EPA-600/2-77-H3 August 1977 Environmental Protection Technology Series ASSESSMENT OF TECHNIQUES FOR DETOXIFICATION OF SELECTED HAZARDOUS MATERIALS Municipal Environmental Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Cincinnati, Ohio 45268 ------- 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 cate- gories were established to facilitate further development and application of en- vironmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The nine series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7. Interagency Energy-Environment Research and Development 8. "Special" Reports 9. Miscellaneous Reports This report has been assigned to the ENVIRONMENTAL PROTECTION TECH- NOLOGY series. This series describes research performed to develop and dem- onstrate instrumentation, equipment, and methodology to repair or prevent en- vironmental 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 Informa- tion Service, Springfield, Virginia 22161. ------- EPA-600/2-77-143 August 1977 ASSESSMENT OF TECHNIQUES FOR DETOXIFICATION OF SELECTED HAZARDOUS MATERIALS by i Benard J. Brown Milton K. Christensen Bernie E. Hackley, Jr. Ronald L. Kassel Gerald J. Kolaja James H. Manthei Charles E. Williamson Chemical Laboratory, Edgewood Arsenal Aberdeen Proving Ground, Maryland 21010 EPA-IAG-D4-0429 EPA-IAG-D5-0429 EPA-IAG-D6-0429 Project Officer Charles Rogers Solid and Hazardous Waste Research Division Municipal Environmental Research Laboratory Cincinnati, Ohio 45268 MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 ------- DISCLAIMER This report has been reviewed by the Municipal Environmental Research Laboratory, U.S. Environmental Protection Agency, and approved for publica- tion. 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 of recommendation for use. 11 ------- FOREWORD The Environmental Protection Agency was created because of increasing public and government concern about the dangers of pollution to the health and welfare of the American people. Noxious air, foul water, and spoiled land are tragic testimony to the deterioration of our natural environment. The complexity of that environment and the interplay between its components require a concentrated and integrated attack on the problem. Research and development is that necessary first step in problem solu- tion and it involves defining the problem, measuring its impact, and searching for solutions. The Municipal Environmental Research Laboratory develops new and improved technology and systems for the prevention, treat- ment, and management of wastewater and solid and hazardous waste pollutant discharges from municipal and community sources, for the preservation and treatment of public drinking water supplies, and to minimize the adverse economic, social, health, and aesthetic effects of pollution. This publica- tion is one of the products of that research; a most vital communications link between the researcher and the user community. This report discusses some of the processes used to detoxify pesticides and gives test results for products produced by these processes. Francis T. Mayo, Director Municipal Environmental Research Laboratory iii ------- PREFACE The Environmental Protection Agency has identified a series of hazardous and toxic materials which were manufactured on a large scale during the past few years and now have been found to be harmful. These are characterized by the polychlorinated hydrocarbon insecticides, polychlorinated biphenyls (PCB's) and benzidine. In addition to these materials the EPA has listed 35 chemical pesticides that, because of their widespread distribution, present difficult disposal problems. The first group of materials, which includes four of the pesticides, is no longer to be used and is scheduled for detoxification. Proper disposal of all of these hazardous materials pose problems that are very serious from a health hazard viewpoint and can be very difficult to solve. Municipal waste disposal plants are generally not capable of treating such products, and their release into streams or im- properly designed land disposal sites has led to widespread and highly undesirable environmental contamination. Studies of decontamination methods have been too limited to provide a valid basis for the selection of a suitable detoxification procedure. Studies that have been made have rarely included an adequate assessment of the toxicity of the products obtained. No matter how free of toxicity, the materials produced should be biodegradable and not accumulate in the food chain. In general, the presence of chlorine atoms in chemical compounds contributes to resistance to biodegradation and poor water solubility coupled with high oil solubility. This often leads to accumulation in the food chain and deposition in the body fats. One stipulation of this agreement was that products produced by Edge- wood Arsenal and other EPA Contractors would be subjected to toxicological evaluation. Edgewood Arsenal has been engaged in the study of methods for the detoxification of toxic materials for many years. Continuing studies of this type are a fundamental part of Edgewood Arsenal's basic mission program. This report describes some of the techniques for detoxification and gives results of toxicological studies conducted on compounds produced by these techniques. iv ------- ABSTRACT A review and evaluation of available processes for detoxification of the first group of hazardous materials was conducted during Phase I of the inter- agency agreement (1974 calendar year). The processes used for specific hazardous materials were identified. One process found during this litera- ture survey described the reaction of PCB's with amines giving a variety of products that were supposed to have useful properties. Two of these products that were available were obtained and evaluated toxicologically. Both proved to be highly toxic. Products produced by catalytic decomposition at Worcester Polytechnic Institute were to be studied for toxicity; however, some samples were not large enough for adequate testing and some were insoluble. In many cases the products were not adequately identified as to composition and concentration. For these reasons, though some of the products may have been reduced in toxicity, accurate toxicological evaluation could not be accomplished. Using their expertise in detoxification methods, personnel from the Chemical Laboratory at Edgewood Arsenal have developed a process by which a number of the chlorinated hydrocarbon pesticides have been converted into water soluble compounds. Acute toxicological studies indicated that these products may be less toxic than the pesticides from which they were made. As they are considerably more water soluble than the parent insecticide it was hoped that they would not accumulate in wildlife or man. This should be beneficial for purposes of health and the environment. Unfortunately bioaccumulation studies have not been performed to prove this point. In the preliminary stuides biodegradation did not occur. Incinerator residue samples, produced by Midwest Research Institute, were insoluble in all commonly used solvents so intravenous mammalian evaluations could not be run. Some of the residues were pulverized and put into fish tanks and screened for 96-hr toxicity to bluegills. All but one of the samples were nontoxic at concentrations up to 1000 mg/1. The one exception was considered practically nontoxic with a 96-hr TL50 of 320 mg/1. This report was submitted in fulfillment of Interagency Agreements EPA- IAG-D4-0429, EPA-IAG-D5-0429 and EPA-IAG-D6-0429 by the Toxicology Division, Chemical Laboratory, Edgewood Arsenal, Aberdeen Proving Ground, Maryland, under sponsorship of the U.S. Environmental Protection Agency. The report covers the period from March 1974 to September 1976. ------- CONTENTS Foreword Preface Abstract Figures Tables Acknowledgement 1. Introduction 1 2. Conclusions and Recommendations 2 3. Literature Search 3 4. Amine Reactions 4 Chemistry 4 Toxicity « 5 5. Catalytic Processing 8 Chemistry 8 Toxicity 8 6. Sulf onatlon 11 Chemistry 11 Toxicity 18 7. Incinerator Residues 25 Appendixes A. Description of acute toxicity studies 27 B. Estimate of operating costs of sulfonation process 31 Glossary 33 vii ------- FIGURES Number Page 1 Postulated mechanism for electrochemical oxidation of DDE to DBA 12 2 Some parent compounds and sulfonated products of DDT and ODD 14 3 Sulfonation of three chlorinated hydrocarbon insecticides .... 16 4 Sulfonation of Aldrin 16 5 Attempted sulfonation of Endrin 17 6 Dehydrohalogenation of Chlordane 17 viii ------- TABLES Number Page 1 Toxicity Studies, Millmaster-Onyx Patent 6 2 96-Hr TL50 Static Bioassay-Bluegill 7 3 lexicological Studies of Compounds Produced by Worcester Polytechnic Institute 9 4 Sulfonation of DDT, DDE and ODD 13 5 96-Hr Toxicity Screening-Sulfonates 18 6 IV Mouse LD50 (mg/kg) Sulfonates 19 7 Midwest Research Institute Incineration Residues 25 ix ------- ACKNOWLEDGMENTS During the period of time devoted to this program we were fortunate to have valuable contributions by: J. Cooper, R. Biskup, 0. Owens and other members of Toxicology and Chemical Research Divisions of Edgewood Arsenal. We wish to express our sincere gratitude to the Project Officers, B.P. McNamara, Chief, Toxicology Division, Edgewood Arsenal:and Charles Rogers, Solid and Hazardous Waste Research Division, EPA, for their advice and interest. x ------- SECTION 1 INTRODUCTION Edgewood Arsenal has been engaged in the study of methods for the detox- ification of toxic materials for many years. Continuing studies of this type are a fundamental part of Edgewood Arsenal's basic mission program. In 1974, based on this experience, Edgewood Arsenal and the Environmental Pro- tection Agency entered into an interagency agreement to study methods for detoxification of a group of hazardous and toxic materials identified by EPA as Aldrin, Dieldrin, Endrin, DDD, DDE, DDT, Toxaphene and the PCB's and benzidine. Studies of methods for deactivation of these compounds had involved only the aspects of chemical transformation, ignoring the question of toxicity of the resultant product. It was necessary, therefore, to review and evaluate existing chemical processess, characterize the resultant products, and assess their toxicity. These products will hopefully be non- toxic, and either have useful properties or be biodegradable. For the second year effort the Toxicology Division was asked, in addition to the original group of hazardous materials, to assess techniques for detoxification and disposal of small amounts (5 gal, or 50 Ib) of 35 common pesticides. ------- SECTION 2 CONCLUSIONS AND RECOMMENDATIONS This report discusses some of the processes investigated as methods of eliminating hazardous and persistant materials from the environment. Two of the processes, sulfonation and incineration, show some promise and should be subjected to addtional investigation. There are other processes, not yet studied, that may solve the problem. These should be studied. Efforts should continue to seek new and more effective detoxification processes. Assessments should be made for the toxicity of the products obtained and the safety of the processes used. Reaction products showing a low level of toxicity, water solubility or biodegradability should be studied further. ------- SECTION 3 LITERATURE SEARCH A literature search was conducted in two phases. One, a machine search, made use of the computerized information retrieval facilities of NERC, Cincinnati. It emphasized the retrieval of existing information concerning the reaction of the subject compounds. The other phase was manual search of pertinent literature and included older literature published prior to that compiled in the computerized system. Also included was the chemistry of related compounds that might provide leads for new approaches to detoxifica- tion of the subject compounds. The search was completed in December 1974. A comprehensive report was prepared and submitted to EPA at that time.* * A. Rednor and G. M. Steinberg, Assessment of Techniques for Detoxification of Selected Hazardous Materials, A literature search, Dec 1974. ------- SECTION 4 AMINE REACTIONS CHEMISTRY While searching the literature a patent was found for a process that seemed to offer promise.* The patent, held by the Millmaster-Onyx Corp., New York, N.Y., described reactions of PCB's with amines to give a variety of substituted amino-polychlorobiphenyls which were supposed to have some useful properties. The Millmaster-Onyx Corporation was contacted to obtain information about the processes and samples for toxicological testing. The PCB reactions were no longer being considered, but two available samples were sent to us. They were analyzed for composition and purity then dissolved in suitable solvents so they could be used for animal toxicity studies. The glass-like solid AM 959 (from Aroclor 1260) was dissolved in water producing solution with pH of 6.4. The viscous AM 1078 (from Aroclor 1248) was dis- olved in PEG-200 producing a solution with a pH of 8.5. To determine whether the Millmaster-Onyx process reduced the toxicity of the PCB's,testing of the parent compounds was necessary. Aroclor is the trade name of PCB's manufactured in the U.S.solely by the Monsanto Chemical Company. An Aroclor is a complex mixture of isomers of PCB's. The various Aroclors are differentiated by a four-digit number, with the last two digits indicating the percentage of chlorine in the mixture. Aroclor 1242, for example, is a mixture containing 42% chlorine; Aroclor 1254 contains 54% chlorine. The Aroclors used in the Millmaster-Onyx reaction (1248 and 1260) are no longer being made. From the Monsanto Chemical Company samples of Aroclor 1242 and 1254 were obtained. These were used as comparative samples to judge the toxicity of the original Aroclors. It must be realized that the Aroclor 1242 and 1254 cannot be accepted as an absolute standard for comparison to Aroclor 1248 and 1260. It is hoped that they might provide a rough estimate for the toxicity of the originals. * J.J. Merianos, E.G. Shay, B. Mead and A.N. Petrocci, U.S., E.663, May 16, 1972. "N-(Halogenated Biphenyl)-Diethylenetriamines". ------- TOXICOLOGY Comparative toxicity evaluations of Aroclor 1242, Aroclor 1254, diethylenetriamine and the two PCB reaction products AM 959 (from Aroclor 1260) and AM 1078 (from Aroclor 1248) were conducted. Intravenous LDSO's were determined in mice, oral toxicity was estimated in rats, and skin and eye irritation evaluations following FDA procedures were performed in rabbits.* Results, as summarized in Table 1, show the PCB reaction products AM 959 and 1078 are 15 to 25 times more toxic to the mouse than the Aroclors to which they were compared. These reaction products are also more toxic (5 - 7 X) than diethylenetriamine in the mouse. Results in rats, though limited by small samples sized for testing, also show that the reaction products are more toxic than the Aroclors but about equally toxic to diethylenetriamine. Results of the irritation evaluations show the reaction products to be more irritating to the eye and equally irritating to rabbit skin as compared to the Aroclors. Diethylenetriamine was a severe irritant to both eyes and skin and by FDA standards would be classified as a primary irritant. These findings regarding irritation are not unexpected as it is known the amines, in general, are often culprits in this regard. In addition to above mammalian toxicity evaluations, a 96-hr static bioassay in Bluegill Sunfish was performed using solutions of AM 959 and AM 1057. Concentration levels between 1.0 and 100 ppm of each product were used. All fish died within a few minutes at the 100 ppm level and at 4.8 ppm all fish died within 24 hours. The 96-hr TL50 for AM 1057 was found to be about 2 ppm and for AM 959 about 1.0 ppm. Results are shown in Table 2. * See Appendix A ------- TABLE 1. TOXICITY STUDIES - MILLMASTER-ONYX PATENT Compound I.V. Mouse Oral, Rat 24-hr LD50 mg/kg 1 gm/kg Irritancy, Rabbit Eye (0.1 ml/eye) Skin Aroclor 1242 1242 (neat) Aroclor 1254 975 (neat) Diethylenetriamine 373 (neat) AM 959* 48.7 (from Aroclor 1260) AM 1078** 66.9 (from Aroclor 1248) 1/10 0/10 3/10, 343 min, over night, >24 <48 hr 4/10 >24< 48 hr(2) >48 <72 hr (2) 3/10 overnight (2) 48 hr (1) 0/6, Negative test non-irritant 1/6, Negative test non-irritant 6/6, Positive test irritant compound 6/6, Positive test irritant compound 6/6, Positive test irritant compound P.I.I.=2.16*** non-irritant P.I.I.=0.69 non-irritant P.I.I.=6.50 irritant compound P.1.1.=0.79 (neat) P.1.1.=2.25 P.1.1=2.13 (neat) P.1.1.=2.46 non-irritant * concentration =65.8 mg/ml in water for I.V. mouse study 1.038 gm/ml in water for other studies ** concentration = 295.1 mg/ml in PEG 200 for I.V. mouse study 0.9995 gm/ml in PEG 200 for other studies *** P.I.I = Primary Irritation Index, ^5 = primary irritant ------- TABLE 2. 96-hr TL STATIC BIOASSAY - BLUEGILL Compound Cone . ppm AM - 959 0 1.0 2.4 4.8 7.5 10.0 AM - 1057 0 1.0 2.4 4.8 7.5 10.0 1 2 0/6 0/6 0/6 0.6 1/6 6/6 6/6 0/6 0/6 0/6 0/6 0/6 4/6 6/6 6/6 5 0/6 0/6 2/6 6/6 - - - - - 3/6 - _ Deaths in hours 7 8 0/6 0/6 0/6 4/6 - _ - - - _ 4/6 - - - 24 0/6 0/6 6/6 - - - - - 1/6 6/6 - — 32 48 96 0/6 0/6 0/6 2/6 3/6 3/6 6/6 6/6 6/6 6/6 0/6 0/6 3/6 5/6 5/6 6/6 6/6 6/6 ------- SECTION 5 CATALYTIC PROCESSING CHEMISTRY As part of the interagency agreement between EPA and Edgewood Arsenal (EA), compounds from other sources were to be submitted to EA for toxicolog- ical characterization. Dr. Wilmer Kranich of Worcester Polytechnic Institute, studying catalytic decomposition of chlorinated hydrocarbons, was a principal source of compounds for evaluation. TOXICOLOGY Some difficulty was encountered in evaluating these compounds primarily because the samples were too small and/or insoluble for toxicity testing. In spite of these diffIculities attemptes were made to evaluate their toxicity. To date, a total of 24 compounds submitted by Dr. Kranich have been evaluated in the mouse. Five are products from Aroclor, eleven are products from DDT, two are products from Toxaphene, and six are products from Dieldrin. Results of these tests are given in Table 3. These results are very difficult to interpret as solutions received were not characterized by composition or concentration. As a consequence, results could only be expressed in volume of material injected per kilogram of body weight. Other materials were received as solids and could therefore be weighed,and the weight of material per kilogram of body weight is used. There is no way to make a direct comparison between the two expressions until something is known about the solutions tested (specific gravity, concentra- tion) that would allow translation of volume units to weight units. For the Aroclor compounds, except for compound WPI-2, it would appear that the products from Dr. Kranichfs catalytic processing are about as toxic as the reference Aroclor tested. One, WPI-1, is almost half as toxic (0.65 ml/kg) and one, WPI-13, twice as toxic (0.22 ml/kg). ------- TABLE 3. TOXICOLOGYICAL STUDIES OF COMPOUNDS PRODUCED BY WORCESTER POLYTECHNIC INSTITUTE Sample Number Starting Material 14-day mouse, iv LD50 (95% CL) Reference WPI - 1 WPI - 3 WPI - 2 WPI - 12* WPI - 13 Aroclor 0.37 (0.30-0.45) ml/kg " 0.65(0.63-0.68) ml/kg 0.48(0.40-0.59) ml/kg " 114.9 (104.7-126.2) ml/kg " 0.37(0.34-0.41) ml/kg ^ 0.22(0^20-0.25) ml/kg Reference WPI - 4 WPI - 5 WPI - 6 WPI - 7 WPI - 8 WPI - 9 WPI - 10 WPI - 11 WPI - 22 WPI - 23 WPI - 24 DDT 76. not 194. 1. 1. 0. 199. " 162. 351. 0. o. 0. 8(68.1-86.7) mg/kg tested-bottle broken 4(155.5-243.0) mg/kg 0(0.95-1.05) ml/kg 41(1.29-1.54) ml/kg 071(0.064-0.079) ml/kg (164-242) mg/kg (144-182) mg/kg (320-384) mg/kg 40 (0.37-0.43) ml/kg 79(0.73-0.86) ml/kg 56(0.56-0.56) mg/kg Reference WPI - 14 WPI - 15 Toxaphene 20.5(19.6-21.4) mg/kg 0.39(0.33-0.45) ml/kg 11 0.14(0.12-0.16) ml/kg Reference WPI - 16 WPI - 17 WPI - 18 WPI - 19 WPI - 20 WPI - 21 Dieldrin ii n n ii n 10.5(9.3-11.8) mg/kg 0.29(0.26-11.8) ml/kg 0.35(0.31-0.40) ml/kg 0.11(0.10-0.14) ml/kg 0.40(0.37-0.43) ml/kg * Supernatant fluid ------- For DDT residues (expressed in mg/kg) compared with the reference compound, it appears the residues WPI-5, 9, 10 and 11 are approximately 2 to 4.5 times less toxic than reference DDT. No other comparisions are possible at this time. No comparisions are possible for the Toxaphene compounds. For the Dieldrin compounds the reference compound can only be compared with WPI-21. In this case WPI-21 is about 13 time less toxic than Dieldrin. A comparison with Dieldrin cannot be made for the other products, WPI-16 variation being a factor of 4, etc. 10 ------- SECTION 6 SULFONATION CHEMISTRY Background Since compounds were not being received from outside sources, in June 1974 EPA suggested that Edgewood Arsenal might try chemical processess for detoxification of the chlorinated hydrocarbons. Edgewood Arsenal personnel have, since September 1974, been working on this problem. The first attempts were to convert DDT to water soluble compounds. The hope was that this would prevent accumulation in the food chain. DDA has been found to be a metabolite of DDT in several animal species and is excreted in the urine various species including man. It is, therefore, not expected to accumulate in the food chain. DBA is obtained by the basic hydrolysis of either DDT or its elimination product l,l-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE) via alcoholic potassium hydroxide or in ethylene glycol containing barium hydroxide. The metabolism and fate of DBA is unknown to us. DDT is notable for its lipophilicity and reluctance to enter the aqueous phase. In order to cause reaction between DDT and nucleophilic reagents, a suitable reaction medium is necessary. To accomplish this non-aqueous sol- vents, bi-phasic aqueous-organic solvent mixtures and aqueous solutions con- taining detergents or phase-transfer catalysts were considered. As a class, nucleophilic reactions are base catalyzed. In the presence of even mild base, DDT eliminates HC1 to produce DDE. For this reason, DDE is usually a product of the nucleophilic reaction of DDT and is resistant to further nucleophilic attack. The conversion of DDT to DDA by phase-transfer catalysis was attempted in a mixture of DDT, toluene, sodium hydroxide, water and tetrabutyl- ammonium iodide by heating to 88°C for 6 hours. The DDT was completely con- verted to this dehydrochlorination product DDE. No DDA was detected. 11 ------- DDA was successfully prepared from DDT by the action of potassium hydroxide in diethylene glycol at 130°C for 6 hours. The yield, however, was not quantitative and the product was fairly toxic (84 mg/kg, iv mouse). The recently reported electrochemical oxidation of DDE to DBA is of considerable interest. A postulated mechanism is outlined in Figure 1. -HC1 1 Figure 1. Postulated mechanism for electrochemical oxidation of DDE to DBA. Several attempted conversions of DDT to DBA using basic potassium permanga- nate with phase-transfer conditions according to the following scheme results in the conversion of DDT to DDE with little or no oxidation taking place. OH~ DDT ^ DDE———?^ 7 DBA -HOI __ <;- Mn04 The attempted reaction of DDT with sodium thiosulfate by phase-transfer catalysis using benzene as the orgainic solvent and tetrabutylammonium iodide as the catalyst yielded the quantitative return of DDT. The fusion of molten sodium hydroxide and DDT yielded a product that was not water soluble (probable DDE). The fusion of molten sodium thiosul- fate with DDT produced essentially the same results except two phases were visible in the melt. The product was apparently unreacted DDT. The attempted reaction of DDT with sodium thiosulfate in an aqueous- detergent mixture also yielded only unreacted DDT. DDT was heated in an aqueous solution of sodium thosulfate to which 25% (V:V) of Tween 40 ( a nonionic detergent) had been added. Although the DDT appeared to dissolve 12 ------- at 60° to 70°C, no reaction occured and DDT was recovered quantitatively. In attempts to prepare sulfate derivatives of DDT and DDE, several experiments were performed. DDT was added to an aqueous solution of sulfuric acid and cetyltrimethylammonium bromide. Heating to the boiling point did not cause the DDT to dissolve. In other experiments, DDE was heated with concentrated sulfuric acid at 80°C, at 160°C and in a refluxing solution of sulfuric acid in DMF. In none of these instances did reaction occur. These reactions demonstrate properties of DDT that govern its behavior in the environment. Although these attempts were intended to solublize and degrade DDT, they clearly demonstrated, instead, that this insecticide can exist under certain reaction conditions even more severe than those encountered in the environment. Although DDT is reactive as an electrophile, its solubility is such that it can only rarely contact nucleophilic reagents. When this does occur, elimination of HC1 readily yields DDE which is more resistant to further attack. Sulfonation Reaction DDT, DDE, ODD A report of a water soluble sulfonation product of undetermined structure was found in the patent literature. Investigations have been conducted for sulfonation of DDT, DDE and ODD under a variety of conditions. Results are summarized in Table 4. TABLE 4. SULFONATION OF DDT, DDE AND ODD Substrate Purity %SO, Temperature* * S.B., Steam Bath; R.T., Room Temperature ** U, Unsymmetrical; S, Symmetrical; UK, Unknown *** Contains 20% o,p' DDT **** Contains 25% o,pf ODD Product** DDT DDT DDT DDT DDT DDE DDE DDE DDD ODD DDD 99% 99% 99% 99% Tech*** 99% 99% 99% Tech**** Tech**** Tech**** 30 30 20 20 20 30 20 20 30 20 30 S.B 150° S.B. R.T. S.B. S.B. S.B. S.B. 130° R.T. S.B. U U S S S&UK S S s&u UK S&UK U&UK 13 ------- When DDT is treated with fuming sulfuric acid containing 20 percent free SO,,, overnight at room temperature or for 5 hours on a steam bath, 2,2-bis(3-sulfo- 4-chlorophenyl)-l,l-trichloroethane (I) is formed. (Fig. 2) Upon treatment with base during workup, hydrogen chloride is eliminated as with DDT to form 2,2-bis(3-sulfo-4-chlorophenyl)-l,l-dichloroethylene disodium salt (II). When DDT is treated with fuming sulfuric acid containing 30 percent free SO on the steam bath or at 150°, product isolated is 2-<3,5-disulfo-4-chloro- phyenyl)2-(4-chlorophenyl)-l,l-dichloroethylene disodium salt (III). II SO' Na Cl Cl VII VIII Figure 2. Some parent compounds and sulfonated products of DDT and ODD In our ODD sulfonation experiments, technical grade ODD was used. It is a mixture of approximately 75 percent p,p' DDD (IV) and 25 percent o,p' ODD (V), and yields a mixture of products upon sulfonation. The p,p' DDD appears to be sulfonated similarly to DDT in that treatment at room temperature with 20 percent S0« oleur.i*leads to the symmetrically substituted productCvi^ and sulfonation with 30 percent S0_ oleum leads to the unsymmetrically substitut- ed product (VII), In both cases, the o,p' isomer (V) gave rise to a product or products whose structure(s) could not be determined by Nuclear-Magnetic reasonance (NMR) while in mixture VI on VII. Sulfonation with 30 percent S0_ oleum at 130° gave a more complex mixture. Its NMR spectrum was too complex to interpret. * A heavy oily strongly corrosive solution of sulfur trioxide in anhydrous sulfuric acid. 14 ------- When technical DDT containing 20 percent of o,p' isomer(VIII)was sulfonated with 20 percent S0_ oleum on a steam bath, a mixture of the symmetrically substituted product,(III} and other unknown product or products were found. The sulfonation of pure, DDE, both with 20 and ,30 percent fuming sulfuric acid, on a steam bath, led to the symmetrical product. However, a recent run has produced a mixture of 76 percent of the symmetrical isomer and 24 percent of the unsymmetrical isomer. This result is not yet understood. Polychlorinated Biphenyls (PCB's) The polychlorinated biphenyls(rCB's) are mixtures of biphenyls which have been chlorinated to varying degrees. Theorethically 210 different chlorination products can exist. In the U. S., the Monsanto Co. produces these mixtures under the trade name Aroclor. We have undertaken the sul- fonation of Aroclor 1242 and 1254 (products containing 42% and 54% chlorine by weight, respectively). Both Aroclor 1242 and Aroclor 1254 when heated at 95° with fuming sulfuric acid for 5 hours yield highly water soluble ammonium sulfonates along with sulfur containing a material which is insoluble in acid, base,water,and a wide variety of organic solvents. It is probably a sulfonation product of highly chlorinated PCB's. Because of the higher toxicity of the water soluble products (417 rag/kg and 247 mg/kg, i.v. mouse, for PCB 1242 and 1254 sulfonates respectively) further investigations of these products has not been continued. Other Chlorinated Hydrocarbon Insecticides (See Figure 3 below) Diuron (la) and Linuron (Ib) are readily converted to 3-(4,5-dichloro- 2-hydroxysulfonylphenyl)-ll-dimethylurea (Ila) and 3-(4,5-dichloro-2-hydroxy- sulfonylphenyl)-l-methoxyl-l-methylurea (lib), respectively. Diuron sulfon- ate was isolated as the free acid and Linuron sulfonate as the ammonium salt. Chloraben (3-amino-2,5-dichlorobenzoic acid) III, was treated for 5 hours at 95° with 30 percent oleum. The reaction was worked up to yield the water soluble ammonium salt of the sulfonation product. The NMR spectrum shows a singlet in the aromatic region but the site of sulfonation could not be determined by this technique. 15 ------- a; R = CH3 b: R = OCH R CO.H III Figure 3. Sulfonation of three chlorinated hydrocarbon insecticides. Aldrin, when heated at 100° with 30 percent fuming sulfuric acid, yields what NMR and mass spectrometry suggest to be the hydroxy sulfonate I. The primary product of the sulfonated reaction is probably the sultone, II, which yields the hydroxy sulfonate upon hydrolysis. (See Figure 4 below) SO, H \ -C-0 -c-so2 H H20 H I -C-OH I -C-SO.H I 3 H II Figure 4. Sulfonation of Aldrin 16 ------- When Endrin was treated with fuming sulfuric, an exothermic reaction ensued. The product from this reaction is ket^ endrin, a metabolite of Endrin known to form under acidic conditions. (See Figure 5 below) H.SO, 0 Endrin Figure 5. Attempted sulfonation of Endrin Chlordane was recovered almost quantitatively after treatment with 30 percent oleum on a steam bath for 5 hours. Treatment with alcoholic potassium hydroxide led to the formation of the diene. (See Figure 6 below) Cl KOH Cl Chlordane Figure 6. Dehydrohalogenation of Chlorodane Attempted sulfonation of the diene resulted in the formation of a material of unknown composition which contained no sulfur. Workup of the reaction mixture of heptachlor and 30 percent fuming sulfuric acid with ammonium hydroxide led to the recovery of ammonium chloride but no sulfonation product. Toxaphene on treatment with 30 percent oleum did not yield a sulfonated product. 2,4-Dichlorophenoxyacetic acid (2,4-D) reacted exothermally with charring when treated with 30 percent fuming sulfuric acid and no clean product was isolated. 17 ------- An estimate of the approximate per pound cost for detoxification of small and large amounts of pesticide using the sulfonation process is enclosed as appendix B. TOXICOLOGY Acute Acute 96-hr toxicity screening tests were conducted using DDE and DDE disulfate sodium salts against bluegills. Six concentrations were used for each compound: 100, 10, 1, 0.1 and 0.001 mg/1 for DDE. For the DDE disulfate the lowest concentration was changed to 0.005 mg/1. The DDE was dissolved in acetone. Control tanks were used with acetone equal to the in the DDE solution. Four fish were exposed at each concentration. Table 5 gives the results of this study. The sulfonate produced no mortalities while the unconverted DDE was toxic to fish at concentration for 1 mg/1 and up. Table 6 shows the I.V. mouse LDSO's for reference samples and some of the sulfonated compounds TABLE 5. 96 Hr TOXICITY SCREENING SULFONATE Compound Species Toxicity DDE disulfate sodium salt DDE (in acetone) Acetone Control Bluegills No mortality at concentra- tion from 0.005 to 100 mg/1 Bluegills * 50% mortality at concentra- tions of 10 and 100 mg/1 100% mortality at concen- tration of 1 mg/1 Bluegills No mortality at concentra- tions equal to those used with the DDE * Lower mortality at higher concentrations possible caused by DDE comming out of solution in water. 18 ------- TABLE 6. I.V. MOUSE LD50 (rag/kg) SULFONATES Compound Aldrin (Ref . Sample) Aldrin (Sulf onate) Aldrin (Sulfate Na Salt) Aroclor 1242 (Ref. Sample) Aroclor 1242 (Ammonium Sulfonate) Aroclor 1254 (Ref. Sample) Aroclor 2154 (Ammonium Sulfonate) Chlordane (Ref. Sample) Chlordane (from Base) DDT (Ref. Sample) DDE (Disulfonate Sodium Salt) ODD (Disulfate Sodium Salt) LD50 24 hr 15.65 147 800.8 925 417 1214 288.8 159.6 171.5 80.7 648.2 1118.5 LD50 14 day 14.31 same 702.1 813 same 608 246.6 127.5 167.6 76.8 same same Eggshell Study The effect of decreasing eggshell thickness and weight due to DDT or DDE ingestion has been shown to occur both naturally and in controlled laboratory experiments. Morphologic alterations in the eggshell gland were seen in mallard ducks (Anas platyrhynchos) fed 75 ppm DDT for 6 weeks prior to egg production in experiments conducted in this laboratory. DDE has been shown to cause inhibition of Ca ATPase in in-vitro experiments. Ca ATPase is an enzyme responsible for transport of eggshell calcium. A study was under- taken to determine the effects of DDT, DDE and their sulfonated derivatives on eggshell production. To be examined were (1) eggshell measurements in- cluding weight, length, width, thickness, and the ratio of weight/length x width; (2) light and electron microscopy of eggshell gland, liver and kidney and (3) Ca ATPase activity. Young adult mallard ducks obtained from a local supplier were randomly assigned to cages, 5 females and 1 male per cage, and maintained on commercial poultry laying mash. After a 2 month acclimatization period egg production was induced by regulating the photoperiod. When peak egg production was reached feeding continued with either 10 or 50 ppm of DDT, DDE, DOT-SO, or DDE-SO added to the same poultry laying mash. Four groups were fed the normal diet. Eggs were collected daily from each group for 30 days. The contents were removed from the eggs and the hollow shells were 19 ------- air dried and stored until measurements were made. A total of 434 eggs were measured for (1) weight (grams), (2) overall length and width (cm), and (3) shell thickness (mm). Four measurements were made around the girth of each egg. One hen from each group was sacrificed after 1 week of feeding the compounds. The remaining hens were sacrificed after 30 days. Sections of eggshells gland, liver and kedney were fixed in 4% formaldehyde, 1% glutaraldehyde and 200 millimols PO, buffer for evaluation by light and electron microscopy. Additional sections of eggshell gland were collected and processed to obtain a microsomal fraction for Ca ATPase determination. Sections of fat, brain and eggshell gland were taken from each group to be analyzed for pesticides by gas chromatography. Statistical analysis of all data was done by Least-Squares and Maximum Likelihood General Purpose Program.* In all statistical analyses performed, no differences were seen between dose levels of the compound fed and the 10 and 50 ppm groups are considered together. Figure 1 shows the results of eggshell thickness measurements over the 30 day experimental period. There were no statistical differences in mean thickness of control eggs between the days measured; the mean value was .401 mm. As expected, the thickness of the eggs from ducks fed DDE was significantly reduced (p.01) at day 1 and remained thinner for the entire 30 day period. The eggs from the ducks fed DDT remained as thick as control eggs until day 14 but were significantly thinner (p. 01) for the remainder of the experimental period. The DDT-SO, and DDE-SO ducks produced eggs which were identical in thickness measurements and were grouped together. The sulfonated groups laid eggs which were the same thickness as controls except on day 18. Where there was significant difference (p. 01). The thickness returned to control levels at day 27 and remainder of the experi- ment. Figure 2 shows the R-values** obtained for eggshells from ducks fed DDT, DDE, sulfonated derivatives and control diets. The purpose of the R-values is to correct for eggshell weight in relation to size. A significant reduc tion is shown in the R-values for eggshells from DDT and DDE fed ducks when compared to controls. There was no significant difference between the R-val- ues obtained from the sulfonated and control eggshells. The DDT-SO, and DDE- SO, values did not vary significantly and were considered as one group. The graph in figure 2 shows a sharp decline at day 18 because heat drying was used instead of air drying from this day until the end of the experiment. Since all groups were treated in the same manner, the relationship between the groups remained constant. The weights of the eggshells followed the same pattern as thickness measurements. Significant differences were seen in length and width measurements of eggshells from the DDE-SO, and DDT fed ducks. *I wish to acknowledge the assistance in computer programming and statis- tical analysis of the cfataby Mr. Elden Leighton and Dr. Jerry F, Hardisty. ** R = Weight Length X Width 20 ------- H O .410- .400- .390- .380. .370- .360- .350- .340- .330- .320- \ 10 —T 15 ~T 20 T 25 ~T 30 DAYS Figure 1. Mean Eggshell Thickness From Ducks Fed DDT, DDE, Sulfonates and Control Diets ------- N) .270" .260* .250- .240- .230- .220- .210- .200- .190- .180-- Control R-Value = weiSht T 10 15 I 20 I 25 30 DAYS Figure 2. Mean R-Values for Eggshells From Ducks Fed DDT, DDE, Sulfonates and Control Diets ------- These differences were corrected for by using R-values. The tissues collected for electron microscopy are being processed and results will be available soon. All samples collected for Ca ATPase analysis are being stored at -60°C. In vitro analysis of DDT, DDE and sulfonated compounds will be performed. The results of this experiment show to that while DDT and DDE fed at levels of 10 and 50 ppm cause significant alterations in eggshell measure- ments such as thickness, weight, and R-values, their sulfonated derivatives do not share these characteristics. Thickness measurements show that while the sulfonated compounds cause a reduction of thickness at day 18 this decreased thickness is not as severe as that caused by DDT or DDE and is transitory effect. The R-values show that DDT and DDE are potent agents in causing a reduction of the weight to size of eggshells but the sulfonated compounds cause no change. The final portion of this study, the electron microscopic study of eggshell gland, liver and kidney and the Ca+ ATPase measurements should be of additional value in determining whether these sulfonated derivatives share some of the toxic properties of the parent compounds. BIODEGRADATION STUDIES One of the hoped for goals of any pesticide conversion product is that it be biodegradable. Several experiments have been carried out to determine if some of the water soluble sulfonates described above are biodegradable. In our first experiment, sodium salts of unsymmetrical disulfonic acid, (derived from DDT). symmetrical disulfonic acid (derived from DDE), and an undefined mixture of sulfonation products derived from ODD, all at a concentration of 98 mg/1, were incubated at room temperature in a basal mineral medium which was inoculated with 5 volume percent of raw sewage from the Sod Run Sewage Treatment Plant of Harford County, Md. Substarate concentrations were determined spectrophotometrically on a periodic basis. After seven weeks no change was observed. Since soil contaiminated with DDT might contain microorganisms capable of utilizing sulfonated DDT derivatives as a source of carbon, additional experiments were performed. Such a soil was obtained from the manufacturing area of Pine Bluff Arsenal throught the courtesy of Robert Donald, Ecological Research Office, Biomedical Laboratory. The sulfonates derived from DDT and DDE (150 mg/1) were incubated in the medium of which two weight percent of 23 ------- soil was added. The samples were shaken continuously on a rotary shaker. Aliquots were periodically taken, centrifuged, and the level of the pesticide remaining in the supernatent was determined. After eight weeks, no change was observed. Recent investigations have indicated, however, that mixed bacterial cultures can mineralize some chlorinated aromatic compound which do not sustain microbial growth, if they are supplied with another source of carbon and energy, the so called "co-substrate enrichment technique." In our experiments using this method, we chose as substrates, the symmetrical and unsymmetrical sulfonates of DDT, the sulfonates of diuron,linuron, and as positive controls, 2,4-D and p-chlorobenzoic acid, both of which are known to undergo microbial degradation. The chlorinated substrates were added to the medium at a concentration of 25 mg/1. Each compound under study was incubated both with glucose as a co-substrate (500 mg/1) and without glucose. The cultures were inoculated with 2.7 volume percent of sewage from the Sod Run Plant and incubated at ambient temperature on a rotary shaker. Levels of substrates were determined as above. After 24 hours, all systems to which co-substrate had been added had become quite turbid indicating bacterial growth. After 20 days incubation, 47 percent of the original 2,4-D absor- bance at 283 mm remained in the culture*no co-substrate, and no absorbance was observed in the culture with co-substrate. Both p-chlorobenzoic acid cultures has about 45 percent of their origi- nal absorbance at 267 mm. No change was observed in the other systems. 24 ------- SECTION 7 INCINERATOR RESIDUES Twenty-four incinerator residue, samples, produced by Midwest Research Institute (Table 7), were submitted by EPA for toxicological testing. These samples were insoluble in all commonly used solvents so i.v. mammalian evaluations could not be run. Since standard methods could not be used, 11 of the residues were pulverized, placed in fish tanks and screened for 96-hr toxicity to bluegills. Most of the material settled out after 24-48 hours with the highest concentration (1000 mg/1) remaining quite turbid after 96 hours. Of all samples only Captan run #148 horizontal stack residue produced mortality below 1000 mg/1. The 96 hr TL50 for this sample was 320 mg/1. All other samples appeared to be non-toxic at concentration up to 1000 mg/1. TABLE 7. MIDWEST RESEARCH INSTITUTE SAMPLES Test No. Pesticide Residue Sample(s) After After After After After After 44* DDT Dust 45 DDT Dust 61* Aldrin Granules 64 Aldrin Granules 86 Picloram Pellets 87 Picloram Pellets 104* Malathion Dust 105 Malathion Dust 122 Toxaphene Dust 124* Toxaphene Dust 146 Captan Dust 148** Captan Dust 149 Zineb Dust 150 Zineb Dust 170 Mirex Bait 172 Mirex Bait 148** Captan Dusts Tests 159 Zineb Dust Tests 159 Zineb Dust Tests 126 Toxaphene Dust Tests 50 DDT Dust Tests 126 Toxaphene Dust Tests Primary and Secondary Chambers Primary and Secondary Chambers Primary and Secondary Chambers Primary and Secondary Chambers Primary Chamber (Ground) Primary Chamber Primary and Secondary Chambers Primary and Secondary Chambers Primary and Secondary Chambers Primary and Secondary Chambers Primary and Secondary Chambers Primary and Secondary Chambers Primary and Secondary Chambers Primary and Secondary Chambers Primary Chamber Primary Chamber Horizontal Stack Residue Scrubber 1 Residue Vertical Stack Residue Scrubber 1 Residue Scrubber 1 Residue Horizontal Stack Residue 25 ------- Table 7. continued Test No. Pesticide Residue Sample(s) After 106 Malathion Dust Tests Horizontal Stack Residue After 50* DDT Dust Tests Horizontal Stack Residue *Single sample tested - these samples were tested for toxicity in fish. **2 samples tested - these samples were tested for toxicity in fish. 26 ------- APPENDIX A DESCRIPTION OF ACUTE TOXICITY STUDIES ACUTE LD50 DETERMINATION IN THE MOUSE Male mice from the Edgewood Arsenal colony are used in these tests. All animals are acclimated to the test environment at least 24 hours before test. Ten animals are tested per dose level and a minimum of 4 logrithmical- ly spaced dose levels are used in an effort to produce 0% mortality, 100% mortality and two partial mortality fractions. All injections are made into the lateral tail vein. LDSO's with 95% confidence limits are calculated for 24 hours results as well as for 14 day observation results. Where possible doses are expressed in mg/kg values. When solutions of unknown characteri- zation is tested doses are expressed in ml/kg. ORAL TOXICITY TESTS Rats from the Edgewood Arsenal colony are used in these tests. Except for the species and route of administration (stomach tube), tests are conducted in a manner similar to that described for mice. Where insufficient sample amounts are available to perform a complete test a selected dose or two of material are given to the animals and the result out toxicity response com- pared. SKIN IRRITATION (CFR, TITLE 21, PARA 191.11) Primary irritation to the skin is measured by a patch-test technique on the abraded and intact skin of albino rabbits whose backs were clipped free of hair 24 hours prior to compound application. Six animals are used for each material tested. The test compound, as a liquid (0.5 ml) or a solide (0.5 gm) is applied under a gauze patch to the abraded and intact skin of each animal. Immediately after compound application the animals trunk is wrapped withimpermeable plastic to retard evaporation. After 24 hours of exposure the plastic and gauze are removed from each animal and the resulting reactions to the skin are evaluated and scored according to the FDA 27 ------- procedure. See Table A-l. Readings are again made 72 hours after initia- tion of exposure. TABLE A-l. FDA SCORING TABLE FOR SKIN IRRITATION Skin Reaction Value Erythema and Eschar Formation No erythema 0 Very slight erythema 1 Well defined erythema 2 Mod to severe erythema 3 Severe erythema/eschar 4 Edema Formation No edema 0 Very slight edema 1 Slight edema 2 Moderate edema 3 Severe edema 4 To establish the primary irritation index score (PII), readings obtained for skin reactions against abraded and jutact skin are added together for both the 24-hour readings for both eyrthema/eschar formation and for edema formation. Thus, a total of four values for erythema/eschar and four values for edema are obtained. The total of the eight values are added together and divided by four to give the primary irritation index score for the compound. When the PII score equals or exceeds a value of 5, the compound is rated as a primary skin irritant. No ratings are provided for this test by the FDA for values fo less than 5 though it is clear that com- pounds having a PII score between 3 and 4.9 are significant skin irritants but would not, by definition, be classified as a primary skin irritant. 28 ------- EYE IRRITATION TEST (CFR, TITLE 21, PARA, 191.12) Six albino rabbits are used to evaluate eye irritancy potential of each test material. Both eyes of test animals are examined prior to testing using flucrescein and UV light to assure that only animals without eye damage or irritation are used for testing. All animals are maintained in facilities free of sawdust, wood chips, or other type bedding material that may produce eye irritation. Each test animal is given 0.1 ml of liquid compound or 100 mg of solid compound into one eye, The other eye serves as a comparative control. The test substance is placed into a cup formed by gently pulling the lower lid out. After instillation of the test compound the eye lids are held together for approximately five seconds to insure thorough distribution. Test com- pounds are not washed out of the eye until 24-hours after instillation at which time they are flushed thoroughly with copious quantities of distilled water. Eyes are examined, graded, and recorded for ocular reaction at 24, 48 and 72 hours after compound instillation. After recording the observations at 24 hours, all eyes are further examined after instillation of fluorescein dye using ultraviolet light. The test is considered positive if four or more animals in the test group exhibited a positive reaction. If only one animal exhibits a reaction the test is regarded as negative. If two or three animals exhibit a positive reaction the test is repeated using another group of six animals. In the second test if three or more animals exhibit a positive reaction the test is positive. If one or two animals exhibit positive reaction the test is repeated again. If none of the animals exhibit positive irritation the test is negative. In the third test if one or more animals exhibit a positive response the test is positive and if no positive responses are seen the test is negative. Grades for ocular lesions as defined by the FDA in OFR, Title 21, para. 191.12 are shown in Table A-2. 29 ------- TABLE A-2. GRADATION OF EYE EFFECTS Grade Cornea (C) No ulceration or opacity 0 Scattered or diffuse areas of opacity (other than slight dulling of normal luster), details of iris clearly visible 1* Easily discernible translucent areas, details of iris slightly obscured 2 Nacreous areas, no details of iris visible, size of pupil barely discernible 3 Iris (I) Normal 0 Markedly deepend folds, congestion, swelling moderate circumcorneal injection (any of these or combination of any thereof), iris still re- acting to light (sluggish reaction is positvie) 1* No reaction to light, hemorrhage, gross destruc- tion (any or all of these) 2 Conjunctival Redness (R) (refers to palpebral and bulbar conjunctivae excluding cornea and iris) Vessels normal 0 Some vessels definitely injected 1 Diffuse, crimson red, individual vessels not easily discernible 2* Diffuse beefy red 3 Chemosis (CH) No swelling 0 Any swelling above normal (includes nictiating membrane) 1 Obvious swelling with partial eversion of lids 2* Swelling with lids about half closed 3 Swelling with lids more than half closed 4 * Indicates lowest grades considered positive under Section 191.12 of the Federal Hazardous Substances Labeling Act Regulations. 30 ------- APPENDIX B APPROXIMATE OPERATING COSTS OF PROPOSED PROCESS We have applied commodity costs taken from current Chem. Marketing Reporter and current labor costs in Chemical Process Technology Branch to the process information you gave us on 25 Feb. From this, we arrived at estimates for the process of chemical destruction of DDT (representative of chlorinated aromatic hydrocarbons) in batch quantities of 50 and 2000 Ibs per day. The estimated costs are for rough labor and material only. Not included are facility acquisition costs or the costs of any further disposition of the reaction products. PROCESS DATA USED 1. 30% fuming sulfuric per kilo DDT =1.5 liter 2. NaOH equivalent to all of acid used. 3. Digestion of DDT in acid for 5 hrs at 95°C. 4. Neutralization of reaction mass with aqueous NaOH. COMMODITY DATA 1. Acid - $53.25/ton (less than carload lots) for 100% acid X 1.045 for 20% fuming (30% not listed). 2. NaOH - 76% beads $15.00/100 Ibs. MATERIAL REQUIREMENTS AND COST PER POUND OF DDT 1. 2000 Ibs DDT equivalent to 910 Kg, equivalent to 13551- acid 1355 1- acid equivalent to 375 gals 375 gals at 1.9 sp. g. (approx) = 5940 say 6000 Ibs 6000 Ibs acid at 53.25 X 1.045 $/ton = $167 = $0.083/lbs DDT 31 ------- 2. 30% fuming H SO *106.7% total H SO 1.067 X 6000 X 80/98 * 5226 Ibs NaOH (100%) 5226/0.76 = 6876 say 6900 Ibs 76% NaOH 6900 Ibs at $15.00/100 Ibs - $1035 $1035/2000 Ibs DDT = $0.52/lbs DDT 3. Total material requirements and costs: Fuming sulfuric acid - 3 Ibs/lb DDT - $0.083/lb DDT 76% NaOH - 3.45 Ib/lb DDT- 0.52/lb DDT $0.63/lb DDT Round off to $0.75/lb DDT to account for steam, water and power. ESTIMATED LABOR COSTS 50 Ibs DDT/day basis - 8 man hours 2000 Ibs DDT/day basis - 16 man hours At prevailing Cml Proc Tech stabilized labor rate of $30.38/hr, labor costs are: 50 Ibs/day rate - 243 say $250 = $5.00/lb DDT 2000 Ibs/day rate - say $500 = $0.25/lb DDT LABOR AND MATERIAL COSTS SUMMARY 50 Ibs/day rate $0.75 H- $5.00 = $5.75/lb DDT 2000 Ibs/day rate $0.75 + $0.25 = $1.00/lb DDT * The authors wish to thank Mr. Robert E. Cox of Chemical Process Technology Branch, Chemical & Plants Div., Manufacturing Technology Dir of this estimate. 32 ------- GLOSSARY DBA: 1,1-dichloro benzilic acid DBA: l,l-dichloro-2,2-bis(p-chlorophenyl)acetic acid DDD: 1,l-dichloro-2,2-bis(p-chlorophenyl)ethane DDE: 1,l-dichloro-2,2-bis(p-chlorophenyl)ethylene DDT: 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane DDF: dimethylformamide 33 ------- TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing} 1. REPORT NO. EPA-600/2-77-143 3. RECIPIENT'S ACCESSION NO. 4. TITLE AND SUBTITLE ASSESSMENT OF TECHNIQUES FOR DETOXIFICATION OF SELECTED HAZARDOUS MATERIALS 5. REPORT DATE August 1977 (Issuing Date) 6. PERFORMING ORGANIZATION CODE 7. AUTHOR(S) Benard J. Brown, Milton K. Christensen, Bernie E. Hackley, Jr., Ronald L. Kassel, Gerald J. Kolaja, James H. Manthei, Charles E. Williamson 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS Chemical Laboratory, Edgewood Arsenal Aberdeen Proving Ground, Maryland 21010 10. PROGRAM ELEMENT NO. 1DC618 11. CONTRACT/GRANT NO. EPA-IAG-D4-0429 EPA-IAG-D5-0429 EPA-IAG-D6-0429 12. SPONSORING AGENCY NAME AND ADDRESS Municipal Environmental Research Laboratory—Cin., OH Office of Research and Development U.S. Environmental Protection Agency Cincinnati, Ohio 45268 13. TYPE OF REPORT AND PERIOD COVERED 14. SPONSORING AGENCY CODE EPA/600/14 15. SUPPLEMENTARY NOTES Project Offier: Charles Rogers (513-684-7881) 16. ABSTRACT A review and evaluation of available processes for detoxification of the first group of hazardous materials was conducted during Phase 1 of the inter- agency agreement (1974 calendar year). The processes used for specific hazardous materials were identified. One process found during this literature survey described the reaction of PCB's with amines to give a variety of products that were supposed to have useful properties. Two of these products that were available were obtained and evaluated toxicologically. Both proved to be higly toxic. Products produced by catalytic decomposition were also evaluated for toxicity. In many cases the products were not adequately identified chemically and accurate toxicological evaluation could not be accomplished. 7. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS b.lDENTIFIERS/OPEN ENDED TERMS COSATI Field/Group Detoxification Incinerators Wastes Pesticides Disposal Catalysts Treatment Pesticide Waste Hazardous Waste 13B 6F 8. DISTRIBUTION STATEMENT RELEASE TO PUBLIC 19. SECURITY CLASS (This Report) UNCLASSIFIED 21. NO. OF PAGES 44 20. SECURITY CLASS (Thispage) UNCLASSIFIED 22. PRICE EPA Form 2220-1 (Rev. 4-77) 34 £ U.S. GOVERNMENT PRINTING OFFICE: 1977-757-056/61(96 Region No. 5-11 — ------- |