A-110) U.S. Environmental Protection Agency 401 M Street, S.W. Washington, D.C. 20460 -81- �B. Consequences of Filing a Hearing Request Under PIPRA Section 6( c) I 3) the emergency suspension order becomes effective immediately and, unless stayed/ continues in effect until completion of the expedited hearing and issuance of a final order of suspension* The statute provides that where an administrative hearing is requested, the emergency order is subject to District Court review on the emergency finding. The final suspension order issued by the Administrator after a hearing may keep the suspension in effect, modify it, or terminate it. A final suspension order issued following a hearing is then reviewable in the Court of Appeals. The statute provides that if a hearing is requested on the Administrator's emergency suspension actions regarding 2,4,5-T before the end of the five-day notice period, the hearing stage is to begin within five days after receipt of the request, unless the registrant and the Agency agree that it shall begin at a later time. No party, other than the registrant and the Agency, is to participate, except that any person adversely affected may file briefs within the time allowed by the Agency's rule. Hearings on emergency suspension, like hearings on ordinary suspension, are subj ect to the provisions of subchapters II of Title 5 of the United States Code, except that the presiding -82- �officer need not be a certified hearing examiner. The presiding officer has ten days from the conclusion of the presentation of evidence to submit recommendations to the Administrator, who in turn has seven days to issue a final order on the issue of suspension. C. Consequences of Not Filing a Hearing Request Under the statutory scheme, if there is no request for a hearing on the Administrator's suspension actions within the five-day notice period, the emergency suspension order becomes a final suspension order, which remains in effect until the conclusion of the cancellation proceedings, unless modified or vacated sooner (40CFR 164.130). Court review of an emergency suspension order, including the special review before the District Court discussed in Part II is available only if an administrative hearing has been requested within the applicable five-day period [FIFRA Section 6(c)(2), 6(c)(3)]. D. Supplementary Procedures EPA's rules of procedures for expedited hearings are set forth at 40 CFR Part 164, Subpart C. I do not know if a hearing will be requested on these suspensions. If it is, however, I am establishing the following procedures to supplement the existing regulations in governing its conduct* -83- �1. A deadline is being established for the comple- tion of all hearing procedures and the rendering of a recommended decision under 40 CFR 164.121(j). That dead- line is 90 calendar days from the first prehearing conference, which shall be held in accordance with the time requirements described below. 2. I am naming certain EPA employees to serve as a hearing panel in any hearing arising out of this notice (see Appendix A)• I am naming certain additional persons to be available to provide technical advice and staff support to the hearing panel (see also Appendix A). If questions arise at the hearing which persons in this category are uniquely qualified to assess, they may be called on to serve on the panel either in addition to, or in substitution for, the three panel members named above. The panel will conduct the hearing and submit a recommended decision to me under 40 CFR Section 164.121(j). None of the persons named above is subject in the normal course of their duties to the supervision or direction of any employee or agent of EPA who is a member of the Agency trial staff named below. 554(d)(2). -84- See 5 U.S.C. Section �Since 5 U.S.C. Section 554( dH 1) provides that those presiding at adj udicatory hearings may not "consult a person or party on a fact in issue [in the course of preparing their decision] unless on notice and opportunity for all parties to participate," neither myself nor my appellate staff will consult with the panel or its supporting staff on any matters involving this case from the date of notice until a recommended decision is issued. Members of my appellate staff are also listed in Appendix A. We will conduct an independent review of the questions presented on appeal of any recommended decision• However, in doing this we will feel free to consult with the hearing panel and the support panel, since they will have conducted the initial proceedings and brought expert knowledge to evaluating the record. The following Agency bureaus or divisions, and their staffs, are designated to perform all investigative and prosecutorial functions in this case: Office of */ the Deputy Administrator— , Office of Toxic Substances, the Office of General Counsel, and the Office of Enforcement. ^_/ The Deputy Administrator may properly be included in the trial staff since the prohibitions of 5 U.S.C. Section 55<(d) do not apply to "the agency". Her inclusion is necessary if guidance on general policy matters is to be available to the trial staff and, to free a high agency official to talk to outside interested persons about the questions involved without the constrains otherwise imposed by the ex parte provisions of the APA and the Government in the Sunshine Act. The Deputy Administrator will take no part in the detailed work of preparing and presenting the Agency's case. -85- �From the date of this notice until any final decision, no member of the hearing panel, its support staff, my appellate staff, or myself, shall have any ex parte contact with any trial staff employees, or any other interested person not employed by EPA, on any of the issues involved in this proceeding. However, persons interested in this case should feel free to contact any other EPA employee, including both trial staff and persons not explicitly named as panel members or assistants, with any questions they may have. 3. I am directing the hearing panel to proceed as follows to streamline proceedings in this case. a. My findings on imminent hazard and emergency for suspended uses of 2,4,5-T together with supporting information are in my opinion and order, which is available for inspection in the Office of the Hearing Clerk. Additional supporting information, including references cited in the opinion and orders, is also available for inspection in the Office of the Hearing Clerk. Together these documents **/ constitute the Agency record in this m a t t e r . — E P A has also attempted to put this information in perspective through a narrative summary and analysis. **/ Some of the documents in the record may be entitled to confidential treatment under FIFRA Section 10, as amended. Parties to the hearing may have access to such documents if appropriate protective arrangements are made. See also the footnote to this Order concerning confidentiality of data [in Section IV.A.i 1H aK i) ] . -86- �b. The scheduling of any hearing, particularly in its earlier stages, involves a balancing between the need to conduct an expeditious hearing and a concern that the hearing not proceed too far before the identity of those registrants requesting a hearing is established. In arranging for the first prehearing conference, I have attempted to accommodate both interests. The hearing panel shall convene the first prehearing conference within five days after receipt of the last request for a hearing by a registrant or 15 days after the issuance of my opinion and order, whichever comes earlier. The 15 day maximum should ensure that all registrants wishing to participate in the hearing have been given ample time to file a hearing request after receiving notification of my suspension actions. c. Within ten days from the first prehearing conference, any person requesting a hearing shall submit focused written comments on this opinion and order consisting of a counterstatement of proposed findings on the issue of imminent hazard presented by 2,4,5-T together with supporting information. A narrative summary explaining its bearing on the case should also be included. d. The Agency trial staff shall have seven days thereafter to file supplemental information and comments• -87- �e. Within five calender days from the filing of any supplemental information by the Agency staff, the panel shall convene a second prehearing conference* At this conference all parties shall appear prepared to present arguments on the signficiance and relevance of the material already presented. This prehearing conference shall also hear all requests for oral presentation of direct evidence and crossexamination, and the reasons supporting them. At this time each party shall present the names of witnesses available for cross-examination on the matters the party is putting into issue. The party may list documents (or portions thereof) on which the potential witness is available for cross-examination in lieu of filing a formal witness f. statement. Within five days after the prehearing conference is over/ the panel shall issue a hearing order setting the schedule for oral presentation of witnesses and cross-examination. ( 1) Requests for oral presentation of direct testimony shall be granted only if it is demonstrated that the testimony can be presented meaningfully only in that form; in all other cases/ direct testimony shall be in writing. -88- �(2) Requests for cross-examination shall be granted only if all of the following showings are made: i. The request concerns factual matters* Cross- examination will not be granted on matters of policy or law. ii. The factual matters are legitimately in dispute in light of the record. iii. The factual matters are material to the decision to be made. iv. Cross-examination is the most efficient way of resolving the dispute over these factual matters (as opposed to such alternatives as production of further information, or informal conferences). v. There is a reasonable expectation that crossexamination will resolve the issue of material fact in a way likely to influence the final decision. g. The testimonial phase of the hearing shall begin three days after issuance of the order setting the hearing schedule. At the hearing, the panel shall take an active role in the development of the record through questioning of witnesses and by issuing procedural orders where necessary. -89- �h. At the end of the initial testimonial phase, the hearing panel may permit the introduction of additional information designed to rebut the contentions made by opposing parties. i. The panel may revise any of the procedural provisions of this notice other than the overall 90-day deadline for rendering .- a recommended decision.the time for which starts running after the first pre-hearing conference. A discussion of some aspects of these procedures follows: ( 1) Deadlines Deadlines for completing proceedings under FIFRA have been twice endorsed by the National Academy of Sciences [National Academy of Sciences, Decision Making in the Environmental Protection Agency, Vol. II, p. 84 ( 1977) ; National Academy of Sciences, Decision Making for Regulating Chemicals in the Environment, p. 30 [ 1975)]. In addition, Congress has demonstrated a concern for speedy action where suspensions based on a potential threat to human health are concerned. It has required a hearing on such a suspension to begin five days after it is -90- �*/ requested— , and has allowed ten and seven days respectively for preparation of the initial and final decisions once the hearing is over [FIFRA Section $ c) I 2) ] . FIFRA was amended in 1975 to require consultation by EPA with the Department of Agriculture and a scientific advisory panel before taking action in many cases; suspensions based on human health grounds, however, were exempted from those requirements to allow speedy action where speedy action was desirable [121 Cong. Rec. H 9895-96 ( daily ed. Oct. 9, 1975); 121 Cong. Rec. Section 19820-21 I daily ed. Nov. 12, 1975)]. Deadlines for completing the hearing have been imposed in prior suspensions. See, e.g., In re; Vesicol Chemical Co., et al., 41 F.R.7552, 7553 (Feb. 19, 1976) [Notice of Intent to Suspend Heptachlor and Chlordane], and In re; Dibromochloropropane, 42 FR 48915 ( Sept. 26, 1977) . [Notice of intent to suspend and conditionally suspend registrations of pesticide products]. The requirements set forth in this order simply carry forward that practice. ±/ I do not regard the procedures set forth below as inconsistent with this directive. What concerned Congress was plainly that the hearing stage of Agency decisionmaking begin promptly, not that the oral hearing itself start unconditionally in less than a week. To interpret the law otherwise would forbid the use of such accepted aids to efficient decisions as prehearing conferences in precisely the cases where efficiency is most required. -91- �(2) Use of a Panel Despite the need for speedy action, the issues involved in suspension are complex* Under the statute, a judgement of "imminent hazard" must be based on consideration of costs and risks of all types [FIFRA Sections 2(1), 2(bb)]. Given the necessary time constraints and the preliminary nature of suspension as a remedy, factual certainty may be elusive* "[T]he function of the suspension decision is to make a preliminary assessment of evidence, and probabilities, not any ultimate resolution of difficult issues" [Environmental Defense Fund, Inc• v. EPA, 510 F.2d. 1292, 1298 (D.C. Cir. 1975), quoting from Environmental Defense Fund, Inc. v. EPA, 465 F.2d. 528, 537 (D.C. Cir. 1972)]. Arriving at even such a preliminary assessment can present formidable difficulties. Considering risks, questions can arise concerning the dispersion and persistence of the pesticide in the environment and certain parts of it, the conduct of animal feeding studies, the meaning of those studies for human health, the validity of relevant epidemiological studies, the reliability of using known human exposure from one use pattern as a predictor of potential human exposure in other use patterns, and finally on what the upper and lower boundaries of any risks may be and how firmly they are established. -92- Considering benefits, �questions can be raised about the extent of use/ the availability/ practicality/ and effectiveness of substitutes both now and in the future, and the range of the probable economic impacts of a temporary ban on the pesticide, or some use of it, in the light of all these factors. The job will be easier and better performed, if I am allowed to rely directly on the talents of EPA employees with expert knowledge of the technical fields involved and with the professional ability to assess problems arising in them. I believe it is for this reason that Congress has provided that those presiding over suspension hearings need */ not be hearing examiners— . (3) Conduct of the Hearing Overuse of cross-examination and courtroom formalities, I believe, has made many FIFRA proceedings than was consistent with any rational purpose. far longer The overwhelm- ing bulk of legal analyses by those who have studied the problem, and EPA's own experience demonstrate that scientific and economic issues can be clarified by the exchange of written material far more efficiently th,an through courtroom hearings. I am directing that written submissions be used ^/ The fact that more than one person will preside is of no legal significance. Even when 5 U.S.C. Section 556 requires a hearing to be presided over by an examiner (or a person representing the Agency), it also specifies that "one or more" of those qualified may preside. -93- �here to focus the issues in an attempt to implement those lessons. At the same time/ particularly where Congress has explicitly called for formal hearings, the accompanying rights to reasonable cross-examination and oral presentation must be preserved. All three elements of these supplementary procedures are meant to work together. The use of a panel will ensure that expert knowledge is indeed brought to the task of making a decision. The provision for preliminary written submissions will allow that panel to screen the issues and narrow the formal part of the hearing down to those that are legitimately in dispute and suited to adjudicatory resolution. Finally/ setting a schedule for decision will help ensure that the potential gains in efficiency repres /^l / ted by the first two reforms ara'rearli/zed in Douglae Administrat FEB 2 8 1979 Dated: -94- �APPENDIX A HEARING PANEL Charles Gregg, Chairperson William Brungs Robert Coughlin TECHNICAL SUPPORT PANEL Robert Chapman, M.D. Neil Chernoff Arnold Kuzmack Dr. James Lichtenberg ADMINISTRATIVE APPELLATE PANEL Ronald L. McCallum Charles R. Ford Dr. Edwin H. Clark Ms. Mary Ann Massey Dr. Richard M. Dowd Dr. Stephen J. Gage � 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. 179 Folder The folder containing the original item. 5257 Series The series number of the original item. Series VIII 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 Costle, Douglas M. Date A point or period of time associated with an event in the lifecycle of the resource February 28 1979 Title A name given to the resource Typescript: Decision and Emergency Order Suspending Registrations for the Forest, Rights-of-way, and Pasture Uses of 2,4,5-Trichlorophenoxyacetic Acid (2,4,5-T) ao_seriesVIII 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. 197 Folder The folder containing the original item. 5529 Series The series number of the original item. Series VIII 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 Crawford, Mark Source A related resource from which the described resource is derived Science Date A point or period of time associated with an event in the lifecycle of the resource May 22 1987 Title A name given to the resource R & D Eroding at EPA ao_seriesVIII 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. 197 Folder The folder containing the original item. 5543 Series The series number of the original item. Series VIII 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 Daschle, Tom Title A name given to the resource Clipping: Deaf Ear Turned to Pleas of Veterans Exposed to Dioxin ao_seriesVIII https://www.nal.usda.gov/exhibits/speccoll/files/original/b48021aba5b402b1fa22001b79d4ec8a.pdf ae5383d0532729eebd9ca88f5f446757 PDF Text Text Item D Number 05264 Author D Deukmejian, George NotSMnnBfl Office of the Attorney General, State of California Report/Article Titlfl Opinion of George Deukmejian, Attorney General, and Clayton P. Roche, Deputy Attorney General; No. CV 78/105, March 2, 1979 Journal/Book Title Year Month/Day Color March 2 D Number of Images ° DeSOrlptOD Notes Opinion on the right of a county board to adopt an ordinance banning the application of phenoxy herbicides. Tuesday, March 05, 2002 Page 5264 of 5363 �OFFICE OF THE ATTORNEY GENERAL • State of California 4+ . * £ ,„ *%% «%..f&>/# .^'A/^ GEORGE DEUKMEJIAN ~\ Attorney General ' OPINION No. CV 78/105 of GEORGE DEUKMEJIAN Attorney General MARCH 2, 1979 CLAYTON P. ROCHE Deputy Attorney General THE HONORABLE JOHN A. DRUMMOND, COUNTY COUNSEL, MENDOCINO COUNTY, has requested an opinion on the following question: May either the Mendocino County Board of Supervisors, or the county voters through the initiative process, adopt an ordinance banning the application of phenoxy herbicides including, but not limited to ".2,4-D", "2,4,5-T" and silvex in Mendo-' cino County, or is such matter goveme'd exclusively by the provision of si_ate. law, specifically section 14001, et seq. of the Food and Agriculture Code? The conclusion is: Neither the Mendocino Co'inty Board of Supervisors nor the county voters through the initiative process may adopt an ordinance banning the application of phenoxy herbicides, including but not limited to "2,4-D", "2,4,5-T" and silvex, in Mendocino County as such matter is governed exclusively by the provisions of section 14001 et seq. of the Food and Agriculture Code and related statutes and regulations. Additionally,-the matter appears to be preempted by federal law insofar as local agencies of the state are concerned. • ' ' ANALYSIS A county has only those powers expressly granted to it by the constitution or the general laws of the state, or those powers which may be necessarily implied therefrom. • (Upton v. City of Antioch (1959) 171. Cal.App.2d 858, 861, and. cases cited 1. �D. Preemption 3y Federal Law The Federal Environmental Pesticide Control Act of 1972 provides for the comprehensive regulation of pesticides, including their registration and use. The legislative history of that act indicates that it did not intend to preempt states from legislating in the same field but it did intend to prohibit local entities of states from doing so. Section 24 of that Act provides (7 U.S.C. 3 136v) : "(a) A State may regulate the sale or use of any pesticide or device in the State, but only if and to the extent the regulation does not permit any sale or use prohibited by this subchapter; "(b) Such State shall not impose or continue in effect any requirements for labeling and packaging in addition to or different from those required pursuant to this subchapter; and "(c) a State may provide registration for pesticides formulated for distribution and use within that State to meet special local needs if that State is certified by the Administrator as capable of exercising adequate controls to assure that such registration will be in accord with the purposes of this subchapter and if registration for such use has not previously been denied, disapproved, or canceled by the Administrator. Such registration shall be deemed registration under section 136a of this title for.all purposes of this subchapter, but shall authorize distribution and use only within such State and shall not be effective for more than .90 days if disapproved by the Administrator within that period." (See also 7 U.S.C. § 136b(a)(2) regarding "state certification" of "state plans." With respect to the 1972 federal law, Senate Report No. 92-838 stated in part: "4. The Senate Committee considered the decision of the House Committee to deprive political subdivisions of States and other local authorities of any authority or jurisdiction over pesticides and concurs with 20. CV 78/105 �the- decision of the House of Representatives. Clearly, the fifty States and the Federal Government provide sufficient jurisdictions to properly regulate pesticides. Moreover, few, if anyr local authorities whether town, counties, villages, or municipalities have the financial wherewithal to provide necessary expert regulation comparable with that provided by the State and Federal Governments. On this basis and on the basis that permitting such regulation would be an extreme burden on interstate commerce, it is the intent that section 24, by not providing any authority to political subdivisions and other local'authorities of or in the States, should be understood as depriving such local authorities and political subdivisions of any and all jurisdiction and authority over pesticides and the regulation of pesticides," (1972 U.S. Code Congr, & Admin. News at pp. 3993, 4008.) (See also further indication of this legislative intent in Senate Report No. 92-970, wherein a proposed amendment is set forth and discussed to give, "local governments the authority to regulate the sale or. use of a pesticide beyond the requirements imposed by State and Federal authorities." The amendment was, of course, not accepted as is evident from the report of the Conference Committee as well 'as the terms of Section 24 of the law as enacted.(See 1972 U.S. Code Congr. & Admin. 'Jews at pp. 4092, 4111, 4128, 4130, 4134.) Accordingly, the legislative history of the Federal Environmental Pesticide Control A it of 1972 indicates virtually conclusively an intent that the federal law should preempt any regulation of pesticides by any local entity of a state. CONCLUSION State and federal law both preempt and preclude Mendocino County, either through its board of supervisors or the electorate, from prohibiting the use, aerial or otherwise, of phenoxy herbicides in the county. "Whether this is or is not wise policy is not for this office to determine but is a question to be directed to the State Director of Agriculture, the State Legislature, the Environmental Protection Agency, and Congress. 13/ 13. We note the news releases this, date to the effect that the Environmental Protection Agency has in fact just used its emergency powers to impose a partial ban upon "2,4,5-?" and silvex, (See, e.g., San Francisco Chronicle, March 2, 1979, p. 4.) PV 7R/10S � 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. 180 Folder The folder containing the original item. 5264 Series The series number of the original item. Series VIII 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 Deukmejian, George Clayton P. Roche Description An account of the resource <strong>Corporate Author: </strong>Office of the Attorney General, State of California Date A point or period of time associated with an event in the lifecycle of the resource March 2 1979 Title A name given to the resource Opinion of George Deukmejian, Attorney General, and Clayton P. Roche, Deputy Attorney General; No. CV 78/105, March 2, 1979 ao_seriesVIII https://www.nal.usda.gov/exhibits/speccoll/files/original/540344e8f9e76df4b7bf8d3dc10b45f5.pdf 9cfadd8db61d5708776c5e405f89dad0 PDF Text Text Item D Number °5189 Author Dominick, David D. D (jot Scanned Corporate Author Report/Article Title Environmental Protection Agency, Trichlorophenoxyacetic Acid, Intent to Hold Hearing and Statement of Issues JOUmal/BOOk Title Federal Register Year 1979 Month/Day Julv24 Color Number of Images D ° Descrlpton Notes Friday, March 01, 2002 Page 5189 of 5263 �flDIRAl RtCIStfR, VOl. 3d, NO. 141—TULSDAY, JUtY 54, 1973 19R50 11)800 38 ENVIRONMENTAL PROTECTION AGKNCY ' 2,4,5-TniCHLOPOPhtNOXYACETIC ACID Intent To Hold Hearing Please take notice tint pursuant to the authority vested in me by section 6U>) <2) of the Federal Insecticide, Funr.iclde and Rodcnticldc Act, as amended, I hereby issue a notice of my intention to hold a hearing on all registered uses of 2,4,5TrichlorophenoxyiieeUc Arid • (2,1,5-T) other than on the iisc for rice which was was cancelled on May 1, 1070 (USDAPRD 70-13), as reainrmed by Order of August 6, 1071 (36 FH 1477, AUK, 11, 1971). It is my intention that the public hearing concerning the use on rice, (I. P. & n. Consolidated Docket Nos. 42, 44, 45 & 48) be consolidated with the hearing I have called today for all other uses and that all hearings commence in April, 1974. The start of the hearing is being delayed until then to permit the Agency to complete :m environmental and human monitoring project on the presence of the tetnichlorodioxin impurity found in 2,4,5-T and the extent to which the dioxin may adversely a f f e c t human and animal health. Please take further notice that any person wislunfl to become a p a r t y to this hearing called by me today on all oilier uses of 2,4,5-T shall file a response to the. accompanying statement ol issues, published herewith, with t h e Hearmc Clerk, Environmental Protection Agency, Waterside Mall, Washington, D.C. 204GO, on or before August 23,1973. Done this 19th day of July 1973. DAVID D. DOMINICK, .Assistant Administrator for Hazardous Materials Control. (PU Doc.73-16189 Tiled 7-23-73;8:45 am] 2,4,5'TRIClll.OROPHCNOXYACt:TIC ACID Stalcmcnt of Itsuc-s Pursuant to the accompanying; notice of intent to hold a hearing, it Is hereby ordered that the followinn issues be addressed by such hearing together with any other issues which the Administrative! Law Judpc deems relevant, namely: I. Whether 2,4.5-Trlchloropheno.xyacetlc Acid (2,4,5-T) products presently registered, or other material submitted in support of these registrations, complies with the provisions of the Federal Insecticide, Fungicide and Rocicntlclde Act, as amended; and II. Whether 2,4,5-T will perform its Intended function without unreasonable adverse effects on the environment. in. Whether, when used In accordance with widespread and commonly recoriilzod practice, 2,4,b~T generally causes trnrea-sonnble adverse effects on the environment, as defined by the Fedcial Insecticide. Funeicldc and Kodenticide Act, as amended. IV. Whether the registrations of 2.4,5-T should be cancelled or its clas.sifl"'Hlon changed. V. The answers to these issues should relate to thr following subsidiary qurstion.s, as wi-11 as to the ten Issues d e l i n e ated In the 2,4,5-T Orders of the A d m i n istrator ol November 4, 1971 and April 13, 1372; (I. F. & R. Docket No. 42 and No. 44) and to such additional questions as the A d m i n i s t r a t i v e Low Judge finds relevant, namely: A. The health hazards to man and to other animals which may be caused by 2,4,5-T and/or Its rxl.remely toxic contaminant, 2,3,7.U-tctrachlorocliben70-i>dioxin (TCIJU), with emphasis on the following: 1. Is 2,4.5-T or TCDD ft tenvtoi'en? 2. Doca 2,4.n-T or TCDI) Induce other adverse reproductive! piiects? 3. Is 2.4,.r>-T or TCDD n m u t a n e n ? 4. Its 2.4,5-T or Tt:])D a cari-lni-rcn'' 6. Cnu<.'>:po.',ure to 2.4,5'Tor 'iron I n c l i n e oub-lotlml chronic health eCeots? 6. Can chronic, low-lovH r s f n v . u r o ti> 2.4.5T imcl/or M C D D cause delayed l e l l n i l l t y ? IJ T)ie extent of the health risk'for m n n and other animals tx>R«l by H.4.5-T and TCDD, with emphasis on the following conditions: 1. Can additional TCDD be gencralod In thu Environment, by tho thermal strcsa of 2,4,5-T or Its metarjoirt'o? 2. Ccm 2.4,.r>--T or TCDD persist und blonccumulate In tlio environment? 8. What arc the tivenue-s of hurmiu and animal exposure to 2,4 5-T and TCDD? For example, «ui ucrlal drift or water tmiu,por. of 2,4,5-T or TCDD cause mo\«n\cvkt of lUcss compounds away from t!-,c site of application 1 4. Are 2,4.5-T or TCDD residues bclni; stored and Becumula'ed In the human footf supply and In h u m a n and animal tissue. Inclvullng humnns and wildlife directly exposed to 2,4.5-T? 6. Arc other clloxlns and elm'lar cont.vmlnanU, besides TCDD, present In 2.4 5-T and. If to, what rU'k.5 to h e a l t h do they constitute' 1 C. Whtvt are other envlromncnUl sources of dloxlnr, particularly TCDD. and do thtse scmrcfcs enhunco tho total dioxin body burden and exacerbate the h e u l t h risks rnl.icr) by 2.4.5--T mid related TCDD? 7. What are the current levels of dloxlnr, in registered 2,4.5-T products and In technical matctlul vi.U'd to formulate tlicst) products 1 0. Do the current methods of m a n u f a c t u r e of 2.1,5-T provide for con.MPtcntly low level* of dU-xln;; in the final u-chnl.'al product and what arc the q u a l i t y control measures us«d to mlnlmli'O dioxin levels? C The necessity for the continuation of cho registered uses of 2,4,5-T, with emphasis on the following: 1. What arc the pests which each rcclstercd xi&o Is intondi'j to control and the de-. grec of control achieved by cuch use? 2. What Li tho ccmt. timing, and ruto of uppUcfttlon of 2,4,5-T for each use? 3. -What alternative? controls exist for *ach registered u.no and what la the cost and offc'ctlvcnc-sH of each altcrnatlvo. 4. Do a l t e r n a t i v e pc.-,llclde prodvicta caviseadverse e i i v l r i . n m r n t a l vlliv.ta? 5. What are the economic Implications of tlicsu alternatives, Including that of no control? Done tliis 19th day of July 1073. DAVID D. DOMINICK, Assistant Administrator /or Hazardous Materials Control. [TO Doc 7;1-151<JO Hied 7 - 2 3 - f 3 ; B ; 4 8 am) |I. F. ft U. Docket No. 2D5) �*"••• * 39 1. A contaminant of 2,4,5~T ,— tetrachlorodibcnzoparadioxin (TCDD, or dioxin) — is one of the most tet-atbgdnte chemicals known. The registrants have not established that 1 part per million of this contaminant — or even 0.1 ppni — in 2,4,5~T does not pose a danger to the public health arid safety, 2. There is a substantial possibility that even "pure" 2,4,5-T is itself a hazard to man and the environment. 3. The dose-response curves for 2,4,5-T and dioxin have not been determined, and the possibility of "no effect" levels for these chemicals is only a matter of conjecture at this time. 4. As with another well-known teratogen, thalidomi.de, the possibility exists that dioxin may be many times more potent in humans than in test animals (thalidomide was 60 times more dangerous to humans than to mice, and 700 times more dangerous than to hamsters; the usual margin of safety for humans is set at one-tenth the teratogenic level in test animals). 5. The registrants have not established not accumulate in body tissues. that the dioxin and 2,4,5-T do If one or both does accumulate, even small d«.->es could build up to dangerous levels within man and animals, and possibly in the toot! chain as well. 6. The question of whether there are other sources of dioxin in the environment has not been fully explored. Such other sources, when added to the amount of dioxin from 2,4,5-T, could result in a substantial total body burden for certain segments of the population. 7. The registrants have; not established that there is no danger from dioxins other than TCDD, such a:; th.C'hexa- and heplndioxln Isomera, which also can be present in 2,4,5-T, and which arc known to be teratogenic. �40 8. There in evidence that the polychlorophenolo in 2,4,5-T may decompose into dioxin when exposed to high temperatures, such as might occur with incineration or even in the cooking of food. 9. Studies of medical records in Vietnam hospitals and clinics below the district capital level suggest a correlation between the spraying of 2,4,5-T defoliant and the incidence of birth defects. 10. The registrants have not established the need for 2,4,5~T in light of the above-mentioned risks. Benefits from 2,4,5-T should be determined at a public hearing, but tentative studies by this agency have shown little \ necessity for those uses of 2,4,5-T which are now at issue. � 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. 176 Folder The folder containing the original item. 5189 Series The series number of the original item. Series VIII 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 Dominick, David D. Source A related resource from which the described resource is derived Federal Register Date A point or period of time associated with an event in the lifecycle of the resource July 24 1979 Title A name given to the resource Environmental Protection Agency, Trichlorophenoxyacetic Acid, Intent to Hold Hearing and Statement of Issues ao_seriesVIII 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. 199 Folder The folder containing the original item. 5633 Series The series number of the original item. Series VIII 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 Doss, M. H. Sauer R. von Tiepermann A.M.Colombi Source A related resource from which the described resource is derived Int. J. Biochem. Date A point or period of time associated with an event in the lifecycle of the resource 1984 Title A name given to the resource Development of Chronic Hepatic Porphyria (Porphyria Cutanea Tarda) with Inherited Uroporphyrinogen Decarboxylase Deficiency under Exposure to Dioxin ao_seriesVIII https://www.nal.usda.gov/exhibits/speccoll/files/original/7b09e6635ba76a8aacefd3e369884afa.pdf 7e92f23b98e0a2d4b7d01ff965f7737d PDF Text Text Home Number °5333 Author Dryden, Forrest E. Corporate Author Walk, Haydel & Associates, Inc., New Orleans, Louisian D N0t scanned RODOrt/ArtiClBTitlO Dioxins: Volume III. Assessment of Dioxin-Forming Chemical Processes Journal/Book Title YBaP Month/Day Color Number of Images June n ° Volume III of a three-volume series. Contract No. 68-032579; EPA-600/2-80-158 Tuesday, March 05, 2002 Page 5333 of 5363 �United States Environmental Protection Agency Industrial Environmental Research Laboratory Cincinnati OH 45268 Research and Development &EPA Dioxins Volume III. Assessment of Dioxin-Forming Chemical Processes EPA-600/2-80-158 June 1980 �RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into nine series. These nine broad categories were established to facilitate further development and application of environmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The nine series are: 1. 2. 3. 4. 5. 6. 7. 8. 9. Environmental Health Effects Research Environmental Protection Technology Ecological Research Environmental Monitoring Socioeconomic Environmental Studies Scientific and Technical Assessment Reports (STAR) Interagency Energy-Environment Research and Development "Special" Reports Miscellaneous Reports This report has been assigned to the ENVIRONMENTAL PROTECTION TECHNOLOGY series. This series describes research performed to develop and demonstrate instrumentation, equipment, and methodology to repair or prevent environmental degradation from point and non-point sources of pollution. This work provides the new or improved technology required for the control and treatment of pollution-sources to meet environmental quality standards. This document is available to the public through the National Technical Information Service, Springfield, Virginia 22161. �EPA-600/2-80-158 June 1980 DIOXINS: VOLUME III. ASSESSMENT OF DIOXIN-FORMING CHEMICAL PROCESSES by Forrest E. Dryden, Harry E. Ensley Ronald 0. Rossi, E. Jasper Westbrook Walk, Haydel & Associates, Inc. New Orleans, Louisiana 70130 Contract No. 68-03-2579 Project Officer David R. Watkins Industrial Pollution Control Division Industrial Environmental Research Laboratory Cincinnati, Ohio 45268 INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 �DISCLAIMER This report has been reviewed by the Industrial Environmental Research Laboratory Cincinnati (lERL-Ci), U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. �FOREWORD :; When energy and; material resources are extracted, processed, converted, and used, the related :pollutional impacts on our environment and even on our health often require, that new and increasingly more efficient pollution control methods be used. The Industrial Environmental Research LaboratoryCincinnati (lERL^Ci) assists in developing and demonstrating new and improved methodologies that will meet these«needs both efficiently and economically. This report is one of a three-volume series dealing with a group of hazardous chemical compounds known as dioxins. The extreme toxicity of one of these chemicals, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), has been a concern of both scientific researchers and the public for many years. The sheer mass of published information that has resulted from this concern has created difficulties in assessing the overall scope of the dioxin problem. In this report series the voluminous data on 2,3,7,8-TCDD and other dioxins are summarized and assembled in a manner that allows comparison of related observations from many sources; thus, the series serves as a comprehensive guide in evaluation of the environmental hazards of dioxins. Volume I is a state-of-the-art review of dioxin literature. Detailed information is presented on the chemistry, sources, degradation, transport, disposal, and health effects of dioxins. Accounts of public and occupational exposure to dioxins are also included. Volume II details the development of a new analytical method for detecting part-per-trillion levels of dioxins in industrial wastes. It also includes a review of the analytical literature on methods of detecting dioxins in various types of environmental samples. Volume III identifies various routes of formation of dioxins in addition to the classical route of the hydrolysis of chlorophenols. The possible presence of dioxins in basic organic chemicals and pesticides is addressed, and production locations for these materials are identified. For further information, contact Project Officer David R. Watkins, Organic and Inorganic Chemicals Branch, lERL-Ci. Phone (513) 684-4481. David G. Stephan Director Industrial Environmental Research Laboratory Cincinnati m �PREFACE This report is Volume III in a series of three reports dealing with a group of hazardous chemical compounds known as dioxins. This volume details the chemistry of dioxin formation, and identifies the types of organic chemicals and pesticides which may have dioxins associated with them as impurities or byproducts. Other volumes of this series examine the occurrence, environmental transport, toxicity, and disposal of this class of compounds, analytical techniques used to identify dioxins, and commercial products with potential for containing dioxin contaminants. An extensive body of published literature has appeared during the past 25 years that has been concerned primarily with one extremely toxic member of this class of compounds, 2,3,7,8-tetrachlorodibenzo-p-dioxin. Often described in both popular and technical literature as "TCDD" or simply "dioxin," this compound is one of the most toxic substances known to science. This report series is concerned not only with this compound, but also with all of its chemical relatives that contain the dioxin nucleus. Throughout these reports, the term "TCDD's" is used to indicate the family of 22 tetrachlorodibenzo-p-dioxin isomers, whereas the term "dioxin" is used to indicate any compound with the basic dioxin nucleus. The most toxic isomer among those that have been assessed is specifically designated as "2,3,7,8-TCDD." The objective in the use of these terms is to clarify a point of technical confusion that has occasionally hindered comparison of information from various sources. In particular, early laboratory analyses often reported the presence of "TCDD," which may have been the most-toxic 2,3,7,8-isomer or may have been a mixture of several of the tetrachloro isomers, some of which are relatively nontoxic. Throughout this report series, the specific term 2,3,7,8-TCDD is used when it was the intent of the investigator to refer to this most-toxic isomer. Since early analytical methods could not dependably isolate specific isomers from environmental samples, the generic term "TCDD's" is used when this term appears to be most appropriate in light of present technology. IV �ABSTRACT Concern about potential contamination of products and wastes by dibenzo-p-dioxins in the production of organic chemicals and pesticides is the reason for this study of products and processes subject to such contamination. In addition, speculative consideration is given to other possible dioxin sources. Chemical reaction mechanisms by which dioxins may be formed are reviewed, particularly those likely to occur within commercially significant processes. Various routes of formation are identified in addition to the classical route of the hydrolysis of trichlorophenol. Basic organic chemicals and pesticides with a reasonable potential for dioxin byproduct contamination are surveyed as to current and past producers and production locations. Classifications are presented both for general organic chemicals and for pesticides that indicate likelihood of dioxin formation. Conditions are noted that are most likely to promote dioxin formation in various processes. This report was submitted in fulfillment of Contract No. 68-03-2579, by Walk, Haydel & Associates, Inc., under the sponsorship of the U.S. Environmental Protection Agency. This report covers the period October 31, 1978, to March 16, 1980, and work was completed as of March 16, 1980. �CONTENTS Page Foreword Preface Abstract List of Figures List of Tables List of Abbreviations Acknowledgment ill iv v viii x xi xii 1. Introduction 1 2. Conclusions 3 3. The Chemistry of Dibenzo-p-Dioxins 4 4. Speculative Sources of Dioxins 39 5. Organic Chemicals 43 6. Pesticide Chemicals 64 7. Chemicals, Producers, and Plant Locations 90 References Bibliography vii �FIGURES Number ' Page 1 4-Bromo-2,5-dichlorophenol . • '' 2 2-Chloro-4-f1uoropheno1 54 3 Decabromophenoxybenzene 55 4 2,4-Dibromophenol 56 5 2,3-Dichlorophenol 57 6 2,4-Dichlorophenol 58 7 2,5-Dichlorophenol 59 8 2,6-Dichlorophenol 60 9 3,4-Dichlorophenol 61 10 Pentabromophenol 62 11 2,4,6-Tribromophenol 63 12 2,4,5-Trichlorophenol, 2,4,5-T and esters and salts 71 13 Silvex and esters and salts 72 14 Ronnel 73 15 Erbon and Sesone 74 16 2,4-D and esters and salts 76 17 2,4-DB 77 18 2,4-DP 78 19 Dicapthon and Dichlofenthion 79 20 Bifenox 80 viii 53 �FIGURES (continued) Number Page 21 Nitrofen 81 22 Dicamba 82 23 Pentachlorophenol (PCP) via phenol 83 24 Pentachlorophenol (PCP) via hexachlorobenzene 25 Chloranil 26 Hexachlorophene and Isobac 20 27 2,3,4,6-Tetrachlorophenol : . 84 . 85 . 87 88 ix �TABLES Number Page 1 Perhalo Dibenzo-p-Dioxins via Free Radical Reactions 6 2 Ullman Condensation Reactions 10 3 Catechol-Based Reactions 25 4 Substitution Reactions 29 5 List of Organic Chemicals 45 6 List of Pesticide Chemicals 65 7 Higher Chlorinated Dioxins Found in Commercial Pesticides 70 8 Pesticide Raw Materials 89 9 Class I Organic Chemicals 91 10 Class II Organic Chemicals 92 11 Class III Organic Chemicals 93 12 Organic Chemical Producers 94 13 Former Organic Chemical Production Locations 95 14 Pesticide Chemicals - Classes I and II 96 15 Pesticide Chemical Producers 97 16 Former Pesticide Production Locations 98 �LIST OF ABBREVIATIONS DBDCDD's DBDD's DCDD's dibromodichlorodibenzo-p-dioxins dibromodibenzo-p-dioxins dichlorodibenzo-p-dioxins Dioxins Hepta-CDD's dibenzo-p-dioxins di f1uorodi benzo-p-di oxi ns dimethyl sulfoxide dinitrodibenzo-p-dioxins hexachlorodibenzo-p-dioxins heptachlorodibenzo-p-dioxins OBDD OCDD PCP octabromodibenzo-p-dioxin octachlorodi benzo-p-di oxi n pentachlorophenol Penta-CDD's pentachlorodibenzo-p-dioxins tetrabromodi benzo-p-di oxi ns tetrachlorodi benzo-p-di oxi ns DFDD's DMSO DNDD's Hexa-CDD's TBDD's TCDD's 2,3,7,8-TCDD TCP Tri-CDD's 2,3,7,8-tetrachlorodibenzo-p-dioxin trichlorophenol trichlorodibenzo-p-dioxins xi �ACKNOWLEDGMENT This report was prepared by Walk Haydel & Associates, Inc. under the direction, contribution, and contract management of Forrest E. Dryden. Contributing authors included Harry E. Ensley, Ronald J. Rossi, and E. Jasper Westbrook. Final compilation of this report for integration into the three-volume dioxin series was done by PEDCo Environmental, Inc., Cincinnati, Ohio, with Mr. R. W. Gerstle as Project Director and Ms. M. Pat Esposito as Project Manager. Information on natural compounds as potential precursors of dioxins was provided by PEDCo Environmental, Inc. The cooperation of the many organizations and individuals who assisted in the collection, editing, and critiquing of this material is appreciated. Particular thanks to Robert J. Planchet, Jerome F. Pankow, and William J. Kimsey, Jr. for their contributions. xii �SECTION 1 INTRODUCTION A dioxin is any of a family of compounds known chemically as dibenzbpara-dioxins. Each of these compounds has as a nucleus a triple-ring structure consisting of two benzene rings interconnected to each other through a pair of oxygen atoms. Shown below are the structural formula of the dioxin nucleus and also the abbreviated structural convention used throughout the report series'. 9 1 Halogenated dibenzo-p-dioxins (dioxins), and in particular chlorinated dioxins such as 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), are known to be toxic even at low concentrations. Such contaminants have been found in a number of commercial organic chemical products, primarily pesticides of the 2,4,5-T type. For this reason an analysis was undertaken of the chemical products and processes likely to be conducive to the formation of dioxins. This report reviews the chemical mechanisms by which commercial organic processes might produce dioxins as byproducts and tabulates those chemicals likely to be associated with dioxins as a consequence. In addition, it lists known producer locations for such chemicals, indicating potential sources of current and past contaminated wastes. In approaching this study, the investigators proceeded as follows. 1. Reviewed current theories on mechanisms of the formation of dioxins under various reaction conditions. 2. Tabulated reported laboratory preparations of dibenzo-p-dioxins. 3. Established criteria for structure and reaction conditions conducive to dioxin formation in chemical processing. 4. Postulated conditions under which dioxins might be formed other than in commercial chemical production. 5. Differentiated between pesticide chemicals and all other types of organic chemicals for purposes of this study. �6. Reviewed commercially significant chemicals, using as primary sources the Stanford Research Institute Directory of Chemical Producers, the Merck Index, The Farm Chemicals Handbook, and other reference materials. 7. Designated those products in which the chemical structures might indicate association with dioxins. 8. Further screened the list by consideration of reaction conditions, processing sequence, and intermediates, 9. Categorized general organic chemical products ,in three classes. Class I: strong likelihood of polyhalogenated dibenzo-p-dioxin association . , • . . , . • • Class II: strong likelihood of other dioxin association Class III: moderate probability of dioxin association 10. Categorized the target pesticide chemicals as belonging in Class I or Class II. 11. Identified the dioxin compounds and formation mechanisms expected to be related to each Class I compound. 12. Listed known locations in the United States in which production occurs or has occurred in the past 10 years. The primary source was the Stanford Research Institute Directory of Chemical Producers covering the years 1968 through 1978. Some recent regulatory restrictions on the use of some herbicides, such as 2,4,5-T and silvex, may result in curtailed production. This study does not address the effects of any such curtailment (e.g., production shutdowns). Although there is a substantial range of toxicity among the various substituted dibenzo-p-dioxins, processes indicating potential for generation of the less-toxic forms are included for two reasons: 1. Dioxins other than those that might be hypothesized by straightforward mechanisms have been found in a number of commercial products (Fishbein 1973). 2. Disproportionation and other composition changes may cause shifts in content, possibly from lower to higher toxicity forms (Buser 1976). Subjective judgement was exercised with respect to inclusion and classification of chemicals and processes. In addition, although every reasonable effort was made to avoid omissions, some are inevitable in view of the number of organic chemical compounds to be dealt with. �SECTION 2 CONCLUSIONS 1. Dibenzo-p-dioxins should be expected as byproduct trace contamination in a number of commercially manufactured organic chemicals. These include not only the frequently cited herbicides of the 2,4,5-T type, but also numerous other ortho halogenated phenols and related structures commonly made or used in organic chemical processing. 2. Processing conditions of elevated temperatures plus either alkalinity or the presence of free halogen—conditions often necessary for dioxin formation—are frequently encountered in the manufacture of these organic compounds. 3. The particular dibenzo-p-dioxins found as trace byproduct materials are often at variance with those anticipated on the basis of straightforward mechanisms. This variance is possibly due to mechanisms more complex than those that have been proposed or to disproportionate (shifting of halogens) of the initially produced halogenated dioxins. 4. Dioxin contamination resulting from the manufacture of many organic chemicals could follow either of two paths. First, it could appear as trace contamination of the finished chemical product; second, it could appear as a component of wastes from leakage, handling, purification, neutralization, and "off-spec" production. This report does not consider the formation of dioxins in subsequent consumptive uses. 5. Plant locations of present and past commercial production of potentially dioxin-assoeiated chemicals are widespread over the United States. 6. Sites of exposure or contamination are not necessarily defined by production locations, because wastes are often dumped at sites remote from the production facility. Exact locations of disposal sites would require investigation of individual plant practices. 7. There is a variety of potential dioxin sources other than commercial production by syntheses of organic chemicals. Among these are laboratory preparation of dioxins in small quantities but high concentrations, and the combustion of mixed wastes containing potential dioxin precursors. 8. Reaction conditions ranging from temperatures as low as 145°C, and the presence of weak to strong bases acting on the organic and pesticide products can result in production of trace quantities of dioxins. �SECTION 3 THE CHEMISTRY OF DIBENZO-p-DIOXINS Concern has recently arisen about the occurrence of trace quantities of halogenated dibenzo-p-dioxins (hereafter referred to as halogenated dioxins) and in particular 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) in the environment. A study of the reported laboratory procedures for preparation of dioxins can serve as a guide to the chemical conditions that are most likely to lead to dioxin formation. This review of the literature is not limited to methods for the preparation of halogenated dioxins; rather it delineates the known procedures ^for the preparation of dioxins of any substitution pattern. LABORATORY PREPARATIONS OF DIOXINS The first report of intentional preparation* of this class of compounds occurred in 1872, when Merz and Weith described the preparation of "perchioropheny1enoxyd" by thermolysis of potassium pentachlorophenate ( ) 1. Hugounenq (1890) reported that the treatment of pentachloroanisole (2) with concentrated sulfuric acid also gives "perchlorophenylenoxyd." ) () + OK • • PERCHIOROPHENVLENOXYO * -* Cl () 2 According to scientists of Dow.Chemical ^(Rawls ,1979), dioxins have been prepared since "...Prometheus stole fire from the gods and brought it to mankind...". , .... , �Soon after these reports Zinke (1894) and Blitz (1904) showed that heating heptachlorohexenone (3) to 200°C gave "perchlorophenylenoxyd." Not until 1960 was it shown that "perchlorophenylenoxyd" is octachlorodibenzop-dioxin (OCDD)(4) (Denivelle 1960). 200°C The mechanism of the reactions reported by Zinke and Blitz remained unknown for over a half-century. In 1961 Kulka showed that heptachlorocyclohexenone (3) eliminates a molecule of hydrogen chloride at about 180°C to give hexachlorocyclohexadienone ( ) Kulka proposed that this compound, 5. on heating to 200°C, loses a chlorine radical to give the pentachlorocyclohexadienone radical (6) (or its resonance isomer, the pentachlorophenoxy radical ( ) , which then dimerizes to give (4) and a molecule of chlorine. 7) CI2 The mechanism that Kulka proposed, supplemented with earlier work by Denivelle (1959, 1960), initiated numerous reports on the preparation of halogenated dibenzo-p-dioxins under neutral or acidic conditions. A number of these reactions are listed in Table 1. Bayer (1903) patented a process for the preparation of dibenzo-p-dioxin (8) from sodium o-chlorophenylate ( ) This procedure, which is an exten9. sion of the earlier work reported by Merz and Weith (1872), is based on �TABLE 1. Item PERHALO DIBENZO-p-DIOXINS VIA FREE RADICAL REACTIONS Conditions Reactant Product (Yield) * Cl Cl 250 o. 30Q o c 25 (83W min Cl Cl OH + CI2 Cl REFLUXING 1,2,4 TRICHLOROBENZENE 16 h (83%) Cl Cl Cl Cl Cl 25 g O Cl Cl 270°-280°C 30 min (73%) O Ci Cl ci a Cl Cl OH Cl Cl ci Cl 1 , 2 , 4 TRICHLOROBENZENE Cl Cl REFLUX 16 h (52%) Cl 25 g Cl Cl OH Cl Cl 1 , 2 , 4 TRICHLOROCENZENE REFLUX 16 h Cl (continued) (23%) O CI Cl Cl Cl Ref. �TABLE 1 (continued) IA Item Conditions Reactant Product OH Br o r CI 2 \ + ° r Br 2/ 320°-360°c Br Br Br (52%) Br Br Br OH Br (62%) (15g) r CI 2 \ 300°-350°C ^ o r Br 2 J 30 min Br Cl Cl 0.2 g OH Br Cl Cl 30 g c 35 min Cl Cl 0.2 g Br 35 g (Yield) Ref. Cl d e 300°C f Cl Cl Cl Cl Cl Cl Cl Cl Cl xxW- O - ^—- CI 260°C Cl Cl ¥ i Cl Cl Cl O Cl Cl Cl Cl 260°C Cl Cl (continued) �TABLE 1 (continued) Item Reactant Conditions Product (Yield) Ref. 260-280°C Cl OH Cl Cl 120-200°C Cl Cl^Xi^O Cl Cl Cl Cl Cl Cl 0 nYCI O^Y^CI 120-200°C Cl Cl Cl 62 g Cl Cl Cl Cl Cl Cl Cl OH Cl Cl (80%) Cl Cl Cl + 270°C IN QUINOLINE Cl Cl o Cl Cl o Cl Cl Cl P If no yield is stated, no value is reported in reference "I/..TI-—. "1 rt /" I™ Kulka 1965. Kulka 1961. Denivelle, Fort, and Pham 1959. t - ^ . _ J l _ l _ T _ 1 r t T / l 9 Gribble 1974. Sandermann, Stockmann, and Casten 1957. Kaupp and Klug 1962. 8 �(9) Ullmann's preparation of diphenylamines (Ullman 1903) and generally referred to as a modified Ullman condensation (Aniline 1973). Although the yields of the modified Ullmann reaction rarely exceed 30 percent, this procedure was standard for the preparation of both substituted and unsubstituted dioxins until the early 1970's. Examples of the utilization of this process are given in Table 2, showing minor as well as major products of reaction, where applicable. As the reactions in Table 2 show, dioxins have been formed from the alkali metal salts of ortho-halophenols through pyrolysis at temperatures of 200° to 300°C for several hours, usually in the presence of copper powder or copper salts. Entries 23 and 24 in Table 2 show that much milder conditions (pyridine as the base and a temperature of only 145°C for 2 to 3 hours) can give significant concentrations of dibenzo-p-dioxins (Ueda 1963). The mechanism for this type of reaction was generally believed to involve a nucleophilic attack of the phenoxy ion on a second phenol ate ring (Buser 1975), followed by expulsion of the halide to give the o-halophenoxyphenate (10) (also known as predioxin). An intramolecular nucleophilic aromatic substitution followed by expulsion of a halide gives the dibenzop-dioxin ( 1 . 1) (II) X= leaving group (e.g. Cl, F, Br, I, NO,, SO-jR) M=alkali metal cation Y=any substituent group 9 �TABLE 2. Item ULLMAN CONDENSATION REACTIONS Conditions Reactant Product (Yield) Ref. (25%) b ONa 220°, 10 h Cl CH, CH3 OK CH 190-200°C Cu, Cu(OAc)2 Br CH3 CH, CH3 190-2QO°C Cu, Cu(OAc) 2 CH OK CH30 CH3 CH3 190-200°C Cu, Cu(OAc) 2 Br CH3O OK CH OK -f Br Br CH3 OCH3 CH, CH, CHr OCH3 OCH3 CH, CH, CH3O (continued) 10 �TABLE 2 (continued) Item Conditions Reactant (Yield) Ref. OK ^W^Br OK Br Product + (I OCH3 OCH 3 OCH3 CH30 O 160°C ONa Cu 1 h Cl Cl 1BQ°C Cl o- Cu 1 h I60°-220°C Cu, Br OK 6 g (50%) f 110 min 200°C, Cu 3 h (continued) n (o.2g) g �TABLE 2 (continued) Item Reactant Product Conditions (Yield) Ref. 190°C Cu 2 h 3.5 g (0.09 g) h,j (0.08 g) N (TRACE) OCH, 180°C 30 min OCH3 180QC KOH, Cu 30 min H J (0.164 g) 6.58 g OCH3 (0.287 g) O OCH3 (0.132 g) OCH3 (continued) 12 k �TABLE 2 (continued) Item Reactant Conditions Yield Ref. Product Cl 200°C Cu 2 h (20 mg) Cl 3.25 g Br 200°C Cu Br Br 2 h Br Br O (40 mg) Br Br Br 3.15 Br Br g Br OK Br Br 185°C Cu 1.5 h (40 mg) Br 3.25 g Br Br OK 180°C Cu Br 1.5 h (40 mg) Br 1.75 g Cl ONa Cl 210°C 0.3g Cu 3 h (0.9 Cl Cl 3.7 g (continued) 13 g) m �TABLE 2 (continued) Item Conditions Reactant OK Product (Yield) Ref. (25*) Cu 4 h CH3 OK 195°C Cu POWDER 30 tnin (BO 2 9 CH OK CH3O Br 200°C Cu POWDER, (250 mg) n (3.1 g) o (10 mg) o 1.5 h OCH3 CH3 10 g Br Br OK Br I90°C Cu POWDER 1 h 6 g Br Br OH 145°C Cu POWDER, PYRIDINE 2.5 h ig Br (continued) 14 �TABLE 2 (continued) a Item Reactant Conditions Product a^ CH3 s^x-OH f 145 C Cu POWDER, P Y R I D I N E (Yield) CH3 /5 CH3x^ 55^Ov(x'xNY^Cn3 ]| I T I (8 ®CHA o c H3 1.-17 g CH3 Cl OK + Cl Cl CH3 Cl Cl 290°C 1-4 h o Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl 15 Cl o o Cl (continued) Ref. Cl Cl Cl m 9) ^ �TABLE 2 (continued) M Item Reactant OK Product Conditions OK Cl Cl Cl Cl 01 ci (Yield) Ref. r^W CIX\^XCI 290°C 1-4 h o o Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl ci ci X ci x^A^ o Y WT^CI .i II ^I ii c\^-f^°^f^c\ Cl OK OK Cl Cl Cl Cl Cl CK/i^^Cl 290°C 1-4 h Cl Cl Cl Cl Cl o Cl Cl Cl Cl Cl (continued) 16 Cl Cl �TABLE 2 (continued) Item Reactant Conditions Product OK OK Cl Cl Cl Cl Cl Cl 290°C 1-4 h Cl Cl Cl Cl o (Yield) Ref. Cl xC1 ifS o^^ Cl Cl Cl Cl Cl .O-^^-CI ci-^^oCl Cl Cl -oCl Cl •oCI^^N^O' Cl Cl Cl Cl Cl Cl Cl (continued) 17 �TABLE 2 (continued) Item Reactant Conditions Product (Yield) Ref. OK 9qnor ^^ " OK Cl 290°C 1-4 h CI-^v^^CI Cl OK OK Cl + Cl Cl Cl Cl Cl 290°C 1-4 h Cl Cl O' (continued) 18 �TABLE 2 (continued) M Item Reactant Conditions Product (Yield) Ref. OK Cl Cl 290°C 1-4 h C! Cl Cl Cl OK OK Clx^-W^CI Cl Cl Cl Cl Cl Cl 290°C 1-4 h Cl (continued) 19 �TABLE 2 (continued) u Reactant Item OK CI^A^CI Cl Cl Cl Conditions Product OK Cl Cl C! (Yield) Ref. Cl Z90°C 1-4 h Cl Cl Cl Cl Cl Cl CI\X^^o Cl O Cl Cl MINOR Cl 'Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl OK OK Cl Cl 290°C 1-4 h Cl Cl Cl Cl Cl (continued) Cl 20 �TABLE 2 (continued) Item Reactant Conditions Product (Yield) Ref. 290°C 1-4 h Cl (MINOR) Cl a If no yield is stated, no value is reported in reference. b Cullinane and Davies 1936. k Inubushi et al. 1959. 1 Tomita 1933. Narisada 1959. m Tomita, Ueda, andand Hai 1960. Tomita and Tani 1942. Denivelle, Fort, n Ueda 1962. Julia and Baillarge 1953. o Ueda and Akio 1963. Tomita, Nakano, and Hirai 1954. Ueda 1963. Tomita and Yagi 1958. Fujita and Gota 1955. Buser 1975. Fujita et al. 1956. 21 �In 1974 Cadogan, Sharp, and Trattles proposed a more reasonable mechanism involving the a-ketocarbene (12), which is attacked by the phenoxide to give ( 0 . 1) ONa -NaBr Br Br y*> OS) They also proposed that the conversion of the o-halophenoxyphenate to dibenzo-p-dioxin occurs via a benzyne intermediate (13). O Br -HBr f| (JO) The evidence in favor of this mechanism is quite convincing since both ortho- and meta-halophenoxyphenates are converted to the same dibenzodioxin, as shown below. 22 �As shown in Table 2 (items 5, 6, 11, 13, 25-28, and 31-35), complex mixtures result from attempts to prepare unsymmetrical dibenzo-p-dioxins using the modified Ullmann reaction. An early attempt to circumvent this problem involved the synthesis of a protected form of the unsymmetrical predioxin intermediate (14) (Tomita 1938) followed by its conversion to the dioxin in a separate procedure as shown below (Tomita 1938; Kermatsu 1936). 4- KBr O CH3CH3 I HBr HOAC HBr HO OH This procedure has the advantage of giving a single dibenzo-p-dioxin isomer; however, it is limited, in that yields of the dioxin rarely exceed 10 percent (Tomita 1938). A newer and more general procedure for the preparation of unsymmetrical (as well as symmetrical) dibenzo-p-dioxins involves the reaction of catechol salts with ortho-dihalobenzenes in dimethylsulfoxide (DMSO) (Pohland 1972; Kende 1974). DMSO REFLUX This procedure is a modification of a much earlier approach to the synthesis of dibenzo-p-dioxin, which suffered low yields (Tomi 1932) or no dioxin formation (Fujita 1955). The improved process gives very high yields of dibenzo-p-dioxins when dimethylsulfoxide is used as the sol vent Whether this result is simply a solvent effect or DMSO plays a chemical role in the reaction has not been determined. Examples of the utiliza tion of this reaction for the preparation of dibenzo-p-dioxins are include in Table 3. 23 �TABLE 3. CATECHOL-BASED REACTIONS Item Reactant Conditions Product (Yield) Ref. 200°C Cu POWDER CllN03 3 h 190°C Cu POWDER 2 h Cl OH Cl OH Cl^^^Cl Br OH Br KOH DMSO,A KOH DMSO.A KOH DMSO, OH (NO REACTION) Br O'^^^Br O^S^^F Cl KOH DMSO.A o O'\^ ->ci OH CI^^^CI Cl KOH DMSO.A Cl (continued) 24 e (41%) e Ov.x'^xF Cl Cl (25%) �TABLE 3 (continued) Item Reactant Product Conditions (Yield) Ref. Cl Cl H Cl -tOH Cl Cl Cl KOH DMSO.A Cl Cl (35% e TOTAL) Cl Cl Cl Cl OH KOH Cl DMSO.A o Cl Cl TOTAL) Cl OH Cl CH3 OHCI CH3 Br CH3 H Br + OH Br Cl Cl CH3 Br CH3 Br C! Cl ^xOH Cl + OHCI CH3 CH3 Cl CH3 Br Cl KOH KOH DMSO,A Cl KOH DMSO.-A (continued) 25 C1 (50%) Cl G �TABLE 3 (continued) Item Reactant Conditions Product (Yield) Ref. KOH DMSO,A OH CI OH CI KOH DMSO,A KOH DMSO,A t Evenly distributed carbons. ^ Preparation of uniformly labelled ^C TCDD isomers (148 millicune/mini mole). If no yield is stated, no value is reported in reference. Tomita 1932. Fujita and Gota 1955. Pohland and Yang 1972. Kende et al. 1974. Rose et al. 1976. 26 �Although no mechanistic studies of this reaction have been reported, it is clear that the initial attack of the catechol dianion on the polyhalobenzene does not occur via a benzyne intermediate, since in item 3 of Table 3 one would expect two different dioxins, which is not the result. This does not preclude the possibility that a benzyne intermediate is involved in the conversion of the predioxin (15) to the 2,3-dichlorodibenzo-p-dioxin (16), as has been proposed for similar predioxin cyclizations (Cadogan 1974). (16) oONLY OBSERVED PRODUCT NOT OBSERVED Numerous approaches to the preparation of substituted dioxins are based on elaboration of the dibenzo-p-dioxin skeleton via electrophilic aromatic substitution reactions. These applications are summarized in Table 4. As indicated in Table 4, electrophilic aromatic substitution occurs first at position 2. (The dioxin numbering sequence is shown in item 1.) If the newly introduced substituent is deactivating (halogen or nitro), the next attack occurs at either position 7 or 8. Gilman (1957; 1958) found that position 1 can be metalated by treatment of dibenzo-p-dioxin with alky! or phenyllithium reagents allowing this position to be substituted. MISCELLANEOUS DIOXIN PREPARATIONS Buser (1976) has developed a method for the preparation of qualitative standards of polychlorinated dioxins based on the photodechlorination of octachlorodioxin (Crosby 1971; 1973). Irradiation of octachlorodibenzo-pdioxin yields a mixture of tri-, tetra-, penta-, hexa- and heptachlorodibenzo-p-dioxin that is useful for the analysis of materials suspected to contain polychlorodioxins. 27 �TABLE 4. SUBSTITUTION REACTIONS Reactant Item 9 1 0 Br '""N ° fl 7 3 ^ 'x^o'*^' 6 5 Product Conditions 1 + (Yield) Ref. Br Br0 «* B Br Br2 Fe(Br) 3 ,CAT. Br Cl + Cl CI2 Cl Cl + Cl, Fe(CI), (LOW) I Cl + PENTA-CDO AND T R l - C O O Cl Cl Cl Cl Br + Cl CI2 (76%) Br, Br Br Br Br + Cl Br (67*) Br2 (continued) 28 c �TABLE 4 (continued) Item Reactant Conditions Product (Yield) Cl + ci, Cl C! + TRITIUM CAT Cl T Cl Cl Cl CI2 Cl FeCI3,l2(CAT) OCH3 OCH3 Br -O- O + Br2 -O' OCH3 Br OCH3 NO2 O NO 2 NO 2 O O NO; nnuo HOAC,0°C O O O2N HN03,A 29 O2N NO- Ref. �TABLE 4 (continued) Item Reactant Conditions Product (Yield) Ref. « + RCOCI Aid -, 3 H 2 /Pd O2N NH2 c\ HONO.CuCI (i g) j,k CI 2 , HOAc 1.PHENYLITHIUM O 9.2 g O O KBr j,k j.k KBrOg.HOAc, 120°C O O (l g) 2.Br 2 Br B r 2 , H O A c , 120°C 4.6 g (continued) 30 (0.6 g) j,k �TABLE 4 (continued) Item Reactant Conditions Product (Yield) Ref. Br 2 ,HOAc, 120°C CI 2 , FeCI 3 , I 2 (20 g) 1 Br 2 , HOAc (60 g) m CI, (0.7 g)n Bfr O 0.5 g O 0.2 g 0 O Cl. Br, 0.5 g If no value is stated, no value reported in reference. Gil man and Dietrich 1957. '.' Ueo 1941. r Oilman and Dietrich 1957. 5 Kende et al. 1974. Vinopal, Yamamoto, and Casida 1973. Oilman and Dietrich 1958. Sanderman, Stockmann, and Casten 1957. f Ueda 1963. Tomita, Ueda, and Narisada 1959. I Tomita 1935. 9 Tomita 1937. Denivelle, Fort, and Hai 1960. 31 �Lester and Brennan (1972) have patented a process for the direct conversion of substituted phenols to substituted dibenzo-p-dioxins with a palladium-copper catalyst. l l m m o l PdCI2 340mmol CuCl 0 lOOmmol NaOAc HOAc. REFLUX R - H,CH3,CH2CH3, OCH3, NO 2 Although the mechanism of the reaction has not been studied, the reaction is important in light of the widespread industrial uses of phenol and phenol derivatives. An interesting procedure for preparation of dihydroxydibenzo-p-dioxins is based on the oxidative coupling of polyhalocatechols found by reduction of the resulting quinone (Frejka 1937). Cl NaNO, HOAC,H2O Cl Cl Cl Although the yields from this process are modest (15 to 35 percertt), the reaction proceeds under very mild conditions. DISCUSSION OF REACTION CHEMISTRY On the basis of the data presented thus far, certain generalizations can be made about the conditions under which formation of dioxins (both halogenated and nonhalogenated) is probable. 32 �First, and most likely, is the formation of dioxins on treatment of o-halophenols with base at elevated temperatures. The strength of the base required to effect this reaction depends on the particular phenol involved; however, there is adequate precedent for the ability of relatively weak organic bases such as pyridine or quinoline to effect dioxin formation. The temperature range required for dioxin formation varies with the particular o-halophenol; however, 1 percent yields of halogenated dioxins have been formed at temperatures as low as 145°C. (See Table 2, item 23.) The presence of an ortho-halogen on the phenolic starting material is not an absolute requirement for dioxin formation. According to the mechanism proposed by Cadogan, Sharp, and Trattles (1974), all that is required is a substituent ortho to the phenol that is capable of acting as a leaving group. •*- Dioxins Other substituents should be capable of elimination to give the orketocarbene and thus dioxins. Among those in addition to the halogens are Sulfonic acids Sulfonate esters Nitro groups Carboxylate esters A second possible source of dioxins is the treatement of halogenated phenols with reagents conducive to the formation of the corresponding polyhalogenated phenoxy radical (i.e., treatment with halogens or other mild oxidizing agents). Although this reaction has been used only for the preparation of perhalo dioxins (in yields of more than 80 percent and 200-gram quantities), there is no reason why the reaction could not produce the lower halogenated derivatives of dioxins. (See Table 1, item 2.) A common practice in the preparation of polyhalobenzenes by electrophi lie halogenation is neutralization of the acid byproduct with alkali hydroxides. This process (or simply a basic wash of product during the isolation procedure) can lead (via nucleophilic substitution) to a halogenated phenol, which upon distillation may produce dioxins. Dioxins 33 �The treatment of catechol salts with o-dihalobenzenes is a particularly efficient method for the formation of dioxins, both halogenated and nonhalogenated. Also, the treatment of polyhalocatechols with mild oxidants can produce significant quantities of halogenated dihydroxy-dioxins. Of particular concern is the treatment of aromatic compounds under oxidizing conditions at elevated temperature. Several industrial processes involve the oxidation of benzene, toluene, and naphthalene under "semicombustion" conditions. In liojht of the studies such as that by Dow Chemical (Rawls 1979) on combustion sources of dioxins, the "tars" from these processes (which are often generated in considerable quantities) deserve further study. The mechanistic aspects of dioxin formation discussed in this section represent the current understanding of these reactions; however, several experimental observations about dioxin formation cannot be explained by the current theories. The formation of four isomers of hexa-CDD on pyrolysis of 2,3,4,6-tetrachlorophenate (Higginbotham 1968; Langer 1973), including the 1,2,3,7,8,9 hexa-CDD (Buser 1975), can be explained in terms of the predioxin intermediates, (17) and (19), undergoing the Smiles rearrangement as shown on the following page. As the diagram shows, the initially formed predioxin intermediate can proceed directly toward dioxin formation (path a) or can undergo the Smiles rearrangement (path b), which leads to new predioxin intermediates 18 and 20. The newly formed predioxins can then react further to give a different dioxin or can undergo the Smiles rearrangement to regenerate the original predioxin. This interconvertability of predioxins often leads to mixtures of dioxin products which are otherwise difficult to understand. An equally disturbing mechanistic point is the observation that numerous pesticides are contaminated by polychlorodioxins, which would not be anticipated on the basis of the feedstock materials and reaction conditions. An example reported by Fishbein (1973) is the presence of significantly higher concentrations of hepta- and octachlorodioxins than hexachlorodioxin in commercial 2,3,4,6-tetrachlorophenol, also known as Dowicide-6 (see Table 7). The Dow Chemical Company (Rawls 1979) has proposed that the polychlorodibenzo-p-dioxins undergo disproportionate and establish an equilibrium mixture of halogenated dioxins. No experimental evidence in support of this proposal has been published. 34 �Cl ©0 Cl ONa NaC! Cl Cl (18) PREDIOXIN Cl Cl Na© ci C| +NaCI Cl Cl Na© 1,2,4,6,7,9-HEXA-CDD + NaCI S O" "v" "Cl Cl T.CI 6 ^ "Ci Cl ^Na+ Cl (18) 1,2,3,6,7,8-HEXA-CDD PREDIOXIN © Cl PREDIOXIN Cl NaCI Ci ci 1,2,3,7,8,9-HEXA-CDD 35 ci 1,2,4,6,8,9-HEXA-CDD �SECTION 4 SPECULATIVE SOURCES OF DIOXINS Dioxins can enter the environment in a variety of ways: 1. As contaminants in commercial chemical products whose normal processing conditions generate the dioxins as byproducts. Sections 5 and 6 detail the mechanisms by which this can occur in some of these commercial chemicals. 2. As contaminants in chemical processing under improperly controlled reaction conditions (Rappe 1978). Thus, dioxins would be present in the wastes from "bad batches." Chemical manufacture that might lead to dioxin presence under such circumstances is also reviewed in Sections 5 and 6. 3. As products of intentional dioxin preparations in the laboratory. Although the quantities involved from such sources probably would not be large, the concentrations would be high. Therefore any failure to practice proper disposal could be serious because of the high toxicity and concentration potential. Reported laboratory dioxin preparations are noted in Section 3. 4. As deliberate or unintentional products of reactions carried out by uninformed or irresponsible persons. The hazards in such cases would be enhanced because the dioxins formed would likely be subject to improper use or disposal. 5. As products of combustion of general municipal, commercial, and industrial wastes. Such wastes are likely to contain materials required for dioxin formation. The chlorine content of municipal waste is relatively high because of the widespread use of polyvinyl chloride and other chlorinated polymers. 6. As combustion products and residues from burning vegetation that has been sprayed with chlorinated herbicides (and other pesticides). This potential source is of two-fold interest. First, chemicals such as 2,4,5-T, 2,4-D, and others noted in Section 6 might be degraded to dioxins under relatively mild combustion conditions (Buu-Hoi 1971). Second, formation of dioxins might occur under combustion conditions, even from chemicals not directly related to dioxins, such as many insecticides (DDT, aldrin, dieldrin, etc.). 36 �7. As incidental products of fires in facilities such as chemical and pesticide warehouses, farm buildings in which pesticides are stored, and facilities for storage of chemically treated wood products such as lumber or poles (Buu-Hoi 1971). 8. As waste disposal byproducts of materials such as polychlorinated biphenyls (PCB). These materials have been used extensively in electrical transformers, as heat transfer media, as lubricants, and in carbonless paper. 9. As derivative wastes from pentachlorophenol (PCP) and other woodtreating agents. Agents used in the treatment of wood products are likely to remain with the wood through its use cycle. Thus they are subjected to the same extremes of exposure as the wood, including ultimately combustion, which leads to dioxin formation (Buu-Hoi 1971). 10. As an unsuspected byproduct of the treatment of aromatic compounds under oxidizing conditions at elevated temperature. Several industrial processes involve the oxidation of benzene, toluene, and naphthalene under "semicombustion" conditions. In light of such studies as that by Dow Chemical (Rawls 1979) on combustion sources of dioxins, the "tars" from these processes (often occurring in considerable quantities) warrant further study. 11. As byproducts of miscellaneous chemical syntheses that may not be commercially significant at this time. An example might be the detected presence of 2,3,7,8-TCDD in chlorinated polyphenylene ethers (such as 21), which can be produced from 2,4,5-trichlorophenol (Cox 1965). Cl / ( NaOH *• A .Cl HO ci These polymers are not known to be of commercial significance, but serve as a cautionary example. 12. As a result of the combustion of naturally occurring compounds. Recent reports by chemists at the Dow Chemical Company maintain that dioxin formation is a natural consequence of combustion (Dow 1978). There are numerous naturally occurring compounds that could, during the complex process of combustion, serve as precursors of dioxins. Combustion of these compounds in the presence of chlorine-containing compounds (e.g., DDT or polyvinyl chloride) 37 �could lead to the formation of chlorinated dioxins. Examples of such naturally occurring "potential" dioxin precursors are given below. OH I CH3NHCH2CH OH OH OCH3 (24) (22) GUAIACOL CATECHOL ADRENALINE (EPINEPHRINEJ Catechol (22) occurs in nature as the product of phenol biodegradation and as a major product of tannin pyrolysis (Wertheim 1939). Guaiacol (23) occurs as the major phenolic component in several hardwood trees and is also prepared synthetically for use as an ingredient in cough syrups (Merck 1978; U.S. EPA Draft 1979). Adrenaline (24) is a naturally occurring mammalian hormone and is also prepared synthetically for use in many drug formulations (U.S. EPA Draft 1979). Other naturally occurring compounds that contain the orthohydroxy or alkoxy groups include vanillin (25), which is the flavoring ingredient in vanilla extract; urushiol (26), a mixture of compounds that are the toxic constituents of poison ivy; eugenol (27), the pungent principle of cloves; capsaicin (28) the pungent principle of various peppers; and safrole (29), the major volatile constituent of sassafras. CHO OCH3 OCH3 CH2CH=CH2 OH (27) EUGENOL (25) VANILLIN OCH3 URUSHIOL O CH2NHC-(CH2)4-CH=CHCH(CH3)2 CH 2 CH—CH 2 (29) SAFROLE (28) CAPSAICIN 38 �Among many plant alkaloids that include the structure are reserpine (30), glaucine (31), and colchicine ( 2 . Other 3) potential dioxin precursors are found in the fomecin (33) series of antibiotics, produced by a fungus, and also in one of the active ingredients of creosote. A constituent of animal urine is 4-hydroxy-3-methoxymandelic acid (Merck Index 1978). Since the structure is so common in living organisms, it is also often used in synthetic medicinal compounds, including phem'sonone, isoproterenol, estil (an anaesthetic), methocarbanol, and the high-volume drugs guaifenesin and methyldopa (U.S. EPA 1979). OCH3 OCH, OCH3 CH30 CH3O2C CH30 CH3O (31) GLAUCINE (30) RESERPINE CHO HOH2C OH NHCOCH3 OH OH (33) FOMECIN COLCHICINE At least one natural compound may be by itself a precursor for a chlorinated dioxin. A microorganism species creates a defensive chemical known as drosophyllin A (34), (p-methoxytetrachlorophenol) (Merck Index 1978). In theory it could, when heated, form a substituted hydroxy or methoxy chlorinated dioxin, one possibility of which is: OCH3 2HCI CH30 Cl 39 Cl �SECTION 5 ORGANIC CHEMICALS Organic chemical products with the greatest potential for byproduct formation of dioxins are considered in this section. Pesticides and pesticide manufacture are covered separately in Section 6. Toxicity of the many substituted dibenzo-p-dioxins varies widely. None are excluded from consideration here since disproportionation and other composition shifts may bring about changes from lower toxicity forms to higher (Buser 1976). Because of the very large number of organic compounds and their varying proclivities to form dioxins, the compounds were screened initially on the basis of: Molecular structure Process sequence Commercial significance As a means of focusing attention on those organic chemicals most likely to be associated with the formation of dioxins, they were placed in the following classifications: Class I - Polyhalogenated phenols, primarily with a halogen ortho to the hydroxyl group, with a high probability of dioxin formation. Products with such compounds appearing as intermediates are also considered. Manufacture of these materials normally involves reaction conditions of elevated temperature plus either alkalinity or free halogen presence, either of which is conducive to formation of halogenated dioxins. Class II - Ortho-halophenols and ortho-halophenyl ethers where the substituted groups are a mixture of halogens and nonhalogens. Processing conditions are similar to those defined for Class I and produce mixed substituted dioxins. The distinction between Classes I and II is arbitrary and does not indicate necessarily a difference in likelihood of dioxin formation. Class III - Other chemicals having the possibility, but less likelihood, of dioxin formation. These include 1) ortho substituted aromatic 40 �compounds requiring an unusual combination of reaction steps to produce dioxins, 2) aromatic compounds that might form dioxins because of their production under semicombustion conditions, and 3) products that might contain dioxins by way of contamination of their starting materials. Since only commercially significant products are of interest in this study, the listing is limited to those produced in quantities in excess of 1000 pounds per year and/or whose sales reach $1000 per year, as required for listing in the SRI Directory of Chemical Producers. The product lists are based on commercial production during the past 10 years. Table 5 lists and classifies commercial organic chemicals selected as having a relationship to dioxin formation or presence. Structures are shown for Classes I and II, the chemicals of primary importance. Class III compounds are listed by name only. Most of the organic chemicals considered are used as manufacturing intermediates or at least are subjected to subsequent formulation or fabrication. Thus further processing may introduce additional possibilities for dioxin formation, contamination, and exposure not contemplated within the scope of this study. The intended reaction mechanisms for each Class I organic chemical are shown in Figures 1 through 11. The sequence is shown from left to right across the top of each figure, and the possible dioxin side reaction mechanism diverges to typical dioxin byproducts at the bottom of the figure. The specific dioxin products shown are those for which reasonably straightforward mechanisms can be postulated. In many cases more complex and secondary mechanisms may produce dioxins in addition to those shown. 41 �TABLE 5. LIST OF ORGANIC CHEMICALS Class OH Cl 4-BROMO-2.5-DICHLOROPHENOL Cl Br OH Cl 2-CHLORO-4-FLUQROPHENOL Br Br Br Br DECABROMOPHENOXYBENZENE Br Br Br Br OH Br 2,4-DIBRQMQPHENQL OH Cl 2,3-DICHLOROPHENOL Cl (continued) 42 �TABLE 5 (continued) Class I (continued) OH Cl 2,4-DICHLOROPHENOL Cl OH Cl 2,5-DICHLOROPHENOL Cl OH 2,6-DICHLOROPHENOL OH 3,4-DICHLOROPHENOL Cl Cl OH PENTABROMOPHENOL Br (continued) 43 �TABLE 5 (continued) Class 1 (continued) OH 2,4,6-TRIBROMOPHENOL Br OH 2,4,5-TRICHLOROPHENOL Cl Cl Class M OC2H5 -Br BROMOPHENETOLE OH 0-BROMOPHENOL Br OC2H5 Cl 2-CHLORO-1,4-01ETHOXY-5-NITROBENZENE OC2H5 NH, OCH3 5-CHLORO-2,4-DIMETHOXY-ANILINE Cl OCH3 (continued) 44 �TABLE 5 (continued) Class II (continued) OH Cl CHLOROHYDROQUINONE OH OH Cl 0-CHLOROPHENOL 2-CHLORO-4-PHENYLPHENOL 4-CHLORORESORCINOL OH Cl OH 2,6-DIBROMO-4-NITROPHENOL NO2 COOH OH 3,5-DICHLOROSALICYLIC ACID (continued) 45 �TABLE 5 (continued) Class II (Continued) OH 2,6-DIIODO-4-NITROPHENOL NO2 COOH OH 3 ,5-DIIODOSALICYLIC ACID OCH3 0-FLUOROANISOLE OH 0-FLUOROPHENOL TETRABROMOBISPHENOL-A C CH3 Cl Cl TETRACHLOROBISPHENOL-A C I HO Cl (continued) 46 CH3 OH Cl �TABLE 5 (continued) Class 111 3-Amino-5-chloro-2-hydroxybenzenesulfonic acid 2-Amino-4-ch!oro-6-nifrophenol o-Anisidine Benzaldehyde Bromobenzene o-Bromof I uorobenzene o-Chlorofluorobenzene 3-Chloro-4-fluoro-nitrobenzene 3-Chloro-4-fluorophenol 4-Chloro-2-nitrophenol Chloropenfaf I uorobenzene 2,4-Dibromof I uorobenzene 3,4-Dichloroaniline o-Dichlorobenzene 3,4-DIchlorobenzaldehyde 3,4-Dichlorobenzotrichloride 3,4-Dichlorobenzotrifluoride 1,2-Dichloro-4-nitrobenzene (continued) 47 �TABLE 5 (continued) Class III (continued) 3,4-Dichlorophenylisocyanate 3,4-Difluoroaniline o-Difluorobenzene l,2-Dihydroxybenzene-3,5-disulfonic acid, disodium salt 2,5-Dihydroxybenzenesulfonic acid 2,5-Dihydroxybenzenesulfonic acid, potassium salt 2,4-Dinitrophenol 2,4-Dinitrophenoxyethanol 3,5-Dinitrosalicylic acid Fumaric acid Hexabromobenzene Hexachlorobenzene Hexaf I uorobenzene Maleic acid Maleic anhydride o-Nitroanisole 2-Nitro-p-cresol o-Nitrophenol (continued) 48 �TABLE 5 (continued) Class III (continued) Pentabromochlorocyclohexane Pentabromoethylebenzene Pentabromotoluene Pentachloroaniline Pentaftuoroaniline o-Phenetidine Phenol (From chlorobenzene) l-Phenol-2-sulfonic acid, formaldehyde condensate Phenyl ether Phthalic anhydride Picric acid Sodium pi crate Tetrabromophthalic anhydride 1,2,4,5-Tetrachlorobenzene Tetrachlorophthalic anhydride Tetrafluoro-m-phenylenediamine Tribromobenzene 1,2,4-Trichlorobenzene 2,4,6-Trinitroresorcinol 49 �4-BROMO-2,5-DICHLOROPHENOL ,2,4-TRICHLOROBENZENE Cl 2,7-DCDO 2,8-OCOO Figure 1. 4-Bromo-2,5-dichlorophenol 50 2,7-OB-3,8-DCOD �2 - CHLORO - 4 - FLUOROPHENOL 2,7 - OFDD Figure 2. 2-Chloro-4-f1uorophenol 51 �DECABROMOPHENOXYBENZENE OH Br Br y Br Br PENTABROMOPHENOL Br' Figure 3. Decabromophenoxybenzene. 52 �2,4 - DIBROMOPHENOL OH -f OTHER BROMOPHENOLS + OTHER BROMOPHENOXY RADICALS PHENOL Br O + O Br 2,7-DBDO Figure 4. 2,4-Dibromophenol 53 OTHER BROMOOIOXINS �2,3-DICHLOROPHENOL Cl Cl S03 H2S04 Cl 1,2,3-TRICHLOROBENZENE O Cl ^ S03 Figure 5. 2,3-Dichlorophenol 54 �2,4 - DICHLOROPHENOL OH OH Cl Cl -f- OTHER ISOMERS CATALYST Cl PHENOL Cl + OTHER CHLOROPHENOXY RADICALS -f OTHER CHLORODIOXINS Cl Cl Cl o o 2,7 - DCDD Figure 6. 2,4-Dichlorophenol 55 �2,5 - OICHLOROPHENOL 1,2,4 - TRICHLOROBENZENE 2,7-OCOO 2,8-OCDO Figure 7. 2,5-Dichlorophenol 56 �2,6 - DICHLOROPHENOL CI2 OTHER ISOMERS CATALYST PHENOL 4- OTHER CHLOROPHENOXY RADICALS -f OTHER CHLORODIOXINS Cl 1.6 - DCPD Figure 8. 2,6-Dichlorophenol. 57 �3,4-DICHLOROPHENOL Cl SO3H S03 Cl H2SO4 Cl 1,3,4-TRICHLOHOBENZEHE Cl Figure 9. 3,4-Dichlorophenol. 58 �PEHTABROMOPHENOL OH OH Br Br2 , CATALYST Br PHENOL Br Br Br Br Br Br Br OBDD Figure 10. Pentabromophenol. 59 �2,4,6 - TRIBROMOPHENOL OH OH + OTHER BROMOPHENOLS PHENOL Br Br -f OTHER BROMOPHENOXY RADICALS -I- OTHER BROMODIOXINS Br Br Br O O Br Br 2,4,7,9-TBOD Figure 11. 2,4,6-Tribromophenol, 60 �SECTION 6 PESTICIDE CHEMICALS Pesticides are the most significant group of organic chemicals in relation to dioxin occurrence. This statement is based on the structure and reaction mechanism analogy, reaction conditions, detected presence of dioxins in a number of commercial pesticide products, and a history of environmental contamination problems, particularly with trichlorophenol and 2,4,5-T. Chlorinated dibenzo-p-dioxins are known to be present in at least trace amounts in a number of pesticide chemicals. These include 2,4,5-T, silvex, 2,4-D, erbon, Sesone, DMPA, ronnel, tetradifon, and the various chlorophenols (Fishbein 1973). In addition, the chemical structures, reactions, and process conditions for a number of others indicate dioxin content potential. This study deals with production of the basic pesticide chemicals. Thus it does not address problems of dioxin formation possibly resulting from formulation, storage, distribution, and utilization of the pesticides. If exposure to alkaline formulation media or elevated temperatures is encountered in any of the diverse procedures for handling and use of these pesticides, dioxin formation could be a significant problem. SELECTION AND CLASSIFICATION The pesticide chemicals were selected for evaluation in this study on the basis of molecular structure, from those listed as commercial pesticides in the Farm Chemicals Handbook. The primary criterion was an ortho halophenolic structure, or the derivative esters and salts thereof. Also considered were ortho dihalo aromatic structures, which conceivably could convert to phenols upon exposure to alkaline conditions. A second criterion was a minimum commercial production level of 1000 pounds or $1000 value per year. These correspond to the minimum levels required for inclusion in the Stanford Research Institute Directory of Chemical Producers, which was a primary reference. The lists are based on production during the past 10 years. The pesticide chemicals considered in this study are listed in Table 6. They are grouped into classes representing likelihood of dioxin formation, as follows: 61 �TABLE 6. LIST OF PESTICIDE CHEMICALS General name Chemical name Class I Bifenox Methyl-5-[2,4-dichloroephenoxy]-2nitrobenzoate Chloranil 2,3,5,6-Tetrachloro-2,5-eye1orhexadi ene1,4-dione 2,4-D and esters and salts (2,4-Dichlorophenoxy)acetic acid and esters and salts 2,4-DB and salts 2,4-Dichlorophenoxybutyric acid and salts Dicamba 3,6-Dichloro-2-methoxybenzoic acid Dicamba, dimethyl amine salt 3,6-Dichloro-2-methoxybenzoic acid, dimethyl amine salt Dicapthon Phosphorothioic acid o-(2-chloro-4nitrophenyl) o,o-dimethyl ester Dichlofenthion Phosphorothioic acid o-2,4-dichlorophenyl o,o-diakyl ester Disul sodium (Sesone) 2,4-Dichlorophenoxyethyl sulfate, sodium salt 2,4-DP 2-[2,4-Dichlorophenoxy] propionic acid Erbon 2,2-Dichloropropanoic acid 2-(2,4,5trichlorophenoxy) ethyl ester Hexachlorophene 2,2'-Methylene bis (3,4,6-trichlorophenol) Isobac 20 2,2'-Methylene bis (3,4,6-trichlorophenol), monosodium salt Nitrofen 2,4-Dichlorophenyl-p-nitorphenyl ether Pentachlorophenol (PCP) and salts Pentachlorophenol and salts (continued) 62 �TABLE 6 (continued) General name Chemical name Ronnel Phosphorothioic acid, o,o-dimethyl 0-(2,4,5-trichlorophenyl) ester Si 1 vex and esters and salts 2-(2,4,5-Trichlorophenoxy) propionic acid and esters and salts 2,4,5-T and esters and salts (2,4,5-Trichlorophenoxy) acetic acid 2,3,4,6-Tetrachlorophenol 2,4,5-Trichlorophenol Class II o-Benzyl-p-chlorophenol Bromoxynil and esters 3,5-Dibromo-4-hydroxybenzonitrile Carbonphenothion Phosphorodithioic acid s-[[(4-chlorophenyl) thiojmethyl] o,o-diethyl ester DCPA 2,3,5,6-Tetrachloro-l,4-benzenedicarboxylic acid dimethyl ester Dichlone 2,3-Dichloro-l,4-haphthalenedione Dinitrobutylphenol, ammonium salt 2,4-Dinitro-6-sec-butyl phenol, ammonium salt \Loxynil 3,5-Diiodo-4-hydroxybenzonitrile L"jndane I X 1,2,3,4,5,6-Hexachlorocyclohexane, gamma isomer MCPA (4-Chloro-o-toloxy) acetic acid MCPB 4-(2-Methyl-4-chlorophenoxy) butyric acid Mecoprop 2-(4-Chloro-2-methylphenoxy) propionic acid Parathion Phosphorothioic acid o,o-diethyl o-(4nitrophenyl) ester PCNP Pentachloroni trobenzene (continued) 63 �TABLE 6 (continued) Chemical name General name Pipecolinopropyl-3,4-dichlorobenzoate Piperalin 3-(2~methylpiperidino)propyl-3,4dichlorobenzoate Propanil 3,4-Dichloropropionanilide Tetradifon 1,2,4-Trichloro-5-[(4-chlorophenyl)sulfonyl] benzene 2,3,6-Trichlorobenzoic acid 2,3,6-Trichlorophenylacetic acid and sodium salt Triiodobenzoic acid 64 �Class I - Highly likely to be associated with the presence of halogenated dibenzo-p-dioxins because of the presence of an ortho-halogenated phenol in the reaction sequence, with subjection to elevated temperature (>145°C+) plus either alkalinity or the presence of free halogen. Class II - Reasonable but lesser probability of such dioxin association because of the presence of phenolic or aromatic structures related to dioxins; although not directly involving dioxin precursive conditions, such chemicals might form dioxins under irregular operating conditions. CHEMICAL REACTIONS Higher chlorinated dioxins have been detected in samples of a number of pesticides produced from 1950 to 1970. Data from these analyses were summarized by Fishbein (1973), as shown in Table 7. Many of the dioxins present differ from those expected on the basis of the straightforward mechanisms hypothesized. Possible reasons for this may be that other mechanisms are at work or that substantial disproportionate is occurring among the dioxins initially formed, as has been suggested by Dow Chemical (Rawls 1979) and others (Buser 1976). Reaction mechanisms for the Class I pesticide products are shown in the following figures. The intended product reaction sequence is from left to right across the top of each figure, and the possible dioxin side reaction mechanism diverges to typical dioxin byproducts at the bottom of the figure. The specific dioxin products shown are those for which reasonably straightforward mechanisms can be postulated. In many cases, more complex and secondary mechanisms may produce dioxins in addition to those shown, as evidenced by their analytical detection in a number of products (Fishbein 1973). The initial reaction steps in producing many of the Class I pesticides are very similar and thus the pesticides are grouped by common mechanism. Similarity is noted in 2,4,5-T, silvex, ronnel, 2,4-D, erbon, Sesone, dichlofenthion, dicapthon, bifenox, and dicamba. The final substitution pattern differs in each case, as does the precise halophenol or chlorobenzene starting structure. The first step in production of 2,4,5-T, silvex, ronnel, and erbon is identical (Figures 12 through 15). Treatment of 1,2,4,5-tetrachlorobenzene with caustic yields 2,4,5-trichlorophenol. The reaction conditions are sufficiently drastic, including alkalinity and elevated temperature, to cause formation of the a-ketocarbene, which reacts with the chlorophenylate to give the predioxin, which then reacts to yield 2,3,7,8-TCDD. Continued alkaline processing, which occurs with each of these product items, also contributes to the same transient intermediates and consequently to formation of 2,3,7,8-TCDD. 65 �TABLE 7. HIGHER CHLORINATED DIOXINS FOUND IN COMMERCIAL PESTICIDES' Pesticide Chi orodi benzo-prdi oxi n detected Tetra- Hexa- Hepta- Octa- Sample Number Number contaminated tested Phenoxyal kanoates 2,4, 5-T Si 1 vex 2,4-D Erbon Sesone ++ + ++ - + ++ + 23 1 1 1 1 42 7 24 1 1 Chlorophenols TriTetraPenta-(PCP) Others0 - + ++ ++ + ++ ++ + ++ ++ 4 3 10 6 3 11 - ++ ++ + 5 22 jj Fishbein, 1973. concentration range: ++ = >10 ppm + = 0.5 to 10 ppm - = <0.5 ppm DMPA, ronnel, and tetradifon were found to contain chlorodioxin contamination. 66 �2.4.5-T COOH Cl ESTERS Cl T Cl CICH2CO2 "\ Cl AMINE SALTS 2,4,5-TRICHLOROPHENOL CI- 'Cl Figure 12. 2,4,5-Trichlorophenol, 2,4,5-T and esters and salts. 67 �SILVEX COOH CH3-CH ESTERS SALTS CHLOROSENZENE 2,4,5-TRICHLOROPHENOL 30Na© Cl Cl Cl Figure 13. Silvex and esters and salts. 68 Cl �2,4,5-TRICHLOROPHENOL RONNEL SNs/)CH3 00Na© ' Cl SPCI3 2.3,7,8-TCOD Figure 14. 69 Ronnel �(DISUL SODIUM) SESONE X=H O OC2H4OS-OH OC2H4OS-ONa P1 O J^ ^Ct O NaOH OH O O CH2CH2O-C-CCI2CH3 ERBON = CI Figure 15. Erbon and Sesone. 70 �The normal reaction sequences for 2,4-D, 2,4-DB, 2,4-DP, disul sodium (Sesone), dichlofenthion, bifenox, and nitrofen (sequences shown in Figures 15 through 21) are analogous in their early steps to those of 2,4,5-T and others in the group just described, but occur via 2,4-dichlorophenol rather than 2,4,5-trichlorophenol. The dioxin formation sequence is likewise analogous but typically would produce 2,7-DCDD. Note that the reaction mechanism for disul sodium is presented in the same figure (Figure 15) with that for erbon. This placement is not meant to imply that they are co-products, but rather is intended to demonstrate the analogous reaction patterns of typical pesticides differing as to halogenation and substitutions. Similar analogies can be drawn among nearly all of the pesticide chemicals studied. Another point, important to dioxin formation, is demonstrated in Figure 16, showing the reaction for 2,4-D. The reaction sequence conventionally cited is chlorination of phenol to 2,4-dichlorophenol, followed by reaction with chloroacetic acid in the presence of caustic to produce 2,4-D. This last step with the dichlorophenol under alkaline conditions can result in dioxin formation. An alternative process sequence cited in the patent literature (Manske 1949) reverses the order of chlorination, as shown in the upper tier reaction of Figure 16. This sequence would be expected to reduce the likelihood of dioxin formation. A commercially feasible yield in excess of 80 percent is noted, but the extent of commercial utilization is not known. This reaction sequence could possibly be adapted to other dihalogenated phenoxyalkanoates, with an expected reduction in dioxin formation. Dicamba (Figure 22) with its dimethylamine salt presents one of the more complex dioxin derivation patterns because of the continued alkaline conditions under which various substitutions are made. First, preparation of 2,5-dichlorophenol and its subsequent further exposure to caustic results in transient intermediates and predioxins that form 2,7-DCDD and 2,8-DCDD. In addition, similar alkaline processing of the carboxyl and methyl substituted forms can result in variously substituted dioxins, only two of which, for simplicity, are shown in Figure 22. Pentachlorophenol (PCP), a commercially high-volume chemical, can be manufactured by two basic methods. One involves direct chlorination of phenol (Figure 23) in the presence of an A1C13 catalyst. The presence of normal excess chlorine is conducive to formation of a free-radical intermediate, then of the predioxin, and ultimately of OCDD. The alternative process based on caustic treatment of hexachlorobenzene (Figure 24) produces chlorinated transient intermediates analogous to the 2,4,5-T series but fully chlorine substituted. These in turn form the predioxin and finally OCDD. The complex free-radical mechanism by which chloranil is made (Figure 25) results in transient intermediates similar to those occurring as byproduct derivatives of PCP. Therefore, OCDD should be expected as a dioxin contaminant. 71 �PHENOL PHENOXYACETIC ACID OCH2COOH OH NaOH Cl CH2COOH Cl 2,4- D OH OCH2COONa OCH2COOH Cl NaOH CICH2COOH ESTERS [2 Cl 2,4-OICHLOROPHENOL ©ONa© Cl Figure 16. 2,4-D and esters and salts. 72 AMINE SALTS �2,4-DB CH2CH2CH2 COOH OH ONa >L Cl £1 N?OH 50-200°C ESTERS r AM1NE SALTS Cl 2,4-DICHLOROPHENOL O QONa Cl Cl Cl Cl Cl 2,7 - DCDD Figure 17. 73 2,4-DB. �2,4 - DP H I CHg ~" C OH o Cl I Cl NaOH, CH CH -CO H 3 2 Cl Cl 2,4 - DICHLOROPHENOL Cl Cl Figure 18. 74 2,4-DP. �(X=N02) DICAPTHON or"" DICHLOFENTHION (X=CI) OH ©9Na© Cl ©?Na© Cl O0N 2,7-ONOD Figure 19. Dicapthon and Dichlofenthion. 75 �BIFENOX H = Na, K X= Cl, Br R = H or A l k y l Cl 2,7-OCDO Figure 20. 76 Blfenox. �NITROFEN Cl OH Cl Gl 2,4-DICHLOROPHENOL NO2 CHLORO-4-NITROPHENOL Cl 2,7-OCOD Figure 21. Nitrofen. 77 �,2,4-TRICHLOROBENZENE 2,5-OICHLOROPHENOL DICAMBA Cl Cl Cl Cl Cl Figure 22. 78 Dicamba. �PENTACHLOROPHENOL(PCP) PCP, Na SALT ONa Cl QCOD Figure 23. Pentachlorophenol (PCP) via phenol. 79 �PENTACHLOROPHENOL (PCP) CI- Cl Cl Cl Cl Cl Cl Cl Cl OCDD Figure 24. Pentachlorophenol (PCP) via hexachlorobenzene. 80 �CHLORANIL REACTION VIA COMPLEX \ FREE RADICAL MECHANISM/ HCI , O2 220-260°C BENZENE Figure 25. 81 Chloraml. �Hexachlorophene and its sodium salt, Isobac 20, (Figure 26), are produced from 2,4,5-trichlorophenol whose preliminary production from 1,2,4,5tetrachlorobenzene is carried out by reaction with caustic. This first step potentially forms dioxin precursors similar to the equivalent step in the manufacture of 2,4,5-T. Consequently, 2,3,7,8-TCDD is the anticipated byproduct dioxin. The production of 2,3,4,6-tetrachlorophenol (Figure 27) by chlorination of phenol would be expected to yield trace byproducts of various isomeric hexachlorodibenzo-p-dioxins via a free-radical mechanism. Again, because of the analytical evidence of many dioxins other than those hypothesized in these mechanisms, no specific dioxin presence should be presumed or excluded. As an indication of the critical processing that might precede the reactions shown in this section, Table 8 summarizes the primary raw materials. Those materials potentially carrying trace dioxins are reviewed in Section 5. 82 �HEXACHLOROPHENE ISOBAC 20 Cl' 01 C! Cl 2,3,7,8-TCDO Figure 26. Hexachlorophene and Isobac 20. 83 �2,3,4,6 - TETRACHLOROPHENOL OH CI2 .CATALYST OTHER CHLOROPHENOLS PHENOL -f OTHER CHLOROPHENOXY RADICALS CI HEXA-CDD'S Figure 27. 2,3,4,6-Tetrachlorophenol. 84 �TABLE 8. PESTICIDE RAW MATERIALS Pesticide product Raw materials Bifenox 2,4-Dichlorophenol 3-Halo-o-nitrobenzoic acid ester NaOH Chloranil Benzene Hydrogen chloride Oxygen 2,4-D and esters and salts Phenol Chloroacetic acid NaOH C12 Alcohols (for esters) Amines (for amine salts) 2,4-DB and salts Phenol C12 NaOH Butyrolactone Alcohols (for esters) Amines (for amine salts) Dicamba 1,2,4-Trichlorobenzene NaOH C02 Dimethyl sulfate Dicapthon 2-Chloro-4-nitorphenol NaOH Chiorodimethylthi ophosphonate Dichlofention 2,4-Dichlorophenol NaOH Chiorodimethylthi ophosphonate Disul Dodium (Sesone) 2,4-Dichlorophenol NaOH Ethylene oxide Chlorosulfonic acid 2,4-DP 2,4-Dichlorophenol 2-Chloropropionic acid NaOH (continued) 85 �TABLE 8 (continued) Pesticide product Raw materials Erbon 1,2,4,5-Tetrachlorobenzene NaOH Ethylene oxide 2,2-Dichloropropionic acid Hexachlorophene and Isobac 20 1,2,4,5-Tetrachlorobenzene NaOH Ethylene oxide Nitrofen 2,4-Dichlorophenol Chloro-4-nitrobenzene KOH Pentachlorophenol PCP Phenol C12 (Phenol route) or Benzene C12 NaOH (Hexachlorobenzene route) Ronnel 1,2,4,5-Tetrachlorobenzene NaOH Phosphorus sulfochloride NaOCHg Si 1 vex and esters and salts 1,2,4,5-Tetrachlorobenzene NaOH Chloropropionic acid Alcohols (for esters) Amines (for amine and salts) 2,4,5-T and esters and salts 1,2,4,5-Tetrachlorobenzene NaOH Chloracetic acid Alcohols (for esters) Amines (for amine salts) 2,3,4,6-Tetrachlorophenol Phenol C12 2,4,5-Trichlorophenol 1,2,4,5-Tetrachlorobenzene NaOH 86 �SECTION 7 CHEMICALS, PRODUCERS, AND PLANT LOCATIONS The tables that follow list organic chemicals and pesticides selected for study on the basis of potential dioxin contamination, with known producers and production locations, present and past. The primary source of producer information is the SRI Directory of Chemical Producers. The tabulations are by chemical, with producers and locations; and by producer and location, with chemicals. The tabulations by chemical (Tables 9, 10, 11, and 14) are segregated according to the classifications based on dioxin concern as defined in Section 5 (Organic Chemicals) and Section 6 (Pesticide Chemicals), respectively. The classification information is also noted in the producer location tables by means of Roman numerals following the chemical names. The tabulations by producer and location (Tables 12 and 15) group all of the critical chemicals involved at each manufacturer location. These lists do not necessarily define the site subject to exposure, because many dumps are remote from the plants; they do provide a starting point for such definition. Abandoned production of a chemical or abandoned facilities may present special problems. Therefore, the production facilities noted since 1968 but no longer active in 1978 are footnoted and are also extracted in separate tables (Tables 13 and 16). Some of these sites remain active in other production, and some may retain production capability and/or minor production of the subject chemical. Other plant sites may be totally deactivated or abandoned. The producer listed is the last known operator. Some of the company names of producers designate subsidiary or divisional names, with notation of the parent company. The underlined portion of the name indicates the short-form name used in other tables. Company addresses, from the SRI Directory and from the Thomas Register, are for the last known producer at a given location and are subject to the uncertainties introduced by acquisitions and name changes. 87 �TABLE 9. PRODUCERS OF CLASS I ORGANIC CHEMICALS Chemical Producer Location 4-Bromo-2,5-dichlorphenol Velsicol Beaumont, Tex. 2-Chloro-4-f1uorophenol 01 in Rochester, N. Y. Decabromophenoxybenzene Great Lakes Chem. El Dorado, Ark. 2,4-Dibr'omophenol Dow White Chem. Midland, Mich. Bayonne, N. J. 2,3-Dichlorophenol Specialty Organics Aldrich Diamond Shamrock Irwindale, Cal. Milwaukee, Wis. Neward, N. J.a 2,4-Dichlorophenol Dow Monsanto Rhodia Transvaal Midland, Mich. Sauget, 111. Freeport, Tex. Jacksonville, Ark. 2,5-Dichlorophenol Velsicol Beaumont, Tex. 2,6-Dichlorophenol Aldrich Specialty Organics Milwaukee, Wis. Irwindale, Cal. 3,4-Dichlorophenol Aldrich Milwaukee, Wis. Pentabromophenol Michigan Chem. R.S.A. White Chem. St. Louis, Mich.3 Ardsley, N. Y.a Bayonne, N. J. 2,4,6-Tribromophenol Dow Eastern Chem. Guardian Midland, Mich. Pequannock, N. J. Hauppauge, N. Y. Pequannock, N. J. St. Louis, Mich. Ardsley, N. Y.a Bayonne, N. J. Velsicol R.S.A. White Chem. No longer produced at this location. 88 �TABLE 10. PRODUCERS OF CLASS II ORGANIC CHEMICALS Chemical Producer Location Bromophenetole R.S.A. Ardsley, N. Y. o-Bromophenol Eastman Kodak R.S.A. Rochester, N. Y. Ardsley, N. Y. 2-Chloro-l,4-diethoxy5- nitrobenzene Fairmount Chem. GAF Pfister Newark, N. J. Rensselaer, N. Y. Newark, N. J.a 5-Chloro-2,4-dimethoxyaniline GAF Pfister Rensselaer, N. Y. Ridgefield, N. J. Newark, N. J. Chi orohydroqui none Eastman Kodak Eastern Chem. Guardian Rochester, N. Y. Pequannock, N. J. Hauppauge, N. Y. Pequannock, N. J. o-Chlorophenol Dow Monsanto Midland, Mich. Sauget, 111. 2-Chloro-4~phenyl phenol Dow Midland, Mich. 4-Chlororesorcinol Am. Color & Chem. GAF Lock Haven, Pa. Rensselaer, N. Y. 2,6-Dibromo-4-nitro-phenol Martin Marietta Maumee Sherwin Williams Sodyeco, N. C. St. Bernard, Ohio St. Bernard, Ohio 3,5-Dichlorosalicylic acid Aceto Inmont Corp. Carlstadt, N. J. Carlstadt, N. J.a 2,6-Di iodo-4-nitrophenol R.S.A. Ardsley, N. Y. 3,5-Diiodosal icy! ic acid Morton Chem. R.S.A. Ringwood, 111.3 Ardsley, N. Y. o-Fluoroanisole Olin Rochester, N. Y. o-F1uorophenol Olin Rochester, N. Y. Tetrabromobisphenol-A Dow Great Lakes Velsicol Midland, Mich. El Dorado, Ark. St. Louis, Mich. Tetrachlorobisphenol-A Dover Dover, Ohio3 No longer produced at this location. 89 �TABLE 11. PRODUCERS OF CLASS III ORGANIC CHEMICALS Chemical Producer Location 3-Amino-5-chloro-2hydroxybenzenesulfonic acid Allied Nyanza Toms River Chem. Buffalo, N. Y.a Ashland, Mass. Toms River, N. J. 2-Amino-4-chloro-6nitrophenol Nyanza Ashland, Mass. o-Anisidine Am. Color and Chem. Am. Aniline du Pont Monsanto Lock Haven, Pa. Lock Haven, Pa. Deepwater, N. J. St. Louis, Mo.a Benzaldehyde Crompton and Knowles Dow Fritzsche Kalama Chem. Monroe Chem. F. Ritter Stauffer UOP Velsicol Fair Lawn, N. J. Kalama, Wash. Clifton, N. J.a Kalama, Wash. Eddystone, Pa. Los Angeles, Cal. Edison, N. J. Nixon, N. J. Fords, N. J. Garfield, N. J. East Rutherford, N. J. a Chattanooga, Tenn. Bromobenzene Dow Velsicol Midland, Mich. a St. Louis, Mich. o-Bromof 1 uorobenzene 01 in Rochester, N. Y. o-Chlorof lurobenzene 01 in Rochester, N. Y. 3- Chi oro-4-f luoro- nitrobenzene 01 in Rochester, N. Y. 3- Chi oro-4-f luorophenol 01 in Rochester, N. Y. 4-Chloro-2-nitorphenol du Pont Maumee Sherwin Wi 1 1 iams Deepwater, N. J. St. Bernard, Ohio3 St. Bernard, Ohio Chi oropentaf 1 uorobenzene Whittaker San Diego, Cal .a 2, 4- Dibromof 1 uorobenzene 01 in Rochester, N. Y. Tenneco (continued) 90 �TABLE 11 (continued) Chemical Producer Location 3,4-Dichloroaniline Blue Spruce Bound Brook, N. J. Edison, N. J. Metuchen, N. J. Deepwater, N. J. Sodyeco, N. C.a Luling, La. Sauget, 111. Chem. Insecticide du Pont Martin Marietta Monsanto o-Dichlorobenzene Allied Chem. Products Dover Dow du Pont Hooker Monsanto Montrose Chem. Neville Chem. 01 in PPG Solvent Chem. Speciality Organics Standard Chlorine 3,4-Dichlorobenzaldehyde Syracuse, N. Y.a Cartersville, Ga. Dover, Ohio Midland, Mich. Deepwater, N. J.a Niagara Falls, N. Y. Sauget, 111. Henderson, Nev. Sante Fe Springs, Cal. Mclntosh, Ala. Natrium, W. Va. Niagara Falls. N. Y. Maiden, Mass. Irwindale, Cal. Delaware City, Del. Kearny, N. J. Tenneco Fords, N. J. 3,4-Dichlorobenzotrichloride Tenneco Fords, N. J. 3,4-Di chlorobenzotri f1uoride Tenneco Fords, N. J.a l,2-Dichloro-4-nitrobenzene Bound Brook, N. J. Edison, N. J. Metuchen, N. J. Sodyeco, N. C. Sauget, 111 Gulfport, Miss. Blue Spruce Chem. Insecticide Martin Marietta Monsanto Plastifax 3,4-Dichlorophenylisocyanate Mobay Chem. Ott Chem. New Martinsville Muskegon, Mich. 3,4-Di f1uoroani 1 i ne Rochester, N. Y. Olin (continued) 91 S. C. �TABLE 11 (continued) Chemical Producer Location o-Di f 1 uorobenzene 01 in Rochester, N. Y. l,2-Dihydroxybenzene-3,5disulfonic acid, di sodium salt Sterling Drug New York, N. Y.a 2,5-Dihydroxybenzenesulfonic Eastman Kodak acid Nease Chem. Rochester, N. Y.a State College, Pa. 2 ,5-Di hydroxybenzenesul f oni c Nease Chem. acid, potassium salt State College, Pa.a 2,4-Dinitrophenol Martin Marietta Mobay Sodyeco, N. C. Bushy Park, S. C. 2,4-Dinitrophenoxyethanol Hummel Chem. Neward, N. J.a South Plainfield, N. J. 3,5-Dinitrosal icyl ic acid Eastman Kodak Hummel Chem. Rochester, N. Y. Newark, N. J. South Plainfield, N. J. Charles City, Iowa Salsbury Labs Alberta Gas Hooker , Monsanto Petro-Tex Pfizer Reichhold Stepan Chem. Tenneco U. S. Steel Buffalo, N. Y.a Moundsville, W. Va. Duluth, Minn. Arecibo, P. R. St. Louis, Mo. Houston, Tex. Terre Haute, Ind. Morris, 111. Fieldsboro, N. J. Garfield, N. J. Neville Island, Pa. Hexabromobenzene Velsicol Dover St. Louis, Mich. Dover, Ohio3 Hexachlorobenzene Hummel Chem. Neward, N. J. South Plainfield, N. J. Louisville, Ky.a Fuman'c acid Allied Stauffer (continued) 92 �TABLE 11 (continued) Chemical Producer Location Hexaf1uorobenzene PCR Whittaker Gainesville, Fla. San Diego, Cal. Louisville, Ky. Maleic acid Allied Buffalo, N. Y.a Marcus Hook, Pa. Moundsville, W. Va.' Rochester, N. Y. Waukegan, 111. Eastman Kodak Pfanstiehl Labs Maleic anhydride Allied Amoco Asland Chevron Koppers Petro-Tex Monsanto Reichhold Standard Oil of Ind. (see Amoco above) Tenneco U.S. Steel Moundsville, W. Va.' Joilet, 111. Neal, W. Va. Richmond, Cal. Bridgeville, Pa. Cicero, 111. Houston, Tex.a St. Louis, Mo. Elizabeth, N. J. Morris, 111. Fords, N. J. Neville Island, Pa. o-Nitroanisole du Pont Monsanto Deepwater, N. J. Sauget, 111. St. Louis, Mo. 2-Nitro-p-cresol Sherwin Williams du Pont Chicago, 111. Deepwater, N. J. o-Nitrophenol Monsanto du Pont Sauget, 111. Deepwater, N. J. Pentabromochlorocyclohexane Dow Midland, Mich. Pentabromoethylebenzene Hexcel Sayreville, N. J. Pentabromotoluene White Chem. Bayonne, N. J. (continued) 93 �TABLE 11 (continued) Chemical Producer Location Pentachl oroani 1 i ne 01 in Rochester, N. Y. Pentaf luoroani 1 ine Whittaker San Diego, Cal . o-Phenetidine Am. Aniline Monsanto Lock Haven, Pa. St. Louis, Mo.a Phenol (from chlorobenzene) Dow Hooker Midland, Mich.3 Union Carbide Marietta, Ohio l-Phenol-2-sulfonic acid, formaldehyde condensate Allied Diamond Shamrock Rohm and Haas Buffalo, N. Y. a Cedartown, Ga. Philadelphia, Pa. Phenyl ether Dow Fritzsche Monsanto Midland, Mich. Clifton, N. J.3 Chocolate Bayou, Tex. Phthalic anhydride Allied Buffalo, N. Y.a Chicago, 111. North Tonawanda,aN. Y. South Shore, Ky. El Segundo, Cal. BASF Wyandotte Chevron Commonwealth Oil Conoco Exxon W. R. Grace Hooker Koppers Monsanto Reichhold Frankford, Pa. a Ironton, Ohio Kearny, N. J. Perth Amboy, N. J.a Richmond, Cal. Penuelas, P. R. a Hebronville, Mass. Baton Rouge, La. Fords, N. J. Arecibo, P. R. Bridgeville, Pa. Chicago, 111.9 Cicero, 111. Bridgeport, N. J. Chocolate Bayou, Tex. St. Louis, Mo. Texas City, Tex. Azusa, Cal. Elizabeth, N. J. Morris, Ill.a Sherwin Wil 1 iams (continued) Chicago, 111.3 �TABLE 11 (continued) Chemical Producer Phthalic anhydride (continued) Stand. Oil Co. Cal (see Chevron) Stepan Chem. Union Carbide U.S. Steel Witco Chem. Location Elwood, 111. Millsdale, 111 Institute, W. Va. South Charleston, S. C.' Neville Island, Pa. Chicago, 111. Perth Amboy, N. J. Picric acid Allied du Pont Hummel Chem. Martin Marietta Buffalo, N. Ya Deepwater, N. J. South Plainfield, N. J.' Sodyeco, N. C. Sodium pi crate Hummel Chem. Martin Marietta Northrop South Plainfield, N. J. Sodyeco, N. C. Asheville, N. C. Tetrabromophthal ic anhydride Velsicol St. Louis, Mich. 1,2,4,5-Tetrachlorobenzene Dover Dow Hooker Solvent Chem. Standard Chlorine Dover, Ohio Midland, Mich. Niagara Falls. N. Y.' Maiden, Mass. Delaware City, Del. Tetrachlorophthali c anhydride Hooker Monsanto Niagara Falls, N. Y. Bridgeport, N. J. Tetrafluoro-m-phenylenediamine Whittaker San Diego, Cal.a Tri bromobenzene Velsicol Northrop St. Louis, Mich. Asheville, N. C. 1,2,4-Trichlorobenzene Chris Craft Dover Dow Hooker Neville Chem. Sobin Chems. Solvent Chem. Standard Chlorine Newark, N. J.a Dover, Ohioa Midland, Mich. Niagara Falls, N. Y. Sante Fe Springs, Cal.' Neward, N. J. Maiden, Mass. Delaware City. Del. Kearny, N. J. Chester, S. C. Sun Chem. (continued) 95 �TABLE 11 (continued) Chemical Producer Location 2,4, 6-Tri ni troresorc i nol Northrop Asheville, N. C. East Alton, 111. 01 in . No longer produced at this location. Possibly two plants. 96 �TABLE 12. ALPHABETICAL LIST OF ORGANIC CHEMICAL PRODUCERS Producer Location Chemical (class) Aceto Chem. Co., Inc. 126-02 Northern Blvd. Flushing, N. Y. 11368 Arsynco, Inc. Subsid. Carlstadt, N. J. 3,5-Dichlorosalicylic acid (II) Alberta Gas Chems. Inc. Address not available Duluth, Minn. Fumaric acid (III) Aldrich Chem. Co., Inc. 940 West St. Paul Ave. Milwaukee, Wis. 53233 Milwaukee, Wis. 2,4-Dichlorophenol (I) 2,6-Dichlorophenol (I) 3,4-Dichlorophenol (I) Allied Chem. Corp. Buffalo, N. Y. Columbian Rd. and Park Ave. Morristown, N. J. 07960 Chicago, 111. El Segundo, Cal. Frankford, Pa. Ironton, Ohio Marcus Hook, Pa. Moundsville, W. Va. Syracuse, N. Y. 3-Amino-5-chloro-2hydroxybenzenesulfom'c acid Fumaric acid (III) Maleic acid (III) l-Phenol-2-sulfonic acid, formaldehyde condensate (III)C Phthalic anhydride (III) Picric acid (III) Phthalic anhydride (III) Phthalic anhdyride (III) Phthalic anhydride (HI), Phthalic anhydride (III) Maleic acid (III) Fumaric acid (III) Maleic acid (III) Maleic anhydride (III) o-Dichlorobenzene (III) American Aniline Lock Haven, Pa. Products, Inc. 25 McLean Blvd. P.O. Box 3063 Paterson, N. J. 07509 Owned by Pepi , Inc. 52% and Kopper Co., Inc. , 48% o-Anisidine (III)a American Color and Chem. Corp. 11400 Westinghouse Blvd. P.O. Box 1688 Charlotte, N. C. 28201 o-Anisidine (III) 4-Chlororesorcinol (ID Lock Haven, Pa. (continued) 97 �TABLE 12 (Continued) Producer Location Chemical (class) Amoco Chems. Corp. 200 E. Randolph Dr. Chicago, 111. 60601 Affiliate of Standard Oil Co., Ind. Joilet, 111. Maleic anhydride (III) Arsynco See Aceto Ashland Oil , Inc. 1409 Winchester Ave. P.O. Box 391 Ashland, Ky. 41101 Neal, W. Va. Maleic anhdyride (III) BASF Wyandotte Corp. 100 Cherry H i l l Road Parisppany, N. J. 07054 Kearny, N. J. Phthalic anhydride (III) Blue Spruce Co. 1390 Valley Road Stirling, N. J. 07980 Bound Brook, N. J. 3,4-Dichloroaniline (III) l,2-Dichloro-4-nitrobenzene (III) 3,4-Dichloroaniline (III)3 l,2-Dichloro-4-nitrophenol (III)a Edison, N. J. Chemical Insecticide Corp. 30 Whitman Ave. Metuchen, N. J. 08840 No current address Metuchen, N. J. 3,4-Dichloroaniline (III)C l,2-Dichloro-4-nitrobenzene (III) Chemical Products Corp. 48 Atlanta Road Cartersville, Ga. 30120 Cartersville, Ga. o-Dichlorobenzene (III) Chevron Chem. Co. 575 Market Street San Francisco, Cal. 94105 Subsid. Standa'rd Oil Co. of Cal. Richmond, Cal. Perth Amboy, N. J. Maleic anhydride (III) Phthalic anhydride (III) Phthalic anhydride (III) Chris 600 New See Newark, N. J. 1,2,4-Trichlorobenzene (III)C Craft Industry, Inc. Madison Avenue York, N. Y. Montrose Chem. (continued) 98 �TABLE 12 (Continued) Producer Location Chemical (class) Commonwealth Oil Refining Co., Inc. 245 Park Avenue New York, N. Y. 10017 Penuelas, P. R. Phthalic anhydride (III) Continental Oil Co. Hebronville, Mass. (Conoco) Petrochemicals Dept. Saddle Brook, N. J. 07662 Phthalic anhydride (III)C Crompton and Knowles Corp. 345 Park Ave. New York, N. Y. 10022 Fair Lawn, N. J. Benzaldehyde (III) Diamond Shamrock Corp. 1100 Superior Ave. Cleveland, Ohio 44114 Cedartown, Ga. l-Phenol-2-sul fom'c acid, formaldehyde condensate (III)C 2,4-Dichlorophenol (I)3 Dover Chem. Corp. West 15th Street Dover, Ohio 44622 Affiliate of ICC Industries, Inc. Dover, Ohio o-Dichlorobenzene (III) Hexachlorobenzene (III) 1,2,4,5-Tetrachlorobenzene (III)3 Tetrachlorobisphenol-A (II) 1,2,4-Trichlorobenzene (III) Dow Chem. U.S.A. 2020 Dow Center Midland, Mich. Kalama, Wash. Midland, Mich. Benzaldehyde (III)3 o-Chlorophenol (II) 2-Chloro-4-phenylphenol (II) 2,4-Dibromophenol (I) o-Dichlorobenzene (III) 2,4-Dichlorophenol (I) Pentabromochlorocyclohexane Phenol (III) Phenyl either (III) Tetrabromobisphenol-A (II) 1,2,4,5-Tetrachlorobenzene (III) g 2,4,6-Tribromophenol (I) 1,2,4-Trichlorobenzene (III) Newark, N. J. (continued) 99 �TABLE 12 (Continued) Producer Location Chemical (class) E.I. du Pont de Nemours and Co. , Inc. 1007 Market Street Wilmington, Del. 19898 Deepwater, N. J. o-Anisidine (III) 4-Chloro-2-nitrophenol 3,4-Dichloroaniline (III) o-Dichlorobenzene (III) 2-Nitro-p-cresol (III) o-Nitrophenol (III)8 o-Nitroanisole (III) Eastern Chem. Corp. Now Eastern Chem. D i v . of Guardian Chem. Corp. Pequannock, N. J. Chlorohydroquinone (II) a 2,4,6-Tribromophenol (I) Eastman Kodak Co. 343 State Street Rochester, N. Y. 14650 Rochester, N. Y. o-Bromophenol (II) Chlorohydroquinone (II) 2,5-Di hydroxybenzenesulfonic acid (III) 2,5-Dinitrosalicylic acid (III) Maleic acid (III) Exxon Corp. 1251 Ave. of the Americas New York, N. Y. 10020 Baton Rouge, La. Phthalic anhydride (III) Fairmount Chem. Co., Inc. 117 Blanchard Street Newark, N. J. 07105 Newark, N. J. 2-Chloro-l,4-diethoxy-5nitrobenzene (II) Fritzsche Dodge and Olcott, Inc. 76 Ninth Ave. New York, N. Y. 10011 Clifton, N. J. Benzaldehyde (III)! Phenyl ether (III)C GAF Corp. 140 West 51st St. New York, N. Y. 10020 Rensselaer, N. Y. 2-Chloro-l,4-diethoxy-5nitrobenzene (II) 5-Chloro-2,4-dimethoxyaniline (II) 4-Chlororesorcinol (II) W. R. Grace and Co. 7 Hanover Square New York, N. Y. 10005 Fords, N. J. Phthalic anhydride (III)' (continued) 100 �TABLE 12 (Continued) Producer Location Chemical (class) El Dorado, Ark. Great Lakes Chem. Corp. Hwy. 52, Northwest West Lafayette, Ind. 47906 Decabromophenoxybenzene (I) Tetrabromobisphenol-A (II) Guardian Chem. Corp. 230 Marcus Blvd. Hauppauge, N. Y. 11787 Hauppauge, N. Y. Chlorohydroquinone (II) 2,4,6-Tribromophenol (J) Hexcel Corp. 11711 Dublin Blvd. Dublin, Cal. 94566 Sayreville, N. J. Pentabromoethylbenzene (III) Hooker Chem. Corp. 1900 St. James PI. Houston, Tex. 77027 Subsid. Occidental Petroleum Corp. Arecibo, P. R. Furmaric acid (III) Phthalic anhydride (III) o-Dichlorobenzene (III) Tetrachlorophthalic anhydride (III)a 1,2,4,5-Tetrachlorobenzene (III) 1,2,4-Trichlorob ;nzene (III) Phenol (III) ' ° Phenol (III) ' Niagara Falls, N. Y. North Tonawanda, N. Y. South Shore, Ky. Hummel Chem. Co. , Inc. P.O. Box 250 South Plainfield, N. J. 07080 Newark, N. J. South Plainfield, N. J. 2,4-Dinitrophenoxyethano1 (III)a 3,5-Dinitrosalicylic acid (III) Hexachlorobenzene (III) Picric acid (III)a 2,4-Di ni trophenoxyethanol (III) 3,5-Di nitrosalicylic acid (III)a Hexachlorobenzene (III) Picric acid (lll)a Sodium picrate (III) ICC Industries See Solvent Chem. Inmont Corp. Carlstadt, N. J. 1133 Ave. of the Americas New York, N. Y. 10036 NOTE: Carlstadt Plant (Subsid. of Carrier Corp.) listed under Interchemical Corp. which was acquired by Inmont Corp. (continued) 101 3,5-Dichlorosalicylic acid (III)a �TABLE 12 (Continued) Producer Location Chemical (class) International Minerals and Chem. Corp. IMC Plaza Libertyville, 1 1 1 . 60048 Newark, N. J. 1,2,4-Trichlorobenzene (III) Kalama Chem., Inc. The Bank of Cal. Center Suite 1110 Kalama, Wash. 98164 Kalama, Wash. Benzaldehyde (III) Kopper Co., Inc. Koppers Bldg. Pittsburgh, Pa. 15219 Bridgeville, Pa. Maleic anhydride (III) Phthalic anhydride (III) Phthalic anhydride (III)3 Maleic anhydride (III) Phthalic anhdyride (III) Martin Marietta Corp. 6801 Rockledge Dr. Bethesda, Md. 20034 Sodyeco, N. C. 2,6-Dibromo-4-nitrophenol (II)3 3,4-Dichloroaniline (III)a l,2-Dichloro-4- nitrobenzene (III)a 2,4-Dinitrophenol (III) Picric acid (III) Sodium picrate (III) Maumee Chem. Co. Presumed to be acquired by Sherwin Williams Address not available St. Bernard, Ohio 2 ,6-Oebrorao-4-nitropheno1 4-Chloro-2-nitrophenol Mobay Chem. Co. Penn Lincoln Parkway West Pittsburgh, Pa. 15205 New Martinsvilie, W. Va 3,4-Dichlorophenylisocyanate (III) 2,4-Dinitrophenol (III) Monroe Chem. Co. Saville Ave. at 4th St. Eddystone, Pa. Subsid. of Kalama Chem. , Inc. (see Kalama) Eddystone, Pa. Benzaldehyde (III) Monsanto Co. Bridgeport, N. J. Phthalic anhydride (III) Tetrachlorophthalic anhydride (III) Phenyl ether (III) Phthalic anhydride (III) 3,4-Dichloroaniline (III) 800 North Lindbergh Blvd. St. Louis, Mo. 63166 Chicago, 111. Cicero, 111. Chocolate Bayou, Tex. Luling, La. (conti nued) 102 �TABLE 12 (Continued) Producer Location Chemical (class) Monsanto (continued) Sauget, 111. Texas City, Tex. o-Chlorophenol (II) 3,4-Dichloroaniline (III)a o-Oichlorobenzene (III) l,2-Dichlor-4-nitrobenzene (III)C 2,4-Dichlorophenol (I) o-Nitroanisole (III)a o-Nitrophenol (III) o-Anisidine (III) Fumaric acid (III) Maleic anhydride (III) o-Nitroanisole (HI) o-Phenetidine (III) Phthalic anhydride (III)a Phthalic anhydride (III) Montrose Chem. Corp. of Cal. 2401 Morris Ave. P.O. Box E Union, N. J. 07083 (Jointly owned by Chris Craft Industries, Inc. and Stauffer Chem. Co.) Henderson, Nev. o-Dichlorobenzene (III) Morton Chem. Co., Div. Morton-Norwich Products, Inc. 110 North Wacker Dr. Chicago, 111. 60606 Ringwood, 111. 3,5-Diiodosalicylic acid (II)1 Nease Chem. Co., Inc. P.O. Box 221 State College, Pa. 16801 State College, Pa. 2,5-Di hydroxybenzenesulfonic acid (III)3 2,5-Dihydroxybenzenesulfonic acid, potassium salt (III) Neville Chem. Co. Neville Island Pittsburgh, Pa. Sante Fe Springs, Cal. o-Dichlorobenzene (III)a 1,2,4-Trichlorobenzene (III)C St. Louis, Mo. 15225 Northrop Corp. 1800 Centruy Park, East Los Angeles, Cal. 90067 Asheville, N. C. (continued) 103 Sodium picrate (III) Tribromobenzene (III) 2,4,6-Trinitroresorcinol (III) �TABLE 12 (Continued) Producer Location Chemical (class) Ashland, Mass 3-Amino-5-ch1oro-2hydroxybenzenesulfonic acid (III) 2-Amino-4-chloro-6nitrophenol (III) East Alton, 111. Mclntosh, Ala. Rochester, N. Y. 2,4,6-Trinitroresorcinol (III) o-Dichlorobenzene (III)3 o-Bromofluorobenzene (III) o-Chlorofluorobenzene (III) 3-Chloro-4-fluoronitrobenzene (III) 2-Chloro-4-fluorophenol (I) 3-Ghloro-4-fluorophenol (III) 2,4-Dibromofluorobenzene (III) 3,4-Difluoroaniline (III) o-Difluorobenzene (III) o-Fluoroanisole (II) Pentachloroaniline (III) Gainesville, Fla. Hexafluorobenzene (III) Houston, Tex. Fumaric acid (III) Maleic anhydride (III)C Northwest Industries (See Velsicol) G 300 Sears Tower Chicago, in. 60606 Nyanza, Inc. 200 Sutton St. North Andover, Mass. 01721 Occidental Petroleum Corp. (See Hooker) 10889 Wilshire Blvd. , Suite 1500 Los Angeles, Cal. 90024 01 in Corp. 120 Long Ridge Road Stamford, Conn. 06904 Ott Chem. Co. See Story Chem. PCR, Inc. P.O. Box 1466 Gainesville, Fla. 32602 Petro-Tex Chem. Corp. 8600 Park Place Houston, Tex. 77017 Jointly owned by FMC Corp. and Tenneco, Inc. (continued) 104 �TABLE 12 (Continued) Producer Location Chemical (class) Pfister Chem., Inc. Linden Avenue Ridgefield, N. J. 07657 Newark, N. J. 2-Chloro-l,4-diethoxy-5nitrobenzene (II)a 5-Chloro-2,4-dimethoxyaniline (II) 5-Chloro-2,4-dimethoxyaniline (II) Ridgefield, N. J. Pfizer, Inc. 235 East 42nd St. New York, N. Y. 10017 Terre Haute, Ind. Fumaric acid (III) Plastifax, Inc. Indust. Seaway Blvd. P.O. Box 1056 Gulfport, Miss. 39501 Gulf Port, Miss. l,2-Dichloro-4nitrobenzene (III) PPG Industries, Inc. One Gateway Center Pittsburgh, Pa. 15222 Natrium, W. Va. o-Dichlorobenzene (III) Azusa, Cal. Reichhold Chems., Inc. Elizabeth, N. J. RCI Bldg. White Plains, N. Y. 10603 Morris, 111. Phthalic anhydride (III) Maleic anhydride (III) Phthalic anhydride (III) Fumaric acid (III) Maleic anhydride (III) Phthalic anhydride (III) Rhodia, Inc. 600 Madison Ave. New York, N. Y. 10022 Freeport, Tex. 2,4-Dichlorophenol (I) F. Ritter and Co. 4001 Goodwin Ave. Los Angeles, Cal. Los Angeles, Cal. Benzaldehyde (III)C Rohm and Haas Co. Independence Mall West Philadephia, Pa. 19105 Philadelphia, Pa. 1-Phenol-2-sulfonic acid, formaldehyde condensate (III) R.S.A. Corp. 690 Saw Mill River Road Ardsley, N. Y. 10502 Ardsley, N. Y. Bromophenetole (II) o-Bromophenol (II) 2,6-Di iodo-4-nitrophenol ( ) Ha 3,5-Oiiodosalicylic |cid (II) Pentabromophenol (I) 2,4,6-Tribromophenol (I) 90039 (continued) 105 �TABLE 12 (Continued) Producer Location Chemical (class) Salsbury Labs 2000 Rockford Road Charles City, Iowa 50616 Charles City, Iowa 3,5-Dinitrosalicyclic acid (III) Sherwin Williams Co. 101 Prospect Ave. Cleveland, Ohio 44101 Chicago, 111. 2-Nitro-p-cresol (III) a Phthalic anhydride (III) 2,6-Dibromo-4-nitrophenol 4-Chloro-2-nitrophenol (III) St. Bernard, Ohio Sobin Chems. Inc. See International . Minerals and Chems. Corp. Solvent Chem. Co., Inc. Maiden, Mass. 720 Fifth Avenue New York, N. Y. 10011 Affiliate if ICC Industries Niagara Falls, N. Y. o-Dichlorobenzene (III) 1,2,4,5-Tetracnlorobenzene (III)a 1,2,4-Trichlorobenzene (III)a o-Dichlorobenzene (III) Specialty Organics, Inc. 5263 North Fourth St. Irwindale, Cal. 91706 Irwindale, Cal. 2,3-Dichlorophenol (I) 2,6-Dichlorophenol (I) o-Dichlorobenzene (III) Standard Chlorine Chem. Co. , Inc. 1035 Belleville Turnpike Kearny, N. J. 07032 Delaware City, Del. o-Dichlorobenzene (III) 1,2,4,5-Tetrachlorobenzene (III) Kearny, N. J. Standard Oil Co.(Cal.) (See Chevron) 575 Market St. San Francisco, Cal. 94105 Standard Oil Co. (Ind.) (See Amoco) 910 South Michigan Ave. Chicago, 111. 60605 Standard Oil Co. (N.J.) (See Exxon) (continued) 106 1,2,4-Trichlorobenzene (III) o-Dichlorobenzene (III) 1,2,4-Trichlorobenzene (III)C �TABLE 12 (Continued) Producer Location Chemical (class) Stauffer Chem. Co. Westport, Conn. 06880 Edison, N. J. Nixon, N. 0. Louisville, Ky. Benzaldehyde (III) Banzaidehyde (III)a Hexachlorobenzene (III) Stepan Chem. Co. Edens and Winnetka Rd. Northfield, 111. 60093 Elwood, 111. Fieldsboro, N. J. Millsdale, 111. Phthalic anhydride a(III) Fumaric acid (III) Phthalic anhydride (III) Stering Drug Inc. 90 Park Avenue New York, N. Y. 10016 New York, N. Y. l,2-Dihydroxy-3,5-disulfonic acid, disodium salt (III)a Story Chem. 500 Agard Muskegon, Ott Chem. Muskegan, Mich. 3,4-Dichlorophenylisocyanate (III) Chester, S. C. 1,2,4-Trichlorobenzene (III)C Corp. Road Mich. 49445 Co., Div. Sun Chem. Corp. Box 70 Chester, S. C. 29706 Tenneco Chems. Co. Fords, N. J. Park 80 Plaza, West Saddle Brook, N. J. 07662 (Part of Tenneco, Inc.) Garfield, N. J. Benzaldehyde (III) 3,4-Dichlorobenzaldehyde (III) 3,4-Dichlorobenzotrichloride (III) 3,4-Dichlorobenzotrifluoride (III) Maleic anhydride (III) Fumaric acid (III) Benzaldehyde (III) f\ 3-Amino-5-chloro-2hydroxybenzenesulfonic acid (III) Toms River Chem. Corp. P.O. Box 71 Toms River, N. J. 08753 (80% Ciba-Geigy and 20% Sandoz AG) Toms River, N. J. Transvaal, Inc. Marshall Road P.O. Box 69 Jacksonville, Ark. 72076 (Subsid. of Vertac) Jacksonville, Ark. 2,4-Dichlorophenol (I) Union Carbide Corp. 270 Park Avenue New York, N. Y. 10017 Marietta, Ohio Phenol (III)a,b (continued) 107 �TABLE 12 (Continued) Producer Location Chemical (class) UOP, Inc. Ten UOP Plaza Algonquin and Mt. Prospect Roads Des Plaines, 111. East Rutherford, N. J. Benzaldehyde (III) U.S. Steel Corp. Sixth and Grant Pittsburgh, Pa. 15230 Neville Island, Pa. Fumaric acid (III) Maleic anhydride (III) Phthalic anhydride (III) Velsicol Chem. Corp. 341 East Ohio St. Chicago, 111. 60611 (Subsid. of Northwest Industries, Inc.) Beaumont, Tex. 4-Bromo-2,5-dichlorphenol (I) 2,5-Dichlorophenol (I) Benzaldehyde (III) Hexabromobenzene (III) Pentabromophenol (I) Tetrabromobisphenol-A (II) Tetrabromophthalic anhydride (III) Tribromobenzene (III) 2,4,6-Tribromophenol (I) 60016 Chattanooga, Tenn. St. Louis, Mich. Vertac, Inc. (See Transvaal) 2414 Clark Tower Memphis, Tenn. 38137 White Chem. Corp. P.O. Box 278 Bayonne, N. J. 07002 Bayonne, N. J. 2,4-Dibromophenol (I) Pentabromophenol (I) Pentabromotoluene (III) 2,4,6-Tribromophenol (I) Whittaker Corp. 10880 Wilshire Blvd. Los Angeles, Cal. 90024 San Diego, Cal. Hexafluorobenzene (III) C Pentafluoroani1ine (III) Chloropentafluorobenzene (III) Tetraf1uoro-m-phenylenediamine (III)a Witco Chem. Corp. 277 Park Avenue New York, N. Y. Chicago, 111. Perth Amboy, N. Phthalic anhydride (III)! Phthalic anhydride (III)e 10017 No longer produced at this location. From chlorobenzene. 108 �TABLE 13. FORMER LOCATIONS OF ORGANIC CHEMICAL PRODUCTION Producer Location Chemical (class) Aldrich Milwaukee, Wise. 2,4-Dichlorophenol (I) Allied Buffalo, N. Y. Syracuse, N. Y. 3-Amino-5-chloro-2-hydroxybenzenesulfonic acid (III) Fumaric acid (III) Maleic acid (III) l-Phenol-2-sulfonic acid, formaldehyde condensate (III) Phthalic anhydride (III) Phthalic anhydride (III) Phthalic anhydride (III) Phthalic anhydride (III) Fumaric acid (III) Maleic acid (III) Maleic anhydride (III) o-Dichlorobenzene (III) Am. Aniline Lock Haven, Pa. o-Am'si dine (III) Blue Spruce Edison, N. J. 3,4-Dichloroarn line (III) l,2-Dichloro-4-nitrobenzene (III) Chem. Insecticide Metuchen, N. J. 3,4-Di'chloroaniline (III) l,2~Dichloro-4-nitrobenzene (III) Chem. Products Cartersville, Ga. o-Dichlorobenzene (III) Chevron Richmond, Cal. Perth Ambay,.N. J. Maleic anhydride (III) Phthalic anhydride (III) Chris Craft Newark, N. J. 1,2,4-Trichlorobenzene (III) Commonwealth Oil Penuelas, P. R. Phthalic anhydride (III) Conoco Hebronville, Mass. Phthalic anhydride (III) Dover Dover, Ohio o-Dichlorobenzene (III) Hexachlorobenzene (III) 1,2,4,5-Tetrachlorobenzene (III) Tetrachlorobisphenol-A (II) 1,2,4-Trichlorobenzene (III) Diamond Shamrock Cedartown, Ga. l-Phenol-2-sulfom'c acid, formaldehyde condensate Chicago, 111. Frankford, Pa. Ironton, Ohio Moundsvi1le, W. Va. Dow Phenol 3 (III) 2,4,6-Tribromophenol Midland, Mich. (continued) 109 (I) (III) �TABLE 13 (Continued) Producer Location Chemical (class) Dow (continued) Kalama, Wash. Benzaldehyde (III) du Pont Deepwater, N. J. 4-Chloro-2-nitrophenol (III) o-Dichlorobenzene (III) 2-Nitro-p-cresol (III) o-Nitrophenol (III) Eastern Chem. (currently Eastern Chem, Div. of Guardian) Pequannock, N. J. Chlorohydroquinone (II) 2,4,6-Tribromophenol (I) Eastman Kodak Rochester, N. Y. 2,5-Dihydroxybenzenesulfonic acid (III) Maleic acid (III) Fri tzsche Clifton, N. J. Benzaldehyde Phenyl ether W. R. Grace Fords, N. J. Phthalic anhydride Guardian Hauppauge, N. Y. Pequannock, N. J. Chlorohydroquinone (II) Chlorohydroquinone (II) 2,4,6-Tribromophenol (I) Hooker Niagara Falls, N. Y. o-Dichlorobenzene (III) Tetrachlorophthalic anhydride (III) 1,2,4,5-Tetrachlorobenzene (III) 1,2,4-Trichlorobenzene (III) Phenol3 (III) Phenol3 (III) North Tonawanda, N. Y. South Shore, Ky. Hummel Chem. Newark, N. J. South Plainfield, N. J. Inmont (formerly Interchemical Corp. ) Carlstadt, N. J. (continued) no (III) (III) (III) 2,4-Dinitrophenoxyethanol (III) 3,5-Dinitrosalicylic acid (III) Hexachlorobenzene (III) Picric acid (III) 3,5-Dinitrosalicylic acid (III) Hexachlorobenzene (III) Picric acid (III) 3,5-Dichlorosalicylic acid (III) �TABLE 13 (Continued) Producer Location Chemical (class) Koppers Chicago, 111. Cicero, 111. Phthalic anhydride (III) Maleic anhydride (III) Martin Marietta Sodyeco, N. C. 2,6-Dibromo-4-nitrophenol (II) 3,4-Dichloroaniline (III) l,2-Dichloro-4-nitrobenzene (III) Sodium picrate (III) Monsanto Chocolate Bayou, Tex. Saugett, 111. Phthalic anhydride (III) 3,4-Dichloroaniline (III) l,2-Dichloro-4-nitrobenzene (III) o-Nitroam'sole (III) o-Anisidine (III) o-Phenetidine (III) Phthalic anhydride (III) St. Louis, Mo. Morton Chem. Ringwood, 111, 3,5-Diiodosalicylic acid (II) Nease Chem. State College, Pa. 2,5-Di hydroxybenzenesulfoni c acid (III) 2,5-Dihydroxybenzenesulfonic acid and potassium salt (III) Neville Chem, Santa Fe Springs, Cal. o-Dichlorobenzene (III) 1,2,4-Trichlorobenzene (III) 01 in East Alton, 111. Mclntosh, Ala. 2,4,6-Trinitroresorcinol (III) o-Dichlorobenzene (III) Petro-Tex Houston, Tex. Fumaric acid (III) Maleic anhydride (III) Pfister Newark, N. J. 2-Chloro-l,4-diethoxy-5nitrobenzene (II) 5-Chloro-2,4-diroethoxyani1ine Reichhold F. Ritter Azusa, Cal. Elizabeth, N. J. Morris, 111. Los Angeles, Cal. (continued) 111 Phthalic anhydride Phthalic anhydride Fumaric acid (III) Phthalic anhydride Benzaldehyde (III) (III) (III) (III) (II) �TABLE 13 (Continued) Producer Location Chemicals (class) R.S.A. Ardsley, N. Y. 3,5-Diiodosalicyclic acid (II) Pentabrompphenol (I) 2,4,6-Tribromophenol (I) Sherwin Williams St. Bernard, Ohio 2,6-Dibromo-4-nitrophenol (II) 4-Chloro-2-nitrophenol (III) Phthalic anhydride (III) Sobin Chems. (currently International Minerals and Chems. Corp.) Newark, N. J. 1,2,4-Trichlorobenzene (III) Solvent Chem. Maiden, Mass. o-Dichlorobenzene (III) 1,2,4,5-Tetrachlorobenzene (III) 1,2,4-Trichlorobenzene (III) Standard Chlorine Kearny, N. J. 1,2,4-Trichlorobenzene (III) Stauffer Edison, N. J. Louisville, Ky. Nixon, N. J. Benzaldehyde (III) Hexachlorobenzene (III) Benzaldehyde (III) Stepan Chem. Fieldsboro, N. J. Millsdale, 111. Fumaric acid (III) Phthalic anhydride (III) Sterling Drug New York, N. Y. l,2-Dihydroxy-3,5-disulfonic acid, disodium salt (III) Story Chem. Muskegon, Mich. 3,4-Dichlorophenylisocyanate (III) Sun Chem. Chester, S. C. 1,2,4-Trichlorobenzene (III) Tenneco Fords, N. J. 3,4-Dichlorobenzotrifluoride (III) Union Carbide Marietta, Ohio Phenol3 (III) Velsicol Chattanooga, Tenn. St. Louis, Mich. Benzaldehyde (III) Hexabrompbenzene (III) Pentabrpmophenol (I) Tribromobenzene (III) 2,4,6-Tribromophenol (I) (continued) 112 �TABLE 13 (Continued) Producer Location Chemicals (class) Whittaker San Diego, Cal. Hexaf luorobenzene (III) Pentafluoroaniline (III) Chloropentaf luorobenzene (III) Tetraf luoro-m-phenylenediamine (III) Witco Chicago, 111. Perth Amboy, N. J. Phthalic anhydride (III) Phthalic anhydride (III) From chlorobenzene. 113 �TABLE 14. PRODUCERS OF PESTICIDE CHEMICALS, CLASSES I AND II Chemical Producer Location Bifenox Mobil Mt. Pleasant, Tenn. Chloranil Arapahoe Uniroyal Boulder, Colo.3 Naugatuck, Conn. 2,4-D and esters and salts Amchem Ambler, Pa. Fremont, Cal. St. Joseph, Mo. Metuchen, N. J. Class I Chemical Insecticide Corp. Chempar Diamond Shamrock Dow Fallek-Lankro Guth Chem. Imperial Miller Chem. Monsanto PBI-Gordon Rhodia Riverdale Thompson Chem. Thompson-Hayward Transvaal Woodbury Portland, Ore.3 Newark, N. J.a Midland, Mich. Tuscaloosa, Ala. Hillside, 111.3 Shenandoah, Iowa Whiteford, Md.a Sauget, 111.3 Kansas City, Kans. N. Kansas City, Mo.' Portland, Ore. St. Joseph, Mo. St. Paul, Minn. Chicago Hgts., 111St. Louis, Mo. Kansas City, Kans. Jacksonville, Ark. Orlando, Fla. 2,4-DB and salts Amchem Rhodia Ambler, Pa. N. Kansas City, Mo.' Portland, Ore. St. Joseph, Mo. St. Paul, Minn. Dicamba Velsicol Beaumont, Tex. Chattanooga, Tenn. Dicapthon American Cyanamid Warners, N. J.a Dichlofenthion Mobile Charleston, S. C.a Mt. Pleasant, Tenn. (continued) 114 �TABLE 14 (continued) Chemical Producer Location Dimethyl amine salt of dicamba PBI-Gordon Kansas City, Kans. Disul Sodium (Sesone) Amchem Ambler, Pa. Fremont, Cal. Linden, N. J. St. Joseph, Mo. Linden, N. J.a Institue and S. Charleston, W. Va. GAP Union Carbide 2,4-DP Rhodia Transvaal Portland, Ore. Jacksonville, Ark. Erbon Dow Midland, Mich.3 Hexachlorophene Givaudan Clifton, N. J. Isobac 20 Givaudan Clifton, N. J. Nitrofen Rohm and Haas Philadelphia, Pa. Pentachlorophenol (PCP) and salts Dow Merck Monsanto Sonford Chemical Vulcan Matls. Midland, Mich. Hawthorne, N. J. Sauget, 111. Tacoma, Wash. Port Neches, Tex. Wichita, Kans. Ronnel Dow Midland, Mich. Si 1 vex and esters and salts Dow Guth Chemical Mi 11 master Onyx Riverdale Thompson-Hayward Transvaal Midland, Mich. Hillside, 111. Berkeley Hgts., N. J. Chicago Hgts., 111. Kansas City, Kans. Jacksonville, Ark. Reichhold 2,4,5-T and esters and salts Amchem Chemical Insecticide Corp. Chempar (continued) 115 Ambler, Pa. Fremont, Cal. St. Joseph, Mo.a Metuchen, N. J. o Portland, Ore. �TABLE 14 (continued) Chemical Producer Location 2,4,5-T and esters and salts (continued) Diamond Shamrock Dow Guth Chemical Hercules Mi 11 master Onyx PBI-Gordan Riverdale Thompson Chemical Thompson-Hayward Transvaal Newark, N. J. Midland, Mich. Hillside, Ill. a Brunswick, Ga. Berkeley Hgts., N. J.' Kansas City, Kans. Chicago Hgts., 111. St. Louis, Mo. Kansas City, Kans. Jacksonville, Ark. 2,3,4,6-Tetrachlorophenol Dow Sonford Midland, Mich. Port Neches, Tex. 2,4,5-Trichlorophenol and salts Chemical Insecticide Corp. Diamond Shamrock Dow GAP Hercules Hooker N. Eastern Pharmacy Transvaal Metuchen, N. J. Dow Midland, Mich. o-Benzyl-p-chlorophenol Monsanto Reichhold Sauget, 111. Tacoma, Wash. Bromoxynil and esters Amchem Rhodia Ambler, Pa. Portland, Ore. St. Joseph, Mo, Carbophenothion Stauffer Cold Creek, Ala. a Henderson, Nev. Chlorothaloni 1 Diamond Shamrock Greens Bayou, Tex. DCPA Diamond Shamrock Greens Bayou, Tex. Dichlone Aceto FMC Uniroyal Flushing, N. Y.a Middleport, N. Y^ Nangatuck, Conn. 2,4,6-Trichlorophenol Newark, N. J. Midland, Mich. Linden, N. J. Brunswick, Ga. Niagara Falls, N. Y. Verona, Mo. Jacksonville, Ark. Class II (continued) 116 �TABLE 14 (continued) Chemical Producer Location Dinitrobutylphenol, ammonium salt Dow Midland, Mich. 4,6-Dinitro-o-cresol and sodium salt Blue Spruce Bound Brook, N. J. loxynil Amchem Rhodia Fremont, Cal. Portland, Ore. Lindane Hooker Prentiss Niagara Falls, N. Y. Newark, N. J. MCPA and derivatives Diamond Shamrock Dow Fallek-Lankro Guth Chemical Monsanto Newark, N. J. Midland, Mich. Tuscaloosa, Ala. Hillside, 111. Nitro, W. Va. Portland, Ore. Rhodia MCPB Amchem Dow Monsanto Rhodia Ambler, Pa. Fremont, Cal. St. Joseph, Mo. Midland, Mich. Sauget, 111. Portland, Ore. St. Joseph, Mo. Mecoprop Cleary Fallek-Lankro Morton Chem. PBI-Gordon Rhodia Somerset, N. J. Tuscaloosa, Ala. Ringwood, 111. Kansas City, Kans. Portland, Ore. St. Joseph, Mo. Parathion American Cyanamid American Potash Warners, N. J. Hamilton, Miss. Los Angeles, Cal. Anniston, Ala. Mt. Pleasant, Tenn.' Bayport, Tex. a Monsanto Stauffer Velsicol PCNB Monsanto 01 in (continued) 117 Sauget, 111.3 Leland, Miss. Mclntosh, Ala. Rochester, N. Y. �TABLE 14 (continued) Chemical Producer Location Pi pecol i nopropyl -3 ,4dichlorobenzoate Eli Lilly Lafayette, Ind. Piperalin Eli Lilly Indianapolis, Ind. Lafayette, Ind. Propanil Blue Spruce Eagle River Monsanto Sobin Chemical Bound Brook, N. J. Helena, Ark^ Luling, La. Newark, N. 0. Tetradifon FMC Baltimore, Md. 2,3,6-Trichlorobenzoic acid Amchem Ambler, Pa. Fremont, Cal . St. Joseph, Mo. Deepwater, N. J. Fords, N. J.a du Pont Tenneco Amchem Tenneco 2,3,6-Trichlorophenyl acetic acid and sodium salt Triiodobenzoic acid Ambler, Pa. Fremont, Cal. St. Joseph, Mo. Fords, N. J.a Amchem Mallinckrodt Ambler, Pa. Raleigh, N. C. No longer produced at this location. 118 �TABLE 15. ALPHABETICAL LIST OF PESTICIDE CHEMICAL PRODUCERS Producer Location Chemical (class) Aceto Chemical Co., Inc. Flushing, N. Y. Dichlone (II)" Alco Standard Corp. (See Miller Chent. ) Amchem Products, Inc. Ambler, Pa. Brookside Ave. P.O. Box 33 Ambler, Pa. 19002 (Subsid. of Union Carbide) Fremont, Cal. Linden, N. J. St. Joseph, Mo. American Cyanamid Co. Berdan Ave. Wayne, N. J. 07470 Warners, N. J. American Potash and Chem. Hamilton, Miss. Corp. Los Angeles, Cal. Kerr-McGee Chem. Corp. Kerr-McGee Center Oklahoma City, Okla. 73125 (continued) 119 2,4-D and esters and salts (I) 2,4-DB and salts (I) Disul sodium (I) 2,4,5-T and esters and salts (I) Bromoxynil and esters (II) MCPB (II) 2,3,6-Trichlorobenzoic acid and salt (II) Triiodobenzoic acid (II) 2,4-D and esters and salts (I) Disul sodium (I) 2,4,5-T and esters and salts (I) loxynil (II)a MCPB (II) 2,3,6-Trichlorobenzoic acid (II) 2,3,6-Trichlorophenyl acetic acid, sodium salt (II) Disul sodium (I) 2,4-D and esters and salts (I) Disul sodium (I) 2,4,5-T and esters and salts (I) MCPB (II) 2,3,6-Trichlorobenzoic acid (II) 2,3,6-Trichlorophenyl acetic acid, sodium salt (II) Dicapthon ( ) Ia Parathion (II) Parathion (II)° Parathion (II)C �TABLE 15 (Continued) Producer Location Chemical (class) Arapanoe Chem. Div. Syntex Corp. 3401 Hillview Ave. Palo Alto, Cal. 94304 Boulder, Col. Chloranil (IT Blue Spruce Co. Stirling, N. J. Bound Brook, N. J. 4,6-Dinitro-o-cresol and sodium salt (II) Propanil (II) Chemical Insecticide Corp. 30 Whitman Ave. Metuchen, N. 0. 08840 (1971 address) Metuchen, N. J. 2,4-D and esters and salts (I)a 2,4,5-T and esters and salts (I)e 2,4,5-Trichlorophenol (I)a Chempar Chem. Co., Inc. (Address not available) Portland, Ore. 2,4-D and esters and salts (I) . 2,4,5-T and esters and salts (I)c W. A. deary 1049 Somerset St. Somerset, N. J. 08873 Somerset, N. J. Mecoprop (II) Diamond Shamrock Corp. 1100 Superior Ave. Cleveland, Ohio 44114 Greens Bayou, Tex. Chlorothalonil (II) DCPA (II) 2,4-D and esters and salts (I) 2,4,5-T and esters and salts (I)c 2,4,5-Trichloroohenol and salts (I)a MCPA (II) Dow Chemical U.S.A. Midland, Mich. 07980 Newark, N. J. 2,4-D and esters and salts (I) Dinitrobutylphenol ammonium salt (II) Erbon (I)a MCPA and derivatives (II) MCPB (II)a Pentachlorophenol and salts (I) Ronnel (I) Silvex and esters and salts (I) 2,4,5-T and esters and salts (I) 2,4,5-Trichlorophenol (I) 2,4,6-Trichlorophenol (I) (continued) 120 �TABLE 15 (Continued) Producer Location Chemical (class) E.I. du Pont de Nemours and Co., Inc. 1007 Market Street Wilmington, Del. 19898 Deepwater, N. J. 2,3,6-Trichlorobenzoic acid and salts (II)a Eagle River Chemicals, Co. Helena, Ark. 72342 (Subsid. of Vertac, Inc.) Helena, Ark. Propanil (II) Eli Lilly and Co. 740 S. Alabama St. Indianapolis, Ind. Indianapolis, Ind. Lafayette, Ind. Piperalin (II) Pipecolinopropy1-3,4dichlorobenzoate (II) Piperalin (II) Baltimore, Md. Tetradifon (II)a Middleport, N. Y. Dichlone (I) Fallek-Lankro Corp. P.O. Box H Tuscaloosa, Ala. 35401 (Joint venture of Fallek Chem. Corp. and Lankro Chem. Group Ltd. [UK]) Tuscaloosa, Ala. 2,4-D and esters and salts (I) MCPA and derivatives (II) Mecoprop (II) GAF Corp. 140 West 51st St. New York, N. Y. 10020 Linden, N. J. Disul sodium (I) 2,4,5-Trichlorophenol and salts (I) Givaudan Corp. 100 Delawanna Ave. Clifton, N. J. 07014 (Affiliate of L. Givaudan and Cie [Switz.]) Clifton, N. J. Hexachlorophene (I) Isobac 20 (I) Guth Chemical Co. P.O. Box 302 Naperville, 111. Hillside, 111. 2,4-D and esters and and salts (I) Si 1 vex and esters and salts (I)a 2,4,5-T and esters and salts (I)a MCPA (II)a 96206 FMC Corp. One Illinois Center 200 East Randolph Dr. Chicago, 111. 60601 Gulf Oil Corp. (See Millmaster Onyx) (continued) 121 �TABLE 15 (Continued) Producer Location Chemical (class) Hercules, Inc. 910 Market St. Wilmington, Del. Brunswick, Ga. 2,4,5-T and esters and Hooker Chemical Corp, 1900 St. James PI. Houston, Tex. 77027 (Subsid. of Occidental Petroleum Corp.) Niagara Falls, N. Y. 2,4,5-THchlorophenol and Imperial , Inc. West 6th and Grass Sts. Shenandoah, Iowa Shenandoah, Iowa 2,4-D and esters and salts (I) Mai 1inckrodt, Inc. 675 Brown Road P.O. Box 5840 St. Louis, Mo. 63134 Raleigh, N. C. Triiodobenzoic acid (II)' Merck and Co., Inc. 126 East Lincoln Ave. Rahway, N. J. 07065 Hawthorne, N. J. Pentachlorophenol and salts (I)a Miller Chem. and Fertz. Corp. Subsid of Alco Standard Corp. Valley Forge, Pa. 19481 White ford, Md. 2,4-D and esters and salts (I)a Millmaster Onyx Group 99 Park Ave. New York, N. Y. 10016 (Part of Gulf Oil Corp.) Berkeley Hgts., N. J. Silvex and esters and and salts (I) 2,4,5-T and esters and salts (I)a Mobil Chem. Co. Phosphorus Div. P.O. Box 26638 Richmond, Va. 23261 (Div. of Mobil Corp.) Charleston, S. C. Mt. Pleasant, Tenn. Dichlofenthion (I)a Bifenox (I) Dichlofention (I) Monsanto Co. 800 North Lindbergh Blvd. St. Louis, Mo. 63166 Anniston, Ala. Luling, La. Nitro, W. Va. Sauget, 111. Parathion (II) Propanil (II)a MCPA (II) 2,4-D and esters and salts (I)a 19899 (continued) 122 salts (I) a 2,4,5-Trichlorophenol and salts (I) a salts (I)a Lindane (II) �TABLE 15 (Continued) Producer Location Monsanto Co. (continued) Chemical (class) Pentachlorophenol and salts (I) o-Benzyl-p-chlorophenol (II) MCPB PCNB (II) Morton Chem. Co. Div. of Morton-Norwich Products, Inc. 110 North Wacker Dr. Chicago, 111. 60606 Ringwood, 111. Mecoprop (II )a North Eastern Pharmaceutical and Chem. Co. P.O. Box 270 Stamford, Conn. 06904 Verona, Mo. 2,4,5-Trichlorophenol and salts (I) 01 in Corp. 120 Long Ridge Rd. Stanford, Conn. 06904 Leland, Miss. Mclntosh, Ala. Rochester, N. Y. PCNB (II) PCNB (II) PCNB (II)a PBI-Gordon Corp. 300 South Third St. Kansas City, Kans. 66118 Kansas City, Kans. Dimethylamine salt of dicamba (I) 2,4,5-T and esters and salts (I) Mecoprop (II) Prentiss Drug and Chem. Co., Inc. 363 Seventh Ave. New York, N. Y. 10001 Newark, N. J. Lindone (II) Occidental Petroleum Corp (See Hooker) Reichhold Chemicals, Inc. Tacoma, Wash. RCI Building White Plains, N. Y. 10603 Rhodia, Inc. 600 Madison Ave. New York, N. Y. 10022 (Subsid. of RhonePoulenc SA [France]) N. Kansas City, Mo. Portland, Ore. (continued) 123 Pentachlorophenol and and salts (I) o-Benzyl-p-chlorophenol a 2,4-D (I) 2,4-DB (I) 3 loxynil (II)a 2,4-D (I) 2,4-DB (I) (II) �TABLE 15 (Continued) Producer Chemical (class) Location Rhodia, Inc. (cont.) St. Joseph, Mo. St. Paul, Minn. 2,4-DP (I) Bromoxynil and esters (II) MCPA and derivatives (II) MCPB (II) Mecoprop (II) 2,4-D and esters and salts (I) 2,4-DB and salts (I) Bromoxynil and esters (II) MCPA and derivatives (II) MCPB (II) Mecoprop (II) 2,4-D and esters and salts (I) 2,4-DB (I)a Riverdale Chemicals, Inc. Chicago Hgts., 111. 220 E. 17th St. Chicago Hgts.,111. 60411 2,4-D and esters and salts (I) Silvex and esters and salts (I) 2,4,5-T and esters and salts (I) Sobin Chemicals, Inc. International Minerals and Chem. Corp. IMC Plaza Libertyville, 111. 60048 Newark, N. J. Propanil (II)a Sonford Chem. Co. Pure-Atlantic Hwy. Port Neches, Tex. 77651 Port Neches, Tex. PentachloroDhenol and salts (I)a 2,3,4,6-Tetrachlorophenol ( ) I' Stauffer Chemical Co. Westport, Conn. 06880 Cold Creek, Ala. Henderson, Nev. Mt. Pleasant, Tenn. Carbophenothion (II)a Carbophenothion (II) Parathion (II)a Syntex Corp. (See Arapahoe) Tenneco Chemicals Co. Fords, N. J. Park 80 Plaza West Saddle Brook, N. J. 07662 (Part of Tenneco, Inc.) 2,3,6-Trichlorobenzoic acid and salts (II) (2,3,6-Trichlorophenyl) acetic acid and sodium salt (II)a Thompson Chemicals Corp. 3028 Locust St. St. Louis, Mo. 63103 2,4-D and esters and salts (I)a c 2,4,5-T and esters and salts (I) St. Louis, Mo. (continued) 124 �TABLE 15 (Continued) Producer Location Chemical (class) Thompson-Hayward Chem. Co. 5200 Speaker Rd. P.O. Box 2383 Kansas City, Kans. 66110 (Subsid of North American Philips Corp.) Kansas City, Kans. 2,4-D and esters and salts (I) Silvex and esters and salts (I) 2,4,5-T and esters and salts (I) Transvaal , Inc. Marshall Rd. P.O. Box 69 Jacksonville, Ark. 72076 (Subsid. Vertac, Inc.) Jacksonville, Ark. 2,4-D and esters and salts (I) 2,4-DP (I) Silvex and esters and salts (I) 2,4,5-T and esters and salts (I) 2,3,4,6-Tetrachlorophenol (I) 2,4,5-Trichlorophenol and salts (I) Union 270 New (See Institute and South Charleston, W. Va. Oisul sodium (I)a Uniroyal, Inc. 1230 Ave. of the Americas New York, N. Y. 10020 Naugatuck, Conn. Chloranil (I)" Dichlone (II)C Velsicol Chemical Corp. 341 East Ohio St. Chicago, 111. 60611 (Subsid. of Northwest Industries, Inc.) Bayport, Tex. Beaumont, Tex. Parathion (II)C Dicamba (I) Vulcan Materials Co. P.O. Box Birmingham, Ala. 35223 Wichita, Kans. Pentaclll orophenol and salts (I) Woodbury Chemicals Subsid. of Comutrix Corp. 8373 N. E. 2nd Ave. Miami, Fla. 33138 Orlando, Fla. 2,4-D and esters and salts (I) Carbide Corp. Park Ave. York, N. Y. 10017 also Amchem) Vertac, Inc. (See Transvaal and Eagle River) No longer produced at this location. 125 �TABLE 16. FORMER PESTICIDE PRODUCTION LOCATIONS Producer Location Chemical (class) Aceto Flushing, N. Y. Dichlone (II) Amchem Ambler, Pa. Disul Sodium (I) 2,3,6-Trichlorobenzoic acid and salts (II) Disul Sodium (I) loxynil (II) MCPB (II) Disul Sodium (I) Disul Sodium (I) Fremont, Cal. Linden, N. J. St. Joseph, Mo. American Cyanamid Warners, N. J. Dicapthon (I) Parathion (II) American Potash Hamilton, Miss. Parathion (II) Arapahoe Boulder, Col. Chloranil (I) Chem. Insecticide Corp. Metuchen, N. J. 2,4-D and esters and salts (I) 2,4,5-T and esters and salts (I) 2,4,5-Trichlorophenol and salts (I) Chempar Portland, Ore. 2,4-D and esters and salts (I) 2,4,5-T and esters and salts (I) Diamond Shamrock Newark, N. J. 2,4,5-T and esters and salts (I) 2,4,5-Trichlorophenol and salts (I) MCPA (II) Dow Midland, Mich. Erbon (I) MCPB (II) du Pont Deepwater, N. J. 2,3,6-Trichlorobenzoic acid and salts (II) Eli Lilly Indianapolis, Ind. Piperalin (II) FMC Baltimore, Md. Tetradifon (II) GAP Linden, N. J. Disul Sodium (I) 2,4,5-Trichlorophenol and salts (I) (continued) 126 �TABLE 16 (Continued) Producer Location Chemical (class) Guth Chem. Hillside, 111. 2,4-D and esters and salts (I) Silvex and esters and salts (I) 2,4,5-T and esters and salts (I) MCPA (II) Hercules Brunswick, Ga. 2,4,5-T and esters and salts (I) 2,4,5-Trichloropbenol and salts (I) Hooker Niagara Falls, N. Y. 2,4,5-Trichlorophenol and salts (I) Mallinckrodt Raleigh, N. C. Triiodobenzoic acid (II) Merck Hawthorne, N. J. Pentachlorophenol and salts (I) Miller Chem. Whiteford, Md. 2,4-D and esters and salts (I) Millmaster Onyx Berkeley Hgts. , N. 0. Silvex and esters and salts (I) 2,4,5-T and esters and salts (I) Mobil Charleston, S. C. Dichlorofenthion (I) Monsanto Luling, La. Nitro, W. Va. Sauget, 111. Propanil (II) MCPA (II) 2,4-D and esters and salts (I) MCPB (II) PCNB (II) Morton Ringwood, 111. Mecoprop (I) N. Eastern Pharm. Verona, Mo. 2,4,5-Trichlorophenol and salts (I) 01 in Rochester, N. Y. PCNB ( I I ) Rhodia N. Kansas City, Mo. 2,4-D and esters salts (I) 2,4-DB and salts loxynil (II) 2,4-D and esters 2,4-DB and salts Portland, Ore. St. Paul, Minn. (continued) 127 and (I) and salts (I) (I) �TABLE 16 (Continued) Producer Location Chemical (class) Sob in Chem. Newark, N. J. Propanil Sonford Port Neches, Tex. Pentachlorophenol and salts (I) 2,3,4,6-Tetrachlorophenol (I) Stauffer Cold Creek, Ala. Carbophenothion (II) Tenneco Fords, N. J. 2,3,6-Trichlorobenzoic acid and salts (II) (2,3,6-Trichlorophenyl) acetic acid (II) Thompson Chem. St. Louis, Mo. 2,4-0 and esters and salts (I) 2,4,5-T and esters and salts (I) Union Carbide Institute and South Charleston, W. Va. Disul Sodium (I) Uniroyal Naugatuck, Conn. Chloranil (I) Dichlone (II) Velsicol Bayport, Tex. Chattanooga, Tenn. Parathion (II) Dicamba (I) Woodbury Orlando, Fla. 2,4-D and esters and salts (I) 128 (II) �VOLUME III REFERENCES Aniline, 0. 1973. Preparation of Chlorodibenzo-p-dioxins for toxicologi.cal Evaluation. In: Chlorodioxins-Ongin and Fate, E. H. Blair, ed. , Advances in Chemistry Series, 120, 126. Bayer, F. 1910. German Patent No. 223,367. Chemical Abstracts, 4:2981.4 Blitz, H. 1904. Ueber die Oxydirende Chlorirung des o-Oxy-benzaldehyds und des p-Oxy-benzaldehyds. Ber., 27:4009. Buser, H. R. 1975. Polychlorinated Dibenzo-p-dioxins. Separation and Identification of Isomers by Gas Chromatography - Mass Spectrometry. J. Chromatogr. 114:95. Buser, H. R. 1976. Preparation of Qualitative Standard Mixtures of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans by Ultraviolet and GammaIrradiation of the Octachloro Compounds. J. Chromatogr., 129:303. Buu-Hoi, N. P. 1971. Preparation, Properties, and Identification of Dioxin (2,3,7,8-tetrachlorodibenzo-p-dioxin) in the Pyrolyzates of Defoliants Based on 2,4,5-Trichlorophenoxyacetic Acid and Its Esters and in Contaminated Plants. C. R. Acad. Sci., Ser. D 273:708. Cadogan, J. , J. Sharp, and M. Trattles. 1974. Evidence for 1,2-Ketocarbenes in Thermolysis of Sodium o-Halogenophenoxides and for Sodium o-Bromobenzenethiolates. J. Chem. Soc. , Chem. Commun., 900. Crosby, D. , K. Moilanen, and A. Wong. 1973. Environmental Generation and Degradations of Dibenzodioxins and Dibenzofurnas. Environmental Health Perspectives, 5:259. Crosby, D., et al. 1971. dioxins. Science, 173:748. Photodecomposition of Chlorinated Dibenzo-p- Cullinane, N. M. , and C. G. Davies. 1936. Compounds. Rec. Trav. Chim., 55:881. Synthesis of Some Heterocyclic Denivelle, L., R. Fort, and P. V. Hai. 1960. Oxtachloro- and Octabromodibenzo-p-dioxins and Decachloro- and Decabromodiphenyl Ether. Bull. Soc. Chim. France, 1538. 129 �Dem'velle, L. , R. Fort, and V. H. Pham. 1959. Structural Study on Some Pentachloro(pentachlorophenoxy)phemols Derived Therefrom. Compt. rend., 248, 2766. Denivelle, L. , R. Fort, and V. H. Pham. 1960. Oxtachloro- and Octabromodibenzo-p-dioxins and Decachloro- and Decabromodiphenyl Ether. Bull. Soc. Chim. Fr., 1538. Fishbein, L. 1973. Mutagens and Potential Mutagens in the Biosphere. I. DDT and It's Metabolites, Polychlorinated Biphenyls, Chlorodioxins, Polycyclic Aromatic Hydrocarbons, Haloethers. The Science of the Total Environment, 4:305. Frejka, J. , B. Sefranek, and J. Zika. 1937. New Method of Preparing Some Halogenated Derivatives of Dihydroxydi-o-phenylene Dioxide. Collection Czech. Commun., 9:238. Chemical Abstracts, 31:7074. Fujita, E., and N. Gota. 1955. Synthesis of Diphenylene Dioxide Derivatives. XXII. Synthesis of 7,8-Phenylenedioxyquinoline. J. Pharm. Soc. Japan, 75:28. Chemical Abstracts, 50:1021, 1956. Fujita, E., et al. 1956. Synthesis of Diphenylene Dioxide (Dibenzo-pDioxin) Derivatives. XXIII. Synthesis of Phenylene-dioxyquinolines (Benzo-p-dioxinoquinolines). J. Pharm. Soc. Japan, 76:1097. Chemical Abstracts 51:2791, 1957. Gilman, H., and J. Dietrich. 1957. dioxin. Am. Chem. Soc., 79:1439. Halogen Derivatives of Dibenzo-p- Gilman, H., and J. Dietrich. 1958. Bromomito and Related Derivatives of Dibenzo-p-dioxins. J. Am. Chem. Soc., 80:366. Gribble, G. W. 1974. TCDD[2,3,7,8-tetrachlorodibenzo-p-dioxin]. Molecule. Chemistry, 47:15. Deadly Higginbotham, G. R. 1968. Chemical and Toxicological Evaluations of Isolated and Synthetic Chloro Derivatives of Dibenzo-p-dioxin. Nature, 220:702. Hugounenq, L. 1890. CHim. Phys., 20:546. Derives Chlores 1'anisol et du phenol ordinire. Ann. Inubushi, Y. , et al. 1958. Dibenzo-p-dioxin Derivatives. XXIV. FriedelCrafts Reaction of Dibenzo-p-dioxin Derivatives. Yakugaku Zasshi, 78:581. Chemical Abstracts, 52:18421, 1958. Julia, M., and M. Baillarge. 1953. Substituted p-Phenoxyphenylacetic Acids. Bull. Soc. Chim. France, 644, Chemical Abstracts, 48:5831, 1954. 130 �Kaupp, J. , and H. Klug. 1962. Perchlorodiphenylene dioxide. German Patent No. 1,092,480 to Farbwerke Hoechst A. G. See Chemical Abstracts, 56:14302. Keimatsu, I., and E. Yamaguchi. Pharm. Soc. Japan, 56:680. 1936. Diphenyl Ether Derivatives. J. Kende, A. S. , et al. 1974. Synthesis and Fourier Transform Carbon-13 Nuclear Magnetic Resonance Spectroscopy of New Toxic Polyhalodibenzo-pdioxins. J. Org. Chem., 39:931. Kulka, M. 1961. Octahalogenodibenzo-p-dioxins. Can. J. Chem., 39. Kulka, M. 1965. Perhalodibenzo-p-dioxins. Canadian Patent No. 702,144 to Dominion Rubber Co., Ltd. See Chem. Abstracts, 62:16261. Langer, H. G. , T. P. Brady, and P. R. Briggs. 1973. Formation of Dibenzodioxins and Other Condensation Products from Chlorinated Phenols and Derivatives. 1973. Environmental Health Perspectives, 5:3. Lester, R. G. , and J. F. Brennan. 1972. Catalytic Preparation of Dibenzodioxins. U.S. Patent No. 3,679,704. Chemical Abstracts, 77:114413g. Manske, R. H. F. 1949. 2,4-Dichlorophenoxyacetic Acid. U.S. Patent No. 2,471,575. Assigned to United States Rubber Company, May 31. Merck Index. New Jersey. 1978. 9th ed. , M. Windholz, ed. Merck & Co., Inc., Rahway, Merz, V., and W. Weith. 5:460. 1872. Zur Kenntnis des Perchlorophenols. Ber. , Pohland, A. E. , and G. C. Yang. 1972. Preparation and Characterization of Chlorinated Dibenzo-p-dioxins. J. Agric. Food Chem., 20:1092. Rappe, C. 1978. 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) - Introduction. In: Dioxin-Toxicological and Chemical Aspects, F. Cattabeni, A. Cavallaro, and G. Galli, eds. Spectrum Publications, Inc., New York, pp. 9-11. Rawls, R. L. 1979. Dow Finds Support, Doubt for Dioxin Ideas. Eng. News, 57(7):23-29. Chem. and Rose, J. Q. , et al. 1976. The Fate of 2,3,7,8-Tetrachlorodibenzo-p-dioxin Following Single and Repeated Oral Doses to the Rat. Toxicol. Appl. Pharmacol. 36:209. Sandermann, W. , H. Stockmann, and R. Casten. chlorophenol. Ber., 90:690. 1957. Pyrolysis of Penta- Tomita, M. 1932. Synthesis for Diphenylene Dioxide. J. Pharm. Soc. Japan, 52:429. Chemical Abstracts, 26:4589. 131 �Tomita, M. 1933. Synthesis of Diphylene Dioxide Derivatives. Pharm. Soc. Japan, 53:775. Chemical Abstracts, 28:3391, 1934. III. J, Tomita, M. 1935. The Synthesis of Diphenylene Dioxide Derivatives. VI, The Nitration of Diphenylene Dioxide. J. Pharm. Soc. Japan, 55:1060. Chemical Abstracts, 31:6661, 1937. Tomita, M. 1936. The Synthesis of Diphenylene Dioxide Derivatives. IX. Ring Closure of the Diphenylene Dioxide Nucleus. J. Pharm. Soc. Japan, 56:814. Chemcial Abstracts, 32:8426, 1938. Tomita, M. 1937. Synthesis of Diphenylene Dioxide Derivatives. XII. Friedel-Crafts Reaction on Diphenylene Dioxide. J. Pharm. Soc. Japan., 57:609. Chemical Abstracts, 33:2898. Tomita, M. , and C. Tani. 1942. Synthesis of Dibenzo-p-dioxin Derivatives. XVI. General Synthetic Method for Diphenylene Oxide Derivatives. J. Pharm. Soc. Japan, 62:476. Chemcial Abstracts, 45:5146, 1951. Tomita, M., and J. Yagi. 1958. Dibenzo-p-dioxin Derivatives. XXIV. Friedel-Crafts Reaction of Dibenzo-p-dioxin Derivatives. Yakugaku Zasshi, 78:581. Chemical Abstracts, 52:18421, 1958. Tomita, M. , T. Nakano, and K. Hirai. 1954. Synthesis of Diphenylene Dioxide XXI. J. Pharm. Soc. Japan, 74:934. Chemical Abstracts, 49:10964, 1955. Tomita, M. , S. Ueda, and M. Narisada. 1959. Dibenzo-p-dioxin Derivatives. XXVII. Synthesis of Polyhalodibenzo-p-dioxin. Yakugaku Zasshi, 79:186. Chemical Abstracts, 53:13152, 1959. Ueda, S. 1962. Dibenzo-p-dioxin Derivatives. halodibenzo-p-dioxin. Yakugaku Zasshi, 83:714. XXXI. Synthesis of Poly- Ueda, S. 1963. Dibenzo-p-dioxin (Diphenylene Dioxide) Derivatives. Methylation Product of Dibenzo-p-dioxin. Yakugaku Zasshi, 83:802. XXXVI. Ueda, S., and T. Akio. 1963. Dibenzo-p-dioxin (Diphenylene Dioxide) Derivatives. XXXIII. Substitution Reaction of 1,6-Dimethoxydibenzo-pdioxin and 1,6-Dibromodibenzo-p-dioxin. Yakugaku Zasshi, 83:552. Ueo, S. 16:177. 1941. 2,6-Dichlorodiphenylene Dioxide. Ullmann, F. 1903. Ber., 36:2382. Bull. Chem. Soc. Japan, Uber eine neue Bildungweise von Diphenylaminderivaten. U.S. Environmental Protection Agency. 1978. The Presence of Priority Pollutants in the Synthetic Manufacture of Pharmaceuticals. Draft. 132 �Vinopal, J. H. , I. Yamamoto, and J. E. Casida. 1973. Preparation of Tritium-Labeled Dibenzo-p-dioxin and 2,3,7,8-Tetrachlorodibenzo-p-dioxin. In: Chlorodioxins - Origin and Fate, E. H. Blair, ed. Advanced Chemistry Series, Vol. 120, 7. Wertheim, E. 1939. Textbook of Organic Chemistry. Philadelphia, Pennsylvania. Zinke, T. 1894. The Blakiston Co., Ueber die Einwirkung von Chlor auf Phenole. Ber., 27:550. 133 �VOLUME III BIBLIOGRAPHY Berg, Gordon L. , ed. 1975. Willoughby, Ohio. Farm Chemicals Handbook. Meister Publ. Co., Cattabeni, F. , A. Cavallaro, and G. Galli, eds. 1978. Dioxin - Toxicological ajid Chemical Aspects. Spectrum Publications, Inc., New York. Hawley, G. , 1977. Condensed Chemical Dictionary. Reinhold, New York. Monsanto Research Corp. and The Industrial Organic Process Profiles for Research Triangle Park, 9th Ed. , Van Nostrand- Research Triangle Institute. 1976. Chapter 6: Chemicals Industry - Part I. In: Industrial Environmental Use. EPA-68-02-1302 and 1325, North Carolina. Parsons, T. , ed. 1977. Chapter 8: Pesticides Industry. Process Profiles for Environmental Use. Radian Corp. Research Triangle Park, North Carolina. In: Industrial EPA-68-02-1319, Rawls, L. 1979. Dow Finds Support, Doubt for Dioxin Ideas. News, 57(7): 23-29. Chem. and Eng. Sittig, M. , ed. New Jersey. 1977. Pesticide Process Encyclopedia. Noyes Data Corp., Stanford Research Institute. 1968, 1969, 1971, 1972, 1973, and Directory of Chemical Producers - USA. Menlo Park, California. Thomas Register of American Manufacturers, 1977. Publishing Co. Windholz, M. , ed. New Jersey. 1976. 1978. 67th Ed., Vol. 8, Thomas Merck Index, 9th Ed., Merck and Co., Inc., Rahway, 134 �TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing! 1. REPORT NO. 2. 3. RECIPIENT'S ACCESSION NO. EPA-600/2-80-158 5. REPORT DATE 4. TITLE AND SUBTITLE Dioxins: Volume III Chemical Processes Assessment of Dioxin-Forming JUNE 1980 ISSUING DATE. 6. PERFORMING ORGANIZATION CODE 8. PE-RFORMING ORGANIZATION REPORT NO. AUTHOR(S) F.E. Dryden, H.E. Ensley. R.J. Rossi, and E.J. Westbrook 10. PROGRAM ELEMENT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS Walk, Haydel, & Associates, Inc. 600 Carondelet St. New Orleans, LA 70130 1BB610 11. CONTRACT/GRANT NO. Contract No. 68-03-2579 12. SPONSORING AGENCY NAME AND ADDRESS 13. TYPE OF REPORT AND PERIOD COVERED Final Industrial Environmental Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Cincinnati. Ohio 45268 14. SPONSORING AGENCY CODE EPA/600/12 15. SUPPLEMENTARY NOTES Volume III of a three-volume sen'es on dioxins 16. ABSTRACT Chemical reaction mechanisms by which dioxins may be formed are reviewed, particularly those likely to occur within commercially significant processes. Various routes of formation are identified in addition to the classical route of the hydrolysis of trichlorophenol. Basic organic chemicals and pesticides with a reasonable potential for dioxin byproduct contamination are surveyed as to current and past producers and production locations. Classifications are presented both for general organic chemicals and for pesticides that indicate likelihood of dioxin formation. Conditions are noted that are most likely to promote dioxin formation in various processes. KEY WORDS AND DOCUMENT ANALYSIS 17. DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS Dioxins Organic chemicals C. COSATI Field/Group 07C 2,3,7,8 - TCDD Pesticides Chemical reactions Chemical plants Environmental biology Hydrolysis Chemical manufacturing 19. SECURITY CLASS {This Report) 18. DISTRIBUTION STATEMENT Unclassified RELEASE TO PUBLIC 20. SECURITY CLASS (Thispage) 06F 07C 07A 21. NO. OF PAGES 147 22. PRICE Unclassified EPA Form 2220-1 (Rev, 4-77) P R E V I O U S E D I T I O N is O B S O L E T E U.S. G O V E R N M E N T P R I N T I N G O F F I C E : 1"80--657-165/OP12 � 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. 183 Folder The folder containing the original item. 5333 Series The series number of the original item. Series VIII 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 Dryden, Forrest E. Harry E. Ensley Ronald J. Rossi E. Jasper Westbrook Description An account of the resource <strong>Corporate Author: </strong>Walk, Haydel &amp; Associates, Inc., New Orleans, Louisiana Date A point or period of time associated with an event in the lifecycle of the resource 1980-06-01 Title A name given to the resource Dioxins: Volume III. Assessment of Dioxin-Forming Chemical Processes ao_seriesVIII 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. 186 Folder The folder containing the original item. 5375 Series The series number of the original item. Series VIII 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 Dutton, Julie A. Source A related resource from which the described resource is derived The Stars and Stripes - The National Tribune Date A point or period of time associated with an event in the lifecycle of the resource August 5 1982 Title A name given to the resource Agent Orange Legislation ao_seriesVIII 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. 192 Folder The folder containing the original item. 5428 Series The series number of the original item. Series VIII 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 Dutton, Julie A. Title A name given to the resource Letter from Julie A. Dutton to Alvin L. Young, July 1, 1983 ao_seriesVIII 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. 206 Folder The folder containing the original item. 5791 Series The series number of the original item. Series VIII Subseries III 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 Earley, Pete Source A related resource from which the described resource is derived The Washington Post Date A point or period of time associated with an event in the lifecycle of the resource March 21 1983 Title A name given to the resource Clipping: At Work: VA Medical Director Has Cabinet-Size Job ao_seriesVIII https://www.nal.usda.gov/exhibits/speccoll/files/original/a518bcc2f7b8963a96b0692ad57e00a7.pdf 56e9b4181fffbeb5335af00a10435fb0 PDF Text Text Item D Number 05233 Author D NntSBannefl Edwards, Don Corporate Author Report/Article TltlB VA Action Needed on Agent Orange JOUmal/BOOk TltlB Congressional Record Year 1978 Month/Day May 11 Color Number of Images n ° Doscrlpton Notes Friday, March 01, 2002 Page 5238 of 5263 �lAJNGKiiSSiONAJL j'ik'od to asslmllnted to. Thus Mussolini bad a Him produced on Sclpio Africauus. Stalin must bflvc seen the glorification of his own totalitarian meUiods in tho victorious struggle of Ivan and his police "Oprichnina" against princes, boyars and other dissenters. 'Jlils film Is at the same time an apotheosis of Ivan's absolutism aud a clever Justification of Stalin's dictatorship. It Is Incredible that a big corporation like Exxon, having worldwide interests and many bright bruins, Jms DO one to \varn it from falling into such a propagandistio trnp. Consequently, relations between West and East before ftiul after Helsinki nro the same. In the West-East direction they represent a way to channel Western currencies, goods and know-how into the lagging economy of the Soviet Bloc. In the East-West direction, the Soviet Union and its satellites are amply exploiting our concept of artistic freedom which they don't tolerate at home for the propagation of their socialist ideology. Where is the principle of reciprocity? We do not need be afraid of the Soviet Union the weakness of which Is in its multinational composition. Regardless of the Impressive bigness of the Soviet Union as a mechanism of power, the organic troubles of this last historical empire cannot but increase as the proportion of the Non-Russian population is becoming mftjorltariaii and preponderant. We have missed many opportunities to create efficient leverages when dealing with the Soviet Union. The most powerful of them remains the right of peoples to self-determination. This, of course, is only a logical conclusion of civil and human rights. Consequently, self-determination, if reaffirmed by our Government in proper time and proper terms as a general principle, would produce a magic effect upon Non-Russian populations of the Soviet Union and upon Its satellites. Indeed, if the principle of self-determination, shall be applied In Africa, why not In the Soviet empire and East-Central Europe? The Soviet Union is nn atomic "superpower" with the living standard of nn underdeveloped country. Henry Kissinger's idea that world peace depends on the cooperation of the United States of America and the Soviet Union is false. Our SALT negotiations with the Soviets have no practical sense. Even if there is an agreement to that effect, it will have no legally binding force. We know from the history of the East-West relations that the Soviets may sign anything, but will respect nothing. By willingness to negotiate they make us believe that they moon to reach an agreement. However, whoever knows from history something about Russian shifty mentality, will not rely on their words or signatures. Can Western diplomats forget Stalin's dictum: "Treaties are like cakes: You have to break them to eat them!"? World peace depends on the political and economic solidarity of tho United States, Western Europe end Japan as well as on the willingness of China to cooperate. To further build up this solidarity and cooperation Is a worthy objective for our dlplomacy.ffl INFLATION: CAUSE OF ECONOMY'S PROBLEMS Hon. John E. "Jack" Cunningham OF WASHINGTON IN THE.HOUSE OF REPRESENTATIVES Thursday, May 11, 1978 0 Mr. CUNNINGHAM. Mr. Speaker, everyone Is concerned with the high cost of living. On May 10, 1978, Congress fueled Inflation by approving a budget //, 1978 Extensions -of Remarks target figure which includes a $58 billion deficit. . . . .Recently, George H. Weyerhaeuser, chief executive officer of the Weyerhaeuser Co., wrote an analysis of toe present state of the economy, which I submit for the RECORD: INFLATION: CAUSE OP ECONOMY'S PROULF.MS (By George H. Weyerhaeuser) In my annual report message this year, there was something of an essay on the current ttale of our world. Problems In our European nnd Japanese markets were mentioned, along with the rising costr of energy, capital goods, raw materials, labor . . . and virtually everything else. It would be nice to report today that the situation has changed dramatically. It has not. There are some signs of Improvement In specific and important markets and In controlling specific costs; but the pace of Inflation has also since accelerated, not slowed. And, it is Inflation—tho Inflationary blaa in al! tho developed nations, but particularly the United States—that is the root cause of all of these problems. In this country, we liko to blame the oil crisis—the action of tho OPEC nations several years ago in suddenly quadrupling the price of petroleum— for the current inflation. And, Indeed, that did help accelerate and maintain the inflationary momentum. But inflation already was out of hand before the crisis. We need to recognize, as the leaders of the other Western nations do, that -perhaps the greatest engine of inflation abroad in the world today is the continued mismanagement of the United States economy, the apparent inability of this nation or its leaders, to face up to the hard decisions that must be made. INFLATION ADJUSTMENTS IN TAXES NEEDED The President, in his recent inflation mesr-ago, signified the new awareness in Washington of the problem and that may be a start toward a solution. But, the elements of that solution that must eventually be faced were missing. They must include expenditure cuts at least paralleling tax cuts, prid inflation adjustments for corporate depreciation allowances and for individual and corporate taxes, For example, earlier this week most -of us paid income taxes on tho interest earned In our bank savings accounts, As It happens, tho Inflation rate last year exceeded the Interest paid by banks on savings. Thus, in purchasing power, none of us received any increase in the value of those savings. We suffered a marginal loss, but since the tax code doesn't recognize inflation, we paid taxes on" our savings account interest-anyway. This Identical problem is affecting corporations such as ours, dramatically. We we unable to replace and maintain our plants and equipment "With the funds available from depreciation—they are inadequate to do theJob, with rapidly inflating costs for construction and machinery. We, almost alone among the major nations, have continued since 1973 to try to make simultaneous progress toward all of our national aspirations including those of major pressure groups. Tho pressure to overspend in our governmental system has seemingly been too much to control. We seem to have built into our. system a desire to increase benefits in all areas of our public life, coupled by complete inability to face up to the costs—whether in the Social Security System, our various income transfer programs, or in our proliferating regulatory systems. Wo are, for instance, alone among the Western nations in our refusal to allow consumers to face the real market cost for energy—even though we, as a nation, have a unique ability to rely upon the free market's forces to bring energy supply and demand; Into healthy balance. '. The polls have Indicated for some time that the people of the United States have be£n well ahead of the leaders in recognizing that inflation Is the economy's basic problem, and In sensing some of the solutions. While the leaders have continued to talk in terms of energy shortage, rather than energy price, the people have rightly been skeptical, and tt Is now they who are proven right, v,-lth the world awash in ft glut pf oil. Yet, ouv lenders i>U)l seem itmHiU' to njjust ti> thin situation, to let tho tiwrlset <•»!>« ««>'« «f oil availability and prlco, LKAUEKS INTERFERE IN MARKET'S EFFICIENCY Instead, they argue over which form of bureaucracy; which form of tax; which form of regulation can best bo used to prevent tho market from working its efficiencies—which can best delay tho absorbing of tho effect of the OPEC action, and which thus can best delay tho economy^ adjustment to it. I believe most Americans agree that the adjustment lias been postponed too long already, a-nd would prefer to get the absorption period over with, so that the economy can move forward.® ACTION NEEDED ON AGENT ORANGJS HON. DON EDWARDS ' OF CALIFORNIA IN THE HOUSE OP REPRESENTATIVES Thursday, May 11, 1978 e Mr. EDWARDS of California. Mr. Speaker, many of us have become Increasingly aware of the disturbing allegations being made regarding health hazards experienced by Vietnam era veterans as a result of their exposure to the powerful defoliant, Agent Orange. The defoliant was used in Vietnam between 19G2 and 1970, when it was withdrawn by the Pentagon because of its apparent dangerous effects to human and plant life. . -Along with 13 of my colleagues on the Veterans' Affairs Committee, I have uiitlated a request for nn olliciul response from the VA to provide the committee with a thorough report on Agent Orange and what outreach and research efforts the VA has in mind. While it is perhaps too soon to draw any definite medical conclusions, there are certainly a lot of unanswered Questions about Agent Orange. I think the Congress has a real responsibility to follow up this issue to insure that the needs of our Vietnam veterans are met. In the June issue of the Progressive, there is an excellent article on the filing of Agent Orange related claims in one VA regional oifice—the Chicago office. I think my colleagues will find the article helpful in exploring the work done thus far on this critically Important issue and in clarifying the need for our careful attention to this situation. The article follows: AcrioN NEEDED ON AGENT ORANCR <By Michael Uhl and Tod Ensign) Maude de Victor works behind n colci, steel gray desk in the Benefits Section of the Veterans Administration regional office in Chicago. She Is not your average papershuffier. In recent months, Maude do Victor has Joined the select ranks of whistle blowers— �May 11, 1978 CONGRESSIONAL RECORD —- Extensions of Remark those^ierolo individuals who discover an outrage and, in defiance of bureaucratic inertia or suppression, bring it to public notice. The outrage Maude de Victor discovered \viif) the shocking effect of dioxin poisoning on American veterans who came into contact with the herbicides that were used to defoliate more than five million acres of the Vietnamese countryside between 1962 and 1070. Her efforts have not only focused attention on the plight of these latest victims of the Vietnam war, but have also raised new warnings against the domestic hazards posed by the herbicides. Massive defoliation was a major tactic- pursued by U.S. forces in Vietnam. It had two objectives—to deny guerrillas their Jungle cover, and to destroy food crops so that the peasantry would be compelled to take refuge in controlled resettlement camps. The most widely used defoliant was Agent Orange, a mix of 2,4-D and 2,4,5-T, two herbicides. used in the United States for many years to control crops and forest growth and to clear vegetation along roads and railroad tracks. Dioxin—Its full name is tetrachloro-dibenzoparadioxin, or TCDD—often appears as a biproduct in the manufacture of trichlorophenol. from which 2,4,5-T is made. Dioxin is one of the most toxic contaminants known to humankind, Among the symptoms associated with exposure to the substance are a skin disorder called chloracne, liver abscesses, spontaneous miscarriages, numbing of limbs, reduced sex drive, personality changes, and birth defects among the children of those exposed. Dioxin poisoning is believed to have caused many birth defects in Vietnam in recent years, and a host of ailments among those who suffered exposure. Maude de Victor, a thirty-eight-year-old black woman, had never, heard of Agent Orange or dioxin when she took a random telephone call about a year ago from the wife of a Vietnam veteran named Charles Owens. Her husband, Mrs. Owens said, was dying of cancer, and he blamed it on "those chemicals from Vietnam." Four months later Mrs. Owens called again to say that her husband had died—and that her claim for survivor's benefits had been refused by the VA. That second call prompted Maude de Victor to try to flnd out about the chemicals which Charles Owens believed had caused his fatal illness. She called the office of the Air Force Surgeon General aud-spoke to Captain Alvin Young, who, she points out, holds a Ph.D. degree in plant physiology. Young briefed her thoroughly on the U.S. military's defoliation program in Vietnam and on the symptoms believed to be associated with dioxin contamination. Most of what we know about the toxic effects of dioxin on human beings has been learned from studying the victims of industrial accidents at plants producing trichlorophenol—especially the notorious accident in July 1976 »t Seveso, Italy, where inhabitants were thoroughly doused with the poison. But there have been relatively few laboratory studies to determine the effects on animal systems of less concentrated exposure, and of dio.xln's reported tendency to accumulate in the body's fatty issue. One scientist who has conducted such experiments. Professor Val Woodward of the University of Minnesota, has asserted, "One thing is clear . . . 2,4,5-T is a very effective teratogen [fetus-deforming agent]. It deforms mice in laboratory situations, and very clearly human beings who have been sprayed have a higher incidence of these deformities than people who were not sprayed." Maude de Victor recalls that Captain Young described several major Vietnamese defoliation programs, such as Operation Ranchhand, and that he said there was "no doubt" that anyone who participated in those operations would have been contaminated.. . ' At this point, Maude de Victor was no longer merely following the bureaucratic routine of her Job. She had a special reason for talcing a special interest: In the 1950s, while serving with the Navy medical corps, she attended women with xiterlne cancer who were receiving experimental treatments with radium pellets. Twenty years later, she learned that she had breast cancer. She underwent a mastectomy and has been given a clean bill of health, but she suspects that long-ago exposure to radiation may have Induced her cancer. At the VA, Maude de Victor receives an average of seventy telephone calls and personally interviews about fifteen veterans each day. After her talk with Captain Young she began posing some questions to her clients: "You been in Vietnam? Got any kind of rash? Have any children with deformities?" Often they a:iswered, "Yeah, how'd you know?" With her supervisors' permission, she began logging these cases. In the first two months of 1978, she accumulated twentyseven examples of this new disability. Her informal queries afr the Veterans Hospital txirned up about thirty more—all from the Chicago area. Suddenly, without explanation, her boss ordered her to stop logging potential dioxin poisoning cases; apparently, the higher levels of the VA were becoming concerned. Maude de Victor decided to tell what she had learned to a television news correspondent. . On Match 23, 1978, WBBM, the CBS television affiliate In Chicago, aired an hour-long documentary featuring Interviews with alling veterans, research scientists, and the Air Force's Captain. Young. Before the television cameras, he was less certain about the possible hazards of dioxin poisoning than be had been in conversation with de Victor. When asked about alleged dangers from 2,4,5-T, he said, "I don't think there's any supportive evidence." Dow Chemical, a major herbicide manufacturer, released a statement after the broadcast denying any connection with alleged birth defects. Relying on a National Academy of Sciences study conducted In 1974, Dow asserted that "no conclusive evidence (exists) of association between exposure to herbicides and birth defects in South Vietnam." The statement made no mention of possible links between 2,4,5-T and ailments suffered by veterans, and Dow said It "fully supports further epidemiological studies of military personnel who have health problems associated with service In Vietnam." In previous statements,. Dow had ,claimed that the dioxin content in its herbicides was insignificant. Scientists disagree about whether these are safe levels of dioxin exposure, and whether dloxins enter the luinian food chain and are stored In the body's fatty tissue. Using a solution far less toxic than that found In either Agent Orange or the 2,4,5-T herbicides used in the United States today. Dr. James Allen of the University of Wisconsin found that "low-level consumption even as low as five parts per trillion of dioxin in the diet was capable of causing an Increased incidence of tumors In experimental animals." Though Maude de Victor did not know it, American environmentalists have been fightIng against the use of contaminated defoliants ait home and abroad for years. While Vietnam was being defoliated, there was a sharp corresponding Increase in the use of the same herbicides by state and local agencies. Since I960, the U.S. Forest Service has made increasing use of defoliants containing 2,4,5-T in national parks and forests across the country-. • For years this spraying program went unnoticed and unprotested, but in 1974 a group of citizens to- northern Wisconsin banded to- E2507 gether as the Chequamcgon Concerned Citizens to fight the spraying of the two national forests near their homes. John Stauber, one of the group's founders, recalls. "We collected over two thousand signatures against the spraying In a short period. We really caught the Forest Service by"surprise; they weren't used to dealing with opposition." Wisconsin's Attorney General entered the dispute and won a Federal court injunction against spraying on grounds thftt no proper environmental impact statements baa been filed, in early 1977, th» injunction was withdrawn after the state and the National Forest Servive agreed on some ecological safeguards. Around the country, groups have formed in a number of states to organize opposition to the continued use of herbicides. In February 1978, representatives from sixteen state groups met in Washington and formed thei Citizens National Forest Coalition to coordinate and direct the fight against uncontrolled use of herbicides. Its goal was to win •• a national ban on all products containing 2,4,5-T and to seek an "ecologically sound and Integrated forest management system." One of the most active coalition members, the Citizens Against Toxic Spraying (CATS), has initiated a major court suit in Oregon which has stopped, for the time being, herblcUIal spraying on Federal lands in that state. . , , . Barry Commoner, the distinguished environmental scientist, believes the burden of proof should rest with manufacturers of the herbicides—and with Government agencies that sanction use of the chemicals—to demonstrate beyond-reasonable doubt that they are safe. He told WBBM, "It may well be found [thatj soldiers who were exposed to dioxin In Vietnam accumulated [it] in their body fat with no symptoms . . . except Immediate skin symptoms. Let's say ten years later they become sick and lose weight. They would break down that,fat, releasing the dioxin into the body, and then symptoms would appear." Commoner has proposed that when Vietnam veterans are interviewed for the 1980 Census, questions about possible dioxin exposure be included. "It is simply another cost of the war In Vietnam which we are going to have to pay, even this late," he says. Michael Adams, a twenty-niue-ye.ar-old resident of Evanston, Illinois, is already payIng the price. Ho served hi Vietnam ten years ago as a combat engineer with the Twentyfifth Infantry Division, and one of his duties was to clear forested areas for base camps In the Central Highlands. Often his unit sprayed Agent Orange on the dense vegetation, using hand-pumps, and several times he watched as refitted C-123 aircraft sprayed defoliants on his unit's area of operation. Mike Adams believes he was exposed to the toxic herbicide during these operations. Soon after he returned from Vietnam, large pimple-like sores began to form on his face. An Army medic told him they were "razor bumps" that could easily bo removed, but the sores have persisted and ore probably a form of chloracne, a common symptom of dioxin exposure. After his discharge in 1971, Adarns began to experience numbness in his arms and shoulders. He had difficulty sleeping, and in the past two years he has lost more than- sixty pounds. He also believes he has undergone a personality change: "Before I went to the 'Nam, I was an easy going, cheerful type; now, I often feel on edge and will blow up over Just any little thing," he says. Milton Ross, a twenty-nine-year-old computer programmer from Matteson, Illinois, who served two tours in Vietnam, Is also paying the price. Not only does he suffer from some of the symptoms of dioxin poisonIng, but his six-year-old son, Richard, con- �CONGRESSIONAL RECORD — Extensions oj Remarks celved n'tfcr Ross's return from overseas, was born with the last Joints of his fingers and toes either deformed or missing. Ross and his first wife had a study made of their own genetic histories for possible explanations of their son'8 condition. The research uncovered no genetic disorders on either side, Ross, who served with the Fifth Special forces In the Central Highlands, told us, "Although I wasn't Involved In the spraying operations, I was sprayed upon. The possibilities for exposure were unlimited. They sprayed a lot around the perimeter at Kon Turn, and often the wind would blow the clouds right over our cainp." Ross has not been able" to work since January, when he •was hospitalized for a suspected heart condition, another possible consequence of dloxin exposure. After he was Interviewed on WBBM, Boss began hearing from other Chicago area veterans who also suspect they may be victims of Agent Orange. They are considering the formation of an organization that will bat'tle the VA for disability benefits. Maude de Victor estimates that the Chicago VA has now received more than 500 calls, mostly from Illinois, from veterans reporting difficulties and requesting information and disability claim forms. Both Milton Ross and Maxide de Victor charge the VA Is dragging its feet on these claims. "They've refused to examine these men; they haven't even called them in," Ross complains. "I've gone over their heads to Washington and they tell me there'll be some results in a couple of months." "The VA doesn't even have any rating criteria for chemical disabilities," Maude de Victor points out. "They're not doing any•thing on these cases because they don't have 'any standards for evaluation. Each case Is either denied outright or 'diarled'—that is, placed In a computer where It's programmed to pop up every sixty days for re-review." ' Meanwhile, do Victor is suffering the common fate of whlstleblowers. She has been excluded from staff meetings. "VA doesn't tell me anything any more," she says.* of taxable Income and tax liability by introducing the "zero bracket amount" concept into the tax law. Under the zero bracket amount rules the standard deduction is no longer a deduction to compute taxable income. Instead it is incorporated into the tax rate schedules. This was accomplished by changing the definition of taxable income and recomputing the tax rate schedules. These changes were' intended to have no (or only minimal) effect on taxpayers' tax liabilities. Certain conforming changes were necessitated by this action, one of which was to conform the pre-1977 and post-1976 definitions of taxable income for purposes of computing base period income for income averaging. Two basic methods for making this conforming adjustment were available. The method chosen requires that the '/ero bracket amount be added to taxable income for taxable years beginning before December 31, 1976, in order to make pre-1977 base period taxable income comparable to current year taxable income. This adjustment phases out after 4 years. The result of this approach is an understatement of averageable income, and the potential of a.n increase in,, tax liability for taxpayers electing income averaging. This occurs because, in the course of the income .averaging computations, the base period income is factored up 120 percent. Since -the 'zero bracket amount is added to base period income, it too is factored up by 120 percent. Consequently, when 120 percent of average base period income is deducted from current year income to compute averagable income, avera gable income is lower by 20 percent.of the zero bracket amount. An alternative method would have been to add the xero bracket amount to 120 percent of average base period inBILL TO CORRECT THE PROBLEM come, rather than adding it before mul• WHICH THE ZERO BRACKET tiplying by 120 percent. This approach AMOUNT CREATES FOR TAX- would, however, require subtracting the . PAYERS UTILIZING . INCOME zero bracket amount from taxable income of. any base period year beginning AVERAGING • . after December 31,1976. Thus, this alternative method would require .adjust; . HON. JOSEPH L. FISHER ments in all future years. OF VIRGINIA The method chosen was the simplest, in that it would have required adjust• IN THE HOUSK OF REPRESENTATIVES ments in base period income for only a ' • :.-: Thursday, May 11, 1978 '- • .4-year phase-in period, while the other "• Mr..FISHER. Mr. Speaker, Repre- .method would have required adjustsentative STEIGER and I have Introduced ments to be made in all subsequent years. legislation designed to rectify the prob- The disadvantage of the method chosen lems which the zero bracket amount has is that it can increase the tax liability caused Individual taxpayers seeking to of a taxpayer who uses the income averUtilize the income averaging provisions aging provisions. .' available under the Internal Revenue • The amount of the tax increase can Code. range from just a few dollars to over The income averaging provisions of $1,000, depending primarily on the numthe Code (section 1301 to 1305) are in- ber of tax rate brackets the taxpayer bended to mitigate the adverse effect of "jumped" because of the increase in his our progressive tax rate schedule on the income. Further, the conforming change tax liability of taxpayers whose income can prevent a taxpayer's qualification for fluctuates widely from year to year. income averaging under a $3,000 de miniWithout the income averaging provi- mus rule contained in the income averag: sions, a taxpayer with no taxable income ing provisions. tor 4 years and $100,000 taxable income Mr. STEIGER and I propose to amend • in the fifth year would pay more tax the income averaging provisions to prothan a taxpayer with $20,000 taxable in- vide for use of the alternative method of come in each of the 5 years. conforming the income averaging rules to " The Tax Reduction and Simplificati6n the zero bracket amount. The alternative 'Act of 1977 simplified the computation. method will require that the zero bracket May 11, 1978 amount be added to 120 percent of average base period income. In order to compute average base period income for years after 1976, taxable income will have to be reduced by the taxpayer's zero bracket amount. While this method is somewhat more complex than current law, it is a much more equitable approach and more clearly preserves the tax savings available under the income averaging provisions as they existed prior to enactment of the Tax Reduction and Simplification Act of 1977,» COLLEGE COSTS INCREASE PASTER THAN AFTER TAX INCOME HON. ALBERT H. QUIE OP. MINNESOTA IN THE HOUSE OP REPRESENTATIVES Thursday, May 11, 1978 « Mr. QUIE. Mr. Speaker, the financial burden of sending a son or daughter to college is increasing annually for this Nation's low- and middle-income fam'ilies. The House has been responsive to the needs of these families with children in postseeondary schools. In March, the Education and Labor Committee reported H.R. 11274, the Middle Income -Student Assistance Act, which provides $1.4 billion in increased student grants, loans, and work-study money. Yesterr day, the Rules Committee granted a rule 'on H.R. 12050, the Tuition Tax Credit Act, which provides a tax credit for 25 percent of tuition paid by a taxpayer up •to a maximum credit of $250 in 1980. Both of these bills will assist in insur.ing that no one would be denied the opportunity for a college education for financial reasons alone. I believe Congress should continue to be committed to sharing the burden of college costs. I was therefore initially disturbed by a Congressional Budget Office study released last weekend which stated that college costs, while increasing faster than the cost of living, have been offset by an even larger rise in family incomes. The CBO study implied that increased financial aid to college students and their .parents was not necessary. . . Conversations with constituents and -members of the higher education community had led me to believe that the financial burden of sending students to college was in fact increasing. I therefore asked the Congressional Research Service (CRS) of the Library of Congress to review the CBO's findings and to de•termine whether discretionary income had risen faster in relation to college costs. The findings of the CRS study, which are set forth in the tabfe below, refute the implications of the CBO study that college costs today are not more costly than 10 years ago. The CBO study failed to consider the effects of the increased burden of taxes on discretionary income. \Vhile the national median income has increased 78.8 percent during the period 1967-76, after tax income has risen only 66.8 percent • during that same period. Tills increase in discretionary income, the money from � 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. 178 Folder The folder containing the original item. 5238 Series The series number of the original item. Series VIII 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 Edwards, Don Source A related resource from which the described resource is derived Congressional Record Date A point or period of time associated with an event in the lifecycle of the resource May 11 1978 Title A name given to the resource VA Action Needed on Agent Orange ao_seriesVIII https://www.nal.usda.gov/exhibits/speccoll/files/original/a4e133f946d76a8b08e2d105e17c6c19.pdf 7af7f9e72707cb715b20dccc2df5eaea PDF Text Text Item D Number °5349 Author Eisenbraun, E. J. Corporate Author United States Environmental Protection Agency (EPA), D Not Scanned Roport/Artido Title Project Summary: Polynuclear Aromatic Compounds, Synthesis and Purification Journal/Book Title YBar Month/Day Color 1981 February D Number of Images ° Dascpipton Notes EPA-6oo/S2-so-204 Tuesday, March 05, 2002 Page 5349 of 5363 �United States Environmental Protection Agency Research and Development vvEPA Environmental Sciences Research Laboratory Research Triangle Park NC 27711 EPA-600/S2-80-204 Feb. 1981 Project Summary Polynuclear Aromatic Compounds Synthesis and Purification E.J. Eisenbraun This report reviews and discusses the synthesis and/or purification of polynuclear aromatic (PNA) compounds commonly found as pollutants in the environment. It also presents details of the experimental procedures and techniques as well as the chromotographic and spectroscopic evidence of structure and priority of the compounds supplied to the U.S. Environmental Protection Agency. In addition, it describes the apparatus designed and constructed to meet the synthesis needs together with safety improvements for handling toxic compounds. Introduction The final report upon which this summary is based (see box at end of paper for ordering instructions) provides details of synthesis and purification of 10-g samples of 10 hydrocarbons, 6 nitrogen heterocyclics and 2 oxygen heterocyclics for use as instrumental standards and in other studies at the Chemistry and Physics Laboratory of the EPA's North Carolina Environmental Research Center. The compunds are listed in alphabetical order for each category in Table 1 Compounds Obtained Through Purification of Available Materials Purification Techniques Since several of the compunds needed by EPA were commercially available (3,6,11,12,13,14, and 16), and purification rather than synthesis was indicated, it became important to examine and utilize any and all purification routes. An earlier report (EPA-600/2-78006) described techniques and apparatuses which became important in laboratory practices for safe production of the final pure compounds. Because some of the products and i n t e r m e d i a t e s w e r e suspected carcinogens, final handling procedures w e r e reviewed. Included were development of an improved Soxhlet apparatus, a modified sublimation apparatus, a solid sample dispenser and apparatus for safe cleaning of laboratory equipment. Zone refinement was also used for purification and the refinement apparatus was redesigned to improve refinement methods. The improved Soxhlet and sublimation apparatuses became important for achievement of 'project goals in'this study; they should prove �Table 1. Compounds Supplied to the EPA during the Reporting Period Hydrocarbons Benzo[ghi]perylene (1), mp 276-277°C, 10.4g Benzofejpyrene (2), mp 178-179 °C, 9.96 g Chrysene (3)a, mp 251-253 °C. 11.6g Coronene (4). mp 437-440 °C, 10,5 g 1,2,3,6,7.8-Hexahydropyrene (5)a'ti, mp 133-134°C, 10.0 g sym-Octahydroanthracene (6f'ti, mp 72-73 °C, 13.7g Perylene (7), mp 275-277 °C. 13.2 g 1,2,3,4-Tetrahydroanthracene (8)a'b, mp 89-90 °C, 10.3 g 4.5,9,10-Tetrahydropyrene (9)*'*. mp 139-140 °C, 10.4 g 1,10-Trimethylenephenanthrene (10), mp 80.5-81.0°C, 13.2 g Nitrogen Heterocyclics Acridine (11f, mp 109-110 °C, 12.7 g Benzo[f]quinoline (12)a, mp 90-91 °C, 12.9 g Benzo[h]quinoline (13)a, mp 50.551.5 °C, 11.1 g Carbazole (14)a;°, mp 243-244 °C, 10.5 g 11H-lndeno[1,2-b]-quinoline (15), mp 167-169 °C, 10.7 g Phenanthridine (16)a, mp 106.5107.5 °C, 12.1 g Oxygen Heterocyclics Dinaphtho[2,1-b:1'. 2'-dJfuran (17), mp 156-157 °C, 10.7g peri-Xanthenozanthene (18), mp 241-242 °C, 9.7 g anthracene is described in the final report. Nitrogen heterocyclic PNA compounds were purified using one or more of the techniques listed above. Attempts to purify acridine (11) failed until complexation with catechol proved successful. Since acridine (11) was one of the later compounds used, no experience was available to indicate whether its usage would be practical with other nitrogen heterocyclics. Compounds Synthesized The compounds shown in Table 1, excluding the seven exceptions, were synthesized. In each case, the final report provides the synthesis route and experimental details. Coronene (4) is difficult to synthesize on an increased scale because starting 55/50 material at an advanced stage of synthesis is scarce; also, the higher temperatures required, especially in the sublimation of 4 and its intermediates, adds to the difficulty. A heater, which operates at 500+ °C, was developed. This heater is essential to the scale-up preparation of 1,4, and 7. An improvement in preparation of perylene and development of an alternate route which does not require perylene were major factors in the synthesis scheme. The following reactions provided an increased yield of 1 and eliminated a step in the synthesis of coronene (4). Preparation of 24 (scheme 1 of the final report) is shown by the following partial scheme. Selective reduction through catalytic hydrogenation, dissolving metal reactions, and HI-P4 reductions proved to be important in the synthesis of several PNA compounds (2,8,9,10). The direct conversion of 1-tetralone to napthalene by heating in the presence of a mixture of NaOH-KOH has been extended to the preparation of 1,2,3,4tetrahydroanthracene (8) as shown in the final report (scheme 3). This reaction shows promise for the synthesis of specific hydroaromatics. In "Compound available from commercial source and not synthesized. ""Compound resulted from shared cost and effort. equally useful to other researchers. Design details are shown below (Figures A-1 and A-2 from the final report). Generally, the individual samples were contained in about 100 vials and ranged from 9.9 to 13.7g. The redesigned sampling device greatly aided the safe handling of toxic compounds. Analytical and preparative highpressure liquid chromatography which became available during EPA support of this project were valuable for determining purity of samples. A description of the technique used in purifying a sample of sym-octahydro- Sintered Glass Plate « Teflon Stopcork Glass Seal 0 I Figure A-1. / 2 4 cm Scale-Inches An improved soxhlet apparatus. Figure A-2. An improved sublimation apparatus. �in air pollution studies, other environmental problems requiring high purity standards which involve PNA compounds are bound to emerge as the uses of coal and petroleum products, which are rich in polynuclear aromatics and their hydrogenetive derivatives, continue to increase. Recommendations KOH-NaOH, A compounds are an integral part of petroleum, petroleum products, coal liquids, and shale oil. While there is a current diminished interest in the synthesis of pure aromatic compounds In an earlier report (EPA-600/2-78006) the use of staple isotopes as labels was suggested in PNA aromatics. Their partially hydrogenated derivatives will become more important and systematic synthesis of representative labelled compounds should be initiated. The pure standard samples (labelled and unlabelled) would then be available as advances in instrumentation and pressures for controlling pollution occur. Large-scale synthesis of 13C labelled compounds is a reality; for example, in another project, this laboratory produced 100g samples of two different aromatic hydrocarbons containing a single specific 13C label with a 95% + )3C. Given the rapidly escalating costs of synthesis, some attention should be directed to consolidating inter- and intra-governmental agencies to support future synthesis projects. *Maleic anhydride. A. hPc/C,A. :Ct/z, quinoline. A. contrast, very selective hydrogenation conditions are required to produce 8 from anthracene. Instrumental Studies Gas liquid chromatography and highpressure liquid chromatography were used to determine priority of the intermediate and final PNA compounds. The identity of each was established through the synthesis route and use of spectroscopy studies (IR, UV, 1HNMR, and 13 CNMR) as well as mass spectrometry. From these data, HNMR was. the most definitive. With the exception of coronene (mass spectrum supplied as substitute), a photoreduced 'HNMR trace was included in the final report. Conclusions The synthesis and chemistry of PNA compounds are of interest to a broad spectrum of industrial and governmental laboratories because these E,J. Eisenbraun is with the Oklahoma State University, Department of Chemistry, Stillwater. OK 74078. James E. Meeker is the EPA Project Officer (see below). The complete report, entitled "Polynuclear Aromatic Compounds—Synthesis and Purification." (Order No. PB 81-125015; Cost: $9.50, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Environmental Sciences Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, NC 27711 * U.8. GOVERNMENT PRINTING OFFICE: 1981 -757-012/7008 �United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Official Business Penalty for Private Use $300 r L J Postage and Fees Paid Environmental Protection Agency EPA 335 � 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. 184 Folder The folder containing the original item. 5349 Series The series number of the original item. Series VIII 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 Eisenbraun, E. J. Description An account of the resource <strong>Corporate Author: </strong>United States Environmental Protection Agency (EPA), Environmental Sciences Research Laboratory, Research Triangle Park, North Carolina Date A point or period of time associated with an event in the lifecycle of the resource 1981-02-01 Title A name given to the resource Project Summary: Polynuclear Aromatic Compounds, Synthesis and Purification ao_seriesVIII 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. 176 Folder The folder containing the original item. 5186 Series The series number of the original item. Series VIII 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 Ellefson, Paul V. Source A related resource from which the described resource is derived Journal of Forestry Date A point or period of time associated with an event in the lifecycle of the resource 1973-02-01 Title A name given to the resource Environmental Impact Statements required by NEPA ao_seriesVIII 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. 193 Folder The folder containing the original item. 5448 Series The series number of the original item. Series VIII 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 Epstein, Samuel S. Source A related resource from which the described resource is derived Trial Date A point or period of time associated with an event in the lifecycle of the resource 1983-11-01 Title A name given to the resource Problems of Causality, Burdens of Proof and Restitution: Agent Orange Diseases ao_seriesVIII