State of the Art Report on Pesticide Disposal Research - ACS

Jun 30, 1978 - Midwest Research Institute, 425 Volker Boulevard, Kansas City, MO 64110. Disposal and Decontamination of Pesticides. Chapter 6, pp 73â€...
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State of the Art Report on Pesticide Disposal Research RALPH R. WILKINSON, EDWARD W. LAWLESS, ALFRED F. MEINERS, THOMAS L. FERGUSON, GARY L. KELSO, and FRED C. HOPKINS

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Midwest Research Institute, 425 Volker Boulevard, Kansas City, MO 64110

The goal of this study is to review all published and other available information on the current status of pesticide disposal research with emphasis on high temperature incineration, physical-chemical methods, and bioconversion technology. This paper is being presented in order to acquaint you with our contract and its preliminary findings, and to make contact with knowledgeable persons in this field to obtain additional information. The views expressed in this paper are those of the authors and do not necessarily reflect the views or policies of the U.S. Environmental Protection Agency (EPA). We defer in-depth discussions of Molten Salt Technology, Microwave Detoxification, Thermal Degradation, Photochemical Processes, and Catalytic Hydrodechlorination since these topics are covered by other participants at this symposium. High Temperature Incineration The most recent investigations of the incineration of pesticides include studies of several classes of compounds and of formulations as well as of pure active ingredients. In a study by Midwest Research Institute (MRI) (1975), i t was concluded that organic pesticides may be destroyed with efficiencies approaching 99.999%. EPA recommended conditions for incineration are 2 sec retention time at 1000°C. Other time-temperature combinations are possible; e.g., 1 sec at 1100°C. Excess air is required; 80 to 160% excess is recommended (Carnes and Oberacker, 1976; Ferguson et al., 1975.) 1

This study was sponsored by the Environmental P r o t e c t i o n Agency, M u n i c i p a l Environmental Research Laboratory, C i n c i n n a t i , Ohio, under Contract No. 68-03-2527. Mr. Donald A. Oberacker was the P r o j e c t O f f i c e r . 0-8412-0433-0/78/47-073-073$05.00/0 © 1978 American Chemical Society

Kennedy; Disposal and Decontamination of Pesticides ACS Symposium Series; American Chemical Society: Washington, DC, 1978.

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Environmentally hazardous emissions which must be c o n t r o l l e d p a r t i c u l a t e P2O5 and gaseous HCN, HCl, SO2, and ΝΟχ. R e c e n t l y , i n c i n e r a t i o n of Kepone® and Mirex has been i n ­ v e s t i g a t e d by the U n i v e r s i t y of Dayton Research I n s t i t u t e (UDRI) (1976) and by Midland-Ross C o r p o r a t i o n (1977). A l a b o r a t o r y s c a l e study by UDRI i n d i c a t e d that Kepone® decomposed a t 500°C i n 1 sec and Mirex a t 700°C i n 1 sec. The degree o f e f f i c i e n c y was 99.998%. Roth Kepone® and M i r e x produce intermediate deg­ r a d a t i o n products that are hazardous. For example, i n c i n e r a t i o n of Kepone® can produce hexachlorocyclopentadiene, hexachlorobenzene, and an u n i d e n t i f i e d species (Carnes, 1977a; D u v a l l and Rubey, 1976). The Midland-Ross C o r p o r a t i o n i n c i n e r a t e d small amounts o f Kepone® (4 kg max. sample s i z e ) from January through March 1977. A t o t a l o f 68 kg was destroyed. The i n c i n e r a t i o n temperature was 1100°C. R e t e n t i o n time was reported as 2 sec. Major decomposi­ t i o n products were CO2, H2O, and HCl w i t h traces o f hexachlorobenzene. The d r a f t r e p o r t i s not y e t a v a i l a b l e (Carnes, 1977b). The State o f V i r g i n i a r e c e n t l y a u t h o r i z e d Flood and Asso­ c i a t e s o f J a c k s o n v i l l e , F l o r i d a , t o d e s i g n an i n c i n e r a t o r to d e s t r o y 45,000 kg o f Kepone®. The d e s i g n w i l l u t i l i z e the Mid­ land-Ross C o r p o r a t i o n data base. I n c i n e r a t i o n a t sea o f o r g a n o c h l o r i n e process wastes i s being conducted by S h e l l Chemical Company i n f a c i l i t i e s i n the G u l f o f Mexico under an EPA permit. Although the wastes are not p e s t i c i d e s , the i n f o r m a t i o n gained and technology employed are d i r e c t l y a p p l i c a b l e . Organochlorine wastes were i n c i n e r a t e d a t the r a t e o f 25 m e t r i c tons/hr a t 1200 to 1350°C average flame temperature. E f f i c i e n c i e s approached 99.9%. Emissions were e s s e n t i a l l y H C l , CO2, and H2O and were discharged d i r e c t l y to the atmosphere w i t h o u t scrubbing. Marine m o n i t o r i n g surveys below the e f f l u e n t plume i n d i c a t e d no measurable increase i n organoc h l o r i n e s i n the water o r i n marine l i f e (Wastler e t a l . , 1975). S h e l l Chemical Company i s c u r r e n t l y o p e r a t i n g under a 2-1/2 year s p e c i a l permit to burn 50,000 metric tons of chemical wastes (Environmental Sciences and Technology, 1977). I n c i n e r a t i o n o f 8.7 m i l l i o n l i t e r s of H e r b i c i d e Orange con­ t a i n i n g t r a c e s o f the d i o x i n , TCDD, was accomplished d u r i n g August o f t h i s year by the Dutch i n c i n e r a t o r ship M/T Vulcanus i n the m i d - P a c i f i c Ocean approximately 120 m i l e s from Johnston I s l a n d and 1,000 m i l e s west o f the Hawaiian I s l a n d s . The U.S. EPA permit issued t o the U.S. A i r Force and Ocean Combustion S e r v i c e s , B.V. required a t l e a s t 99.9% combustion e f f i c i e n c y .

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Kennedy; Disposal and Decontamination of Pesticides ACS Symposium Series; American Chemical Society: Washington, DC, 1978.

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P r e l i m i n a r y r e s u l t s of the i n c i n e r a t i o n i n d i c a t e d a greater than 99.99% combustion e f f i c i e n c y . No detectable TCDD was found i n the i n c i n e r a t o r stack samples. The cost of the program was around $5 m i l l i o n (Kansas C i t y Times, 1977; Chemical and E n g i neering News, 1977; P e s t i c i d e and Toxic Chemical News, 1977). In summary, i n c i n e r a t i o n has been shown to be h i g h l y e f f i c i e n t (99.9%), but c a p i t a l investment can be great. Scrubbers are normally r e q u i r e d , although they are not i f i n c i n e r a t i o n i s performed at sea. Many c l a s s e s of p e s t i c i d e s and t h e i r formul a t i o n s have been examined. However, p i l o t p l a n t s c a l e demons t r a t i o n s have not been conducted f o r s e v e r a l c l a s s e s of p e s t i c i d e s i n c l u d i n g a n i l i d e s , ureas, u r a c i l s , and n i t r a t e d hydrocarbons. Other c l a s s e s of p e s t i c i d e s have been examined by o n l y one or two i n v e s t i g a t i n g teams. The data base f o r i n c i n e r a t i o n of p e s t i c i d e s must be expanded. Chemical Treatment Processes Many chemical approaches have been taken to d e t o x i f y or destroy hazardous m a t e r i a l s , i n c l u d i n g p e s t i c i d e s . These approaches g e n e r a l l y i n v o l v e r a t h e r simple treatment i n s o l u t i o n w i t h a l k a l i , a c i d s , c h l o r i n e , oxygen, or h y p o c h l o r i t e , but may i n c l u d e a p p l i c a t i o n of heat and pressure. Some of these methods are capable of d e s t r o y i n g p e s t i c i d e s , e.g., a l k a l i n e h y d r o l y s i s of organophosphate compounds. Others only p a r t i a l l y degrade the a c t i v e i n g r e d i e n t and y i e l d products which are n e a r l y as t o x i c or even more t o x i c than the o r i g i n a l p e s t i c i d e . We s h a l l ment i o n only a few of these examples and i n d i c a t e t h e i r general u s e f u l n e s s , inherent shortcomings, and c u r r e n t s t a t u s . Wet O x i d a t i o n (Zimmerman Process, Zimpro®)—The p r i n c i p l e of o p e r a t i o n i s that a s o l u t i o n of any organic compound can be o x i d i z e d by a i r or oxygen i f s u f f i c i e n t heat and pressure i s a p p l i e d . Thus, a t temperatures of 150 to 340°C and 450 to 2,500 p s i g , sewage sludges w i l l be o x i d i z e d to C0 and H 0 i n 30 to 60 min. S u l f u r , n i t r o g e n , and phosphorus may remain i n s o l u t i o n as s a l t s . Heavy metals may be p r e c i p i t a t e d as s u l f a t e s , phosphates, o x i d e s , or hydroxides, or may remain i n s o l u t i o n ( A s t r o , 1977a). The extent of a c t u a l p e s t i c i d e d e s t r u c t i o n has r a r e l y been determined ; the percent r e d u c t i o n i n t o t a l organic carbon (TOC) i s given i n s t e a d . For example, s t u d i e s on DDT, 2,4-D, and pentachlorophenol (PCP) have been reported i n t h i s manner ( A s t r o , 1977a). Other s t u d i e s of the wet o x i d a t i o n process a p p l i e d to Amiben® h e r b i c i d e process wastes i n d i c a t e 88 to 99.5% d e s t r u c t i o n 2

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o f the a c t i v e i n g r e d i e n t ( A s t r o , 1977b; Adams et a l . , 1976). A t r a z i n e process wastes have been claimed to be 100% destroyed ( A s t r o , 1977b). Wet o x i d a t i o n c o s t s f o r p r o c e s s i n g 160,000 l i t e r s of chemical waste per day have been estimated a t $0.37/kg of a c t i v e i n g r e d i e n t destroyed and a c a p i t a l investment of $2.2 m i l l i o n (Adams et a l . , 1976). Wet o x i d a t i o n has not been demonstrated to be w i d e l y app l i c a b l e to p e s t i c i d e s . This i s p r i m a r i l y true because of the lack o f q u a n t i t a t i v e a n a l y t i c a l data f o r the a c t i v e i n g r e d i e n t s ; merely monitoring the TOC r e d u c t i o n i s inadequate. Secondly, o n l y two c l a s s e s of p e s t i c i d e s have been examined: c h l o r i n a t e d hydrocarbons and t r i a z i n e s . Much i n f o r m a t i o n on p o t e n t i a l p e s t i c i d e d i s p o s a l a p p l i c a t i o n s f o r wet o x i d a t i o n i s yet to be d e v e l oped. C h l o r o l y s i s — E x h a u s t i v e c h l o r i n a t i o n as a method of d i s posing of p e s t i c i d e s and other chemical wastes has been suggested a t l e a s t s i n c e 1974 i n the chemical press (Environmental Science and Technology, 1974). Two U.S. patents d e s c r i b i n g b a s i c improvements i n c h l o r i n a t i o n appeared i n 1972 ( K r e k e l e r e t a l . , 1972a,b). A r e c e n t study f o r the E P A - - I n d u s t r i a l Environmental Research Laboratory, Research T r i a n g l e P a r k — h a s assessed the p o t e n t i a l u s e f u l n e s s and economics of c h l o r o l y s i s to d e s t r o y p e s t i c i d e s and other chlorohydrocarbon wastes ( S h i v e r , 1976). A follow-up r e p o r t , i n c l u d i n g process d e t a i l s and e n g i n e e r i n g cost e s t i m a t e s , i s c u r r e n t l y i n the d r a f t stage (Des R o s i e r s , 1977). Depending on the type of feedstock ( a l i p h a t i c or aromatic) exhaustive c h l o r i n a t i o n takes place over a range of pressures and temperatures. According to a new process developed by Farbwerke Hoechst AG, F r a n k f u r t / M a i n , Germany, hydrocarbons and t h e i r oxygenated or c h l o r i n a t e d d e r i v a t i v e s are completely conv e r t e d to CCI4, COClg, and HCl a t pressures up to 240 a t . and temperatures up to 620°C ( K r e k e l e r et a l . , 1975). P e s t i c i d e s and organic wastes t h a t c o n t a i n s u l f u r , n i t r o g e n , and/or phosphorus may have adverse e f f e c t s on the c h l o r o l y s i s process. Thus, the presence of s u l f u r - b e a r i n g p e s t i c i d e s i n excess of 25 ppm s u l f u r i n the hydrocarbon feedstream may cause severe c o r r o s i o n of the n i c k e l tube c a t a l y t i c r e a c t o r ( S h i v e r , 1976). There i s some q u e s t i o n as to whether NCI3 and PCI3 or PCI5 would be formed i n a p p l y i n g the c h l o r o l y s i s process to Nand P - c o n t a i n i n g p e s t i c i d e s , and o f the hazards i f these produ c t s were formed. F u r t h e r research needs to be performed to o b t a i n i n f o r m a t i o n on these p o i n t s .

Kennedy; Disposal and Decontamination of Pesticides ACS Symposium Series; American Chemical Society: Washington, DC, 1978.

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We do not recommend c h l o r o l y s i s f o r the d i s p o s a l of organom e t a l l i c p e s t i c i d e s without c a r e f u l i n v e s t i g a t i o n and c o n t r o l ; some o f the t o x i c heavy metals (e.g., As and Hg) would form v o l a t i l e chlorides. At l e a s t one cost estimate f o r a c h l o r o l y s i s p l a n t has been made. A p l a n t c a p a c i t y to process 22,700 m e t r i c tons per year of waste hydrocarbons or chlorohydrocarbons could y i e l d from 5 to 14% r e t u r n on investment. S a l a b l e products are C C I 4 , COCLj, and H C l . The c a p i t a l investment f o r primary and a u x i l i a r y f a c i l i t i e s may be as h i g h as $40 to $45 m i l l i o n . The cost to d e s t r o y the c h l o rohydrocarbon may be as h i g h as $0.97/kg ( S h i v e r , 1976). On the b a s i s o f l i m i t e d demonstrations of c h l o r o l y s i s of p e s t i c i d e s we can only i n d i c a t e p o t e n t i a l a p p l i c a t i o n to p e s t i c i d e s . Recently c a n c e l l e d o r g r e a t l y r e s t r i c t e d p e s t i c i d e s are those i n the h i g h l y c h l o r i n a t e d category and those based on d i e n e s t r u c t u r e s . F o r t u n a t e l y , these are the best candidates f o r c h l o rolysis. O z o n e / U l t r a v i o l e t (UV) I r r a d i a t i o n — H o u s t o n Research, I n c . , has developed a method of d e s t r o y i n g or d e t o x i f y i n g hazardous chemicals i n s o l u t i o n , i n c l u d i n g heavy metal cyanides and p e s t i c i d e s , u t i l i z i n g a combination of ozonation and UV i r r a d i a t i o n . The technique i n v o l v e s r a t h e r simple apparatus: a r e a c t o r v e s s e l , an ozone generator, a gas d i f f u s e r or sparger, a mixer, and a high-pressure mercury-vapor lamp. P e s t i c i d e s that have been r e duced to l e v e l s of < 0.5 ppm from an i n i t i a l s o l u t i o n concentrat i o n of — 50 ppm i n c l u d e : PCP, malathion, Vapam® and Baygon®. DDT has been reduced from 58 ppb i n s o l u t i o n to < 0.5 ppb i n 90 min (Mauk et a l . , 1976). To date o n l y two r e a c t o r s , 10 and 21 l i t e r volumes, have been t e s t e d ; both are considered to be bench-scale models. Houston Research, Inc., i n d i c a t e s , however, that scale-up to much l a r g e r s i z e s should be r e a d i l y accomplished. Only three c l a s s e s of p e s t i c i d e s have been s y s t e m a t i c a l l y i n v e s t i g a t e d u s i n g d e s t r u c t i o n by ozonation/UV i r r a d i a t i o n : c h l o r i n a t e d hydrocarbons (DDT and PCP); organophosphate compounds (malathion); and, carbamates (Baygon® and Vapam®). For each of these p e s t i c i d e s the experimental parameters have been optimized to y i e l d "complete d e s t r u c t i o n , " i . e . , 99+%, i n the s h o r t e s t p o s s i b l e time. Thus, s o l u t i o n temperature, i n t e n s i t y of i r r a d i a t i o n , ozonation f l u x , and s t i r r i n g r a t e are a l l important experimental parameters. Other p e s t i c i d e c l a s s e s have not been i n v e s t i g a t e d by t h i s process to the best of our knowledge.

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No cost estimates are a v a i l a b l e f o r t h i s process. Principal c a p i t a l equipment c o s t s i n c l u d e the r e a c t o r , the ozone generator, power supply and c o n t r o l s , and the UV i l l u m i n a t i o n source and power supply. P r i n c i p a l o p e r a t i n g c o s t s i n c l u d e e l e c t r i c a l energy and l a b o r .

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B i o d e t o x i f i c a t i o n of P e s t i c i d e s Much of the research to date on p e s t i c i d e biodégradation has focused on l o s s of d e s i r e d t o x i c i t y under a g r i c u l t u r a l a p p l i c a t i o n and r u n o f f c o n d i t i o n s . L i t t l e of t h i s work provides v a l u a b l e carry-over i n the realm of p e s t i c i d e d i s p o s a l . The l a r g e number of v a r i a b l e s i n v o l v e d i n m i c r o b i a l breakdown tends to make each research approach and r e s u l t r a t h e r unique. Some very important l a b o r a t o r y s c a l e work has been performed by Dr. Douglas Munnecke, formerly w i t h the EPA, now i n West Germany (MUnnecke, 1977; Munnecke and Hsieh, 1975). Emuls i f i a b l e p a r a t h i o n was the s o l e carbon and energy source f o r a mixed b a c t e r i a l c u l t u r e grown from sewage, s o i l , and water samples. A f t e r a 36-day a d a p t a t i o n p e r i o d , the c u l t u r e e x h i b i t e d maximum growth i n a s o l u t i o n c o n t a i n i n g 5,000 ppm p a r a t h i o n and showed o n l y a s l i g h t decrease i n a c t i v i t y when the p a r a t h i o n concentrat i o n was r a i s e d to 10,000 ppm. This higher l e v e l represents an approximation of the c o n c e n t r a t i o n s present i n wash s o l u t i o n s from p e s t i c i d e c o n t a i n e r s and a i r c r a f t spray tanks (Hsieh et a l . , 1972). Three d i f f e r e n t biochemical pathways were used by the c u l t u r e to a t t a c k the e m u l s i f i a b l e p a r a t h i o n under aerobic or low oxygen c o n d i t i o n s . The a c t i v e organisms included f i v e subc l a s s e s o f f l u o r e s c e n t pseudomonads, p l u s species of Brevibacterium, Azotomonas, and Xanthomonas. The maximum c o n c e n t r a t i o n r a t e o f degradation was 50 mg p a r a t h i o n per l i t e r per hr. The success of the c u l t u r e was, i n p a r t , because of the production of the enzyme, p a r a t h i o n h y d r o l a s e . This enzyme was separated from the a c t i v e c e l l s and found to be t o l e r a n t of high temperatures (55°C f o r 10 min without d e a c t i v a t i o n ) and s u i t a b l e for s u b s t r a t e i n d u c t i o n . The b a c t e r i a l mixed c u l t u r e demonstrated the a b i l i t y to hydrolyze seven of e i g h t t e s t e d organophosphate i n s e c t i c i d e s . Only Lebaycid®, w i t h three d i f f e r e n t f u n c t i o n a l groups, was not hydrolyzed. Depending on the p e s t i c i d e , b i o chemical d e t o x i f i c a t i o n r a t e s when using 20 mg p r o t e i n / l i t e r , were 1 to 300 times f a s t e r than i n chemical d e t o x i f i c a t i o n procedures using 0.1N NaOH.

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The s i g n i f i c a n c e o f t h i s s e r i e s o f experiments may be sum­ marized as f o l l o w s : (a) a t o x i c organophosphate i n s e c t i c i d e , p a r a t h i o n , was s u c c e s s f u l l y biodegraded to simpler phosphoric a c i d s and phenols, (b) the m i c r o b i a l c u l t u r e produced was a b l e to degrade s i x a d d i t i o n a l organophosphate p e s t i c i d e s , and (c) the enzyme which was capable o f h y d r o l y z i n g these b i o c i d e s was i s o l a t e d and found to be s t a b l e o u t s i d e the parent c e l l . Dr. Munnecke i s c u r r e n t l y working w i t h Bayer Farbenfabriken of Leverkusen, West Germany to determine the f e a s i b i l i t y o f u s i n g immobilized o r free enzymes f o r the d e t o x i f i c a t i o n o f i n d u s t r i a l p e s t i c i d e p r o d u c t i o n wastes. P r e l i m i n a r y r e s u l t s show that free enzymes can be used t o d e t o x i f y p a r a t h i o n i n formulations and p r o d u c t i o n wastewaters, as w e l l as i n p e s t i c i d e containers. Current research i s i n progress t o s c a l e up to 40,000 l i t e r s o f batch fermentations o f mixed b a c t e r i a l c u l t u r e s . Towards the end o f t h i s summer Munnecke hopes t o begin p i l o t s t u d i e s f o r d e t o x i f i c a t i o n o f 1,000 l i t e r s per hour o f p e s t i ­ c i d e production wastewater. In c l o s i n g t h i s address we wish to note that the MRI team intends to v i s i t s e v e r a l s e l e c t e d s i t e s t o o b t a i n f i r s t - h a n d i n ­ formation on the s t a t e o f the a r t o f p e s t i c i d e d i s p o s a l r e s e a r c h .

Literature Cited 1. Carnes, R. Α., and D. A. Oberacker. Pesticide Incineration. (1976) U.S. Environmental Protection Agency, Municipal Environmental Research Laboratory. 2. Ferguson, T. L., F. J. Bergman, G. R. Cooper, R. T. Li, and F. I. Honea. Determination of Incinerator Operating Con­ ditions Necessary for Safe Disposal of Pesticides. (1975) EPA-600/2-75-041. 3. Carnes, R. A. Thermal Degradation of Kepone®. (1977a) U.S. Environmental Protection Agency, Municipal Environmental Research Laboratory. 4. Duvall, D. S., and W. A. Rubey. Laboratory Evaluation of High Temperature Destruction of Kepone® and Related Pesti­ cides, University of Dayton Research Institute. (1976) Technical Report UDRI-TR-76-21. 5. Carnes, R. A. EPA/MERL, Cincinnati. (1977b) Personal com­ munication to R. R. Wilkinson. 6. Wastler, T. A., C. K. Offutt, C. K. Fitzsimmons, and P. E. Des Rosiers. Disposal of Organochlorine Wastes by Incinera­ tion of Sea. (1975) NTIS PB-253,979. 7. Environmental Sciences and Technology. (1977) 11(3): p. 236-237. Kennedy; Disposal and Decontamination of Pesticides ACS Symposium Series; American Chemical Society: Washington, DC, 1978.

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DISPOSAL AND DECONTAMINATION OF PESTICIDES

The Kansas City Times. (September 8, 1977) p. 13A. Chemical and Engineering News. (September 12, 1977) p. 20. Pesticide and Toxic Material News. (August 10, 1977) p. 33. Astro Metallurgical Corporation. Wooster, Ohio. Summary of Waste Examples Reacted by Wet Oxidation Through 1976. (1977a) Form No. WT-77-3. Astro Metallurgical Corporation. Astrol™ Wet Oxidation Waste Treatment Systems. (1977b) Form No. WT-77-1. Adams, J. T., Ν. J. Cunningham, J. C. Harris, P. L. Levins, J. L. Stauffer, and Κ. E. Thrun. Destroying Chemical Wastes in Commercial-Scale Incinerators. (1976) NTIS PB267. p. 987. Environmental Sciences and Technology. (1974) 8(1): p. 18-19. Krekeler, H., H. Meidert, W. Riemenschneider, and L. H. Hornig. U.S. Patent No. 3,651,157 issued March 21, 1972, and U.S. Patent No. 3,676,508 issued July 11, 1972. Shiver, J. K. Converting Chlorohydrocarbon Wastes by Chlo­ rolysis. (1976) NTIS PB-259. p. 935. Des Rosiers, P. Industrial Pollution Control Division. (1977) Office of Research and Development, Environmental Protection Agency, Washington, D.C., Personal communication to R. R. Wilkinson. September. Krekeler, Η., H. Schmitz, and D. Rebhan. The High-Pressure Chlorolysis of Hydrocarbons to Carbon Tetrachloride--A New Process for the Utilization of Chlorinated Hydrocarbon Wastes. (1975) National Conference on the Management and Disposal of Residues for the Treatment of Industrial Waste­ -waters. Washington, D.C. February 3-5, 1975. Informa­ tion Transfer, Inc., Rockville, Maryland. Mauk, C. E., H. W. Prengle, Jr., and J. E. Payne. Oxidation of Pesticides by Ozone and Ultraviolet Light. (1976) NTIS AD-A028 306. Münnecke, D. M. Properties of an Immobilized PesticideHydrolyzing Enzyme. (1977) App. and Environ. Microbio. (1977) 33(3): p. 503-507. Münnecke, D. Μ., and D. P. H. Hsieh. Development of Micro­ bial Systems for the Disposal of Concentrated Pesticide Suspension. (1975) Meded. Fac. Landbuwwet. Rijksuniv. Gent. (1975) 40 (2, Pt. 2): p. 1,237-1,247. Chem. Abstr. (1976) 84, 131127d. Hsieh, D. P. H., T. E. Archer, D. M. Münnecke, and F. E. McGowan. Decontamination of Noncombustible Agricultural Pesticide Containers by Removal of Emulsifiable Parathion. (1972) Environ. Sci. Tech. (1972) 6(9): p. 826-829.

MARCH 23, 1978 Kennedy; Disposal and Decontamination of Pesticides ACS Symposium Series; American Chemical Society: Washington, DC, 1978.