Document Raw7VQ5N3k1Q7E3LV1mQaMgEX

MPONltO ***T PROGRESS REPORT ORGANIC CHEMICALS DIVISION TECHNOLOGY DEPARTMENT W. M. Mees W. J. Litschgi E. S. Tucker October 1971 YES arrrw-3 fttPOAT HO O* T I 3 10-29-71 LOCATION St. Louis South Second Street JO* NOS 2-21-760.01-13480, 85010, 16300 Thlt docunwnt li the property of MONSANTO COMPANY. It contains CONFIDENTIAL INFORMATION which must not be reproduced, revealed to unauthorited persons or sent outside the Company without proper authorisation. The recipient is responsible lor its safekeeping and destruction. OUT RlBUT ION H. S. Bergen M. W. Farrar *P. B. Hodges If*** H. K. Johnson *R. E. Keller *R. H. Munch *W. B. Papageorge WITH DETAILS T. M. Patrick W. R. Richard *C. W. Roos J. E. Springgate )/ *E. S. Tucker/W.M. Mces/W. J. Litschgi *E. P. Wheeler/G. J. Levinskas , NOJCC T Til Li ENVIRONMENTAL ANALYTICAL STUDIES RESEARCH AND DEVELOPMENT, MANUFACTURING AND OUTSIDE SUPPORT STUDIES .no,IT 1 OOJiCTIVC Identify, locate and assess the magnitude of Aroclor pollution problems, help determine what needs to be done to control pollution sources, verify the effectiveness of proposed pollution control procedures, guide develop ment of recycle and/or disposal methods, and provide collaborative data or legal and regulatory purposes. SUMMARY PCB's typical of our Aroclor products have been found at levels below and above recommended guidelines in: Coated paper and paper coatings Machine oils and plant effluents from one customer manufacturing site Fourteen Monsanto Industrial Chemical Company products from four manufacturing sites . Chicken Chow used as feed by Industrial Bio-Test Laboratories Sewer effluents from one Monsanto Plant site Tissue turkey extrabts from the U.S.D.A. Two competitive products. HONS 058632 2-21-760.01-13480, 85010,16300 Page 2 PCT'b typical of Aroclor 5432 were found in: Plant effluent samples from one customer manufacturing site. A table showing the sample sources, types, and the level and type of Aroclor found as well as the support objective is presented in the details section. Additional external and internal support has been provided in the form of: An on site methodology review for F. B. Chamberlin (Director of Research and Development) and R. M. Wilkinson (Senior Project Manager) representatives of the Alton Packaging Division, Alton Box Board Co. PCB Seminar presentation on analytical methodology for the Research Council of Poultry and Egg Institute of America in Chicago, 111. PCB problem and progress review for T. Katayama (Marketing Manager) and S. Uneno (Product Director) from Mitsubishi Monsanto Chemical Co. Preliminary write up of methods for the determination of PCB's in Santoquin and caMHA. Evaluation of PCB perchlorination for quantitation of altered PCB residues. Analysis of Monsanto and Competitor Aroclor products for poly chlorinated dibenzofurans. General internal and external analytical consultation. Distribution of Aroclor methodology and reference standards. FUTURE PLANS PCB Analysis 1. Three to four J. F. Queeny monthly composite sewer effluent samples. 2. Forty-six machine oil and plant effluent samples from Saginaw Grey ' Iron Casting Plant, Chevrolet Motor Division. 3. Two oil samples skimmed off trade waste settling tanks from Buick Motor Div., General Motors Corp., Flint, Mich. (2 samples). 4. Four coated paper samples from Champion Papers, Hamilton Mill, Hamilton, Ohio (4 samples). 5. Four fluid samples from an imported VW automobile. 6. Five ACL-59 samples from the W.G. Krummrich Plant. 7. Three raw material samples from P.P.G. Industries. 8. Twelve film and paper extracts from St. Regis Paper Co. 9. One fish from a stream associated with a General Electric Plant. 10. Five intra-lab method check samples from a General Electric Plant Laboratory. HONS 058633 2-21-760.01-13480, 85010, 1630f Page 3 PCT Analysis 1. Ten plant effluent samples from Monsanto's Anniston plant. 2. Saginaw Foundries, Chev. Motor Div. plant effluent samples. W. J. Litschgi E. S. Tucker MONS 058634 DETAILS Sample Source General Motors Corp., Buick Div. Champion Paper Company TABLE I CUSTOMER SERVICE Sample Matrix Machine oils Drainage streams around plant No. of Samples 11 2 Level Found Associated Aroclor Per Cent A--1242 PPB A-1242 Paper (writing) Paper Coatings (Micron II) 3 PPM A-1242 \ Per Cent A-5432 \ 3 PPM A-1242 I Per Cent A-5432 / 2-21-760.01-13480, 85010, 16300 Page 4 Support Obiective Pollution Control Pollution Control Pollution Control J. F. Queeny MANUFACTURING SUPPORT Sewer effluent composites HC1 5 PPB 1 PPB A-1242 A-1242 \ Pollution Control / J. F. Queeny, W. G. Krummrich, Del. River, and Everett Finished Products Ag. Division, Nitro Santoquin CaMHA 28 N.D.* to A-1242 PPB COMPETITIVE PRODUCTS 6 PPB 3 PPB A-1242 \ Determination of level and A-1242 ] sources of contamination of competitive animal feed additives HONS `None Detected (Cont'd on next page) DETAILS (Cont'd) Sample Source Inter-Laboratory Round Robin (WGK, JFQ and Anniston) Bio-Test Laboratories, Chicago, 111. RESEARCH AND DEVELOPMENT Sample Matrix No. of Samples Level Found Distilled water 7 PPB tO spiked with known PPM quantitites of Aroclor Ralston-Purina Chicken Chow . 2 PPB Associated Aroclor A-1242 A--1254 A-1260 A-1242 USDA Turkey Extract 1 - A-1248 2-21-760.01-13480, 85010, 15300 Page 5 Support Objective Insure the maintenance of precision and accuracy in Monsanto labs analyzing for PCB's Determination of PCB back ground in feed used in the toxicity studies being performed at Bio-Test Determination of type of PCB and how the PCB contamination occurred o <z/> oUl Uo-i 2-21-760.01-13480, 85010, 16300 Page 6 DETAILS (Cont'd) Customer Service General Motors Corporation - Buick Division Due to Increased pressure from the Michigan State Regulatory Agency concerning PCB releases into the environment, Monsanto was requested to analyze samples of Buick's plant effluent and nearby drainage stream. At the same time, samples of oil used in their presses and machines were submitted to determine residual PCB levels remaining after Buick switched from Pydraul 312 to Pydraul 312A. Sample Description Hater from trade waste prior to Hickory stream Level Found 8 PPB 15 PPB Aroclor A-1242 A-5432 Hater from Hickory rain stream prior to river 13 PPB <5 PPB A-1242 A-5432 Machine fl Machine 12 Machine #3 Machine #4 Machine 45 Machine 48 Machine 49 Trim Press 41 Trim Press 42 Trim Press 48 Trim Press 49 14.8% 2.5% 13.8% 8.9% 3.9% 4.4% 24.3% 11.0% 0.9% 0.8% 16.8% A-1242 A-1242 A-1242 A-1242 A-1242 A-1242 A-1242 A-1242 A-124 2 A-1242 A-1242 Champion Paper Company Coated paper and the used coating (Micron II) samples submitted by Champion Paper Company were analyzed to determine the level of residual PCB's in the PCT's used in the paper coating fluid. Sample Description Paper - 3866F Paper - 3878F Paper - 3758M Micron II - Sample 41 Micron II - Sample 42 Micron II - Sample 43 Level Found 203 PPM 0.29% 140 PPM 0.25% 217 PPM 0.28% 242 PPM 0.48% 331 PPM 0.75% 211 PPM 0.56% Aroclor A-1242 A-5432 A-1242 A-5432 A-1242 A-5432 A-1242 A-5432 A-1242 A-5432 A-1242 A-5432 HONS 058637 2-21-760.01-13480, 85010, 16300 Page 7 DETAILS (Cont'd) Manufacturing Support J. F. Queeny Plant Sample Description Level Found Clean Acid Sewer (August) DA Sewer (August) MSD Gatewell (August) Clean Acid Sewer (September) MSD Gatewell (September) 19 PPB 29 PPB 77 PPB 3 PPB 31 PPB Aroc lor A-1242 A-1242 A-1242 A-1242 A-1242 The DA sewer (August) was supposed to be the Clean Acid Sewer (August) piked with ^20 PPB A-1242. As can be seen, our results reflect only a 50% recovery. Discussion with the J. F. Queeny pollution group is planned in an effort to resolve this problem. Monsanto Industrial Chemicals Company The following Monsanto Industrial Chemicals Company products have been analyzed for PCB's to determine if any of them were significantly contaminated with PCB's. Sample Description Level Found Aspirin QA-1187 9-13-71 N.D. Aspirin QA-1213 10-4-71 N.D. Maleic Anhydride QA-1295 9-16-71 N.D. Maleic Anhydride QA-1333 10-6-71 N.D. Sodium Saccharin QA-153 8-31-71 N.D. Sodium Saccharin QA-168 9-11-71 N.D. Saccharin QA-209 5-5-71 0.03 PPM Saccharin QA-1012 6-23-71 0.02 PPM Vanillin USP Ba#1025 0.20 PPM Vanillin USP Ba#1027 0.18 PPM Tall Oil Rosin Rec'd 1-25-71 N.D. Tall Oil Rosin Rec'd 5-25-71 N.D. CDP-OR175000 <4 0.17 PPM CDP-04175000 #3 KA-79 0.12 PPM S-334F EOT 4A-134 10-4-71 0.26 PPM S-334F EUT IA-135 10-4-71 0.21 PPM S-711 "A" Line 10-6-71 0.27 PPM S-711 "B" Line 10-6-71 0.36 PPM S-160 DA-614 0.36 PPM S-160 DA-803 D.R. 0.35 PPM HB-40 |1 Stg Tk 10-7-71 N.D. HB-40 13 stg Tk 10-6-71 AA-275C N.D. Biphenyl AA-194 9-27-71 0.67 PPM Biphenyl #2 Stg Tk 10-6-71 0.15 PPM Santowax R 10-6-71 N.D. Santowax R Rec'd 9186 10-7-71 N.D. Aroclor A-1242 A-124 2 A-1242 A-1242 A-1242 A-1242 A-1242 A-1242 A-124 2 A-1242 A-1242 A-1242 A-1242 A-1242 HONS 058638 DETAILS (Cont'd) Sample Origin Thompson-Hayward Chemical Co. HIC 7-21-71 Traveler's Rest Traveler's Rest Rexolin Chemical SNS 8-30-71 2-21-760.01-13480, 85010, 16300 Page 8 Competitive Products Sample Description Ethoxyquin (66.7%) Neoquin Santoquin Emulsion Santoquin Mix 6 Ethoxyquin (100%) Abiquin Level Found 749 PPB Aroclor A-1242 184 PPB 151 PPB 570 PPB 155 PPB 133 PPB A-1242 A-1242 A-1242 A-1242 A-1242 Our detection limit based upon observed background and sample was "V50 Roche Ag Lot 2-4-71 Mfgd by Degussa DL-Methionine 2.5 PPB A-124 2 Upland, Calif. A3NG, SNS DL-Mcthionine 21.4 PPB A-1242 Thomps on-Hayward Chemical Co. DL-Methionine 45 PPB A-1242 These samples were analyzed to determine if products in competition with Monsanto's Santoquin and CaMHA were also contaminated with PCB's. In all cases, they were found to contain an equal or greater level than the corresponding Monsanto products. Methods for the determination of polychlorinated biphenyls in Santoquin (Organic Research Method 71-26) and CaMHA (Organic Research Method 71-27) have been written and will be sent to the Nitro plant where they will be used to monitor their Santoquin and CaMHA production. . Research and Development Analysis of Chicken Feed from Bio-Test The chicken feed used in the Bio-Test toxicity studies was purchased from the Ralston-Purina Company. In the past months, attention has focused upon the fact that Ralston's feed has, in some instances, become contamin ated with PCB's. For this reason, two samples of the feed used in the chicken feeding studies were analyzed for PCB's. Sample Origin WCRF-1 WCRF-II Sample Description Chicken Feed Chicken Feed Level Found 240 PPB 263 PPB Aroclor A-1242 A-1242 MCN5 058639 DETAILS (Cont'd) 2-21-760.01-13480, 85010, 16300 Page 9 OSDA Turkey Extracts A USDA extract of a PCB contaminated (Swift) turkey tissue sample was submitted to our laboratory to see if we could establish what original Aroclor product caused the contamination and possibly the type of exposure. Using EC/GC and GC/Mass, we were able to determine that (1) PCB's were really present, (2) Aroclor 1248 was most probably the product involved, and (3) the birds either received a large single dose early in their lives or more probably a lower dose over an extended period of time. PCT Methodology Status A method has been developed and presently is being written (Analytical Method 171-37) for analysis of water and SCAS sludge samples for PCT'b. Recovery data obtained from samples spiked with A-5432 and 5460 were essentially quantitative at a concentration level of >2 PPM. This method is currently being used to analyze samples from the bio degradation studies and is at the same time being adapted for use on customer service and tissue samples. Inter-Plant Round Robin In order to establish the accuracy and precision of the PCB analysis being carried out in Monsanto laboratories, duplicate sets of spiked water samples have been analyzed by Anniston, WGK and Applied Sciences. The results were as follows: PPM PCB (Spiked) A-1242 A^1254 A-1260 1H 2W 0.57 3W 0.57 4H 5.68 5W 5.68 6W 7W* 8W* 1.04 0.10 1.04 0.52 0.10 1.27 - - Applied Sciences A-1242 A-1254 A-1260 0.74 0.86 1.07 5.25 - 0.92 0.92 0.07 0.52 0.06 0.06 - - WGK A-1242 A--1254 A^T260 1.04 0.57 6.70 6.55 - - 8.80 1.05 0.15 1.20 0.07 - - 2.84 - - 4.16 Anniston SrTTfl A-T254 A-1260 1W 2W 0.78 3W 0.45 4W 5.4 5W 9.9 6W 7W* 0.4 8W* 8.4 - 0.75 2.95 0.03 0.2 2.18 - `Applied Sciences 7W = 3W WGK 7W = 1W 8W = 4W Anniston 7W - 2W 8W = 5W MONS 058640 The data have been submitted for statistical analyses. * DETAILS (Cont'd) 2-21-760.01-13480, 85010, 16300 Page 10 National Broiler Council Intra-Laboratory PCB Methodology Check Ten sets of soybean oil and chicken fat were prepared by Monsanto and distributed by Ralston-Purina to government and industrial laboratories analyzing samples for PCB's. The objective of this intra-laboratory check is to establish the validity of the different PCB methods currently being employed. Listed below are the labs responding, however the individual laboratories were not identified. Results PPM IS 2S 3S 4C 5C 6C Spike Level 0 Lab A 0.25 Lab B 0.61 Lab C (Applied Sciences) 0.78 Lab D (1)0.10 (2)0.10 Lab E 0.73 Lab P 0.32 Lab G <0.10 Lab H 1.10 Lab I Lab J WGK Anniston 0.38 5.0 5.31 3.7 5.78 4.17 3.58 4.40 5.10 2.9 1.5 1.54 2.5 2.56 3.0 3.64 1.81 1.83 2.24 2.91 2.0 <0.6 No Report No Report No Report 0.61 5.0 4.00 1.8 4.13 2.05 2.18 2.42 2.62 3.0 <0.6 Received Received Received 0.57 5.0 5.06 4.2 4.08 2.05 2.09 2.68 2.66 3.6 5.5 0.14 2.0 3.86 2.1 3.26 1.53 1.55 2.14 2.22 2.9 5.0 - The results of this inter and intra sample exchange will be submitted for statistical analysis as soon as all laboratories have reported. Chlorodibenzofurans in PCB*s and PCT's Chlorodibenzofurans Found Sample Description Prodelec Phenoclor DP6 Prodelec Phenoclor DP6 Bayer Clophen A60,Lot 931134 Xaneclor KC-300 Shizuki, July 1970 (Composition similar to A-1242) Monsanto A-1242,Lot AK-255 Monsanto A-1254,Lot AK-38 Monsanto A-1260,Lot AK-3 Monsanto MCS-1016,Drum B Monsanto MCS-1016,KA-708 Monsanto A-5442,Lot AI-9 <4Cl/Mol. ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<5 PPM) 4C1/Mol. Detected Detected Detected ND(<2 PPM) ND(<2 PPM) ND{<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND (<5 PPM) 5C1/Mol. Detected (15-30PPI: Detected(15-30PPM Detected ND (<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND (<5 PPM) MONS 058641