Document drRZ0brDBKdR3zz9vpJ8271B

w / Y >-A, s ^ I I ^ EY W O R K PRODUCT A TTO R N EY-O JEN T PRIVILEGE MONSANTO COMPANY Environmental Policy Staff SPECIAL REPORT ON PENTACHLOROPHENOL PRODUCTS/PROCESSES INFORMATION FOR USE IN LITIGATIONS Report No. MSL-4254 Compiled by: W. B. Bennet D. R. Dill H. C. Godt, D. K. Lynch S. H. Vogel CONFIDENTI ALDate November 30, 1984 SUBJECT TO PROTECTIVE ORDER. CONFIDENTIAL - RESTRICTED DISTRIBUTION DO NOT COPY C25286 ATTORNEY W O R K PRODUCT ATTORNEY-CLIENT PRIVILEGE RESTRICTED DISTRIBUTION DO NOT COPY Copy No. 1. T. M. Bistline 2. T. M. Bistline 3. H. C. Godt, Jr. 4. Li tigation Technical Support Archives 5. Technical Reports Library 6. Technical Reports Library 7. T. M. Bistline 8. T. M. Bistline 9. H. S. Scott 10. H. S. Scott 11. H. S. Scott Copy to be checked out from Technical Reports Library only on approval from: R. T. Berendt, T. M. Bistline or D. F. Snively of Corp. Law. CONFIDENTIAL INFORMATION This document is the property of Monsanto Company and the recipient is responsible for its safe-keeping and disposition. It contains confidential information which must not be reproduced, revealed to unauthorized persons, or sent outside the company without proper authorization. *41 T U ) SUBJECT TO PROTECTIVE ORDER. C25287 CONFIDENTIAL - RESTRICTED DISTRIBUTION DO NOT COPY SPECIAL REPORT ON PENTACHLOROPHENOL PRODUCTS/PROCESSES INFORMATION FOR USE IN LITIGATIONS Report No. MSL-4254 Os Compiled by: W. B. Bennet D. R. Dill H. C. Godt, Jr. D. K. Lynch S. H. Vogel Date: November 30, 1984 - COMPANY CONFIDENTIAL - CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER, C25283 TABLE OF CONTENTS Page No I . Introduction 1 II. Chemistry of Pentachlorophenol Basic Products III. Brief History of the Penta and Santobrite Processes IV. Composition of Penta Basic Products and Formulations 8 V. Product/Process Chronology of Penta Products/Processes 17 VI. Safety and Handlingof Penta Products/Processes 73 VII. , References on Sales Reports, Sales Invoices/Purchase Orders, and Customer Contacts/Call Reports 80 VIII. Monsanto Participation in Organizations Related to Penta Products 81 SUBJECT TO PROTECTIVE ORDER. C25289 I. Introduction This report on the history of Monsanto's production and sale of pentachlorophenol products was assembled primarily for use in the Pennsylvania and Georgia litigations. However, it certainly could find use in any future litigations involving the company. The information gathered includes the chemistry involved in the production of pentachlorophenol basic products; a brief history of their processes; the compositions of the basic products and derived formulations; a product/process chronology of significant events; references dealing with the safety and handling of these products/ processes; references to sales reports, sales invoices/purchase orders, and customer contacts/ca11 reports; and organizations related to pentachlorophenol products in which Monsanto participated. The source of this information was part t>f the files on pentachlorophenol products, assembled by the Corporate Law Department, and included: Source Document Numbers Toxicity Documents (DMEH Library) Toxicity Documents (A/O-Nitro files) Manufacturing Documents (WGK plant) Manufacturing Documents (D.B. Edward's file) Design Manual (CED Library) Manufacturing Documents (Coburn, Croft law firm files) Environmental Law Documents (NIOSH files) SMPs and Research Reports (R2C Information Center) Research Reports (R2C Information Center) Research Documents (A/O-Nitro files) Research Documents (W. B. Bennet's files) General Documents ("Penta Bible", Liebmann and Blase files, technical bulletins from Corp. Distribution) General Documents (L. Meyer and B. Russell files) General Documents (A/O-Nitro files) Sales (Marketing) Documents (PCB litigation files) 0000001-002892 0004319-0004894 0010001-0014458 0014459-0015947.01 0015948-0016215 0016216-0018618 0019740 0019782-0019790 0025001-0028105.02 0028106-0029082 0029083-0030087 0030088-0030674 0035001-0036500 0043021-0046219 0046220-0046583 0050001-0050698 C O N F I D A ' J:a* .Hv 1 SUBJECT TO PROTECTIVE ORDER. 1 AnSSs^ S fS S S S C252do II. Chemistry of Pentachlorophenol Basic Products A. Pentachlorophenol (Penta) OH + 3-x CI2 60-120C + 3-x HC1 Chlorine or Chlorophenol fractions x = 0 to 2 2,4,6-Trichlorophenol (Non-isolated intermediate) Hydrogen chloride OH Cl^A^Cl 1 + 2 Cl2 O V" Cl 120-190C. Iron or Aluminum catalyst OH X0 . ci^ y ^ C1 Cl + 2 HC1 Pentachlorophenol Note: Monsanto Penta contained about 90% pentachlorophenol and about 10% 2,3,4,6-tetrachlorophenol (refer to Penta 60 chemistry). B. Penta 60 (60% Pentachlorophenol, 40% 2,3,4,6-Tetrachlorophenol) 8 Cl2 OH OH 2,4,6-Trichlorophenol (Non-isolated intermediate) Pentachlorophenol 2,3,4,6-Tetra chlorophenol TTTTP TT SUBJECT TO PROTECTIVE ORDER. 2 + 8 HCl Hydrogen chloride C2529i C. Sodium Pentachlorophenate (Santobrite) OH C1^ V Ci Cl Cl Cl Pentachlorophenol NaOH 70-90 C.^ (7% aqueous solution) Sodium hydroxide Sodium Water pentachlorophenate Note: Santobrite contains about 90% sodium pentachlorophenate and about 10% sodium 2,3,4,6-tetrachlorophenate. D. By-products Formed (Alkali Insolubles) 1. Chlorinated Dibenzo-p-dioxins and "Predioxins11 Heat and/or Base x = 4 or 5 Tetra- or Pentachlorophenol XSJ HO Cl, ,--C1x-l Chlorinated hydroxy diphenyl ethers ("Predioxins") HC1 Hydrogen chloride Heat 1 -t S H -U Clx cix-1 a .x Ci + HC1 Hexachlorodibenzo-jv-dioxins Heptachlorodibenzo-^-dioxins Octachlorodibenzo-p-dioxin SUBJECT TO PROTECTIVE ORDER. - 3-- C25292 2. Chlorinated Dibenzofurans, Chlorinated Diphenyl Ethers, and Hydroxy Polychlorinated Biphenyls__________________________ Route 1 Heat and/or - Base Tetra- or Pentachlorophenol + H20 Clx Clx Chlorinated diphenyl ethers. Water Clx Route 2 Heat ^ and/or ^ Clx Base Clx-1 + HC1 Clx (x-1) (or Cl2) Hydrogen (Chlori^ Hexachlorodibenzofurans chloride Heptachlorodibenzofurans Octachlorodibenzofurans Heat and/or Base Clx-1 Hydroxy polychlorinated biphenyls + HC1 (x-1) (or Cl2) M SUBJECT TO PROTECTIVE ORDER. - 4 -, Clx (x-1) Hexachlorodibenzofurans Heptachlorodibenzofurans Octachlorodibenzofurans H20 C25293 Hexachlorobenzene (HCB) OH Cl JL Cl Cl CI2 ... Pentachlorophenol Chlorine i*N ey Y Cl x C1 ci "*1 Cl HCB + H0C1 Hypochlorous acid CONFIDENTI AC SUBJECT TO PROTECTIVE ORDER. -5 C25294 III. Brief History of the Penta and Santobrite Processes Monsanto began the production of pentachlorophenol (Penta) in 1936 probably in the W Building pilot plant of the Queeny plant. In October, 1938, manufacture of Penta and Santobrite began in a newly built full-scale production unit (Building BO) of the Krummrich plant. At that time, Penta was called Santophen 20, and Santobrite was called Santophen 20S. A pine oil/methanol/Penta mixture, called Santophen 20 P.A., was also made. Penta was marketed in flake form until 1963. Then Penta and later Penta 60 (60% pentachlorophenol, 40% tetrachlorophenol) were offered in prilled form and the flaking operation discontinued. Penta 60 production began in 1968. In 1971, facilities were in-stalled to make 2000 lb. Penta blocks. Production of 1000 lb. Penta blocks began in 1972. Santobrite was produced in powder, briquette,, pellet, and 30% aqueous solution forms throughout its history. Over the years, numerous formulations involving Penta and Santobrite were produced and sold. The chemistry for the production of Penta and Santobrite remained essentially the same throughout the life of these products. Phenol, or chlorophenol fractions from the production of o- and p-chlorophenol or 2,4-dichlorophenol, was progressively chlorinated to the appropriate crystallizing point (for Penta, 174-182C.; for Penta 60, 145C.). Iron powder was first used as a catalyst; from 1940, aluminum. Santobrite was simply the neutralization of Penta with sodium hydroxide. From 1938 to about 1950, Penta and Santobrite were manufactured in Building B0 of the Krummrich plant. It has long since been dismantled. From about 1950 to 1978 when production of Penta ceased (Santobrite production stopped*TrT^975), these materials were.-produced in Building BD, just east of the Building BO site. Building BD was dismantled in 1979. Concerning the equipment, as demand for these products increased, additional equipment was added. Although modernized and in some instances larger, the new equipment operated essentially in the same manner. With regard to major changes, a jumbo chlorinator (2% times as large as the other chlorinators) was put in operation in March, 1970. In 1971, 0.4-0.5% triphenyl'phosphite (TPPi) and 0.2-0.5% RT-53A [di(t-amylphenyl) acid phosphate] were added to Penta in order to improve the color and solubilize oil insolubles. In 1972, sublimation of the prilled Penta was reduced by addition of Mobil Provalent 4A oil and more effectively by Humble NUSO-38 oil. SUBJECT TO PROTECTIVE ORDER, - 6- C25293 The following gives the Krummrich plant Department Numbers for the various Penta basic products at various points in time. Product 1938-67 1967-78 Molten Penta Flaked Penta Prilled Penta (started 10/20/63) Penta 60 (started 11/68) Santobrite Powder, Pellets, Solution Santobrite Briquettes Dept. 236 Dept. 236 Dept. B-236 Dept. A-236 Dept. A-236 Dept. 236 Dept. 226* Dept. 236 Dept. 225* Dept. 227* 'Same department as in 1938-67 - just renumbered due to machine accounting installation. CONFIDENTI 4.L SUBJECT TO PROTECTIVE ORDER. -7 C25296 IV. Composition of Penta Basic Products and Formulations A. Basic Products 1. Pentachlorophenol, Molten Internally produced - not sold Specifications: (Kef. 0025583) Alkali Insolubles (chlorinated diphenyl ethers, biphenyls, dibenzo-**dioxins, dibenzofurans and related compounds) Pentachlorophenol (by GL'C) Total chlorinated phenols, calc'd as Pentachlorophenol 0-6%, max. 90%, min. 97.5%, min. 2. Pentachlorophenol, Technical Also called: Santophen 20 Penta Monsanto Penta Sold in the following forms: Flakes Oiled Flakes (0.5% fuel oil) Prills . Oiled Prills (0.5% fuel oil) Blocks (1000 lb., 2000 lb.) Analysis: (Ref. 0010080-0010478; 0000108) Range Typical Pentachlorophenol Tetrachlorophenol Highboilers (diphenyl ether types) Total phenols 85-87% 5-7 6.5-8.5 86.5% 6.0 7.5 97.5% Alkali insolubles Penta/hexachlorodibenzo-p-dioxins Heptachlorodibenzo-p-dioxins Octachlorodibenzo--dioxins Chlorinated dibenzofurans Crystallizing point 178-182C 0.6% max. 700 ppm 1000 ppm 2700 ppm not quantified ci SUBJECT TO PROTECTIVE ORDER. - 8- C 25297 Note: "Golden" Penta was Pentachlorophenol, technical, with 0.15% ethylene glycol or water added at the end of the chlorination cycle either in the chlorinator or in the hold tank before start of prilling. This product had a lighter and more uniform prilled appearing color. Such a material was never commercialized. (Ref. 0026086-91) 3. Penta 60 Mixture of Tetrachlorophenol and Pentachlorophenol Form: Prills Analysis: (Ref. 0026167) Pentachlorophenol Tetrachlorophenol Active ingredients (Chlorophenols) Alkali insoluble matter (chlorinated diphenyl ethers, biphenyls, dibenzo-g-dioxins, dibenzofurans, and related compounds) Crystallizing point 48%, min. 28%, min. 95%, min. 0.15%, max. 145C. 4. Penta L A lower assay form of Penta.-. Also lower alkali insolubles. Form: Prills Analysis: (Ref. 0026164) Same as Penta, prilled except; Pentachlorophenol (by GLC) Crystallizing point 82.0%, min. 174-177C. SUBJECT - 9- C25293 5. Sodium Pentachloropheaate, Technical Also called: Santophen 20S Santobrite Santobrite, Alkaline Forms : Briquettes Pellets .Powder Solution Modified Fines ATTORNEYWORKPRODUCT ATTORNEY-CLIENTPRIVILEGE Analysis: (Ref. 0025676) Santobrite: (Ref. 0025676) Sodium Pentachlorophenate Water Free Alkali (as NaOH) 90%, min., 9%, max. 0.5-0.9% Santobrite Solution: (Ref. 0025441) Sodium Pentachlorophenate 29.5-30.5% Santobrite, Alkaline : (Ref. 0025676) Sodium Pentachlorophenate 86.0%, min. Water Free Alkali (as NaOH) 9.0%, max. 3.0-4.0% B. Formulations Note: "Permasan" is a later tradename for "Permatol" 1. Monsanto Brush Treatment 5 parts wood rosin, 90 parts of 50/50 mix of #2 Fuel Oil and Shell Dione lube oil, 5, parts Santophen 20, and 0.0015 parts of Orange dye. (Ref. 0026015) 2. Monsanto Penta Crop Desiccant 10% Penta, tech. 3% Armour RD 1990A (emulsifier) 87% Sovacide 544C (aromatic petroleum solvent) (Ref. 0000956-1000) CONFIDENTIAL. SUBJECT TO PROTECTIVE ORDER. 10 C25299 . 3. Penta Concentrate (Kppers Penta Wood Preservative 1-10 Concentrate) 40% Penta, tech 60% WK-60 Solvent (Eastman Chemical) (Ref. 0046199-215) 4. Penta Solution 40% solution of Penta in KB-3 oil from Wood Treating Chemical Co. (Eastman Waste Oil). Made from precipitated pentachlorophenol from prill fumes caustic scrubber. .(Ref. 0012322, 0014268) 5. Permasan Same as Permatol A Treating Solution. 6. Permasan 116 lbs./lOOO gal. Fish oil 702 Pine oil 350 Aroclor 5460 350 Paraffin wax 70 Nuodex 3 Santophen 20 (Tech. Penta) 368 Solvent (Mineral Spirits) (800 gal) 5194 (Ref. 0026755) 7. Permasan 116 Concentrate 12.03% Tech. Pentachlorophenol 11.56% Steam distilled pine oil 9.22% Cicoil 4.63% Boiled linseed oil 2.31% Refined paraffin wax 60.25% Mineral spirits (Ref. 0026698) CONFIDENTIA L SUBJECT TO PROTECTIVE ORDER. fTTORNBY WOP*' a t t r n ey . c lSn t product PRIVILEGE 11 - C2530J 8. Permasan 167 7/25/40 5.19% Tech. Pentachlorophenol 5.00% Steam distilled Pine Oil 5.00% Aroclor 5460 10.00% Falkovar K Fish Oil 1.00% Refined Paraffin 74.00% Mineral Spirits 0.03 Cobalt dryer (Ref. 0026728-9) 7/17/41 Substitute Cumar 420-S Resin for Aroclor 5460 (Ref. 0026719-21) 7/28/41 Substitute Piccolyte 10G-S instead of Cumar 420-S. (Ref. 0026718) 11/27/42 Substitute Cobalt Nuolate for Cobalt Nephthenate on an equivalent metal basis. (Ref. 0026715) 9. Permasan 167 Concentrate 11/2/40 11.20% Tech. Pentachlorophenol 10.79% Steam distilled Pine Oil 21.59% Falkovar K Fish Oil 10.79% Aroclor 5460 2.16% Paraffin wax 43.46% Mineral Spirits 0.03% Cobalt Metal (dryer) (Ref. 0026710) 8/21//41 Substitute Piccolyte 100-S for Aroclor 5460 (Ref. 0026702) 11/27/42 Substitite Cobalt Nuolate for Cobalt Naphthenate (Ref. 0026701) SUBJECT TO .............. 12 - ,c* G f C2530x 10. Permasati 170 7/25/40 5.19 parts Tech. Pentachlorophenol 5.00 parts Steam distilled Pine Oil 5.00 parts Dehyd. Castor Oil 5.00 parts Aroclor 5460 1.00 parts Refined paraffin 79.00 parts Mineral Spirits 0.03 parts Cobalt as Cobalt Naphthenate (Ref. 0026728-9) 7/17/41 Substitute Cumar 420-S for Araclor 5460 (Ref. 0026719-21) 7/28/41 Substitute Piccolyte 100-S for Cumar 420-S (Ref. 0026718) 11/27/42 Substitute Cobalt Nuolate for Cobalt Naphthenate on an equivalent metal basis. (Ref. 0026715) 11. Permasati 200 12. Permasati 204 Concentrate ATTORNEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. - 13. - 11.21% Tech. Pentachlorophenol 10*83% Steam distilled Pine Oil 21.66% Falkovar K Extra Heavy Fish Oil 8.66% Aroclor 5460 2.17% Dialuminum Stearate 45.46% Mineral Spirits 0.03% Cobalt metal from Cobalt Naphthenate (Ref. 0026675) 11.21% Pentachlorophenol, tech. 10.83% Steam distilled Pine Oil 21.66% Falkovar K Extra Heavy Fish Oil 8.66% Aroclor 5460 2.17% Dialuminum Stearate 45.46% Mineral Spirits 0.03% Cobalt metal (as Cobalt drier solution) (Ref. 0028775) C25302 13. Permasali 204 Treating Solution 1 part Permasan 204 Concentrate 1*$ parts Mineral Spirits (Ref. 0028776) 14. Permasan 300 9/18/41 2.08% Tech. Pentachlorophenol 3.00% 2-chloro-o-phenyl phenol 4.00% Piccolyte 100-S resin 4.00% Steam distilled Pine Oil 4.00% Falkovar Extra Heavy Fish Oil 1.00% Dialuminum Stearate 0.50% Refined paraffin wax 81.5 % Mineral Spirits 0.03% Cobalt (as Cobalt Naphthenate) (Ref. 0026689) 11/27/42 Substitute Cobalt Nuolate for Cobalt Naphthenate on an equivalent Cobalt basis. (Ref. 0026680) 15. Permasan 300 Concentrate 16. Permasan, Reformulated CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. E - 14 - 11/28/41 4.860% Pentachlorophenol, Tech. 7.010% 2-chloro-o-phenyl phenol 9.348% Piccolyte 100-S resin 9.348% Steam distilled Pine Oil 9:348% Falkovar K Extra Heavy Fish Oil 2.337% Dialuminum Stearate 1.169% Refined Paraffin wax 56.580% Mineral Spirits 0.03% Cobalt Metal as Cobalt Naphthenate (Ref. 0026789) 11/27/42 Substitute Cobalt Nuolate for Cobalt Naphthenate on an equivalent cobalt basis. (Ref. 0026781) 9/29/41 2.08% Pentachlorophenol, Tech. 3.00% 2-chloro-o-phenylphenol 5.00% Synthetic Copal Ester Gum 90.00% Standard Oil engine distillate #1. (Ref. 0026742) C2533 17. Permatol A Concentrate 18. Permatol A-PX116 (Permasan 116) Same as Santophen 20 P.A. 5.19 parts Tech. Pentachlorophenol 5.00 parts Pine oil 4.00 parts Cicoil 2.00 parts Boiled linseed oil 1.00 part Paraffin 83.00 parts Mineral Spirits (Refs. 0026007-8, 0026773-9) 19. Pematol A Treating Solution (Also called Permasan) 20. Preservetex Concentrate 4/4/38 5 parts Penta (Santophen 20) 90 parts //2 Fuel Oil , 5 parts Wood Rosin, Filtered (Ref. 0026018) 1/2/45 3.38 parts Penta 1.82 parts Tetrachlorophenol 5.00 parts Synthetic Copal Ester Gum 90.00 parts Shell Range Oil (Ref. 0026011) 40% Tech. Pentachlorophenol 40% Pine Oil 20% Triphenyl phosphate (Ref. 0026650) 21. Santophen 20 P.A. 40% Tech. Pentachlorophenol (Permatol A Concentrate) 30% Pine oil 30% Methanol (Ref. 0026439) 22. Timbertox XX 2.973% Gilsonite 8.920% Refined Linseed Oil 5.08% Tech. Pentachlorophenol 4.373% Synthetic Copal Ester Gum 78.654% Standard Engine Distillate #1. (Ref. 0026658) 23. Timbertox 10-S CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. A 5% solution of Monsanto Penta in a petroleum solvent similar to fuel oil #1 in volatility. (Ref. 0028349) C2534 - 15 -24. Timbertox 12 Concentrate 34.5% Pentachlorophenol, tech. 37.9% Pine Oil 27.6% Velsicol NR-21 solvent (Ref. 0026667) Note: Wood Treating Chemicals Co. formulations of which compositions were not found in the files: Pole-Treat 15 Pole-Life Tritox Wood Treat AA Woodtox Pre-prime Concentrate Woodtox Pre-prime Ready-to-use 16 - C25305 V. Product/Process Chronology of Penta Products DATE EVENT/SIGNIFICANCE 1936 Monsanto began manufacture of pentachlorophenol by chlorinating phenol in the presence of iron as catalyst (probably in Queeny plant "W" Building). 03/19/37 O V 1V37 04/16/37 02/25/38 ,,o 10 0 O^ -O 70 9 m P3 Q2 < n o pS3 O m First process documentation for the production of Santophen 20 (Penta), Santophen 20S (Santobrite), and Santophen 20 P.A. at WGK plant (Plant B). Chlorinated phenol to trichlorophenol and then further chlorination to Penta using iron as catalyst. Reaction of Penta with sodium hydroxide (NaOH) yielded Santobrite. Santophen 20 P.A.= solution of 40% Penta, 30% Pine Oil, and 20% methanol. Santophen 20 = pentachlorophenol, technical - produced in flaked form. Santophen 20S = sodium pentachloro- phenate powder. , Santophen 20 (Penta) Data-Sheet mentions toxicity. Santophen 20S (Santobrite) Data Sheet mentions toxicity. Revision of 1937 process for Santophen 20 and 20S. No major, significant change. Mentions Santophen 20S powder and briquette forms. C25306 - 17 SOURCE Research Summary Report on Penta, 10/40 (First edition of "Penta Bible") DOCUMENT NOS. 0017590 Tentative Process for Santophen 20, 20S and 20 P.A. 0026435-56 Data Sheet on Santophen 20 Data Sheet on Santophen 20S Tentative Process for Santophen 20 and 20S. 0035928-40 0035935-37 0026225-37 DATE 04/04/38 07/29/38 09/26/38 09/29/38 EVENT/SIGNIFICANCE First process documentation for Permatol A Treating Solution and Monsanto Brush Treatment formulations. Permatol A Treating Solution = 5 parts Penta (Santophen 20) 90 parts #2 fuel oil 5 parts of wood rosin C ). LM, T ) n --! O "J VO (0 H ri ('> -1 l'i s- o` :-j J ij r-.*. !!J y ' r Monsanto Brush Treatment = 5 parts wood rosin 5 parts Santophen 20 90 parts 50/50 mix of //2 fuel oil and Shell Dione lube oil. This is the same as "Armatol" by Huttig Sash & Door Co. Monsanto was vying for their business. First documented production of Permatol A Treating Solution. 22,000 gals, prepared in the Queeny plant "W" Building as stock for sales development. Experimental in nature. Product transferred to WGK plant for subsequent manufacture. First use of cell gas chloVine in Penta process. Previously used revaporized liquid chlorine. Cost reduction. Filter change during filtering of sodium pentachlorophenate solution prior to making Santobrite Powder. Reduced time of filtration. C25307 - 18 - SOURCE Tentative Process for Manufacture of Permasan. DOCUMENT NOS. 0026015-19 Final Report - Manufacture of Permatol A Treating Solution. 0028472-79 Addendum to 1938 Tentative Process for Santophen 20 and 20S. Addendum to 1938 Tentative Process for Santophen 20 and 20S. 0026221 0026219-20 DATE 10/11/38 01/15/39 02/25/39 04/03/39 05/15/39 06/09/39 07/12/39 O CZ) 0\ oC O GO 4 EVENT/SIGNIFICANCE Manufacture of Penta began in a newly built scale plant at the WGK plant. A report (10/27/39) documents the process demonstration and standardi zation of operation in this new plant Monsanto Sales Development Bulletin on Santobrite mentions toxicity in paper industry. First documented production of humectant treated Santobrite Powder. Used sulfurated castor oil as humectant. Reduced dusting. Better control of humectant addition in production of Santobrite Powder, humectant treated. Documentation of early production of Penta in the "W" Building of the Queeny plant for sales development and for stock in making Santophen 20S, Permatol A Concentrate, and Permatol A Treating Solution. \ First full-scale manufacture of Santobrite Briquettes. Made by , compressing, granulating, and recompressing Santobrite Powder to make 1-5/8" diameter briquettes weighing about 1 ounce. Documentation of production of about 20,000 gals, of Monsanto Brush Treatment for sales development to Huttig Sash and Door Co. Work done in Queeny plant "W" Building (See 04/04/38 entry). 19 - SOURCE Final Report: Pentachlorophenol Demonstration of Process on Large Scale. DOCUMENT NOS 0028544-53 Monsanto Sales Development Bulletin No. 10 0036488-98 Addendum to 1938 Tentative Process for Santophen 20 and 20S. 0026216-17 Addendum to 1938 Tentative Process for Santophen 20 and 20S. 0026215 Final Report: Manufacture of 0028464-71 Tetrachloro- and Pentachlorophenol for Sales Development. Addendum to 1938 Tentative Process for Santophen 20 and 20S. 0026212-14 Final Report on Monsanto Brush Treatment. 0028536-43 C25309 DATE 07/28/39 10/13/39 01/31/40 04/01/40 Revised: 8/1/44 2/1/47 4/25/52 04/04/40 04/23/40 CO 0c3 t--i m O 0 n H O "0 33 O in n < m o 33 U m EVENT/SIGNIFICANCE Documentation of early production of Santobrite Powder and Briquettes -in the Queeny plant "W" Building for sales development. Also, data for plant design of full-scale production unit at WGK plant was obtained (see 06/09/39 entry). Documents early production of Santophen 20 P.A. in the "W" Building of the Queeny plant for sales development. (see 03/19/37 entry). Santophen 20 P.A. is the same as Permatol A Concentrate. Lab work resulting in recommending use of aluminum instead of iron as catalyst for Penta manufacture. Monsanto Technical Bulletins on Santobrite in paper industry mention toxicity, handling in structions, and applications. First process documentation of Permatol A-PX116 formulation. Later known as Permasan 116. Composed of 5.19 parts of Penta, tech.,*, 4 parts Cicoil, 5 parts Pine Oil, 2 parts boiled linseed oil, 1 part of paraf fin, and 83 parts of mineral spirits. Preparation of test quantities of Santophen 20 P.A. 20 SOURCE Final Report on Sodium Pentachlorophenate (Santobrite). DOCUMENT NOS. 0028453-63 Final Report: Make 10,000 gals. of Santophen 20 P.A. 0028733-42 Final Report: Penta 0028554-64 Monsanto Technical Bulletin 0-5 Tentative Process for Permatol A-PX116 0036480-87 0036464-71 0036456-63 0036444-9 0026007-8 Final Report: Santophen 20 in Pine Oil. 0028726-32 **sS S 8 s & DATE EVENT/SIGNIFICANCE 05/22/40 First process documentation of Permasan 116 Concentrate. Contains 12.03% Penta, tech., 11.56% steam distilled Pine Oil, 9.22% Cicoil, 4.63% boiled linseed oil, 2.31% refined paraffin wax and 60.25% mineral spirits. 06/11/40 Permasan 116 became new name for Permatol A-PX116 formulation. 06/20/40 Revised: 12/1/45 7/1/46 12/9/48 Monsanto Technical Bulletins on Santobrite in tanning industry mention toxicity, handling instructions, and applications. 07/10/40 07/12/40 07/18/40 Started using ground aluminum ingot instead of iron as catalyst in chlorinating from the trichlorophenol stage to Penta in the process. This catalyst change gave better product (less color and higher crystallizing point). tco 1000 gals, of Permasan 116 was made 0CXI in the Queeny plant "W" Building no'--i !-- -3 S' testing a. slight change in the formulation to correct a turbidity -ot 1'11j problem. Followed Tentative Process dated 06/11/40. Again transferred n7O-ro10o o fl ** ii ,] the manufacture of this product back to the WGK plant. Detailed fomulation procedure for r;ii J manufacture of Permasan 116. p: C) nc[`*J: pv-f ii1 > . - 21 - C25310 SOURCE Tentative Process for Permasan 116 Concntrate. DOCUMENT NOS. 0026696-99 Tentative Process for Permasan 116. Monsanto Technical. Bulletin 0-19 Amendment to 1938 Tentative Process for Santophen 20 and 20S. 0026773-79 0036231-36 0036219-23 0036214-18 0036224-30 0026209-11 Final Report: Permasan 116. 0028757-65 Tentative Process for Permasan 116. 0026761-71 DATE 07/25/40 10/02/40 tn * .! t.: ti? . i. M f' EVENT/SIGNIFICANCE First documented processes for water repellant formulations of Penta Permasan 167 and 170. Permasan 167 = 5.19% Penta, tech., 5% steam distilled Pine Oil, 5% Aroclor 5460, 10% Falkovar K Extra Heavy Fish oil, 1% refined paraffin, 74% mineral spirits, and 0.03% cobalt metal as cobalt naphthenate. Permasan 170 = 5.19% Penta, tech., 5% steam distilled Pine Oil, 5% dehydrated castor oil, 5% Aroclor 5460, 1% refined paraffin, 74% mineral spirits, and 0.03% cobalt metal as cobalt naphthenate. Concentrated form of Permasan 167 produced to permit shipping to West Coast and other distant places and dilution by purchasers, thus keeping cost down. Permasan 167 Concentrate = 11.2% Penta, tech., 10.79% steam distilled Pine Oil, 21.59% Falkovar K Extra He.avy Fish Oil, 10.79% Aroclor 5460, 2.16%'paraffin wax, 43.16% mineral spirits and 0.03% cobalt metal as cobalt naphthenate. .i I. C2531 i 22 - SOURCE Tentative Process for Perraasan 167 and 170 DOCUMENT NOS. 0026722-34 Tentative Process for Permasan 167 Concentrate. 0026706-13 DATE 10/03/40 10/08/40 to O 10 32 EVENT/SIGNIFICANCE Process for production of a "non-toxic water repellant treatment for wood" formulation. There was a market for such a product. Had to be of such a nature to allow incorporation of Penta. The formulation was Permasan 167 without the Penta added. Water Repellant Concentrate 202 = 23.81% steam distilled Pine Oil 47.62% Falkovar K Extra Heavy Fish Oil 23.81% Aroclor 5460 4.76% Paraffin wax 0.03% Cobalt metal as cobalt Naphthenate This formulation was to be diluted by the customers with mineral spirits to form the' finished treating solution. Process for an "inexpensive water repellant without toxic" to meet a market need. The material was furnished as a concentrate to be diluted by the customer with mineral spirits. . Water Repellant Concentrate 203 = 45.45% steam distilled Pine Oil, 45.45% Aroclor 5460, and 9.1% paraffin wax. SOURCE Tentative Process for Water Repellant Concentrate 202. DOCUMENT NOS. 0026040-47 Tentative Process for Water Repellant Concentrate 203. 0026032-38 C25313 DATE 01/28/41 05/20/41 07/17/41 tc0o3 n or 3 ? xah 8> p ad i EVENT/SIGNIFICANCE Process documentation for Permasan 300 Concentrate. Contains: 4.86 % Penta, tech. 7.01 % 2-chloro-o-phenylphenol 9.348% Piccolyte Resin S-100 9.348% Steam distilled Pine Oil 9.348% Falkovar K Extra Heavy Fish Oil 2.337% Dialuminum Stearate 1.189% Refined paraffin wax 56.55% Mineral spirits 0.03% Cobalt Metal (as cobalt naphthenate) Preparation of test quantities of Permasan 167, 170, 204 Concentrate and 204 Treating Solution to deter mine the commercial value of these formulations. Permasan 204 Concentrate 11.21% Penta, tech. 10.83% Steam distilled Pine Oil 21.66% Falkovar K Extra Heavy Fish Oil 8.66% Aroclor 5460 2.17% Dialuminum stearate, 45.46% Mineral spirits 0.03% Cobalt Metal (as Cobalt drier solution). Permasan 204 Treating Solution 1 part Permasan 204 Concentrate 1^ parts Mineral spirits Reformulation of Permasan 167 and 170 due to Aroclor 5460 shortage. Used Cumar 420-S. - 24 SOURCE Tentative Process for Permasan 300 Concentrate. DOCUMENT NOS. 0026782-94 Final Report: Permasan 167, 170, 204 Concentrate and 204 Treating Solution. 028766-77 Amendment to Tentative Process for Permasan 167 and 170. 0026719-21 DATE 07/28/41 08/08/41 08/21/41 09/18/41 EVENT/SIGNIF1CANCE Reformulation of Permasan 167 and 170 due to material shortages andperformance. Substituted Piccolyte S-100 for Cumar 420-S. Reformulation of Water Repellant Concentrate 203 because of material shortage of Aroclor 5460. Substi tuted Piccolyte S-100. Reformulation of Permasan 167 Concentrate due to shortage of Aroclor 5460. Substituted Piccolyte Resin S-100. Process documentation of the production of the Water Repellant formulation Permasan 300. It contained: 2.08% Penta, tech. 3.0 % 2-chloro-o-phenylphenol 4.0 % Piccolyte S-100 4.0 % Steam distilled Pane Oil 4.0 % Falkovar K Extra Heavy Fish Oil 1.0 % Dialuminum Stearate 0.5 % Refined paraffin wax 81.5 % Mineral spirits 0.03% Cobalt metal (as Cobalt <i Naphthenate). D r F ~a C25314 25 SOURCE Tentative Amendment to Tentative Process for Permasan 167 and 170. DOCUMENT NOS. 0026718 Tentative Amendment to Tentative Process for Water Repellant Concentrate 203. 0026029-31 Amendment to Tentative Process for Permasan 167 Concentrate. 0026702 Tentative Process for Permasan 300. 0026681-94 C25315 DATE 09/29/41 10/07/41 10/21/41 EVENT/SIGNIFICANCE Permatol A Treating Solution (Permasan) was reformulated. product was called Permasan, Reformulated. The It contained: 2.08% Penta, tech. 3.0 % 2-chloro-o-phenylphenol 5.0 % Copal Ester Gum, synthetic oil 90.0 % Standard Oil Engine Distillate #1. Process for Water Repellant Concentrate 400, a Penta-free product. It contained: (0 O 0 32 Nq M -a 0TO O H PI O w H < % m >n*] O TO o n TO L 45.45% Steam distilled Pine Oil 45.45% Piccolyte S-100 9.1 % Paraffin Wax Process for Permasan 200. Used dialuminum stearate (in Piace of paraffin vax to imprpve paintability. Permasan 200, contains: 11.21% Penta, tech. 10.83% Steam distilled Pine Oil 21.66% Falkovar K Extra Heavy Fish Oil 8.66% Aroclor 5460 2.17% Dialuminum Stearate 45.46% Mineral Spirits 0.03% Cobalt metal (as cobalt naphthenate) - 26 SOURCE Tentative Process for Permasan, Reformulated. DOCUMENT NOS. 0026737-47 Tentative Process for Water Repellant Concentrate 400. 0026021-27 Tentative Process for Permasan 200 Treating Solution. 0026670-78 h 'r , N S C> DATE 12/31/41 10/05/42 11/27/42 06/17/43 EVENT/SIGNIFICANCE Production of a Penta formulation for Wood Treating Chemical Co. called Timbertox XX. It contained: 2.973% GiLsonite 8.92 % Refined Linseed Oil 5.08 % Penta, tech. 4.373% Synthetic Copal Ester Gum 78.654% Standard Engine Distillate #1. Process documentation for Timbertox 12 Concentrate; a product for Wood Treating Chemical Co. It contained: 34.5% Penta, tech. 37.9% Steam distilled Pine Oil 27.6% Velsicol NR-21 Solvent Permasan 167, 167 Concentrate, 300 and 300 Concentrate were reformulated due to poor raw material availability for cobalt naphthenate. Substituted Cobalt Nuolate on an equivalent metal basis. Manufacturing process documentation of use of ground aluminum ingot instead of iron for the chlorination from the trichlorophenol stage to Penta. The change occurred before this time (see 7/10/40 entry). Gave better product (better color and higher crystallizing point). Also safety-precautions described to reduce worker exposure. C25316 - 27 SOURCE Tentative Process for Timbertok XX. DOCUMENT NOS. 0026653-59 Tentative Process for Timbertox 12 Concentrate for. Wood Treating Chemical Co. 0026661-68 Amendment for Tentative Processfor Permasan 167, 167 Concentrate, 300 and 300 Concentrate. 0026715 Process Description for Manufacture of Santophen 20 (Pentachlorophenol, tech.) 0026596-643 ''ie DATE 07/06/43 07/29/43 11/01/43 Revised: 12/1/45 7/1/46 10/1/48 12/15/49 3/30/50 3/25/52 6/55 EVENT/SIGNIFI GANCE Process documentation for Preservetex Concentrate. It contained: 40% Penta, tech. 40% Steam distilled Pine Oil 20% Triphenyl phosphate This formulation was for textile treatment. Documentation of production of Permatol A Concentrate for sales develop ment work from Sept. 1939 to Aug. 1941 Monsanto Technical Bulletins on Penta mention toxicity, handling instructions, and applications. o CO CN 00 <2 - 28 - SOURCE Tentative Process for Preservetex Concentrate. DOCUMENT NOS. 0026645-51 Final Report on Permatol A Concentrate (Santophen 20 P.A.) 0028778-83 Monsanto Technical Bulletin 0-25 __ 0035904-14 0035893-903 0035882-92 0035870-81 0035857-69 0035850-56 0035839-49 0035806-20 DATE 11/24/43 01/02/45 0c1 o 2o m 9 H O O/01/48 04/05/49 EVENT/SIGNIFICANCE Process documentation of Permasan 116 formulation. It contained: lbs. per 1000 gals. 368 Santophen 20 350 Steam distilled Pine Oil 702 Falkovar K Extra Heavy Fish Oil 70 Refined Paraffin Wax 350 Aroclor 5460 3 Nuodex (Cobalt drier) 5194 Sinclair Solvent (mineral spirits). After 7/25/40, this product was manu factured under the name of Permasan 116, Permasan 167 and Timbertox XX. (a Wood Treating Chemical Co. name) Due to the war, Shell if 1 Straw Distillate 2201W was not available. Shell Range Oil replaced the above as dilutent in the Permasan formulation. Published the results of experiments on toxicology and dermatology of Penta and1Santobrite. "Emphasized very sharply the necessity of careful handling." Gave handling instructions for Penta, Santobrite and several of the formulations. Manufacture of Santobrite Pellets from SanLobrite Flakes. Introduc tion of a less dusty form of SanLobrite. C25313 - 29 - SOURCE Manufacturing Process for Permasan. 116 (old 167 formulation) DOCUMENT NOS. 0026749-58 Revision to Tentative Process for Manufacture of Permasan (Permatol A Treating Solution) 0026010-11 "Toxicology and Dermatology of Pentachlorophenol and Sodium Pentachlorophenate" J. D. Fleming (a Monsanto publication) 0045852-71 Tentative Amendment to Tentative Process for Santobrite - Manufac ture of Santobrite Pellets. 0026205-7 DATE 07/15/49 10/12/49 EVENT/SIGNIFICANCE First process description for Santobrite separate from the Penta process. Safety procedures described. Covers Santobrite Powder and Briquettes. Cell gas chlorine authorized to be used during part of the chlorination in the production of Penta. 10/09/53 11/16/53 Revised process for Monsanto Penta No significant changes from the 1943 process. Safety and Fire Protection discussed. UV Light was shown to accelerate deposition of sludge in Santobrite Solution. Did not find suitable process change to recommend. Suspect that this deposition of sludge is the conversion of "predioxins" or other precursors to chlorinated dioxins. 02/01/54 O *i sO W's p gw 02/01/54 n o a -sad Revised process description for Monsanto Penta. No significant change in chemistry. Includes formal specifications for raw materials and finished products. Safety precautions given. (0026065) First detailed process description for Santobrite Pellets. Safety discussed. (025724) 30 C25319 SOURCE Description of Process for the Manufacture of Santobrite. DOCUMENT NOS. 0025665-707 Process Amendment to Description of Process for the Manufacture of Santophen 20. 0026599 Description of Process for the Manufacture of Monsanto Penta. 0026547-95 Final Report: Improvement of Santobrite Quality. 0028106-15 Process Description for the Manufacture of Monsanto Penta. 0026048-74 Process Description for the Manufacture of Santobrite Powder, Pellets, and Briquettes. 0025708-37 DATE 05/26/54 10/04/54 10/25/54 403/17/55 04/01/55 O to O'* CO to o CD c Ci--O mq H O 0 w mi n -H m C; VV?I rs) EVENT/SIGNIFICANCE Orders issued to chlorophenols departments in the WGK plant not to eat or drink beverages in the departments. Diligence in industrial hygiene. First mention of the chloracne problem in Penta production workers. Employees in this pro duction unit have shown evidence of chloracne for several years. Recommendations made for improving the situation (e.g., improve ventilation, eliminate hand con tact with product, etc.) Concern shown for current chloracne problem. A review of the contem plated replacement of the worn-out dry-type dust collector with a wettype one. First mention of moving Santobrite Briquetting to Building BD from Building BO. New dust collector should be capable of handling this new installation. 1 Revised process for Monsanto Penta. No significant, major process changes. Safety precautions given (0026510-11). Also raw material and finished product specifications. Increased the crystallization point specification for Penta to 178C., min. This was accomplished by doubling the aluminum catalyst charge The result: reduced caking tendency. 31 SOURCE M e m o : , H. B. Patrick to H. O. Hehner Memo: J. T. Garrett to R. S. Wobus DOCUMENT NOS. 0018133 0013411-13 Memo: E. W. Mares to C. C. Richiusa 0013522 "^SSSg Revised Process Description for 0026494-520 the Manufacture of Monsanto Penta. Amendment //I to Process Description for Monsanto Penta. 0026491-93 C2532 DATE 04/01/55 04/20/55 05/06/55 07/12/55 04/10/56 04/16/56 06/01/56 EVENT/SICNIFICANCE Use of "sniff" cell gas chlorine in chlorination to produce Penta No significant change in product quality. Start design of Penta expansion to meet Sales forecasts. Research work on physical properties, analytical, formulations, and appli cations for Penta documented. Covers period from Jan. 1947 to April 1955. Documentation of project to increase Penta production at WGK by 2M lbs./year to be completed in 3 months. Use spare Nitro plant chlorinator. A fourth chlorinator was to be installed later to meet 1957 sales. Minor revision of the 1954 Santobrite process. No significant change. Revised process for Monsahto Penta. No significant change. 10 S h B*- ? 3 s> pu M A> Research work on preservation and chemical treatment of cellulosic materials documented. Covers period from Jan. 1953 to May 1956. Includes Timbertox 10S formulation which contained 5% Penta, tech, in a petro leum solvent similar to Fuel Oil //I in volatility. - 32 SOURCE Amendment #2 to Process Description for Monsanto Penta. DOCUMENT NOS. 0026486-90 Job Record, WGK Chem. Engr. Dept. 0016595 Final Report: Application work on Penta and Derivatives. 0028132-341 Memo: R. Peterson/J. Graves to P. G. Marsh 0016599-608 Process Description for Manufacture of Santobrite Powder, Pellets and*Briquettes. Process Description for Manufacture of Monsanto Penta. Final Report: Application work on Wood Preservatives. 0025743-71 0026462-93 0028342-97 * ' * ^ X * * * p tODI DATE 03/14/57 06/57 09/23/57 EVENT/SIGNIFICANCE Added Dow Corning Antifoam B to water in Schneible scrubbing tower to eliminate foaming. The weak Santobrite solution which developed in the scrubbing tower was used in making Santobrite dissolver batches. This defoamer ended up in Santobrite (no deleterious effect on product). Monsanto Technical Bulletin on Santobrite for slime and algae control mentions toxicity and handling instructions. Recommendation by Medical Dept, that eating in Penta production unit be discontinued. Recommen dation implemented. 12/20/57 12/30/57 J2 jp Q Addition of aluminum catalyst at a higher chlorination level and addition of oxalic acid as stabilizer The result was reduced caking tendency and improved color. O ^ Monsanto Penta Crop Desiccant gut (for onions and potatoes) O described. fcsssi S3 M Composed of: 5 tyd 10% Penta, tech. 3% Armour RD 1990A (emulsifier) H 87% Sovacide 544C (aromatic < **"3 petroleum solvent) SH ig Also safe handling and toxicity O ^ of Penta and its salts described. G ^ (0000962-81) *r 33 C25322 SOURCE Tentative Amendment A to SMP for Santobrite, 4/10/56. DOCUMENT NOS. 0025741-2 Monsanto Technical Bulletin 0-15 0036093-98 Memo: J. T. Garrett to E. W. Mares Memo; R. Paterson/D. Castle to Chlorophenol Group Personnel Tentative Amendment A to SMP for Pentachlorophenol, 4/16/56. 0018132 0018134 0026459-61 Special Report: Monsanto Penta Crop Desiccant g O S to .. 0000956-1000 DATE 04/58 05/22/58 07/25/58 07/58 2 O 10/58 Revised: 12/65 11/58 05/25/59 EVENT/SIGNIFICANCE Monsanto Technical Bulletin on Santobrite mentions toxicity and handling instructions. Revised process for manufacture of Monsanto Penta. No significant changes. Process documentation of lab work recommending doubling the catalyst charge and raising the crystallization point. Tested in the WGK plant on 7/19/54. (see 4/1/55 entry) Monsanto Technical Bulletin on Santobrite and Penta for preser vation of paints and water-base additives. Gives toxicity and handling instructions. Monsanto Technical Bulletin on Monsanto Penta (pentachlorophenol, technical). Gives toxicity and handling instructions. Monsanto Technical Bulletin on Santobrite for Preservation of Cellulose Insulating Materials. Gives toxicity and handling instructions. Process for Santobrite updated. Only minor revisions. 01/60 Revised: 11/63 Monsanto Technical Bulletins for Santobrite in paper industry. Gives toxicity and handling instructions. SOURCE Monsanto Technical Bulletin SC-1 (Revised) Process Description for the Manufacture of Monsanto Penta. Final Report on Penta Caking DOCUMENT NOS. 0036081-92 0025876, 0025884-901 0026795-857 Monsanto Technical Bulletin SC-2 0036016-23 Monsanto Technical Bulletin SC-3 0035784-805 0035765-83 Monsanto Technical Bulletin SC-10 0035973-91 Process Description for Santobrite Powder, Pellets, and Briquettes. 0025773-98 Monsanto Technical Bulletin SC-4 0036436-43 0036427-35 ATTORNEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE DATE 01/60 Revised: 3/63 01/60 06/02/60 11/60 02/09/61 wO g0 s 2/13/61 06/61 3 JZ fa r i IJ rn f x j qJ MV <^ o g te * CO o cru 07/13/61 rmn .~V * CO to tf.. EVENT/SIGNIFICANCE Monsanto Technical Bulletins on Handling Precautions for Penta and Santobrite. Toxicity given. Monsanto Technical on Santobrite in the tanning industry. Gives toxicity and handling instructions. Use of recovered 2 ,4-dichlorophenol from 2,4-D production as partial raw material for Penta production. Thus shorter chlorination cycles and increased production. No 2,4-D was in the recovered 2 ,4-dichlorophenol thus no deleterious effect on Penta quality. Data Report on Copper Pentachlorophenate for Preservation of Cellulosic Materials. Gives toxicity and handling instructions. Product never reached full commercialization. Revision of process documentation for Monsanto Penta. No significant changes. Routine revision of process documentation of Santobrite process. No significant changes. Data Report on Santobrite for Laundry Control of Mold and Mildew. Gives toxicity and handling instructions. Lab testing on Penta prilling. 35 SOURCE Monsanto Technical Bulletin SC-9 DOCUMENT NOS. 0035992-6015 0036099-122 Monsanto Technical Bulletin SC-11 (Revised) 0036201-13 Tentative Amendment A to Manufacturing Process for Monsanto Penta, 5/22/58. 0025878-82 Monsanto Chemical Specialties Data Report No. CS-13 0036142-49 Process Description for Monsanto Penta Process Description for Santobrite Powder, Pellets, and Briquettes. Monsanto Chemical Specialties Data Report No. CS-9 0025903, 0025922-44 0025800-22 0036158-65 TSD Report 0012066-88 atto rn ey W ORK PRODUCI a t t o r n e y .CLIENT PRIVILEGE C25325 DATE 07/13/61 09/25/61 03/16/62 03/30/62 08/10/62 01/15/63 01/16/63 EVENT/S1GNIFICANGE Pilot plant testing of prilling Penta in the Inorganic Research Lab (N Bldg.)- Tests were success ful. Plan to make cost estimate for installation in the WGK Penta production unit. Incidence of chloracne cases on the rise in the Penta/Santobrite production unit. Recommendations made to help correct problem. "Better housekeeping than has been seen in years." Lists employees who have received treatment for chloracne in recent months. Review of the case of chloracne in the WGK chlorophenol group indicated an improvement in the situation and under control. cto O CO om H H O "O oP3 fn n m H < m o 'HI o m > rO r Issuance of Project Design Manual describing instruments for Penta quality tests and improvement of chlorine delivery. Forerunner of Penta .Modernization. Research recommends prilling and coating Penta. Studies done in a pilot plant prilling tower. Reason: to meet competition--such a product exhibits less sublimation, caking tendencies, and dusting. Coating was done with Armoflo 67. Issuance of Project Design Manual on basic prilling facilities (Phase I - Penta Modernization). - 36 - SOURCE TSD Report DOCUMENT NOS. 0012066-88 Memo : J. T. Garrett to H. B. Patrick . 00134l4r15 Memo : H. Patrick to H. Carder Memo: H. Carder to R. E. Soden 0013344-45 0013419 Project Design Manual EA 4-398, Project 6299 0016025-63 Final Report: Penta process 0026956-85 studies. *"***3S8S Project Design Manual EA 4-398 Project 6724. 0015948-16024 DATE 02/01/63 02/28/63 10/20/63 03/64 " 7o0 rn o O fO CCOfi to m< o TO Oj n EVENT/SIGNIFICANOE Change Penta product form from flakes to prills to eliminate sublimation, dusting and caking tendency. Also started chlorinating to a higher degree to reduce tetrachlorophenol content. Prills were coated with 0.1% Armoflo 67 (an antidusting agent). Issuance of Project Design Manual to provide necessary facilities to supplement previously installed prilling tower to produce and package prilled Penta. Also modernize electrical facilities. (Phase II - Penta Modernization) Gives outline and purpose of the various parts. Sales bulletin on Prilled Penta issued. Gives handling precautions. Analytical studies on the characterization of the insolubles in Santobrite. The insolubles mainly included material^ contain ing silicon and aluminum.. Also polychlorinated aromatics' were present. Possible structures were chlorinated dibenzo-p-dioxins and dibenzofurans -- the octachloro derivatives are specifically mentioned (0027043). First docu mented evidence of such materials in Penta products . - 37 SOURCE Tentative Amendment B to Manufacturing Process for Monsanto Penta 2/6/61 DOCUMENT NOS. 0025917-19 Project Design Manual EA 4-461 0016064-215 Sales Bulletin 7768-100 Final Report on Santobrite Characterization of Insoluble Material. . 0046453-5 0027026-73 ATTORNEY W O R K PRODUCT ATTORNEY-CLIENT PRIVILEGE C2532 DATE 04/07/64 04/30/64 06/30/64 08/17/64 01/19/65 Q6/65 06/16/65 vi EVENT/SIGNIFICANCE Coating of Santobrite //I Fines and Santobrite Pellets with propylene glycol and/or monoacetin to reduce dustiness. Tested the elimination of mechanical agitation during chlorination. No significant changes were noted in the product. Discontinued mechanical agitation during chlorination in the pro duction of Penta. No apparent effect on quality. Qualification of Alcoa's aluminum D-0X-IT shot and Reynold's HPS aluminum granules as alternate catalyst supply for Penta production. Study of catalyst concentration, catalyst addition time, and rate of temperature rise on Penta quality. Revised procedure to make all grades of Santobrite except Briquettes in a pelletizer-dryer systeiq described. Contains Safety and Toxicity Data. (0025865) H m n H2 [^| o >TO ri xt Process documentation of the allowance of a minimum amount of aluminum catalyst in the range of 2-14 lbs. per batch. This reduced mineral spirits and xylene insolubles prill screen build-up, and did not effect chlorination efficienty. - 38 SOURCE DOCUMENT NOS. Tentative Amendment A to Tentative Process for Santobrite, 2/17/64 0012623-24 Tentative Amendment C to SMP for Penta, 2/9/61 0025915-16 Tentative Amendment D to SMP for Penta, 2/9/61. 0025912-14 Tentative Amendment E to SMP for Penta, 2/9/61 0025910-11 Tentative Amendment F to SMP for Penta, 2/9/61 SMP for Santobrite 0025908-9 0025823-74 Amendment 1 (Tentative Amend- 0025905-7 ment G) to SMP for Penta, 2/9/61. C2532 DATE 11/09/65 07/66 07/66 Revised: 7/69 6/70 07/66 09/01/66 04/01/67 04/26/67 08/67 Ou m o < m o >70 U m L EVENT/SIGNIFICANCE First SMP describing Prilled Penta production. Contains Safety and Toxicity Data. Monsanto Technical Bulletin on Santobrite in paper industry. Gives toxicity and handling instructions. Notes FDA approval. Monsanto Technical Bulletins on Handling Precautions for Penta and Santobrite. Gives toxicity. Monsanto Technical Bulletin on Santobrite in the tanning indus try. Gives toxicity and handling instructions. Documentation of lab tests to validate the use of cumene phenol for all phenolic based products at WGK plant. Sales bulletin on Prilled Penta issued. Gives handling precautions. Trial of change in catalyst in Penta production to 3:1 aluminum, copper. Should get higher Penta assay (89-91%) and lower high boiler content. Toxicity and hazards, effects, First Aid, and protective equipment for Penta and Santobrite documented in Medical Department Bulletin. - 39 - SOURCE SMP for Pentachlorophenol Monsanto Technical Bulletin O/PS-2 0025946, 0025958- 0026005 0036415-26 Monsanto Technical Bulletin O/PS-3 Monsanto Technical Bulletin O/PS-5 TSD Report 0036279-302 0036376-98 0036353-75 0036237-52 0012045-65 Sales Bulletin 7768-100-09-03 0046450-2 Tentative 'Amendment A to SMP for Penta, 11/9/65. 0025956-57 Medical Department Bulletin on Pentachlorophenol and Sodium Pentachiorophena te 0013286-89 5r 3 3 K 5 S DATE 10/17/67 11/08/67 01/08/68 03/22/68 09/16/68 11/01/68 EVENT/SIGNIFICANCE Process change to sparge the chlorinator at the end of the chlorination with hydrogen chloride gas to reduce degradation between chlorination and the prilling system Plan cited to increase capacity of Penta unit to meet 1970-71 sales forecast. Accomplish by debugging prill tower, increase chlorine flow rate, automate department, and add a new chlo rinator. Also quality improvement planned. Monsanto Penta ranked 3rd in quality. Proposed use of Aluminum-Tellurium as catalyst in the chlorination. Reaction rate is more predictable, and gives higher Penta assay with less impurities. Proposed use of Salicylaldhyde as stabilizer after the chlorination to prevent product degradation (formation of alkali insolubles and lower Penta assay). \ Use of Tellurium-Aluminum catalyst and Salicylaldhyde in a 'plant test improved Penta quality. Engineering flow diagram of Penta chlorination. SOURCE Tentative Amendment B to SMP for Penta, 11/9/65. DOCUMENT NOS. 0025953-5 TSD Report 0011565-75 Tentative Amendment C to SMP for Penta, 11/9/65. 0025951-2 Tentative Amendment D to SMP for Penta, 11/9/65. 0025949-50 TSD Report on Penta Improved Quality. Engineering Diagram Flow 0027166-205 0015497 ATTORNEy WORK A n O R N E Y - a S PRODUCT PR/V/lGE C25330 DATE 11/68 11/68 02/13/69 03/11/69 03/11/69 EVENT/SIGNIFICANCE First SMP to indicate the manufac ture of Penta 60. In the production of Penta, there was a change in the aluminum catalyst addition. Two additions--one at 90-120C. at the dichloro stage, and then at the tetrachloro stage. Aluminum-Tellurium catalyst not adopted, HC1 sparging not adopted, Salicylaldhyde stabi lizer not adopted. More detailed Safety and Toxicity section. GLC assay mentioned. Last process documentation to make all forms of Santobrite in cluding briquettes. The pelletizer-dryer system is de scribed. Contains safety and toxicity data (0012006). Good, brief summary of Santobrite production history at WGK plant (0012007-8). Fume control system on Penta operation was improved and ex tended each year since installa tion in 1966. Additional scrubbers have been added where needed. Approval for plant trial' of cumene phenol in place of sulfonation phenol in Santobrite production. Use of cumene phenol as an acceptable substitute for sulfonation phenol in the Penta process. - 41 - SOURCE SMP for Molten Penta, Prilled Penta and Penta 60. 0026076-79 0026114-201 SMP for Santobrite 0011951-12014 Letter: C. Buckley to A. M. Telford (111. Pollution Control Board). 0010596-97 Tentative Amendment A to SMP for Santobrite, 11/68 0011960-1 Tentative Amendment A for SMP for Molten Penta, Prilled Penta, and Penta 60, 11/68. 0026080-82 C2533i CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. DATE 05/16/69 06/03/69 06/05/69 07/69 01/70 02/16/70 3/70 EVENT/SIGNIFICANCE Documentation of a plant demonstration of the use of cumene phenol as an alternate raw material for Penta. Demonstration successful, but may have a color quality problem in Penta. Santobrite quality and color satisfactory. Experimental coating of Santobrite Pellets with monoacetin to reduce dustiness. Eliminate use of Armoflo 67 as coating on Prilled Penta. Customer acceptance of some sublimation ("blooming") of Prilled Penta. Monsanto Technical Bulletins on Handling Precautions for Penta and Santobrite. Gives toxicity. Documentation of instructions in the operation of the Santobrite department (Dept. 225). Shows diligence and completeness of training. Safety and housekeeping covered. List of concerns from Field Safety Review and action plans regarding Penta expansion. Start up of jumbo chlorinator. Step change in chlorinator size with external heat exchanger. - 42 SOURCE TSD Report DOCUMENT NOS. 0011685-713 Tentative Amendment B to SMP for Santobrite, 11/68 0011957-59 Tentative Amendment B for SMP for Molten Penta, Prilled Penta, and Penta 60, 11/80. 0026083-85 Monsanto Technical Bulletin O/PS-3 0036376-98 Training and Reference Manual for Santobrite 0011715-811 Memo: R. L. Fields to E. D. Malone, et al. 0013193-95 Background section of SMP for Molten Penta, Prilled Penta and Penta 60, 1/30/72- 0025648-9 C25332 DATE 04/27/70 05/27/70 06/11/70 07/02-08/70 07/15/70 08/05/70 09/03/70 t/) O C 0CD mt_ o --I a "0 30 O o mH o w h < 2 m oH ri 33 > r EVENT/SIGNIFICANCE Recommendation for a plant trial of adding ethylene glycol to lighten color of Penta. "Golden" Penta process. Proposed addition of 0.1-0.25% by weight of ethylene glycol at the end of the chlorination. This would give a more uniform and lighter color to Prilled Penta. Installed a chlorine vaporizer system in the Penta production unit to protect against explosive hazard resulting from liquid chlorine. Plant trial of "Golden" Penta process. Gave material of more uniform color and a lighter color. Installation of Hum-mer Screener to replace Rotex screening in the Santobrite process described. Excessive maintenance cost was the reason for replacement. Replacement completed 1/20/70. > Installed C02 purge system for chlorinators. Addition of 0.1-0.2% by weight of water to the molten Penta before start of prilling. Produced "Golden" Penta with better appearance. - 43 - SOURCE TSD Report; "Golden" Penta DOCUMENT NOS. 0027227-32 Tentative Amendment C for SMP for Molten Penta, Prilled Penta, and Penta 60, 11/68. 0026086-88 TSD Report 0011595-607 TSD Report: "Golden" Penta, 9/10/40. TSD Report on Santobrite 0027240-66 0027408-36 TSD Report: Bulk C02 Facilities 0027233-39 Tentative Amendment D to SMP for Molten Penta, Prilled Penta, and Penta 60, 11/68 0026089-91 DATE 10/08/70 10/08/70 10/09/70 1971 01/18/71 and 03/09/71 EVENT/SIGNIFICANCE Addition of Del De-Foam Non-Silicon Foam Control Solution to control foam in the prilled Penta off-gas scrubber and Central Fume Scrubber. No effect on product. Use of Del De-foam antifoam added to scrubber solution in Santobrite production to control foaming. Testing of modification for dust control of Santobrite using various coating systems employing sodium hydroxide, monoacetin and water. Facilities were installed to make 2000 lb. Penta blocks. Reports on meeting of Penta manufacturers with USDA and FDA (1/15/71) and under auspices of AWPI (American Wood Preservers Institute) (3/5/71). Monsanto people involved: E. P. Benzing, J. A . Mullendore, J. D . Early, E. P. Wheeler and W. R, Richard. Talks about what can bo done to lower dioxin content in Penta. Table listing dioxin analysis of samples of Penta from several producers. No limit on impurities in Penta were offered to the USDA. C25333 - 44 SOURCE Tenttive Amendment E to SMP for Mlten Penta, Prilled Penta, and Penta 60, 11/68 DOCUMENT NOS. 0026092-4 Tentative Amendment D to SMP for Santobrite, 11/68 Tentative Amendment C to SMP for Santobrite,- .11/68 0011954-56 0011962-64 Scope Commitment Meeting on Upgrading Penta Block Pouring Facilities, 5/9/77 Memos by J. A. Mullendore 0017959 0001043-45 0001016-22 0001027 C25334 DATE 02/15/71 03/23/71 03/24/71 03/29/71 '03/31/71 04/12/71 SO * EVENT/SIGNIFICANCE Process change lowering the temperature in the first part of the chlorination from 90-120C. to 60C. Also other temperature/ time changes. Quality of Penta was improved (reduced impurities). Safety review of addition of triphenyl phosphate and RT-53A additives to Molten Penta. Corrective actions given. Wood Treating Chemicals Co. Penta formulations Woodtox Pre-Prime Concentrate and Woodtox Pre-Prime Ready-To-Use mentioned. Composi tion not given. Addition of a mixture of triphenyl phosphite (TPPi) and RT-53A to the Molten Penta before prilling or pouring into blocks. These addi tives stabilize Penta reducing buildup of alkali insolubles. Mentions 2000 lb. blocks. Plant evaluation of use jof cumeme phenol for Penta production. Found acceptable. Proposed change - add phenol or lower chlorinated phenols as chlorine scavengers to the Molten Penta before prilling or pouring into blocks. Improve quality of Penta by eliminating excess post chlorination. - 45 SOURCE Tentative Amendraent F to SMP for Molten Penta, Prilled Penta, and Penta 60, 11/68 DOCUMENT NOS. 0026095-98 Memo: D. J. Schillinger to J. Dalton, et al. 0013189 Letter: R. F. Simmons to W. Lindsay (Monsanto Canada, Ltd.) 0050654-55 Tentative Amendment G to SMP for Molten Penta, Prilled Penta, and Penta 60, 11/68 0026099-102 TSD Report Tentative Amendment H to SMP -for Molten Penta, Prilled Penta, and Penta 60, 11/68 0012497-519 0026103-6 C25335 DATE 04/19/71 04/28/71 06/03/71 07/06/71 09/09/71 11/01/71 11/15/71 EVENT/SIGNIFICANCE Wood Treating Chemicals Co. Penta formulations Pole-treat 15, Polelife, Tritox, and Wood Treat AA mentioned. Compositions not given Report showing dioxin levels in Penta as measured by various analytical labs. (Dow, Monsanto, FDA). W. R. Richard suggested testing FDA standard Penta for teratogenicity Penta blocks turned down by Monsanto Distribution for test permit for shipping by rail. Safety review of Penta additive facilities. Recommendations made. Test run for 2000 lb. Penta blocks at WGK plant successful. Construe tion of permanent facilities in progress to produce blocks at 3.2 M lb./yr. rate. Testing the addition of coating agents to the Molten Penta prior to prilling to eliminate/reduce sublimation ("Blooming") .* Studies and plant test documentation of additives RT-53A and triphenyl phosphite used to stabilize Penta. Covers period from 12/70-11/71. - 46 SOURCE Letter; R. D. Arsenault to W.Hale (Unity Inter mountain Telephone Co.) DOCUMENT NOS. 0050630 Letter: FDA from W. R. Richard-- 0001080-1106 Multi-Method Study of Dioxins in Chlorophenols. Memo: D. Westbrook from R. D. Arsenault Memo: D. J. Schillinger to F. Elliot, et al. TSD Report 0000799-800 0013188 0012565-72 Tentative Amendment I to SMP for Molten Penta, Prilled Penta and Penta 60, 11/68 Also Tentative Amendment A to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/70 TSD Report - Penta Quality Improvement. 0026107-10 0027338-407 ssg sss s s s s DATE 12/01/71 12/02/71 12/09/71 en O eO 12/71 12/71 1972 m o H < 2 m o 70 a m to EVENT/SIGNIFICANCE Sales contract on Penta between Monsanto and Koppers Company. Material Safety Data Sheet on Penta issued. Give precautions and protection information. 1968 SMP Tentative Amendments reviewed and status indicated. Also accepts HC1 and sparge blanket to chlorinator at the end of a chlorination batch (Amendment B of 1965 SMP). Amendment C to 1965 SMP - Rejected. 1968 SMP Amendments: A - accepted B - accepted C - rejected ("Golden" Penta) D - rejected ("Golden" Penta) E - accepted F - accepted G - rejected H - accepted (additive package) I - in process \ Monsanto Technical Bulletin on Monsanto Penta. Gives labeling, toxicity, and handling instructions Monsanto sold Wood Treating Chemical Co. to Koppers Company. Started making 1000 lb. Penta blocks in fiberpaks. Done in same facilities as for 2000 lb. blocks. C25336 - 47 SOURCE Sales Contract Material Safety Data Sheet DOCUMENT NOS. 0044525-37 0043530-1 Memo: Updating Amendment Status for SMP for Molten Penta, Prilled Penta, and Penta 60, 11/68 0026111-13 CL'NTpp'*V?.l?uGcfr Monsanto Technical Bulletin IC/PS-8 0035681-701 Scope Commitment Meeting on Upgrading Penta Block Pouring facilities, 5/9/77 0017959 DATE 01/12/72 01/20/72 01/30/72 02/15/72 2/72 03/21/72 03/30/72 m n i, j =! m i* 3 fcal D m i ^ EVENT/SIGNIFICANCE 1971 Sales Report by Customer (copy almost illegible). Penta chlorinator optimization by installation of a new heat exchanger which can operate over entire chlorination range. No significant effect on product quality. Last SMP for Penta issued. Jumbo chlorinator mentioned - started up in 3/70. No significant change in operation. Industrial hygiene inspection of Penta and Santobrite production units on 12/20/71 documented. Investigated reported chloracne cases and adequacy of ventilation. Conclusions and recommendations given. Poor housekeeping noted. SMP for Santobrite Briquettes and Solution updated. Describes production of 30% Santobrite Solution, and Santobrite '-Briquettes from Santobrite #1 or #2 fines or Dowcide G Beads or Beads ST. Description of process corrections which reduced emissions temporarily Use of nitrogen purge in place of HC1 and C02 purge as blanket over Molten Penta at the end of chlorination to avoid product degradation. Accepted for full time use. C25337 - 48 SOURCE MIC Specialty Products Sales Report Tentative Amendment B to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72 DOCUMENT NOS. 0044634-40 0025531-34 SMP for Molten Penta, Prilled Penta, and Penta 60. 0025467, 0025535-664 Memo: B. Eley to File 0017803-6 ATTORNEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE SMP for Santobrite Briquettes and Santobrite Solution 0025415-65 TSD Report: Reduce Santobrite Air Pollution. Amendment C to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72 0028105.01 0025525-30 C25333 DATE 04/04/72 04/72 04/72 05/02/72 05/72 06/07/72 EVENT/SIGNIFICANCE Recommendations for elimination of prill spillage at cooler. Necessary to prevent worker ex posure which causes chloracne. States that 50% of workers in the Penta production unit have chloracne. Documents process safety and housekeeping rules for Santobrite Briquettes* Discusses Santobrite air scrubbing system. Documents process safety and housekeeping instructions for Penta operations. Mentions all workers in chlorophenols depart ments must bath at the end of their shifts before leaving the plant. Because of the hazardous operations at WGK plant, work rules were established and docu mented in the Safety Rule Book. Documents process for production of 30% Santobrite Solution (aqueous from Scrubber Liquor. Safety and toxicity discussed. Process safety and housekeeping instructions for Santobrite Solution. Loss Prevention and Environmental Control Research Review on Penta purification project (distillation of Penta) to remove chlorinated dioxins. Not implemented at WGK. - 49 SOURCE Memo: .R. L. Harness to R. R. Sorrell DOCUMENT NOS. 0013175-80 Operator Training and Reference Manual for Santobrite Briquettes 0010787-806 Operator Training and Reference Manual for Chlorophenols Group. 0010763-82 ^sssssss Tentative Process 0014416-40 Operator Training and Reference Manual for Santobrite Solution 0010807-57 Memo: W. Russell to D. Wassan 0018429-33 025339 DATE 06/29/72 08/02/72 08/23/72 08/24/72 08/30/72 09/26/72 g? O fg Qg 10/13/72 11/06/72 QU n // *S --ij oi PO O /v ni o 11/30/72 EVENT/SIGNIFICANCE Evaluated coating Prilled Penta with Mobil Provalent 4A Oil to retard sublimation. Results satisfactory. Safety review of Penta Block installation. Alterations of equipment suggested. Documentation of standard practice of chlorophenols group at WGK to control and clear up chloracne cases Distillation process described which would remove the polychlorodibenzo-p-dioxins from Penta. Not put into practice. Industrial hygiene practice at WGK plant to control chloracne. Safety review of bulk Penta handling. Recommendations for improvement made. __ OSHA tests for excessivq chlorine and noise in the Penta/Santobrite production unit. Chloride results excellent. Noise level may be in violation. Humble NUSO-38 oil used to spray coat Prilled Penta in place of P4A oil. Cooling reduces sublimination ("blooming"). Accepted for full-time use. Location Plans for Penta/Santobrite production units. Locates all pieces of equipment. 50 SOURCE TSD Report DOCUMENT NOS. 0012275-80 Memo: D. J. Schillinger to J. Dalton, et al. 0013187 Memo : R . R . Sorrell to R. L. Fields 0017160 Process for Engr. Design: Distillation of Penta to Remove Polychloro-p-dioxins 0027451-542 Memo : R. R. Sorrell to all production personnel. Memo : D. J. Schillinger to C. Buehler, et al. 0017796 0013174 Memo: D. Rochell to R. Sorrell 0013154 Memo : Disposition of Tentative Amendments A and E to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72 Drawings 0025515 0015500-1 C253 40 DATE 11/72 01/09/73 01/23/73 01/73 02/73 04/11/73 04/15/73 05/05/73 EVENT/SIGNIFICANCE Process safety, housekeeping and handling instructions for Prilled Penta. 1972 Sales Report by Customer. Reinstate oiling of Prilled Penta with NUSO-38 oil. Documentation of Process Safety Audit for Penta operation. Mentions fire hazard from additives. Penta blocking system introduced new personal hazards. Recommendations for improvement made. Monsanto issues Application Manual for Penta and Santobrite. Contains handling precautions and toxicological data. Information on Penta composition, producers, dioxin content and toxicology of dioxins (presentation slides on Dowcide EC-7).( Decreased RT-53A and triphenyl phosphite to 0.2% and 0.4%, respectively, by weight of the Penta batch. Accepted for full time use. Revised process for distillation of Penta (see 8/24/72 for original process). - 51 SOURCE Operator Training and Reference Manual for Prilled Penta. MIC Specialty Products Sales Report TSD Report Safety Audit Report DOCUMENT NOS. 0011868-97 0045316-23 0045447-524 0012281-83 0013305-43 Application Manual for Santobrite and Monsanto Penta 0044197-256 Letter: L. L. Atkins (Dow) to H. S. Bergen (Monsanto) 0001166-90 Tentative Amendment D to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72. 0025512-14 0025520-23 Process for Engr. Design: Distillation of Penta 0027543-625 AATTTTOKRNNEEyYSVV*OP/f product p r iv ile g e C2534 DATE 05/08/73 06/73 08/15/73 08/24/73 [01/09/74 04/04/74 EVENT/SIGNIFICANCE Air pollution source operating permit issued by Illinois EPA for Penta prilling tower and Venturi scrubber. Expiration date, 4/25/78. Shows compliance with regulations. Safety, housekeeping and handling instructions for Molten Penta. Process description for the use of previously sewered prilled Penta scrubber liquor and scrap Penta to make Santobrite Briquettes (previous Tentative Process P-1682 describes production of Santobrite Solution from the above-mentioned waste streams). Improvement of Penta quality by reducing by-product formation (insolubles) by employing lower temperature/heat history during chlorination. t Better management of process. I 1973 Sales Report by Customer. Another process amendment dealing with improving Penta quality by better chlorination management through lower temperature/heat history during chlorination. - 52 - SOURCE Illinois EPA letter and Permit DOCUMENT NOS. 0010568-74 Operator Training and Reference Manual for Molten Penta Process Outline: Drum drying and briquetting Santobrite. 0011813-67 0027626-58 Tentative Amendment F to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72 0025507-11 MIC Specialty Products Sales Sales Report Tentative Amendment H to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72 0045310-15 0025484-87 Of DATE 04/10/74 04/11/74 4th Q/74 *05/14/74 06/28/74 EVENT/SIGNIFICANCE Provision for acceptable means of disposal of Central Fume Scrubber liquor, and scrap and still wash water. Extraction of scrubber liquor with AD-73 oil and sold to Wood Treating Chemical Co. The phenolics in the other streams will be extracted with Santophen I residue and incinerated Previously all of these streams were landfilled. Documentation of the process to recover Penta from the Venturi scrubbing liquor in the Penta prilling operation. Involves extracting the liquor with NB-21 or AD-73 solvent producing a Penta 50% oil concentrate. Gives safety and toxicity information. EPA Santobrite file for Monsanto (File 524-305). A chronology from 1948 to 1974. Loss Prevention and Environmental Control report on Penta Elimi nation of Solid Waste. Recommenda tions made on recovery of Penta from Venturi liquor. Documentation of Research effort on process to recover Penta from prilled Penta scrubber liquor to make a marketable Penta oil solution. Implemented as Tenta tive Amendment G to SMP for Penta and Penta 60, 1/30/72. SOURCE Tentatiive Amendment G to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72 DOCUMENT NOS. 0025488-506 Process for Engineering Design for Recovery of Penta from Venturi Liquor by Extraction into AD-73 Oil. 0045768-813 EPA Santobrite File. Memo: W. W. Russell to D. R. Dill -Research Report #3882 0044157-70 0013171-72 0016784-862 DATE 08/06/74 11/07/74 12/06/74 12/09/74 12/31/74 EVENT/SIGNIFICANCE Pilot plant preparation of Penta Solution for sales development. Documentation of events leading to overchlorinated Penta batch J-9 Provision for disposal of large quantity of aqueous phenolic waste from Penta operation in storage. Extracted with nitrochlorobenzene "meta fractions" and sent to outside incinerator. HOE (Heavy Oxo Ends) and AD-73 oil were shown to be suitable substitutes for Del Defoam for Central Fume Scrubber foam control Amendment I to the SMP for Penta was accepted for full-time use. 1974 Sales Report by Customer 1975 .01/22/75 02/17/75 03/26/75 33 O -m1 n m h < :z m o 33 O M 33 r Santobrite production and sale discontinued. Reduction in the amount 'of Santophen I residue used.to extract aqueous phenolic wastes from Penta process. Reason: less Santophen 1 residue available Penta Solution defined and process documented. It is a 40% solution of Penta in KB-3 Oil (Eastman Waste Oil). Analysis of Penta shows hexachlorobenzene (HCB) at 35-60 ppm levels. 54 C25343 SOURCE ^* kJh TSD Report * h' ? o . Memo: J. Labanosky to R. L. Fields Tentative Amendment J to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72 DOCUMENT NOS. 0012314-26 0017728-33 0025475-7 Tentative Amendment I to SMP Molten Penta, Prilled Penta, and Penta 60, 1/30/72 0025478-83 MIC Specialty Products Sales Report "Sources of Product Information", Monsanto booklet, July, 1984 Tentative Amendment K to SMP for Penta, Prilled Penta, and Penta 60, 1/30/72 0045411-46 0045324-29 0025471-4 Tentative Amendment I to Engineering Design Process for Penta Solution 5/9/74. Memo: R. G. Keley to D. R. Dill 0014268 0017490 DATE 04/07/75 and 05/28/75 04/11/75 04/24/75 EVENT/SIGNIFICANCE 2 -3,7 ,8-TCDD not found in Penta samples at detectable limit of 10 ppm. levels of hexa CDD at 8-15 ppm, hepta CDD at 110-290 ppm, and octa CDD at 870-1980 ppm. Positive chick adema factor appears to be due to other sub stances than the hexa CDD present in Penta. Distillation of Penta removes the positive chick adema factor. Alert to all Monsanto location managers that Penta is on OSHA's hazardous substance list. to O c CD u O m n o TJ o rn n rJ z m O SO rCnJ > ro C25344 - 55 SOURCE Special Study by MIC Applied Sciences Section DOCUMENT NOS. 0017424-7 0017528 Memo: P. L. Wright to D. R. Dill 0017546-8 OSHA Memo #31 on Hazardous Substances 0010858-61 atto rney w o r k atto rney^ PRO D U CT PRIVILEGE DATE 10/28/75 SUBJECT TO PROTECTIVE ORDER. EVENT/SIGNIFICANCE Documentation of the chlorophenol dioxin problem since its onset in 1970. Issued to aid in decision making with respect to future activities. Summary: 1. Hepta- and octachloro dioxins are present in Santobrite and Penta Formed during the later stages of chlorination and during Molten Penta storage prior to prilling. 2. Tetrachloro dioxins (TCDD) were not detected in Penta; but about 1 ppm of TCDD were detected at the early stages of chlorination. 3. Santobrite contains less dioxin than Penta. Some are removed as insolubles in the cone settler. A. Dioxins were not detected in any Penta or Santobrite scrubbing streams. 5. Competitive Penta arid Santobrite are comparable in dioxin content. 6. Dioxin formation can be reduced by lower temperature chlorination. Penta 60 has only one-fourth as much dioxins. SOURCE Mmo: S. H. Vogel to D. P. Roman "Chlorophenol Dioxin History" DOCUMENT wns 0045171-203.02 ATTORNEY W O R K PRODUCT ATTORNEY-CLIENT PRIVILEGI DATE 1976 01/01/76 01/15/76 O to O CO Oj EVENT/SIGNIFICANCE WGK plant industrial hygiene practices in chlorophenols group documented. Conversion agreement with Koppers for Monsanto to make "Penta Concentrate" (Koppers Penta Wood Preservative 1-10 Concentrate). It contained: 40% Penta, tech. 60% WK-60 Solvent (Eastman Chemical) Monsanto provided information to EPA advisory panel and stated conclusions: 1. Did not find the two most toxic species of dioxins (tetra- and pentachlorodioxins) in current Monsanto Penta. 2. Hepta- and octachlorodioxins are several orders of magnitude less toxic than the tetra and penta species. No more toxic than Penta itself. Do not represent a significant risk. ^ "`'- A m^ 3. The level of hexachlorodioxins in Monsanto Penta is sufficiently low not to present a hazard. 4. Our belief is that Penta is a safe product to market for use by professionals in wood treating. - 57 SOURCE Typed table - author unknown Conversion Agreement DOCUMENT NOS. 0016904-8 0046199-211 Letter: L. G. Scharpf, Jr. to R. Ross (EPA Office of Pesticides) 0017815-24 DATE 02/13/76 02/23/76 02/25/76 03/19/76 04/19/76 06/09/76 06/22/76 08/12/76 O IO %2 3M oW El f t =J < SH S> 70 1. O to Cr* CO EVENTSIGNIFICANCE Monsanto Medical Department issues toxicity information on Penta. Gives handling precautions. Penta worker health and environmental concerns were addressed at WGK plant. Action plans developed. Documents a review of present and past chloracne situation at the WGK plant. "To the best of our knowledge, we have never treated any employee for chloracne who was not a production employee in the Penta department." NIEHS (Nat. Inst, of Environ. Health Services) attributed toxic effects of Penta to hexa CDD. Distributor Agreement with Koppers. Analytical data comparing hexa-, hepta-, and octachloro dioxin and dibenzofuran content in Penta samples from Reichhold, Vulcan and Monsanto Data quite similar. Documentation of eruption' of a hold tank following overchlorinated batch of Penta. EPA Penta File for Monsanto. (EPA Reg. No. 524-5) A chronology from 1948 to 1976. 58 SOURCE Monsanto Medical Department Bulletin Memo : J. C. Hume to G. E. Hendrikse Memo: P. Heisler to J. Metcalf DOCUMENT NOS. 0043529 0017027 0015513-15 Memo: P. L. Wright to I. G. Scharpf Distributor Agreement Handwritten table - author unknown Near miss accident report. EPA Penta File 0017532 0044973-45029 0017502 0017734-50 0044171-75 " 2 3 5 S S S S DATE 08/18/76 09/17/76 11/10/76 11/76 01/14/77 02/03/77 J2 O 0 o ow EVENT/SIGNIFICANCE Documentation of research studies on Penta from 1970 to 1976. In cludes analyses, potential dioxin suppression, bioassay studies, postulated chemistry of dioxin formation. AWPI Status Report on EPA's examination of wood preservatives. Describes effort by AWPI to defend Penta against possible suspension or cancellation of Penta registration. Threshhold Limit Value (TLV) Sampling in the Penta production unit. Penta block pouring operation presented a problem (exceeded TLV allowable limit). 1971-76 Safety record of injuries in Chlorophenols group. Revised Toxicity Information of Penta issued by Monsanto DMEH. Gives toxicity and handling precautions. , Spill procedure for Penta established. Requested by Koppers to use internally and to forward it to their customers. Monsanto planned to forward it to their customers. Gives precautions in handling. e n t ia l TECTIVE O R D E R C25343 - 59 SOURCE Final Report: Dioxin and Related Process Maintenance Studies. AWPI Status Report DOCUMENT NOS. 0010050-478 0044002-40 Memo: J. Labanosky to C. Buckley and E. Burke 0013388 Safety Report Monsanto DMEH bulletin 0017727 0045581-2 Memo: J. C. McPhillips to F. A. Provorny 0044519-23 ^"^S S S S S S t DATE 02/07/77 02/09/77 03/01/77 03/03/77 03/03/77 03/08/77 O to CTi CO CO EVENT/SIGNIFICANCE Documentation of an increased trend in number of people and severity of chloracne in the Chlorophenols Group at WGK plant. Standard practice to control chloracne is covered. Chlorophenols Group Safety Meeting planned for 1977 documented. A report to the EPA Office of Pesticide Programs by a task group of the American Wood Preservers Institute (AWPI) relevant to EPA's reregistration of Penta. Monsanto participated in this study (D. P. Roman). Contains much environmental information. tf> o 10 nz 3M <3 ^ SH pi 33 Discussion of the chemistry of chlorination of phenols and dioxin by-product formation. Documentation of studies and issues by the American Wood Preservers Institute (AWPI) relevant to reregistration of Penta by the EPA. Conclusion: Penta fits most appropriately into Catagory II (conditional reregistration subject to long term tests). Disclaimer issued for Penta Spill Procedure. Mentions Monsanto Technical Bulletin IC/PS-3 "Han dling Precautions for Penta and Santobrite" (not attached). - 60 SOURCE Memo: LP. Heisler to W. E. Scruggs DOCUMENT NOS. 0015509-12 Memo: J. Labanosky to J. Starzyk/N. Miller Memorandum by Environ. Programs Task Group No. 6, AWPI. 0018181-2 0017109-56 Presentation to EPA Penta Science Advisory Board by S. Vogel of Monsanto. Memorandum by Subcommittee of Environ. Programs Task Group of AWPI. 0014987-15009 0014738-85 Memo: F. A. Provorny to J. C. McPhillips 0015439 SSSSZSSESS DATE 03/8-9,15 16/77 EVENT/SIGNIFICANCE Corporate Safety Audit held. 03/25/77 04/18/77 04/20/77 Safety and Toxicity information from AWPI. Reishhold, Vulcan and Kopper want Monsanto to join in analytical work. Documentation of simulated OSHA inspection of Penta facilities (Dept. 236-237). Many industrial hygiene and safety problems showed up. Penta strategy and contingency plans. b fifT S & V - 61 SOURCE Mmo : Memo: D. J. Metherd to C. Buckley et al, 2/15/77 R. L. Liss to H. E. Frierstein, 2/28/77 Memo : D. P. Roman to G. J. McEwan DOCUMENT NOS. 0015404 0015426 0000339-96 Memo : J. L. Wolfsberger to D. Metherd/J. Labanosky 0015465-74 Memo: E. Wilcauskas to R. G. Potter 0015378-88 SSSSSSSSSS DATE 04/22/77 04/25/77 04/26/77 EVENT/SIGNIFICANCE Safety assessment of Penta and the manufacturing operation. Mentions Penta is moderately toxic by ingestion and dermal application. Chloracne among workers when operational prac tices deteriorate. Principal impurities in Penta are chlorin ated hydroxy diphenyl ethers, dibenzo-p-dioxins and dibenzofurans. No 2,3,7,8-TCDD found at detection limit of 0.01 ppm. Hexa, hepta, and octachlorodibenzop-dioxins present at 5-20, 200-300 fo and 500-1000 ppm, respectively. ( Conclusion: commercial Penta can riU be handled safely with proper work practices and facilities. The H dibenzofuran and diphenylethers --i contribute to the toxicity of O Penta since the known presence "C and toxicities of dioxins cannot account for it. i 1 4 Purification method for dioxin 7 removal described - Distillation. .....1 .< -.j M Competitive input given. Documentation of poor plant conditions in Penta facilities. MIC authorizes opening a Seattle Penta warehouse. Safety precautions noted. Penta Spill Procedure. PgggO 62 SOURCE Pentachlorophenol Safety Assessment. DOCUMENT NOS. 0015370-77 ^o, A rr S S ^ O i! K Notes for D. E. Munie (no author) Memo: R. L. McFarland to F. H. Kaprive Memo: J. C. McPhillips to D. A. Parkey Penta Spill Procedure. 0015389-91 0015429-30 0015432-35 0015432-35 DATE 04/26/77 04/27/77 05/05/77 05/05/77 05/09/77 05/12/77 05/17/77 O to Or CO Of EVENT/SIGNIFICANCE Preliminary recommendations on industrial hygiene concerns which showed up in Safety Audit. Repor.t on Mid-America Packaging (St. Clair County, 111.) - a site of Penta shipping. Poor industrial hygiene. Environmental aspects below Monsanto and OSHA standards. Recommendation to correct problems (dust collection) or terminate shipping from this site. Suspended the loading of bulk Penta via breaking and emptying bags. Can't protect workers. Report on Detailed Safety Audit of Penta operation conducted 3/8-9, 15-16/77 (see entry). Many bad features. Recommenda tions for corrections made. m j, o H Hm< * -"1 o a m> 4 Proposed plan to upgrade Penta block pouring facilities. Purpose: Reduce operator exposure to Penta fumes and the hazards of- Molten Penta. Minutes of meeting on how to upgrade Penta facilities and product. Much to correct. A review of the Safety Audit of Penta and other Chlorophenols departments. Process problems, exposure problems, and environ mental problems listed. - 63 - SOURCE Memo: R. L. Liss to 0. DeGarmo Trip Report by G. Fort DOCUMENT NOS. 0015459 0015307-13 Memo: VJ. E. Scruggs to J. C. McPhillips Memo: D. E. Munie to R. G. Potter (Safety Audit attached) 0015436 0015447-56 Scope Commitment Meeting background information 0017958-69 Memo: T. W. Cummins to H. E. Blaylock, et al. Memorandum (unsigned) 0015364-69 0014706-12 attorney w o r k PRODUCT ATTORNEY-CLIENT PRI V I L E G C DATE 05/18/77 05/24/77 06/01/77 06/03/77 06/07/77 06/08/77 06/20/77 EVENT/SIGNIFICANCE Estimates for new facilities to produce Penta and refine it. Current facilities in poor condition. Plan and program to continue Penta operations over next 2-3 years. Capital estimates. Plant in poor condition and needed major upgrading. Report on toxicity of Penta and its impurities. Summarizes composition of Penta including dioxin content as well as acute toxicity tests. Dow visited to discuss possible licensing of their Penta purifi cation procedure. Never executed. Names of personnel who have at some time during their employment been assigned full time to the WGK Penta production unit. Dates not ascertained. Discontinued printing and distributing Monsanto Technical Bulletin O/PS-3 on Handling Pre k cautions for Penta and Santobrite, 6/70. It was out-of-date. Industrial hygiene of Penta operation discussed and actions agreed upon to improve conditions. C25352 - 64 SOURCE Memo: R. J. Small to . F. Wilcauskas Notes from D. E. Munie to R. I. Liss Memo: R. L. Liss to W. M. Woelzlein Short Term Capital list Chlorophenols. Memo: D. P. Roman to P. A. Tierney (Report attached) Memo: G.J. McEwan to file Memo: D. J. Metherd to E. Tillman DOCUMENT NOS. 0015343-44 0015345-54 0000192-222 0043363-5 0017783-91 Memo: J. C. McPhillips to R. C. Isham 0036256 Memo: Minutes of meeting on Chlorophenol Industrial Hygiene, D. J. Methard to J. Labanosky, et al. 6/21/77 0015394-95 ATTORNEY W O R K PRODUCT ATTORNEY-CLIENT PRIVILEGE DATE 06/21/77 06/27/77 EVENT/SIGNIFICANCE Request for Penta label to be changed to meet current EPA label requirements. Must have sufficient warning to avoid use of Penta on domesticated animals. Eliminate use in "Paint Preservation" only used in wood treating. Review of the WGK plant plans for complying with the May Safety Audit recommendations. 07/11/77 07/15/77 08/02/77 08/04/77 O CO CTi CO CJ Go in o c. 0dumoo -o 30 O H n o m d < H 3 a m > S3 Proposed new label for Penta. Gives precautionary statements. Monsanto was aware of the industrial hygiene problems in removing 2000 lb. Penta block from the mold probably since the date production started. Recom mended discontinuing 2000 lb. Penta block production. Notes Penta exposure to employees during "Penta block pouring opera tion. Phasing out of 2000 lb. Penta blocks mentioned. Notes again a trend towards an increase in the number of people and severity of chloracne has returned to the levels experienced in 1971-76. Specifically mentions Ralph Jenkins, Joe Stargyk and Roy Purkey. Gives complete list. - 65 - SOURCE Memo: \J. C. McPhillips to M. F. Litteken DOCUMENT NOS. 0043330 Memo: Minutes of 6/22 "Review of Safety Audit Recommen dations Status and Plant," D. J. Methard to T. Cummins, et al. 0015392-93 "Label change" form 0043324-6 Memo: J. C. McPhillips to M. E. Blaylock 0017992 Memo : J. L.. Wo1fsberger_to D. Metherd ____0013503 Memo: P. E. Heisler to W. E . Scruggs 0013504-5 ;a t t o rTMntY.CcLn!EPNMTr PPrRivOileUgCi C25354 DATE 08/05/77 08/12/77 08/26/77 08/29/77 09/28/77 .O/03/77 10/05/77 EVENT/SIGNIFICANCE Production of 2000 lb. Penta blocks will cease in two months because of safety considerations in the plant. Continue to make 1000 lb. blocks. Documentation that embryonal and fetatoxicity of Penta may prevent reregistration of Penta by the EPA. Penta determined in ambient air and wipe samples for OSHA compliance. Cleaning control room with dilute sodium carbonate solution appeared to reduce surface contamination with Penta. The Detergents & Phosphates business group recommends Penta production be discontinued by 4/1/78. Will go ahead with certain expenditures to correct industrial hygiene problems. Proposal to dispose of alkali insolubles in the cone bottom separator in Santobrite manufacture by landfilling, rather than sewering them as currently done. Reason: insolubles contain chlorinated dioxins. Discussion of a Penta suit by an Ohio farmer (Pickering) who claims damages resulting from barn treated with Penta. Alleged death of 230 head of cattle. - 66 - SOURCE Memo: E. F. Wilcauskas to File DOCUMENT NOS. 0044491 Memo: D. P. Roman to G. J. McEwan WGK Anal. Lab Work Proposai Memo: J. R. Pace to D. Metherd, et al. Memo: M. E. Blaylock to B. Eley 0018140 0013407-8 0013223-24 0015457-58 Minutes of Meeting: H. G. Yapp 0016911-14 Memo: R. A. Stohr to G. J. levinskas, et al. 0035634 DATE 10/06/77 10/20/77 and 11/01/77 11/04/77 11/23/77 11/29/77 cw O w um 0 n --i 2 --oj '11/77 12/13/77 O to C7 CO O c. EVENT/SIGNIFICANCE Industry hygiene improvement project in Penta production. To eliminate fumes in Penta Block pouring area, and find acceptable way of disposing of alkali insolubles. Top-level recommendation and approval to retire and dismantle Penta production unit at WGK plant. Documentation of industrial hygiene problem in pouring 1000 lb. Penta blocks due to fumes. Removal of the fumes by a ventilation system is proposed. Penta customer list for Wood Treating Chemicals Dept., Koppers Co. Medical records of 60 employees who have worked in the Penta pro duction unit were reviewed. There is and has been for some years a problem with chloracne. Draft of news release indicating Monsanto will terminate li.S. production of Penta effective 1st Quarter, 1978. Continue to produce at Newport, U.K. Status report on the short and long term actions being taken to correct problems observed in the Detailed Safety audit of 5/5/77. - 67 SOURCE TSD Work Proposal DOCUMENT NOS. 0013488 Retirement. Request Memo: M. E. Blaylock to J. C. McPhillips Letter: J. M. Montgomery (Koppers) to J. McPhillips (Monsanto) Memo: E. Tillman to M. E. Blaylock News Release Draft 0018088-90 0017970 0044557-70.02 0013526-33 0017330-1 Memo: M. E. Blaylock to D. E. Munie, et al. 0013479-83 ATTORNEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE DATE 4th Q/77 01/04/78 02/02/78 02/03/78 02/24/78 .02/78 04/78 O 06/08/78 CO Cv OC EVENT/SIGNIFICANCE Detergents and Phosphates Division recommended to the Corp. Admin. Comm. (CAC) the discontinuance of Penta production by 7/1/78 be cause of major industrial hygiene concerns. 2000 lb. Penta blocks no longer produced. 1000 lb. blocks continued Program outlined for monitoring Penta exposure effects on Penta workers at the WGK plant. Recommendation of a safe way of handling overchlorinated batches of Penta. Addition of determined amount of p-chlorophenol stabil izes overchlorinated Penta. Trend towards an increase in the number of people and the severity of chloracne was still present. Penta production unit was shut down. All Penta operations at the WGK plant were discontinued. All equipment and the building were dismantled by 1st Quarter, 1980. Penta on the 1977 NI0SH Suspect Carcinogen List. - 68 - SOURCE Memo: F. J. Fitzgerald to J. W. Hanley DOCUMENT NOS. 0014550-55 Letter: J. C. McPhillips (Monsanto) to R. Simmons (Koppers) "Penta Sampling Program Strategy" 0044576 0017776-7 Interim Report: Overchlorination 0028069-79 of Penta Memo: P. E. Heisler to W. E . Scruggs 0017773-5 Mentioned in Tentative Amendment L to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72. Letter: P. E. Heisler to I. B. Suskind (Univ. of Cincinnati, 7/21/80) 0025469 0013420-24 1977 NI0SH Suspect Carcinogen List-. 0010862-74 ATTORNEY W O R K PRODUCT S r NEY-CLIENT PRIVILEGE DATE 07/31/78 08/08/78 08/17/78 03/06/79 03/06/79 06/08/79 <rn o 70 orn O CO P Cl eo Cf EVENT/SIGNIFICANCE Discussion of interrogatories on the Pickering case. Mentions that Monsanto encloses a copy of the warning of potential danger in handling Penta with every shipment. Eliminated the use of defoamer agents in the Central Fume Scrubber. Not used because Penta production unit was shut down. Draft of Contract to sell scrap Penta to Koppers Continued discussion of the Pickering case. Long term feeding study on Penta suggested. Necropsy reports on cows included. No record that long-term feeding study was ever performed. Contributors to the Pickering defense fund listed: Reichhold, Monsanto, Olan Belsher, WalkerWilliams, Vulcan, Koppers, McArthur Lumber & Post, Dow, and \ Forshaw. Monsanto developed an Agreed Position Statement on chlorinated dioxins. Agreed to establish state-of-the-art analytical capabilities in MRC to measure chlorinated dioxin levels in products, process waste streams, air samples, spills and other mishaps. Shows diligence in industrial hygiene for workers and safety of the products. - 69 - SOURCE Letter: M. M. Liebman to * C. G. Barclay (Porter, Wright, Morris and Arthur Law firm) DOCUMENT NOS. 0035679-80 Tentative Amendment L to SMP for Molten Penta, Prilled Penta, and Penta 60, 1/30/72 0025469-70 Letter: Director., Marketing to J . Hite (Koppers) Letter : C. D. Barclay to M. M. Liebman 0043576-85 0035618-33 Letter: C. D. Barclay to R. Van Zandt (Travelers Insurance Co.) 0035674-78 Chlorinated Dibenzodioxins Agreed Position Statement 0046477-8 DATE 06/19/79 10/18/79 10/19/79 10/30/79 04/04/80 05/05/80 07/21/80 O CO CTi CO O'i CO o ~o P0 o mo m <m -4 O 70 rn > PU EVENT/SIGNIFICANCE Status report on Pickering vs. McArthur Lumber and Feucht vs. Morton cases. Mentions LeMunyon case. Brick rubble from Penta facility dismantling considered refuse and will be buried on site (WGK plant). Industrial hygiene practices to be observed in dismantling the Penta facilities documented. Status report on dismantling of Penta facilities at WGK. Comple tion expected in December, 1979. Estimated dismantling and retire ment costs: $800,000. Firestone, McConnell, and Schull studies on cattle showed that given the exposure time periods of 70-160 days dioxins do not have serious adverse effects. Draft interrogatory answers on Penta case: Pickering',vs. Monsanto Good summary of history of the technical aspects of producing Penta and Santobrite. - 70 SOURCE Letter: C. D. Barclay to I. Comella and R. Van Zandt Memo: R. H. Sinise to . B. Edwards Memo: D. C. Armstrong to C . Buckley/D. Metherd Penta Discontinuation Project Status : D . B . Edwards DOCUMENT NOS. 0035610-17 0018035 0018034 0018038-9 Letter: C. Barclay to R. Van Zandt 0035668-72 Memo: V. A. Haskins to D. Dill, et al. Letter: P. E. Heisler to I. B. Suskind 0035635-67 0013420-24 sas***8 DATE 11/80 08/81 0 CO C* CO 01 ZC CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. EVENT/SIGNIFICANCE SOURCE DOCUMENT NOS. Tentative conclusions reached that workers exposed to Penta show greater tendency to higher triglycerides and lower HDL cholesterol and bilirubin levels. Significance not stated. States that 2,3,7,8-TCDD not detected in Penta at 10-15 ppb limit of detection, but the hexachloro, heptachloro and octachloro deriv atives were detected (5-10, 25-250 and 1900 ppm, respectively). A further report on "The Biochemical Study of Pentachlorophenol Workers at Newport," R. A. Baxter (DMEH-Europe) 0000002-48 The dioxins in Penta are believed to contribute significantly to its toxicity. Mentions several human fatalities. Also chloracne. Two cases of non-Hodgkins lymphoma out of 158 workers. Good review on toxicity of hexa, hepta, and octachloro dioxins. Hexachloro derivatives most toxic. Mentions composition of Penta, tech. "Review of the Toxicity of Pentachlorophenol" R. J. Fielder. Also other documents to be con sidered by the Health and Safety Executives' Advisory Committee on Toxic Substances on 1/22/82. 0000049-105 5-10% tetrachlorophenols 0.1% trichlorophenqls trace mono- and dichforophenols (below 30 ppift) Dioxins: no tetrachloro (0.01 ppm detection limit) hexachloro 3-8 ppm heptachloro 25-250 ppm octachloro 200-2000 ppm a tto rn ey -cwloiernkt pprriovidluegcet Small amounts of chlorinated dibenzofurans (not quantified). - 71 DATE 09/04/81 06/09/82 EVENT/SIGNIFICANCE Provided process information on Penta and Santobrite to NIOSH. Also gives historical data. Six-month monitoring results on chloracne. Includes all people who worked in the Penta production unit. There appears to be improvement. C25360 - 72 SOURCE Letter: P. S. Park to H. Walderraan (U.S. Dept, of Health and Human Services) Memo: . E. Heisler to . M. Keating DOCUMENT NOS 0019740 0019782-90 0013448 * *a**"*$p*la!,g VI. Safety and Handling of Penta Products/Processes Subject Source Document Nos. 1. Toxicity and handling instructions Monsanto Technical Bulletin 0-5 for Santobrite in paper industry, 4/1/40, 8/1/44, 2/1/47, 4/25/52 0036480-87 0036464-71 0036456-63 0036444-49 2. Toxicity and handling instructions Monsanto Technical Bulletin 0-19 for Santobrite in tan ning industry, 6/20/40, 12/1/45, 7/1/46, 12/9/48 0036231-36 0036219-23 0036214-18 0036224-30 3. Safety precautions described Process Description 0026642-43 for Santophen 20, 6/17/43 4. Toxicity and handling instructions Monsanto Technical Bulletin 0-25 for Penta, 11/1/43, 12/1/45, 7/1/46, 10/1/48, 12/15/49 3/30/50, 3/25/52, 6/55 0035904-14 0035893-903 0035882-92 0035870-81 0035857-69 0035850-56 0035839-49 0035806-20 5. Toxicology and Derma tology of Penta and Santobrite. Handling instructions for these products and several of the formulations. "Toxicology and Dermatology of Pentachlorophenol and Santobrite," J. D. Fleming 1/1/48 0045852-71 6. Safety procedures described Description of Process for the Manufacture of Santobrite 7/15/49 0025665-707 7. Safety and Fire Description of Protection described Process for the Manufacture of CONFIDENTIAL Monsanto Penta 10/9/53 0026547-95 SUBJECT TO PROTECTIVE ORDER. ATTORNEY W O R K p r u d u t i ATTORNEY-CLIENT PRIVILEGE - 73 - C2536 Subject Source Document Nos. 8. Safety precautions described Process Descrip tion for the Manufacture of Monsanto Penta, 2/1/54 0026048-74 9. Safety discussed .1 0 Orders issued to Chlorophenols Depts. at WGK plant not to eat or drink bever ages in the depart ments. Diligence in industrial hygiene. Process Descrip tion for the Manufacture of Santobrite Powder, Pellets, and Briquettes, 2/1/54 Memo : H .B . Patrick to H.O.. Hehner, 5/26/54 0025708-37 0018133 11. Safety precautions given .1 2 Safe handling and toxicity of Penta and its salts Revised Process Description for the Manufacture of Monsanto Penta, 3/17/55 0026494-520 Monsanto Technical Bulletin 0-100, 3/56 , -: 0000962-81 13. Toxicity and handling instructions Monsanto Technical Bulletin 0-15 for Santobrite for slime and algae control, 6/57 0036093-98 14. Recommendation by Medical Dept, that eating in the Penta production unit be discontinued was im plemented . Diligence in industrial hygiene Memo: J.T. Garrett to E .W. Mares, 9/23/57 Memo : R . Peterson/ D. Castle to Chlorophenol Group personnel, 9/3/57 0018132 0018134 15. Toxicity and handling Monsanto Technical 0036081-92 instructions Bulletin SC-1 on CONFIDENTI A1. Santobrite, 4/58 ATTORNEY W O RK PRODUCT SUBJECT TO PROTECTIVE ORDER. ATTORNEY-CLIENT PRIVILEGE - 74 - C2536^ Subject 16. Toxicity and handling instructions 17. Toxicity and handling instructions 18. Toxicity and handling instructions 19. Toxicity and handling instructions 20. Toxicity and handling instructions 21. Toxicity and handling instructions 22. Toxicity and handling 23. Toxicity and handling instructions 24. Safety and Toxicity CONFIDEDNataT! AT. SUBJECT TO PROTECTIVE ORDER. Source Document Nos. Monsanto Technical Bulletin SC-2 on Santobrite and Penta in paints and water-base additives, 7/58 0036016-23 Monsanto Technical 0035784-805 Bulletin SC-3 on 0035765-83 Penta, 10/58, 12/65 Monsanto Technical 0035973-91 Bulletin SC-10 on Santobrite in Cellulose Insulating Materials, 11/58 Monsanto Technical Bulletin SC-11 on Santobrite in the tanning industry, 1/60 0036201-13 Monsanto Technical Bulletin SC-4 for Santobrite in paper industry, 1/60, 11/63 0036436-43 0036427-35 Monsanto Technical 0035992-6015 Bulletin~C-9 on 0036099-122 Handling Precautions for Penta and Santo brite , 1/60, 3/63 Monsanto Chemical 0036142-49 Specialties Data Report No. CS-13 on Copper Pentachlorophenate in cellulosic materials, 11/60 Monsanto Chemical Specialties Data Report No. CS-9 on Santobrite in laundry, 6/61 0036158-65 SMP for Santobrite, 0025823-74 6/65 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE C2530 Subject Source Document Nos 25 Safety, Toxicity Data and Accident Reports SMP for Penta, 11/9/65 0026005.04 26 Toxicity and handling instructions Monsanto Technical Bulletin O/PS-2 on Santobrite in paper industry, 7/66 0036415-26 27 Toxicity and handling instructions Monsanto Technical Bulletin O/PS-5 on Santobrite in tan ning industry, 7/66 0036237-52 28 Toxicity and handling instructions Monsanto Technical Bulletin O/PS-3 on Handling Precau tions for Penta and Santobrite, 7/66, 7/69, 6/70 0036279-302 0036376-98 0036353-75 29, Toxicity and hazards, effects, First Aid, and protective equip ment documented for Penta and Santobrite Medical Dept. Bulletin, 8/67 0013286-89 30, Detailed Safety and Toxicity section SMP for Molten Penta, Prilled Penta and Penta 60, 11/68 -:- 0026076-79 0026114-201 ' 31,. Safety and Toxicity Data SMP for Santobrite, 0012006 11/68 32, Safety and housekeeping covered Training and Reference Manual, 1/70 0011715-811 33. Field Safety Review Penta expansion Memo: R.L. Fields to E.D. Malone, 2/16/70 0013193-95 34. Precautions and protective information on Penta Material Safety 0043530-1 Data Sheet, 12/2/71 35.. Toxicity and handling instructions CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. - 76 Monsanto Technical 0035681-701 Bulletin IC/PS-8 on Penta,, 12/71 ATTORNEY W O R K PRODUCT ATTORNEY-CLIENT PRIVILEGE C25364 Subject Source Document Nos. 36. Safety SMP for Santobrite Briquettes and Solution, 2/72 0025415-65 37. Safety and housekeeping rules for Santobrite Briquettes Operator Training and Reference Manual, 4/72 0010787-806 38. Safety and housekeeping rules for Penta and other chlorophenols Operator Training and Reference Manual for Chlorophenol Group, 4/72 0010763-82 39. Safety and Toxicity of 30% Santobrite Solution Tentative Process for 30% Santobrite Solution, 5/2/72 0014416-40 40. Safety and housekeeping instructions for Santobrite Solution Operator Training and Reference Manual, 5/72 0010807-57 41. Standard practice of Chlorophenols Group at WGK to control and clear up chloracne cases Memo: R.R. Sorrell to R.L. Fields, 8/23/72 0017160 42. Safety, housekeeping and handling instruc tions for Molten Penta Operator Training and Reference Manual,' 11/72 0011868-97 43. Process Safety Audit Penta Operation Process Safety Audit, 1/73 0013305-43 of 44. Safety, housekeeping and handling instruc tions for Molten Penta Operator Training and Reference Manual, 6/73 0011813-67 45. Safety and toxicity information Process for Engi 0045768-813 neering Design for Recovery of Penta from Venturi Liquor, 4/11/74 46. Toxicity and handling precautions CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. Monsanto Medical 0043529 Department Bulletin 2/13/76 attorney w ork product a tto rn ey -client privilege - 77 - C25365 Subject Source Document Nos. 47. Penta worker health and environmental concerns addressed and action plans developed Memo: J.C. Hume to .. Hendrickse, 2/23/76 0017027 48. Toxicity and handling precautions Monsanto DMEH Bulletin, 1/14/77 0045581-2 49. Handling precautions Penta Spill Procedure, 2/3/77 0044519-23 50. Chlorophenols Group safety meetings planned for 1977 documented Memo: J. Labanosky to J. Starzyk/ N. Miller, 2/9/77 0018181-2 51. Industrial hygiene and safety problems Simulated OSHA 0015465-74 inspection, 4/18/77 52. Safety Assessment of Penta Penta Safety Assessment, 4/22/77 0015370-77 53. Preliminary recom mendations on industrial hygiene concerns from Safety Audit Memo: 4/26/77 0015459 54. Detailed Safety Audit Memo: 5/5/77 (Safety Audit attached) 0015447-56 55. Proposed plan to upgrade Penta block pouring facilities. Purpose: Reduce operator exposure to Penta fumes and the hazards of Molten Penta Scope Committee 0017958-69 Meeting background information, 5/9/77 56. Safety of the Manu facturing Process for Penta. Memorandum, 5/17/77, unsigned 0014706-12 57. Industrial hygiene of Penta operations discussed. Actions CONFIDENTIALagreed upon SUBJECT TO PROTECTIVE ORDER. - 78 Memo : 6/21/77 0015394-95 ATTORNEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE Subject Source 58. Review of WGK plans for complying with May, 1977 Safety Audit recommendations Memo: 6/27/77 59. Precautional State ments on Penta "Label Change" form, 7/11/77 60. Monsanto agreed to establish state-ofthe-art analytical capabilities to measure dioxin levels in products, waste streams, air samples, spills, etc. Shows diligence in industrial hygiene for workers and safety of the products. Chlorinated Dibenzodioxins Agreed Position Statement, 6/8/79 61. Safety procedure recommended for overchlorinated batches of Penta Interim Report: Overchlorination of Penta, 2/3/78 Document Nos. 0015392-93 0043324-6 0046477-8 0028069-79 - 79 - C25367 VII. References on Sales' Reports, Sales Invoices/Purchase Orders, and Customer Contacts/Call Reports A. Sales Reports Description 1971 Sales Report by Customer, 1/12/72 1972 Sales Report by Customer, 1/9/73 1973 Sales Report by Customer, 1/9/74 1974 Sales Report by Customer, 12/31/74 Document Nos 0044634-40 0045316-23 0045447-524 0045310-15 0045411-46 0045324-29 B. Sales Invoices/Purchase Orders Document Nos. 0011529-47 0011549-64 Note: In 1978, Monsanto sold Penta products to Koppers Co. but shipped the material directly to their customers. 0044525-37 0050017-42 - 0050044-56 0050096-102 0050111-16 0050118-69 0050177-82 0050189 0050197 0050204-34 0050236-400 0050431 0050444-5 0050646 C . Call Reports/Customer Contacts Document Nos. 0050002-16 0050043 0050057-95 0050103-10 0050117 0050170-6 0050183-8 0050190-6 0050198-203 0050235 0050401-30 0050433-43 0050446-645 0050647-98 ATTORNEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE TONFTDEMTTAT. Sim JETT 7.T T.'.OTE'ITr-'-: - 80 - C25368 Vili. Monsanto Participation in Organizations Related to Penta Products 1. American Wood Preservers Institute (AWPI) 1651 Old Meadow Road McLean, Virginia 22101 (703) 893-4005 ppRrfoV/dLuGct SUBJECT TO PROTECTIVE ORDER* - 81 - C25369 Document Name: PENTA PROD CHRON Requestor's ID: OPR 84 Author's Name: h . c . godt Document Comments: pentachlorophenol chronology C2537 Document Name: PENTA PROD REPORT Requestor's ID: OPR 84 Author's Name: h. c. godt Document Comments: Information for use in litigations; Report No. MSL-4254 SUBJECT TO PROTECTIVE CHEER. C25371