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FROM (N A M E -L O C A T IO N -- P H O N E ) Allan M. Ford - St. Louis A2SA 4-2578 August 9, 19 82 cc SU BJECT REFEREN CE TO T. M. Bistline - E2ND In responding to Dr. Hryhorczuk, we are trying to limit his investigation of our facilities as much as possible. He already has grant money for his study, so I doubt if we can put a stop to it. He uses Tiernan's book, which indicates that we have made several chlorophenols, which in fact were not manufactured there. In addition, with the exception of 2,4,5-T esters, the other chlorophenols Hryhorczuk mentioned would not be expected to form ,3,7,8-TCDD. Finally, with the case of 2,4,5-T,the part of the process likely to give off dioxincontaining waste was not operated in Illinois. We're afraid that if we don't straighten out' Hryhorczuk's thinking we will be accused of something we didn't do! "s u b j e c t TO PROTECTIVE ORDER. jh enclosures / C t u < i- r y L Q A . f)v u ttA L b } >Q J 1 4 -4 A. M. Ford C14164 U h j , AU / L & t A t J i rr\ f t i . k u Lo m o Q x a J l <3 / C Y fd h Y L t/ u J C L* Y U h jx p u * u LC U M /h S A A A A J U r u i ?' AFT 7 August 9/ 1982 Daniel Hryhorczuk, MD, MPH UNIVERSITY OF ILLINOIS SCHOOL OF PUBLIC HEALTH P.O. Box 6998 Chicago, Illinois 60680 My dear Dr. Hryhorczuk: I'm sorry for not giving a more prompt reply to your letter of June 16, but vacation schedules have intervened. In response to your proposal, the production of chlorinated benzenes likely to form chlorinated dibenzo-p-dioxins (CDD's) or chlorinated dibenzofurans at our Sauget, Illinois plant is to the best of our know ledge as reported in'Tiernan's book (DIOXINS, US-EPA-600/2-80-197) , with the exception of ortho nitroanisole and 3,4-dichloroaniline which were not manufactured in the Sauget plant. In addition, 2,4,5-trichlorophenoxy acetic acid (2,4,5-T) was manufactured elswhere and esterified at the Sauget, Illinois plant. I would suggest that Dr. Tiernan at Wright State might be a good source of additional information. SUBJECT TO PROTECTIVE ORDER. Tiernan classifies most of the compounds mentioned in your letter as having a low probability for CDD formation. With the exception of the orthochlorinated phenols, the molecules do not meet the criteria of having ortho-^substitution and good leaving groups. In the case of the orthochlorinated phenols mentioned, with the exception of 2 ,4 ,5- trichlorophenol, the remaining substitution on the ring suggests that the major product of coupling would not be the most toxic 2,3 ,7 ,8tetra-CDD. In any event, our process for production of ortho-, C14165 para- and 2,4-aichlorophenols, the only ones still manufactured at Daniel Hryhorczuk Page 2 August 9, 1982 - DRA. Sauget, is carefully controlled to minimize formation of CDD's arid V ~ . n*. predioxins. The 2,4,5-trichlorophenol was converted to 2,4,5-T outside of Illinois 'arid transferred to the Sauget plant where it was esterified to the ;ri-buty1 '-fester.7-0ft:i/s`'Been over thirteen years since w e 've used 2,4,5-T as fen intermediate at the Sauget plant, but because of the substituents ^suggesting that the '2,3/7/S-TCDD might have been fprmed in the'2,4,5-T process, we, along with a number of other companies, are cooperating fully in an epidemiology study being conducted by NIOSH relating to all phases of the discontinued chlorophenol processes, as well as conducting our own internal research. For your information,. I have enclosed a process description and process chemistry for the discontinued esterifi cation procesa-and the discontinued pentachlorophenol process at Sauget, Illinois. We are currently involved with five other defendants in litigation involving the 2,4,5-']? esters and cannot disclose further detail during the course of this litigation on advice of counsel. The polychlorinated biphenyls (PCB1s) were SUBJECT TO PROTECTIVE manufactured at the ORDER. Sauget plant up., until 1977, at which "time manufacture was discontinued. We. have not found any: of the CDD1s:in-the. P C B 's manufactured by ^ u ~ Monsanto Company nor .have we seen:any., reports...in. the .literature of such findings. C14166 Production and end use of the chemicals you mention are as described by Iil dealing.. w,ith - t- t.- y . 1 C - ; ; / g. C Federal.^regulators, we have requested _that production .statistics remain /.*; , secret and, on advice of counsel, cannot violate that request by dis closure to you. In the same vein, our waste disposal at the Sauget plant Daniel Hryhorczuk Page 3 August 9, 1982 - DRAFT is involvedtin litigation with the State of Illinois. During the course of this litigation, our counsel advises us not to voluntarily disclose plant waste-related information. I hope that we've been of some help to you in your endeavor. Sincerely, pr o tec t iv e o r d e r . subject to C14167 W. G. KRUMMRICH PLANT A RECONSTRUCTION O? PROCESS DEVELOPMENT FOR PRODUCTION OF ESTERS OF 2,4 ,5-TRICHLOROPHSNOXYACETIC ACID (2,4,5-T ACID .ESTERS) In 1960, production of the butyl, isobutyl and isooctyl esters of 2,4,5-T acid was initiated in Dept. 268 of the Krummrich plant, . . , D ept. 268 was also' the site for the production of other esters. In 1965 and 1969, revised Standard Manufacture.Processes were issued for the butyl and isobutyl esters, which incorporated minor cost saving process changes. Copies of the 1965 processes were not located. No revised process'incorporating these ^changes in the isooctyl ester manufacture was issued. This may imply that production of this ester ceased prior to 1969. However, production of. all thre'e esters had definitely stopped by 1970 according to our "Sources'-of Product Information" book. .s^- Over the years, the basic chemistry for the production of these esters did not change. The 2,4,5-T acid was reacted with the appropriate alcohol using a small amount of sulfuric acid as catalyst. The reaction was originally driven to completion by removing the binary alcohol/water azeotrop and, on cooling and separating, recyling the alcohol. The 1969 processes for the butyl and isobutyl esters used toluene as a solvent for increased efficiency in driving the reaction to completion and in the water/alcohol separation. When the reaction was complete, the toluene and excess alcohol were stripped off and the sulfuric acid in the product neutralized by cyclohexylamine. Specific details and flow charts representative of the processes are attached. C14168 Dept. 268 - Proc js Description ISOOCTYL 2,4,5-T SYNOPSIS OF PROCESS 2 / 4 ,5-Trichlorophenoxyacetic acid is esterified with Isooctyl alcohol in the presence of sulfuric acid catalyst. The reaction is carried out at 200 mm. pressure and 135 to 140C. The water of reaction is removed as a binary azeotrope with the alcohol. The column is not used for Isooctyl esters. Condensed azeotrope is separated continuously and the alcohol layer returned to the reactor. Exact quantities of raw materials are used as any excess alcohol is difficult to strip off. At the completion of the reaction the batch is pumped to the neutralizer/ neutralized with cyclohexylamine, filtered and pumped to a steel storage tank, tank cars, tank trucks or 55 gallon drums. pr o tec t iv e o r d e r . SUBJECT TO - C1416 W.G. Krummrich P la n t - -4 Dept. 268 - Process Description ESTERS ' - SYNOPSIS OF PROCESS A. General 2,4,5-Trichlorophenoxyacetic Acid is esterified with butyl alcohol or isobutyl alcohol in the presence of sulfuric acid and toluene./-^The sulfuric acid functions as a catalyst and toluene as a solvent for increased efficiency in wateralcohol separation. The reaction is carried out at 580 mm Hg. abs. pressure and 130c - 140C. Complete reaction occurs through use of excess alcohol and constant removal of water. The alcohol, toluene and water vapors are condensed and separated, and the alcohol - toluene mixture re-fluxed, back to the .reactor. Prior to the reaction step, the particular acid, alcohol and toluene are premixed (at atmospheric pressure and 70c). At the completion of the reaction, excess alcohol and toluene are g g stripped from the batch by maintaining the reactor at 50 mm Hg. abs. pressure and 140 - 150C for two hours. Cyclohexylamine is then added to neutralize the H^SOi* and stabilize the batch. After filtration, the batch is pumped s B. to storage, tank cars, tank trucks, or 55 gallon drums. Butyl 2,4,5-T Ester Reaction o Jr OCH2COH ? Cl H2SC^ o \ CCH2C-0-CH2CH2CH2CH3 Cl + H20 Butyl Alcohol Holi.Wt. 74.12 2,4,5-T Hoi. Wt. 255.45 Butyl 2,4,5-T Ester Hoi. Ht. 311.56 C14171 Water Hoi. Wt. 18. W.G. Krummrich ' ' a n t -5- Dept. 268 - Process Description ESTERS SYNOPSIS OF PROCESS C. Isobutyl- 2,4,5-T Ester Reaction o UJ O ch3 f // H2SOl4 Isobutyl Alcohol Hoi. Wt. 74.12 2 , 4 f5-T Mol. Wt. 255.45 Isobutyl 2,4,5-T Ester M o l .1 Ht. 311.56 Hater Hoi. Wt. 18.01 FLOW SHEETS A. Slurry -(Pre-Mix) B. Reaction C. Ntal:iztr6Rean F ;e-Q r.c neutralize tne rioSOi, and n ,1 SUBJECT TO PROTECTIVE ORDER. But vi h i coho-2 Vv''*t W'?` "7/, * y* t isuv.y-i * * i r.ster . *i,, V'f, . y} >. ; /V > . *\$". \ ; .1> C14172 ' k a ter V.f_ .IQ. rv") f-J- -c>o3 mow ALcottoi ronAcn aruu^ic. Q \<-lO 1f\^ i W MfA>. VVCAU. ci r ' u i 0^_j VATER TO 5CVTEI .V ncru/x coNocNica '`S MHACIAPCT-IO*>0mml l O|l|m rAl lWf t#AV*. - Co, DJLANKCT rnUM PA-Ar^CT ta/<k (ivr 'L j/)yL> *crlahcoitnitoh v^/ i^PC. >nu* IT CAM o Hv H* sl v >' lUV/.AOCTCOAaL, CMLtSmS:o 0 T COMDCMJATC TO JEWtn f\ PI LU VC ALCOMOL STOlVACn J0O0 CAL. ;% V G L A .V S -lW \D >ssv 4?^. _ an'. .p.,u---- fiK" ... V to Kttimitn -a D. REACTION DEPT. 268 BUTYt 2,4)5-T ISO BUTYt 2,4,5-T 894.12 894.28 m wcu. WAT CA rrcAM T*0 JTACt* YACVVMCiOlHTDJC^MTC cfSTTT^TU TOJt f 4C0A0!., (!or : ,; ' . :<' ' ]. 5TAOMO A LCCIIOL JTonAcr: I0vo c a l . Ul Ol i n * . s i T c l 1'i TO JW:*nCAGT TAK* ; TO ALCOftOL TOLVESE * 7 0 V SUBJECT TO PROTECTfVE ORDER. Cl4175 c . MEOTRALIZATIOM.fr FILTRATI DEPT. 2 G li r "V ' --------- V T BUYL 2,4,5-T ISO BUTYL 2/4,5-T 894.12 . 894.28 I Dept- 268 - Procei Description .ESTERS PROCESS IN DETAIL ! A. Pre-Mix (Slurry Tank) General " Butyl alcohol or Isobutyl alcohol and 2 , 4 , 5-Trichlorophenoxyacetic acid are charged by weight according to the ` " ,,'scale on which the 'slurry tank is mounted. The slurry tank is-316 S.C. 4000 gallons, with heating coils and agitator. The temperature is controlled at 70C. The alcohol and.toluene charge.is made.up.by pumping recovered alcohol and toluene from the strong tank. This material - is analyzed for alcohol and toluene composition. The appropriate amount of fresh alcohol and toluene are added to complete the charge. Then 2,4,5-T is charged via the conveying system. When the-.proper., amount of 2,4,5-T has been added/ as determined by the scale setting, the conveying system will automatically shut"'Off. At this time the knife valve on the slurry tank is closed to prevent vapors from entering the conveying system. A constant C O 2 gas purge is maintained on the slurry Pa-nk. kti B, Reaction TO The slurry tank is dropped to the reactor by gravity and vacuum on the reactor. After the weigh tank mix is charged to the 4/000 gallon glass-lined reactor, 20 lbs. of sulfuric acid (6 inches on gage) are added. The vacuum controller is set at 580 mm H g . a b s . pressure and the reactor heated to 130 - 140C. Vapors from the reactor are condensed in a Karbate condenser, and separated in a 400 gallon stainless steel tank. The top layerrqf alcohol and toluene is refluxed back to the reactor. `The waiter layer, containing the water of reaction and1 some* alconol and toluene,r is periodically C14176 W.G.. Krummrich P la n t , , - 1 0 Dept. 268 - Process Description ESTERS PROCESS IN DETAIL B. Reaction . (continued) drained to the 1,000'gallon glass lined, dilute alcohol tank to prevent the water from accumulating in the separator and, being refluxed back to the reactor. The reaction takes place at 580 mmg Hg. abs. p-ressure and 130 - 140C. in the presence of 0.2 mole H 2 SOi*- catalyst. Vapors of alcohol, toluene, and water are condensed, separated, and the alcohol - toluene mix refluxed back to the reactor. Following reaction, excess alcohol and toluene are stripped from the batch, condensed, and collected in the 1,000 gallon steel, strong alcohol tahk. The temperature controller is adjusted to 145C and the pressure controller set at 50 mm Hg. abs. pressure. During the 2 hour strip period, total reflu is stopped and both the separator and weak alcohol tank are by-passed. At the end of the strip period, the vacuum is released by addition of CO2 to the reactor. If at the end of two hours there is an appreciable flow of condensed alcohol and toluene from the' condenser the strip period should be extended. The bottom (water) collected in the weak alcohol tank during refluxing is drained. The remaining alcohol and toluene are used to charge the weigh tank. The alcohol and toluene collected in the strong alcohol tank during stripping operations are also recharged to the weigh tank. These tw'o sources of alcohol and toluene comprise the recovered alcohol which was previously discussed. SUBJECT TO PROTECTIVE ORDER. C14177 ESTERS PROCESS IN DETAIL C. Neutralization and Filtration Catalyst and other acidic compounds are neutralized by the addition o f .cyclohexylamine to the 4 #000 ..gallon, steel, neutralizer *- The batch is agitated'for 30 minutes and sampled. The analyses are performed in the laboratory., : If excess cyclohexylamine is less than 0.01% additional lbs. of cyclohexylamine are added. The batch is again agitated for 30 minutes and resampled.' This continues" uhtll:`the'-" batch is within specifications for excess cyclohexylamine. The batch is circulated through the filter until the forward flowing stream from the filter is clear. Complete analysis of the finished, filtered ester is determined by the --V-V' laboratory. The filter is a Shriver .horizontal -tank-, -- -vertical leaf pressure filter.- The screens are 304 S .S . i2'4 x 'liO irashv lio^precoatris ;necessary:.:-- =-- The batch is then pumped to the 4,000 gallon, steel, product hold tank, drummed, .pumped to tank, trucks, tank cars, or to either 127,000 gallon or 88,000 gallon steel storage tanks. The ester is passed through a 25 micron cartridge polishing filter before being shipped by drum, tank car or tank truck, or stored in the storage tanks. r:.;- G14178 A RECONSTRUCTION OF PROCESS DEVELOPMENT FOR PRODUCTION OF PENTACHLOROPHENOL AND SODIUM PENTACHLOROPHENATE Pentachlorophenol and Its Variants The production of pentachlorophenol apparently began in 1938 in the W Building pilot plant at the Queeny plant to provide sales development quantities. At that time, pentachlorophenol was called Santophen 20. The sodium salt, called Santophen 20S, and a pine oil/alcohol/pentachlorophenol mixture, called Santophen 20 P.A., were also made. Within a year, full production was started at the Krummrich plant. It appears that pentachlorophenol (later called Penta) was marketed in flake form from 1939 until the late 1950s or early 1960s. Then Penta as well as Penta 60 (so called because it contained around 60% pentachlorophenol) were offered in prilled, form and the flaking operation discontinued. From 1970, Penta wa's also offered in 2000 lb. blocks as well as the prilled fo,rm. The sodium salt of Penta (later called Santobrite) was produced in powder, briquette and 30% aqueous solution forms throughout its history. Apparently, . Santophen 20 P.A. was only offered for a few years. The production of Santobrite was discontinued in 1975; Penta and Penta 60 in 1978. Over the years, the chemistry for the production of Penta and Santobrite remained essentially the same. Phenol, or chlorophenol fractions from the production of o- and -chlorophenol or 2,4dichlorophenol was progressively chlorinated with subsequent increases in reaction temperature until the appropriate crystallization point was reached (for Penta, 174-182C; for Penta 60, 145C). Iron powder was first used as catalyst; later, aluminum. Santobrite was simply the neutralization of Penta with sodium hydroxide. In 1972, sublimation of the prilled Penta was reduced by addition of Provalent 4A oil and more effectively by Humble NU50-38 oil. The evolution of the pentachlorophenol and sodium pentachlorophenate processes follows. l,e 0R R" C14179 Record .of. J .F,.....Que.eny,..Pilot'Plant;. ,(W..Building) Demonstration -of the Pentachl-oroDheno-l- Process (1938) " 309 batches of pentachlprophenol and seven of tetrachlorophenol were made on this job. 57,851 lbs. of phenol, 87,903 lbs. of Plant B dichlor fractions and. 441,1.4.1 lbs. of trichlorophenol were used as crude material to be chlorinated and 774,545 lbs. of pentachlorophenol and tetrachlorophenol were produced. ' The quality of the pentachlorophenol was* consistently better -* than that previously produced in the laboratory. A crystallizing point (C.P.) within about 1C of that desired was consistently obtained. This was not achieved in laboratory work. Alkali insoluble'content"was" consistently much lower than !" that obtained in the laboratory ranging from 1-2% compared to 10-12% in the laboratory. " ' ..." v ~'General Outline" of'P eh'tfach1orobheno 1 ~P'r6 'c e s 's `'Demonstration a t 1" the W.G. Krummrich Plant .(1938-39) - rr-- ~r-- -- ' ~ ~ *. W I r i v *'-* - i . ***.:> 'V. ^ f 'T ^ -U- \ -r-'. v - **v '**' --~ * Phenol is chlorinated in a monel chlorinator, iron powder being used as .a catalyst. Temperature is maintained at 60-65C during chlorination to trichlorophenol, 65-70 from trichlor to tetrachlor and slowly raised to 190 during chlorination to penta- chloropheno-1,--keeping 10=-JLS.9-above -the- C . f U.JL U-s54.J*OXi fJOJ. The HC1 evolved is purified by passing through, phenol to remove free chlorine, through a system of coolers and H^SOj, scrubber, to ._remove^ phenol.,. -,-5 ' T,_,v. -The pentachlorophenol is flaked into containers or run molten into a lye solution to form sodium pentachlorophenate. The alkalinity of this solution is adjusted as required, the solution filtered and evaporated to' dryness' o'n a double drum dryer. The dry material is packed directly or briquetted and then packed. C 14180 Y7.G. Krumnurich P la n t , -3- Chlorinations were started on October 11, 1938. When the second chlorinator was installed it was made with a hemi spherical downward dish and central drain so that it would drain clean. The plan was to chlorinate to trichlorophenol in the first chlorinator, in the absence of iron, and complete the chlorination in the second chlorinator. This was done in five batches and the color somewhat improved. Failure of the stirrer in the first chlorinator necessitated complete chlorination in the second chlorinator and it was found that the same improved color was maintained in a single step chlorination in this chlorinator*as were observed in the two step chlorination. Following installation of the second chlorinator the scrubber phenol from each batch was incorporated in the charge for the .. succeeding batch without difficulty. Flaking of the product offered no particular problem. ' The neutralization of pentachlorophenol with NaOH to form the sodium salt offered'no particular problem other than control of the alkalinity. Use of a control -test involving titration to the phenolphthalein endpoint proved unreliable and equipment for plant control by means of potentiometric titration was developed ORDER- iT E C T W E SUBJECT TO PR C14181 PROCESS FLOW SHEETS (1965) FOR: Pentachlorophenol Molten Pentachlorophnol Prilling & Packaging ft \*>r^ '' ; 1 V; i; t o PRO* c t w object Cl4182 C14183 {f t C* & ft A O A \\ 1 \& o. v VP f^CC^CfXT>/f CM\JWr*CNO-#J J CATCV4 pcrr V 7 T M C TTOrfl aEnvoWL la` opr <\a* cwpcMsnR Wt ^ 0 4 * W rt iw< wn. uCUUnUM|MJMmOev ,. fl1J ) TOii*cm#a1ru.AdMMdoiOL;M MANCDI in ACC nrmunn o u cT eUnQtUrJaOiJned MCI OA.% TRACE ttlENC UCj AMO Cl| 1 I ri 1 CONTROL. KANOC CHLORINATION ANO A CtP SCRUBBING DEPT. 235 F L O W SHE LIT Code No. 810.8 IICSTO0 CFARTMCHI Ilf * 11/8/65 n .u. J\A.UUlUitX XTJUdilU 7- SYNOPSIS OF PROCESS Dept, 236 (Molten Penta) Molten Pentachlorophenol is produced by the batchwise chlorination of phenol or chlorophenol fractions from the refined chlorophenols operation. Aluminum'catalyst is added at the dichlor stage. When the crystallizing point reaches the range 174 - 182C, the chlorination is stopped. The basic reaction for the process is: OH + 5C12 Al -A . + 5HC1 kk Phenol (Liquid) (94.05) Chlorine-.(Gas) c l V r cl ci Pentachlorophenol (Molten)" (2 6 6.29 ) Hydrogen Chloride (Gas) (3 6 .4 6 ) The molten Penta is then transferred to the hold tank for use in Santobrite Solution, Prill Penta or cast into blocks. The by-product HC1 produced in the chlorination reaction is scrubbed in successive phenol and sulfuric acid scrubbers. Dept. 226 (Prilled Penta) SUBJECT TO PROTECTIVE ORDER. Prilled Pentachlorophenol is produced by dispersing molten Penta into fine streams using a "shower head" type prill plate, and causing the molten streams to solidify by cooling with ambient air. . The cooling chamber is an 8' diameter x 40' high prill tower. As the prills fall through the tower, they solidify and then -pass from the tower into a Roto-Louvre cooler for further cooling. The prills are then conveyed in a bucket elevator to a storage hopper to await packaging. The prills are packaged into bags or fibre paks using a St. Regis pneumatic packer. C14185 W.G. Krummrich /P - ,^ - 8- The air used for cooling in the prill tower and cooler passes through a'Venturi scrubber where it is scrubbed with a dilute caustic solution. Dept. 236 (Penta 60) Penta 60 is a mixture of about 60% Penta and 35% Tetrachlorophenol. This product is produced essentially the same as Molten Penta, except that the chlorination is terminated earlier. The reaction is terminated when the batch temperature reaches 153-157C (145C crystallizing point). This material prilled in the same manner is Molten Penta. S-- i-i. ii.. li)o, u n u r a c.x o s c runner.; M Bh "j S U W E C T TO PROTECTIVE ORDER- ; i : -T ^ i~ l ---r ; - - . W t. 4^4 W 4 i i . i , r- t Li i ... . - * r. >'* <4 U a ^j L* -* *.>) (v i \%o \* f ; >,.. i t J 'J. U A .1 J '^ "v^ * V-.*-8 ^ i.4 V ft7.^ .O'**H k i-rr, ^ C14186 4 * V . School o f Public Health U N I V E R S I T Y OF IL.L.TN'OIS T H E MEDICAL. C E N T E R , O H IC A Q O Area Code 312, Telephone 996-6620 M ailing Address: P.0, Box 6998 Chicago, Illinois 60680 June 16, 1982 Z 1 /$ Mr. Garth Fort Regulatory Management Director, State Monsanto Company 800 N. Lindbergh St. Louis, Mo. 63166 Dear Mr. Fort: We are requesting your cooperation in a study being conducted by the University of Illinois School of Public Health under contract with the Illinois Institute for Energy and Natural Resources entitled "Identification of Potential Sources of Environmental Contamination with Polychlorinated Dibenzodioxlns and Polychlorinated Dibenzofurans in the State of Illinois." The purpose of this study is to collect existing data on sources of PCDDs and PCDFs in Illinois and to propose epidemiologic study designs to assess the degree of hazard, if any, associated with these sources. Our strategy is summarized in the following tasks: 1. Identify and contact Illinois producers of organic chemicals and pesticides, the production of which may lead to the inadvertant production of trace amounts of PCDDs or PCDFs. 2. Identify hazardous waste disposal sites in Illinois which may be contaminated with trace amounts of PCDDs or PCDFs. 3* Identify all municipal and industrial incinerators in Illinois. 4. Identify past usage of PCDD/PCDF contaminated pesticides in Illinois. 5. Identify industries with potential occupational exposure to PCDDs or PCDFs. 6 . Design epidemiologic studies to assess the degree of hazard associated with PCDD and PCDF sources. Please note that we are relying entirely on existing data and will not be undertaking any sampling as part of this project. Also, we will be examining the feasibility of various epidemiologic study designs; we are not carrying out an actual epidemiologic study. r PROTECTIVE o r d e r . SUBJECT TO C14188 School o f Public Health Tj'TIV-HIRSITY O P 'U jU N Q J B A.T THE3 M ED IC A L. C E N T E R , C H IC A G O Area Code 312, Telephone 996-6620 M ailing Address: P.O. Box 6998 Chicago, Illinois 60680 The completed study will be published as an ENR Report entitled Identification of Potential Sources of Environmental Contamination with Polychlorinated Dibenzodioxins and Polychlorinated Dibenzofurans in the State of Illinois and will be generally available as a scientific document. The report will contain a literature review which will emphasize the wide range- of- toxicity among the. various PCDD and PCDF isomers and the importance of isomer specific analysis. The data which your company provides will be carefully, referenced. If data from a specific comp l y r>ot available. we will r e l y on the list of potential sources compiled by Esposito. Tiernan. and Dryden in Dioxins, Publ. No. 600/2^80-197," USEPA, 1980. _j I have attached a list of questionswhich we are sending to all chemical producers identified through the Stanford Research Institute's Directory of Chemical Manufacturers as producers of pesticides and chemicals which may have been contaminated with PCDDs or PCDFs. The SRI Directory,lists your Sauge.t. plant..a s having, produced 2,4-dichlorophenol, o-chlorophenoTi" o-dichlotobenzene, p-dichlorobenzenev 0-nitrophenol, chlorobenzene, l-chloro^2-nitrobenzene, l-chloro-4-nitrobenzene, 3,4-dichloroaniline, 1 ,2.rdichlo.ror4rn:itrobenzene, o-nitroanisole, p-chlorophenol, and polychlorinated biphenyls. r 1 understand that'your company has considerable technical expertise in this area and welcome any assistance which you may be able to provide. We have allocated funds for out-of-state travel and would gladly meet with your scientific staff if you believe this will expedite or request. I was very encouraged by. our phone conversation and look forward to your reply. 2^ 1 a / n ^ y* 'f Daniel Hryhorczuk, M.D., M.P.H Assistant Professor 312-996-2597:. ORD R t Cl.il89 School o f Public Health U N I V E R S I T Y O F I L L I N O I S A.T T H E M E D IC A L C E N T E R , C H I C A G O Area Code 312,Telephone 996-6620 Mailing Address: P .0, Box 6998 Chicago, Illinois 60680 U of Ill/ENR Contract: Sources of PCDDs and PCDFs in Illinois CHEMICAL/PESTICIDE PRODUCER QUESTIONNAIRE 1. Is your company currently, or has your company ever, produced or used as an intermediate any of the chemicals or pesticides listed in Appendix A (List modified from Esposito, M.P.; Tiernan, T.O.; and Dryden, F.E. 1980. Dioxins, Publ. No. 600/2-80-197. Cincinnati, OH: USEPA)? 2. If yes, can you furnish us with present and past production statistics for these chemicals or pesticides for your Illinois facilities? 3. What were or are the major uses for these products? 4. Which processes does or did your company use for the synthesis of these chemicals or pesticides? 5. In the opinion of your chemists, can your processes lead to the inadvertant production of trace amounts of PCDDs or P'CDFs? Why or why not? 6. Have you ever sampled your product, byproducts, or process wastes for PCDDs or PCDFs? If yes, what were the results of those analyses? 7. How do or did you dispose of wastes from these processes (such as still bottoms)? If you dispose of your own wastes, do you monitor your disposal sites for environmental release of trace amounts of PCDDs or PCDFs? What are the results of such monitoring? 8 . How many employees were or are involved in the production of these chemicals or pesticides? Has your medical surveillance detected any abnormalities suggestive of PCDD or PCDF exposure? Are you conducting any epidemiologic studies regarding potential employee exposure to PCDDs or PCDFs? 9. What precautions does your company take to reduce occupational and environmental exposure to PCDDs and PCDFs? 10. Do you wish to inform us of any other studies which your company is conducting in this area? Daniel Hryhorczuk, HD, MPH Principal Investigator 312-996-2597 ^^5 Cl4190 0 ^ D o u g l a s Hoffman Research Associate 312-633-5310 a p p e n d ix a . In addition to the organic chemicals and pesticides listed below, we are requesting information on CHLORINATED BENZENES A POLYCHLORINATED BIPHENYLS X to ' X4 sr T A B L E 7 . ORGANIC CHEMICALS RELATED TO DIOXIN FORMATION Class I Ur O H & 4-BR0H0-2.5 -0 lCHLQRQPHENQL X p r-5l I I *V 2-CHLQRQ-4-FUJQR0PHEH0L X A i i r-X'. DECABR0H0PHWOXY 3ENZEKE r.*i. 2 .4 -0 1 BR0M0PHEHCL tXr & _ 2.3-DICHlQRQPHESOl ^ Qv* 4V (continued) 38 G14191 A* :-!r ^ v w .\ v jl.'"r*1v *'i V * :* 2 ,5 - 0 1CHLOROPHEN0L 2.8-DICHl0a0PHEN0l 3,4-DICHlORQPHENOL PENTA3RCH0PHENOL 2,4,6-TRIMOXOPHENOL (continued) 39 .^sX ' ,.>*v. ..J SUBJECT TO PROTECTIVE ORDER. Cl4192 TA BLE 7 (continued) Class I (continued) 2,4,5-TRICH10R0PHEN0L r'\: Class II BkOHOPHENETOLE O-BROHOPHEKOL o c 2h 5 . ^ 2-CH iO RO -l,4-01ETHQXY-5-NITROBENZENE / 5-CHL0R0-2.4-DIMETHOXY-AHlLINE CHL0R0HYDP.0QU I HONE (continued) ~r] ' I TABLE 7 (continued) C l a s s II (continued) D-CHLOROPHENOL i / 2-CHLORO-4 -PHEHYLPHENDL 4-CHL0K0RESQRC11JQL 2,6-0 13ROMO-4-NITRQPHENOL 3 ,5 -0 1CHL0R0SAL1CYL!C ACID 2 ,6-Dll 000-4-K1TROPHENOL (continued) Cl4194 I. TABLE 7 (continued) Class II (continued) 3 ,5-DlI0D0SAL1CYLIC ACID O-FLUQROANISQLE 0-FLU0R0PHEN0L TETRABROMOBISPHENOL -A TETRACHLOROBISFHEHOL-A HO C la ss III 3-Amino-5-ch)oro-2-hydroxybenzenesuIfbnic acid 2-Amino-4-chloro>6-nitrophenol o -A n isid in e -- Benzaldehyde Bromobenzene o-Bromofluorobenzene (continued) 42 SUBJECT TO PROTECTIVE ORDER. WH,II> ij III j M 'y C14195 ^m.' a-Chlorofluorobenzene 3-Chloro-4-fluoro-nitrobenzene 3- Chloro-4-fluorophenol 4- Chloro-2-nitrophenol Chloropentafluorobenzene 2.4- Dibromofluorobenzene 3.4- Dichloroaniline o-Dichlorobenzene 3.4- Dichlorobenzaldehyde 3.4- Dichlorobenzotrichlorida 3.4- Dichlorobenzotrifluoride 1.2- Dicbloro-4-nitrobenzene 3.4- Dichlorophenylisocyanate 3.4- Difluoroaniline Difluorobenzene 1.2- 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 Hexafluorobenzena Maleic acid <- Maleic anhydride O'Nitroanisole 2-Nitro-p-cresol o-Nitrophenol Pentabromochlorocyclohexane Pentabromoethylebenzena Pentabromotoluene Pentachloroaniline Pentafluoroaniline 0- Phenetidine Phenol (from chlorobenzene) 1- Phenol-2-sulfonic acid, formaldehyde condensate Phenyl ether Phthalic anhydride Picric acid Sodium picrate Tetrabromophthalic anhydride l,2 A 5 -T e tra e h lo ro b en ze n e Tevaehlorophthalic anhydride Tetrafluoro-m-phenylenediamine Tribroim o b e n z e n e 1,2,4-Trichlorobenzene 2.4.6- Trinitroresorcinol SM rr> - ?. _*. fc- e " ;terete >-X ... . '.*/.V-rW-''** TABLE 7 (continued) C Uss 111 (continued) a-Chlorofluorobenzene 3 -C h to ro -4 -flu o ro -n itro b e n z e n e 3- Chloro-4-fluorophenol 4- Chloro-2nitrophenol Chloropentafluorobenzene 2 #4 -Dibromofluorobenzene 3.4- Dichloroaniline o-Dichlorobenzene 3.4- Dichlorobenzaldehyde 3.4- Dichlorobenzotrichloride 3.4- Dichlorobenzotrifluoride 1.2- Dichloro-4-nitrobenzene 3 .4 - Dichloroph eny li socya nate 3.4- Oifluoroaniline -Difluoroberizene 1.2- Dihydroxybenzene-3.5-disulfonic acid, disodium salt 2.5- Dihydroxybenzenesulfonic acid 2.5- Dihydroxybenzenesulfonic acid, potassium salt 2.4- Dinitrdphenol 2.4- Dinitrdphenoxyethanol 3.5- Dinitrosalicylic acid f umaric acid Hexabromobenzene Hexachlorobenzene Hexafluorobenzene Maleic acid ^ Maleic anhydride o-Nitroanisole 2-Nitro-p-cresol o-Nitrophenol P entab rom och lo rocycloh exan e Pentabromoethylebenzene Pentabromotoluene Pentachloroaniline Pentafluoroaniline o-Phenetidine Phenol (from chlorobenzene) t-Phenol-2-suIfonic acid, formaldehyde condensate Phenyl ether Phthalic anhydride Picric acid Sodium picrate Tetrabromophthalic anhydride 1.2.4.5- Tetrchlorobenzene Tetrachlorpphthalic anhydride Ttrafluoro-/n-phenylenediamtne Tribromobenzene 1 r2,4-Trichlorobenzene 2.4.6-Trinitroresorcinol :.'Cir P EST IC ID E CH EM ICALS Pesticides H it'.'the^ ^ o s t signjiftcant 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 ith trichlorophenol and 2,4,5-T. Chlorinated dibezo-y>dQXns are known to be present in at least trace amounts in 3 number of pesticide chemicals. These include 2,4,5-T. silvex. 2,4-D, erbon. sesonc, DMPA, rdnncl, tetradlfon.and the various chlorophcnols ( Fishbcin 1973). In addition, the chemical structures, reaaions. and process conditions for a number of others indicate dioxin content potential. This study deals with production of the basic pesticide chemicals. Thus it d oes not address problems of dioxin formation possibly resulting from formulation. storage, distribution, and utilization of the pesticides. If exposure to alkaline formation 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 forevaluation 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 concei vably could convert to phenols upon exposure to alkaline condition's. ' A second criterion was a minimum commercial production level of 1000 pounds or SI000 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 8. They a rt grouped into classes representing likelihood of dioxin formation, as follows: Class 1--Highly likely to be associated with the presence of halogenated dibenzo-/?-dioxins because of the presence of an ortho-halogenatcd phenol in the reaction squence, with subjection to elevated temperature (>145 C+) plus either alkalinity or the presence of free halogen. Class H--Reasonable but lesser probability of such dioxin association because df the^presence of?phenolic or aromatic structures related to dioxins; although not directly involving dioxin preciirsive conditions, such chemicals might form dioxins under irregular operating conditions. T A B L E 8 . U S T O f PESTIC ID E CH EM ICA LS General name Class I Brfenox Chi ora nil (continued) Chemical name M ethyl-5 -{2 .4 -d ich lo ro e p he n o xy ]-2 nitrobenzoate 2,3,5,6-Tetrachloro-2,5-cycIorhexdiee1 4-tione 55 SUBJECT TO PROTECTIVE ORDER. "T- j , iw j i .w m r n w i i i 5P,r.'w>jp i G14197 TABLE 8. (continued) General name 2 .4 - D and esters and salts 2 .4 - DB and salts Dicamba Dicamba. dimethyiamine salt Dicapthon Dicblofenthion Disul sodium (sesone) 2 .4 -D P Erbon Hexachlorophene Isobac 20 Nitrofen Pentachiorophenol (PCP) and salts Ronnel Silvex and esters and salts 2,4,5-T and esters and salts C la s s II Bromoxyhil and esters (continued) iL J PROTECTIVE ORDER. Chemical name (2.4-Dichlorophenoxy) acetic acid and esters and salts 2.4-Dichiorophenoxybutyric acid and salts 3 .6 - Dichlqro-2-methoxybenzoic acid 3.6- Dichlord-2-methoxybenzoic acid, dimethylamine salt Phosphorothioic acid o-(2-chloro-4- nitrophenyl) o.o-dimethyl ester Phosphorothioic acid o-2.4-dichIoropheny! o.o-diakyl ester 2;4-Dichlorophenoxyethyl sulfate, sodium salt 2-{2.4-Dich!orophenoxy] propionic acid 2,2-Dichloropropanoie acid 2-{2,4,5- trichlorophenoxy) ethyl ester 2,2'-Methylene bis (3.4.6-trichlorophenol) 2 ^ #-M ethylene bis (3.4.6-trichIorophenol). monosodium salt 2 .4 -Dichlorophe nyI-p-nitrophenyl ether Pentachiorophenol and salts Phosphorothioic acid, o.o-dimethyl 0-(2,4,5-trichlorophenyl) ester 2-{2.4,5-Trichlorophenoxy) propionic acid and e ste rs and salts (2.4.5-Trichlorophenoxy) acetic acid 2.3.4,6-T etrachlorophenol 2.4.5-T richlorophenol o-Benzyl-p-chlorophenol 3 .5 -D ib ro m o -4 -h y d ro x y b e n 2 o n itriIe 56 C14198 TABLE 8. (continued) General nam e Carbonphenothion OCPA Dichlone Dinitrobutylphenol. ammonium salt Loxynil Lindane MCPA MCP8 Mecoprop |P a ra th io n PCNP Piperalin -- Propantl Tetradifon ~ -- Chem ical nam e Phosphorodithioic acid s-[I(4-chloro- phenyl)thio]methyl] 0,0-diethYl ester 2 ,3 ,5 .6 - T e t r a c h lo r o - 1 f4 -b e n z e n e d i* carboxylic acid dimethyl ester r > 2 ,3 -O ich lo ro -1 .4 -h a p h th a le n e d io n e 2,4-Dinitro-6-sec-butyl phenol. . _ ammonium salt 3,5-Diiodo-4-hydroxybenzonitrile ,r. l,2 ,3 ,4 ,5 ,6 -H e x a c h lo ro cy cl6 h x a n e * gamma isomer (4-Chloro-o-toloxy) acetic acid 4-<2-Methyl-4-chlor6phenoxy) butyric . -` ' acid '; 2^4-Chforo-2-methylphenoxyj propionic, acid ; : Phosphorothioic acid o,o-diethyl o-<4- nitrophenyl) ester ` ^ *. Pentachloronitrobenzene if A Pipecolinopropyl-3,4-dichlorobenzoate 3-(2-Methylpiperidino)propyl-3.4dichlorobenzoate 3 .4 - Dichloropropionaniljde t 1 s-v) >i ' U=, 1 .2 .4 - Tfichloro-S-{(4-chlorophenyf)- sulfonyi) benzene 2,3,6-Trichlorobenzoic acid 2,3,6-Trichlorophenyldcetic acid and tsodium salt w Triiodobenzoic acid -Surfer** ^ v;V;Av"v--.;^ ^.^r-:-A-r-.vrf g i a s iW.SP"-. '..V---:.*.'>?.-&'.\*r.?*,..,, j| ^r;.::^3;- ^ j| ^ -.!|A " * ; r ^ K * r ; ? l v.:'.'. .- *.;'-./.>-. . *.V--*,-`.v}..-:s%.VV.yv, C hem ical R eactions Higher chlorinated dioxins have been detected in samples of a number o f pesticides produced from 1950 to 1970. Data from these analyses were summarized by Fishbein (1973), as shown in Table 9. 57 iO .N F F Q 'F .H T L SUBJECT TO PROTECTIVE ORDER r 4s C14199