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PROGRESS REPORT
ORGANIC chemicals DIVISION TECHNOLOGY OEPAATMENT
W. M. Mees W. . Litschgi
E. S. Tucker
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October 1971 YES
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3 10-29-71
L PC 4 T ON
St. Louis - South Second Street
JO* NOV
2-21-760.01- 13480, 85010, 16300
Thit docuR***! it th property of MONSANTO COMPANY \\ co*uinv CONFIDENTIAL INFORMATION which n>uit net ba 'fproauesri rcvalad lo unauthorized psrtonv ot wm outfit)* th Compaq **'Kout proper outhonution Tti* rtcipi*At ii rt*pomibt* 'or ' utrbMptn-j 4*4 dattru^tion.
RESTRICTED TO:
DISTRIBUTION
H. S. Bergen M. W. Farrar
B. Hodges K. Johnson *R. E. Keller * R. H. Munch *W. B. Papageorge
** wrTW06TAJCS
T. M. Patrick *W. R. Richard
*C. W. Roos
J. E. Springgate *E. S. Tucker/W. M. Mees/W. J. Litschgi *E. P. Wheeler/G. J. Levinskas
rrqjic r ruci
ENVIRONMENTAL ANALYTICAL STUDIES RESEARCH AND DEVELOPMENT, MANUFACTURING AND OUTSIDE SUPPORT STUDIES
*OJlC T O UI c tt t
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 extracts from the U.S.D.A. Two competitive products.
HONS 202097
2-21-760.01--134 SO, 35 :10,163 Page 2
PCT's typical of Aroclor 5432 were found in:
Plant effluent samples from one customer manufacturing site. xr
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.
MOMS 202098
2-21-760.0 1 -13480 r 85010 , 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 . S. Tucker
HONS 202099
DETAILS
Sample Source
General Motors Corp., Buick Div.
Champion Paper
Company
'
TABLE I
2-21-760.01-13480, 85010, 16300
Pa<*e 4
CUSTOMER SERVICE
Sample Matrix Machine oils Drainage streams around plant
Paper (writing)
Paper Coatings (Micron II)
No. of Samples
11
2
Level Found
Associated Aroclor
Per Cent A-1242
PPB A-1242
Support Obiective Pollution Control Pollution ContrBl
3 PPM
A-1242 \
i
Per Cent A-5432 \l
3 PPM
A-1242 J| Pollution Control
Per Cent A-5432 /
J. F. Queeny
J. F. Queeny, W. G. Krummrich, Del. River, and Everett
Ag. Division, Nitro
MANUFACTURING SUPPORT
Sewer effluent composites
HC1
5 PPB 1 PPB
Finished Products
28 N.D.* to PPB
A-1242 A-1242 A-1242
1 Pollution Control
/
Santoquin CaMHA
COMPETITIVE PRODUCTS
6 PPB 3 PPB
A-1242 A-1242
'i Determination of level and \ sources of contamination of 1 competitive animal feed I additives
*None Detected
'
(Cont'd on next page)
HONS 202100
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
spiksd with known
PPM
quantitites of
Aroclor
Ra 1ston-Purina Chicken Chow .
2 PPB
Associated Aroclor
A-1242 A-12 54 A-1260
A-1242
USDA
Turkey Extract
1 -- A-1248
2-21-760.01-134 80 , 85010, 16300
Page 5
Support Objective
Insure the maintenance of precision an<^ accuracy in Monsanto labs analyzing for PCB's
l
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
HONS 202101
2-21-760.01-13480, 8571 0, 163 CO
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
Water from trade waste prior to Hickory stream
Level Found
8 PPB 15 PPB
Aroclor
A-1242 A-5432
Water from Hickory rain stream prior to river
13 PPB <5 PPB
A-1242 A-5432
Machine ffl Machine f2 Machine #3 Machine 14 Machine fS Machine #8 Machine 19
Trim Press #1 Trim Press #2 Trim Press f8 Trim Press 19
14.8% 2.51
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-1242 A-1242 A-1242
Champion Paper Company
Coated paper awl the used coating (Micron XI) samples submitted by Champion Paper Company were analyzed to determine the level of residual PCB's in the PCX's used in the paper coating fluid.
Sample Description Paper - 3866F Paper - 387.8F Paper - 3 758M Micron II - Sample #1 Micron II - Sample 12 Micron II - Sample f3
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 202102
2-21-760.01-13460, 83010
16300 Page 7
DETAILS (Cont'd)
l: J. F. Queeny Plant
Manufacturing 5upport
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
Aroclor
A-1242 A-1242 A-1242 A-1242 A-1242
The DA sewer (August) was supposed to be the Clean Acid Sewer (August) spiked with ^20 PPB A-1242. As can be seen, our results reflect only a SOI 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 EUT #A-134 10-4-71
0.26 PPM
S-334F EUT *A-135 10-4-71
0.21 PPM
S-711 "A" Lin* 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 #3 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-1242 A-1242 A-124 2 A-124 2
A-1242 A-1242
HONS 202103
DETAILS (Cont'd)
i 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 'vSO
Roche Ag Lot 2-4-71 Mfgd by Degussa
DL-Methionine
2.5 PPB A-1242
Upland, Calif. A3NG, SNS
DL-Methionine
21.4 PPB A-1242
Thompson-Hayward Chemical Co.
DL-Methionine
45 PPB
A-1242
These samples were analysed 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 Raiston-Purina Company. In the past months, attention ha9 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
MOMS 202104
DETAILS (Cont'd)
2-21-760.01-13480, 85010 t
16300 Page 9
USDA 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) PCS'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's. 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-124 2 A-1254 A-1260
1W 2W 0.57 3W 0.57 4W 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 ik-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-1260
1.04 0.57 6.70 6.55
-
8.80
1.05 0.15
-
1.20 0.07
-
-
2.84
-
-
-
4.16
Anniston A-12 4 2 a-12$4 A-1266
1W 2W 0.78
3W 0.45 4W 5.4 5W 9.9 6W
7W* 0.4
8W* 8.4
0.75
-
2.95 " 2.18
0.03 0.2
:
Applied Sciences 7W - 3W
WGK 7W * 1W SW s 4W
Anniston 7W = 2W 8W * 5W
The data have been submitted for statistical analyses.
HONS
202105
DETAILS (Cont'd)
2-21-760,01-13480, 85010,
16300 Page 10
National Broiler Council Intra-Laboratory PCB Methodology Check
Ten seta 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 n 7fl
Sciences)
u* 0
Lab D
#1)0.10
#2)0.10
Lab E
0.73
Lab F
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 Phssibclor DP6 Prodelec Phenoclor DP6 Bayer Clophen A60,Lot 931134 Kaneclor 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,Drura B Monsanto MCS-l0l6,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)
4Cl/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)
SCl/Mol.
Detected(15-3OPPr Detected(15-30PP) Detected
ND(<2 PPM)
ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<2 PPM) ND(<5 PPM)
MONS 202106