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POLYCHLORINATED BIPHENYLS A PRESENTATION TO THE ONTARIO HYDRO ELECTRIC COMMISSION CANADIAN INTERDEPARTMENTAL WORKING PARTY ON PCBs CANADIAN CAPACITOR AND TRANSFORMER MANUFACTURERS November, 1972 by MONSANTO CANADA LIMITED MONS 090554 HISTORICAL SUMMARY OP PCB ENVIRONMENTAL ISSUE By W. B. Papageorge Polychlorinated biphenyls have been commercially available for over ^0 years, and, as many of you are aware, are produced world wide in many of the industrially developed nations. As with many industrial chemicals, early studies to determine the toxicity properties of these materials were designed to provide the appropriate information to guide the manufacturers and users in its proper handling, storage and shipping. This understanding of the polychlorinated biphenyls resulted, through the years, in a remarkable record of very few incidences of human exposures re sulting in observable effects. In each reported Instance the existing evidence indicated that improper Industrial hygiene prac tices were being followed. During the late 1950`s and 1960's increased interest in the pres ence and effects in the environment of chlorinated hydrocarbon pesticides resulted in the development of sophisticated analytical methodologies with capabilities of detecting these substances at extremely low levels of concentration. In the use of gas-liquid chromatography for the determination of DDT and its metabolites. Investigators were puzzled by the pres ence of response peaks which could not be identified. Generally, these peaks were ignored, and, in some laboratories, they were considered as possible metabolites of DDT. In late 1966, Drs. Jensen and Widmark, Analytical Chemistry Lab oratories, University of Stockholm, identified these peaks as poly chlorinated biphenyls and claimed to have found these materials in many foods, human milk, infant hair, pine needles and in feathers from a mounted eagle in a museum. The results of this study were published in 1967. During 1967 other investigators, using Jensen's method, established the presence of polychlorinated biphenyls in samples from the environ ment. By late 1967 and early 1968, presence in the environment was fairly well established, but in many instances could not be explained. All of the early reports indicated that the polychlorinated biphenyls being identified represented mixtures of the higher chlo rinated isomers. At this point, Monsanto launched a multi-point program aimed at obtaining more information about polychlorinated biphenyls and their presence and Impact on the environment. This program Included the following: 1. Develop analytical methodology 2. Conduct biodegradation studies M0NS 090555 2 3. Conduct animal toxicity studies 4. Develop alternative materials for PCB applications 5. Develop a program for the recycle or proper disposal of scrap polychlorinated biphenyls 6. Develop a continuing program of Informing our cus tomers of significant developments 7. Cooperate Tully with Industrial, governmental and academic laboratories Studies performed throughout the world have resulted In the fol lowing findings: 1. The presence of polychlorinated biphenyls In the environment has been confirmed. 2. Some Isomers of polychlorinated biphenyls are more resistant to degradation than others. 3. The early claims indicating that PCBs result in widespread thinning of eggshells in wild birds have not been confirmed. b. Massive fish kills attributed to PCBs have not been confirmed. 5. Biological magnification in the food chain does occur. 6. Some species of marine and wildlife are very sen sitive to low levels of PCBs, e.g. brown shrimp, some species of fish. Invertebrates, mink. 7. PCBs Identified in samples obtained In remote areas represent the higher chlorinated isomers. Samples obtained near a source of the commercial material contain the lower chlorinated Isomers. 8. High doses of polychlorinated biphenyls present in rice bran oil resulted In the presence of toxic effects In over 1,000 Japanese. 9. The effects of chronic long-term, low-level exposure to humans has not been established. 10. High levels found in human food and animal feeds are traceable to known sources. Because of Its presence In the environment and indicated effect on some species of wildlife, coupled with the concern regarding MQNS 090556 j 3 the effect on humans of low-level, long-term exposure, Monsanto voluntarily Instituted a worldwide program for terminating the sale of polychlorinated biphenyls to those uses In which control of escape to the environment was Impractical. HONS 090557 ASSESSMENT OP THE BIOLOGICAL PERSISTENCE OP POLYCHLORINATED BIPHENYLS By Dr. E. S. Tucker Presented by W. B.Papageorge The research I will review today will focus upon one aspect of Kon- ' santo's efforts to understand tho environmental impact and behavior of our polychlorinated biphenyl or pen products. This research was initiated early in 1969 after development of the necessary PCB analytical methodology ar.d subsequent confirmation of Dr. Soren Jensen's identification of PCB residues in fish and bird3 in Sweden. At this point in time, PCB residue data from Monsanto and external environmental monitoring programs indicated that at the previous rate of use and release- of these products that some PCB homologs were beginning to reach detectable levels in fish, birds and mammals. Conversely, these data indicated to us that with the exception of localized, controllable contamination, PCB homologs with less than five chlorine atoms per molecule had not accumulated to detectable levels; even though it was known that significantly greater amounts of the PCB horaologs with less than 5 chlorine atoms per molecule had been manufactured and used over the years. Mow, before discussing our biological studies, I would like to review for you the gross homoleg composition of our Aroclor products and then in a very brief fashion, try ar.d illustrate to you the complexity of those materials and hence the complexity of the problem. In the first slide (#1), is shown the most recent data on the weight l composition of four of our Aroclor products as a function of each detectable PCB homolog. The first column on the left lists the homolog in question and the subsequent columns under each product show the weight % distribution of each FCE homolog in each product. As most of you probably know, with the exception of Aroclor 1016, the last two digits of each product number refer to the degree of chlor ination. For example, Aroclor 1221 contains 21% chlorine by weight, and so on. Aroclor 1016 is a special case in that while it contains about 41% chlorine by weight, it3 penta, hex?., and hept&chloro biphenyl content has been significantly reduced with respect to Aroclor 1242, a product produced by direct chlorination, containing 42% by weight Chlorine. Please note that the penta, hexa, and hepf.aeh.loro biphenyl homologs in Aroclor 1016 have been reduced by factors of about 8, 10, and 10, respectively, with reference to Aroclor 1242. Aa you can also see, the chief constituents of Aroclor 1221 are the mono- and dichloro biphenyls, while Aroclor 1016 and Aroclor 1242 contain predominantly di-*, tri-, and tetrachioro biphenyls, and Aroclor 1254, tetxa, penta, and hexachloro biphenyls. HUNS 090558 -2- As I indicated earlier, this table represents our most recent efforts at determining the homolog distribution of our PC13 products and as such a number of you may have soon estimations of the homolog content of those products which are significantly different. The analytical methodology used is currently .in a vary dynamic state and our understanding of the contents of these products increases as the methodology is improved. At this point in time, we regard these numbers as the most accurate ones currently available. In the next slide (#2) are shown examples of low resolution - packed column electron capture chromatograms of Aroclor 1221, Aroclor 1242, Aroclor 1254, and Aroclor 1260. This is what these products look like to a residue analyst using the most commonly employed detection system. From these chromatograms, it can be readily seen that we are dealing with multi-component products, which of course, increases the com plexity of assessing every aspect of this problem - relative to a well defined single component system such as DDT. I should mention at this point, that the PCB residues generally found in wildlife are most similar to Aroclor 1254 and Aroclor 1260 chromatograms. The next slide (13) demonstrates that in reality, these materials are even more complex than is generally realised. In the upper right portion of this slide is again shown a low resolution electron capture gas chromatogram of Aroclor 1242 under the optimum conditions normally employed by residue analysts. Under these conditions, Aroclor 1242 would appear to be a 15 component system. In the lower portion of this slide is a flame ionization gas chromato gram of the same material using a high resolution S.C.Q.T. column. If one carefully inspects this chromatogram, our simple 15 component product has now been resolved into 55 different components. These facts simply indicate that all PCB products cannot be lumped together in terms of either their environmental impact or persist ence. The type of biological studies which we have carried out to date are shown in the next slide (45). For discussion purposes, they can be conveniently divided into two categories: "Primary Bacterial Degradation Studies", an area in which research on PCBs is just beginning, and "Residue Accumulation Studies". Most of our bacterial degradation work has been centered around the fairly well known semicontinuous activated sludge degradation test. Our residue accumulation studies have been fairly extensive and have involved the exposure of better than 2100 fish, chickens, rats and dogs to the various Aroclor products; resulting in the collection of over 1200 samples of which approximately 500 pooled samples were eventually analyzed for PCB residues. The prime objective of these studies is given on Slide |6. MQNS 090559 -3- Slido (>7. The semi-continuous activated sludge test procedure we used to evaluate the primary bacterial degradation rates of the Aroclor products is the test method recommended by the Soap and Detergents Association for the evaluation of the biodegradability of linear alkyl benzene sulfonate type surfactants [JAOCS 42, 986 (1965) & 46, 432 (1969) ] . Primary Biodegradation - Minimum alternation of the chemical structure of the material in question to an extent that characteristic properties of the original material are no longer evident. This procedure employs sludge from a sewage treatment plant as the source of microorganisms to which a specific amount of the material being evaluated and a synthetic sewage mixture are fed on a periodic basis in a specially designed aeration chamber. The next slide (#8) graphically illustrates what the aeration chamber looks like. It is simply a large glass cylinder with provisions for aeration, auxiliary stirring, a siphon for periodic removal of the supernatant and a septum for introduction of the test material. The mixed liquor (sludge + water) obtained from the sewage treatment plant is initially adjusted with tap water to a suspended solids concentration of about 2500 mg/1, and 1500 ml of this mixture is then charged to the aeration chamber. The mechanical cycle employed is shown in the next slide (J9). Each cycle is initiated by the addition of the synthetic sewage and 1 mg of the PCB product being tested. Since the PCBs are quite water insoluble, they are fed to the unit via injection of 200 pis of a concentrated ethanol solution. In this manner, homogenous dispersion of the PCBs on the bacterial sludge is obtained. After about one hour of aeration an aliquot of the mixed liquor is withdrawn from the chamber and analyzed for PCBs via UV spectro photometry and/or electron capture gas chromatography. Aeration is continued for about 48 hours and a second sample is withdrawn for analysis. At this point, the aeration is stopped and the sludge allowed to settle, the sludge volume and pH are then checked to insure that the unit is operating satisfactorily. Two-thirds of the supernatant is withdrawn and replaced with tap water; aeration is then resumed. The cycle is re-initiated by the addition of the syntl'.etic sewage and Aroclor in question. This cycle is continuously repealed until a steady state and consistent degradation rates are obtained. The per cent degradation rate is calculated as shown in the equation on the slide from the amounts found in the samples analyzed during each cycle. Degradation testing of the Aroclor products shown in the next slide (f!10) have been carried out over an eight month period in our laboratories. In this slide, we have shown graphically the results observed to date. Here we have plotted the mean per cent degradation MONS 090560 -4- rates for biphenyl, Aroclor 1221, MCS 1043 , a research material containing 301 by weight chlorine, Aroclor 1016 (411 chlorine), Aroclor 1242, and Aroclor 1254 versus the weight per cent chlorine present in each. The actual mean per cent degradation rates and 951 confidence limits for each material are shown in the lower left portion of the slide. These data -were all obtained by UV spectro photometry which in essence follows the decrease in the aromatic ring content and is indicative of bacterial ring cleavage. The important point to note here is that as the degree of chl-orination decreases the degradation rate increases. In order to give you a feeling for the degradation rates observed with other materials, Aroclor 1221 degrades at about the same rate as a non-linear ABS surfactant. We have also used this technique to study p,p'-DDT and have at this point in time noted no significant primary degradation. The next slide (#11) shows the changes in homolog distribution observed for Aroclor 1242 via electron capture gas chromatographic analyses. The upper chromatogram shows the character of the residue one hour after addition. The numbers above each peak indicate the dominant homolog or homologs present in each. The lower chromatogram is of the residue after 72 hours of exposure to the bacterial sludge. It can be readily seen by comparing the two chromatograms that all the dich.loro biphenyls, most of the trichloro biphenyls, and a significant portion of the tetrachloro biphenyls are degraded in 48 hours under these test conditions. The conclusions which we draw from this preliminary data are shown in the next slide (#12). Next, I will discuss our "Aroclor Residue Studies" (Slide #13). Our white leghorn chicken studies (Slide #14) have consisted of a 90 day oral exposure, of Aroclor 1242, Aroclor 1254 , and Aroclor 1260 at 1, 10, and 100 ppm feed levels and a repeat 90 day study of Aroclor 1242 at the 2, 4, and 8 ppm feed levels. 336 Chickens were employed from which a total of 521 tissue, chick, and egg samples were collected. Of these 112 pooled samples were analyzed for PCB residues. In the next slide (#15) are shown the results of the 90 day oral exposure of white leghorn chickens to Aroclor 1242. On the left side, we have shown the oral exposure levels which were 1, 10, and 100 ppm, the theoretical residue in ppm, which would have been found in the lipid if the chickens had retained all of the Aroclor 1242 which they orally injested. As you can see, these levels are M.25, 1250, and 12,500 ppm. Next is shown the actual average level in ppm found in the lipid of the muscle, fat, and liver samples and then the levels found after 30 days on a PCB free diet. The important points to note are that a.90% of all the Aroclor 1242 consumed is directly excreted and/or metabolized and that after 30 days on a PCB free diet 35%, 44%, and 57% of the PCBs retained after 90 days of continuous exposure at the 1, 10, and 100 ppm levels was excreted and/or metabolized. . HONS 090561 -5- On the right hand side of this slide is shown the horaolog distri bution of the product fed and that of the residues isolated from the tissues after 90 days of exposure and 30 days on a PCB free diet. Tile numbers across the top simply refer to the number of chlorine atoms per biphenyl molecule. As you can see, Aroclor 12d 2 contains dominant amounts of the di- through pentachlorobiphenyls and a minor amount of hexachlorobiphenyl. After 90 days of exposure the dichlorobiphenyl was no longer observable and the dominant components were the tri- through pentachloro biphenyl homologs. After 30 days on a PCB free recovery diet, the'hex'achloro biphenyl is now a dominant component because of continued excretion and/or metabolism of the lower chlorinated homologs. In the next slide (116) are shown the results for the 90 day oral exposure of Aroclor 1254 in white leghorn chickens at the 1, 10, and 100 ppm exposure levels. The theoretical residues are the same as before and .we have again ^iown the actual levels found in the tissues after 90 days of continuous exposure and 30 days on a PCB free diet. In this instance, ^70-72% of the Aroclor 1254 ingested was directly excreted and/or metabolized and after 30 days on a PCB free diet, "\,4 5% of the residues retained were excreted and/or metabolized. The homolog distribution of the product and residues is shown on the right of the slide, the product Aroclor 1254 contains minor amounts of the tri- and heptachloro homologs and dominant amounts of the tetra-, penta-, and hexachtoro biphenyls. The residue after 90 days of exposure did not contain detectable amounts of the trichloro biphenyls and the tetrachloro biphenyls were no longer a dominant component. The dominant homologs were penta- and hexa chtoro biphenyls. After 30 days on a PCB free diet, the tetrachloro biphenyls were now not detectable, the pentachloro biphenyls were a minor component, and the hexachloro biphenyls the dominant component. In the next slide (#17) are the results for Aroclor 1260. Again, the oral exposure level and theoretical residue levels are the same and the PCB residues found in the tissues after 90 days of continuous exposure and 30 days on a PCB free recovery diet are shown. After 90 days of exposure, 57-52% of all Aroclor 1260 consumed was directly excreted and/or metabolized and after 30 days on a PCB free diet M0% of the residues retained were excreted and/or metabolized. As shown on the right, Aroclor 1260 contains dominant amounts of penta-, hexa-, and heptachloro biphenyls and a minor amount of octachloro biphenyl. The residues after 90 days of exposure and 30 days on a PCB free recovery diet contain minor amounts of the pentaand octachloro homologs. In both cases, the dominant nomologs were the hexa- and heptachloro biphenyls. Our albino rat work (Slide #18) has consisted of 30 dav oral, 2 year chronic oral and a 3 generation rat reproduction exposure study with Aroclor 1242, Aroclor 1254, and Aroclor 1260 and a 90 day subacute MONS 090562 -e- oral exposure of Al'oclor 1221. Approximately 1400 animals wore vised in those exposure studios from which about 400 muscle, liver, anil fat samples wore collected. Two hundred of these samples wore analysed for PCC residues. In tho next slide (it 19) are shown the results of our two year chronic oral exposure study of Aroclor 1242 in albino rats. The oral exposure levels were 1, 10, and 100 ppm and the theoretical residues were vBOO, 8000, 80,000 ppm, respectively. The actual residues found in the tissue lipid are shown after 3, 12, and 24 months of exposure. Comparison of the residues found after 24 months to the theoretical residue levels indicates that 99% of the Aroclor 1242 fed was directly excreted and/or metabolized at all exposure levels. As is shown on the right, Aroclor 1242 contains dominant amounts of the di- through pentachloro biphenyl homologs and a minor amount of the hexa-. The residues after two years did not contain a signifi cant amount of the dichloro biphenyls and the dominant components were the tri-, tetra-, and pentachloro biphenyl homologs. In the next slide (#20) are shown the results of the two year chronic oral exposure of albino rats to Aroclor 1254. The exposure and theoretical residue levels are the same as with Aroclor 1242. The residues found after 3, 12, and 24 months of exposure are also shown. Comparison of the residues after two years to the amount ingested demonstrates that 95-98% of the Aroclor 1254 consumed is directly excreted and/or metabolized. The homolog distribution of Aroclor 1254 and the residues are shown on the right. Aroclor 1254 contains minor amounts of the tri- and heptachloro biphenyl homologs and dominant amounts of the tetra-, penta-, and hexachloro biphenyl homologs. The residues did not contain detectable levels of the trichloro homologs and the tetrachloro biphenyls were no longer a dominant component. The dominant homologs were the penta- and hexachloro biphenyls. The next slide (#21) shows the the results for the two year exposure of Aroclor 1260 in albino rats. Again, the exposure and theoretical residue levels are the same and the residues found in the tissu.es after 3, 12, and 24 months of exposure are shown. In this case 93-95% of all Aroclor 1260 ingested was directly excreted and/or metabolized. The dominant homologs in Aroclor 1260 and the residues isolated from the tissues were similar in all cases. In order to demonstrate the relationship between residue storage levels and the degree of chlorination of the product fed (slide #22). I have plotted the average ppm PCD found in the lipid vs the weight per cent chlorine in the product fed. These data were taken from our 90 day subacute albino rat studies with Aroclor 1221, Aroclor 1242, Aroclor 1254, and Aroclor 1260 at an exposure level of 100 ppm. As you can see, the residue storage levels decrease exponentially as the weight per cent chlorine decreases, simply demonstrating the relationship between the higher homolog content of an Aroclor product and the tissue storage level. HONS 090563 -7- Our beagie dog studios (slide 23) have consisted of a two year chronic exposure of Aroclor 1242, Aroclor 1254, and Aroclor 1260 and a DO day subacute study of Aaroclor 1221. In these studies, 108 beagle dogs v.'ere used, resulting in the col lection of 263 samples, and the analyses of 146 for PCB residues. 1 The next slide ("24) shows the results of one two year'study of Aroclor 1242 at exposure levels of 1, 10, and 100 ppm. In this study, the theoretical residue levels are "v-DOO, 5000, and 50,900 ppm respectively. We have also shown on this slide the residue levels found after two years of exposure and after 30 and 60 day periods on PCB free recovery diets. The beagle dogs directly excreted and/or metabolized 99.61 of the Aroclor 1242 consumed and after 60 days on PCB free diets, 50-60% of PCB residua retained after two years of exposure was excreted and/or metabolized. Aroclor 1242 contains dominant amounts of the di-, tri-, tetra-, and pentachloro homologs and a minor amount of the hexa- homolog. The residue found after two years of exposure contained no detectable levels of the dichloro homologs and dominant levels of the tri-, tetra-, hepta-, and octac.hloro biphenyls. The pentachloro homolog, although dominant in the product fed, was not a dominant component of the residue. After 30 days on a PCB free recovery diet, the di-, tri-, and tetrachloro biphenyls were not detectable components of the residue. At this point, the dominant components were the hexa-, hepta-, and octochloro biphenyls. The trend toward excretion and/ or metabolism of the lower chlorinated homologs continued to the extent that after 60 days on the recovery diet the hexachloro biphenyl was no longer a dominant component, and the hepta- and octachioro bi phenyls became the dominant constituents in the residue. In the next slide (25) ore the results for the two year exposure of beagle dogs to Aroclor 1254. The oral exposure and theoretical residue levels are the same and the PCB residue levels found in the tissues after two years of exposure and after 30 and 60 day periods on PCB free recovery diets are again shown. In this instance, the dogs excreted and/or metabolized 98-99% of all Aroclor 1254 consumed over a two year period. After 60 days on a PCB free recovery diet, 30-40% of the residues retained were excreted and/or metabolized. The product fed, Aroclor 1254, contains minor amounts of the tri- and heptachloro biphenyls and dominant amounts of the tetra-, penta-, and hexachloro homologs. After two years of exposure, the residue retained from the product did not contain detectable levels of the tri- or tetrachloro biphenyls, the penta-, and hexachloro biphenyls remained dominant components, and the heptachloro biphenyls became dominant constituents. After 30 days on the PCB free recovery diet, the pentachloro homologs became a minor component of the residue, the hexa- and heptachloro biphenyls remained dominant components and the octachioro homologs became a minor component. After 60 days on the PCB free recovery diet, the pentachloro biphenyls were excreted and/or metabolized to the extent that the octachioro homologs became a dominant constituent of the residue. MUNS 090564 -8- Thc next slide ('(26) shows the results for the two year oral exposure residue study of Aroclor 1260 in beagle clogs. The exposure and theoretical residue levels are the same as those for the Aroclor 1242 and Aroclor 1254 studies, next is shown the residues which accumulated after two years of continuous exposure and the residues retained after 30 and 60 day recovery periods on PCB free diets. With this Aroclor 98-99% of the amount consumed over two years was directly excreted and/or metabolized. After 60 days on the recovery diet a.13% of the retained residues were excreted and/or metabolized. The homolog distribution of Aroclor 1260 is as shown, dominant amounts of the penta-, hexa-, and heptachloro biphenyls with a minor amount of the octachloro homologs. After two years, the PCB residue contains no detectable level of the pentachloro homologs, a minor amount of the heptachloro biphenyls, and dominant amounts of the hoxachloro and octachloro homologs. After 30 days on the recovery diet, the dominant homologs are now the hexa-, hepta-, and octa chloro biphenyls becoming a dominant component of the residue via loss of some of the hexachloro biphenyls. After 60 days on the recovery diet, the hexachloro biphenyls are no longer dominant components of the residua and it is now mainly the hepta- and octachloro biphenyl3. The next slide (#27) illustrates the residue fall off as a function of Aroclor and recovery period. These data are from the two year beagle dog studies and the exposure level is 1 ppm. In this graph, I have plotted the average ppm PCB found in the lipid for Aroclor 1260, Aroclor 1254, and Aroclor 1242 after two years of continuous oral exposure and then after 1 month and 2 month recovery periods on PCB free diets. This plot simply demonstrates that the PCB residues retained from Aroclor 1242 fall off more quickly than those retained from Aroclor 1254 and Aroclor 1260. The table in the next slide (#28) shows the relative ability of fowl, small mammals, and large mammals to retain orally ingested PCBs. These data are for Aroclor 1242 at the exposure levels and periods shown. The concentration factor is calculated by dividing the maximum PCB level found in the lipid by the exposure level. As you can see from the factors, chickens retain PCBs to a greater extent than do rats or dogs. Our fish residue work is not very extensive at this point primarily because we have had problems in finding consulting laboratories capable of carrying out dynamic low level fish exposure studies, and secondly, because government laboratories such as those in Duluth, Minnesota, Columbia, Missouri, and Gulf Breeze, Florida were, and are, still in better positions to carry out snd evaluate these types of studies. We have done some very preliminary 21 day dynamic exposures of cat fish and bluegill fingerlings to some of our Aroclor products and it generally supports the conclusions which can be drawn from literature data. The general conclusions which we draw from these residue studies are shown in the next three slides. HONS 090565 -9Slidc #29 - Build-Up - Conclusions Slide 130 - Fall-Off - Conclusions Slide #31 - Alteration of Homolog Distribution - Conclusions In summary, we feel that the results of our preliminary research support, what has and is being observed via residue analysis of environmental samples; that is to say, from a residue viewpoint, that the bulk of the PCB homologs released to the environment (PCBs with less than 5 chlorines) are subject to environmental degradation of one sort or another at measurable rates and as such have not accumulated. E. S. Tucker MQNS 090566 TYPICAL % COMPOSITION OF POLYCHLORINATED BIPHENYL PRODUCTS HOMOLOG 11 /BIPHENYL 0 1 2 3 4 5 6 7 B AROCLOR 1221 11 51 32 4 2 <0.5 ND ND ND AROCLOR 1016 <0.1 1 20 57 21 1 <0.1 ND ND AROCLOR 1242 <0.1 1 16 49 25 8 1 <0.1 ND AROCLOR 1254 <0.1 <0.1 <0.5 1 21 48 23 6 NO PER CENT (W/W) BY GC/MASS USING AREA CORRECTION FACTORS BY HOMOLOG RESPONSE NONE DETECTED, <0.01* * ND HONS 090567 Electron Capture Gas Chromatograms MOWS 090568 |i Aroclor 1242 Electron Capture Gas Chromatogram Low Resolution - 6* Pocked Column MONS 090569  PCB PRODUCTS ARE NOT A SINGLE ENTITY, BUT COMPLEX MULTI COMPONENT MIXTURES PCB RESIDUES FOUND IN WILD LIFE ARE DOMINANTLY PENTA-, HEXA-, HEPTA-, AND OCTACHLORO BIPHENYLS PCB RESIDUE ARE MOST SIMILAR TO AROCLOR 1254 AND AROCLOR 1260 PRODUCTS PRIMARY BACTERIAL DEGRADATION STUDIES SEMI-CONTINUOUS ACTIVATED SLUDGE DEGRADATION RESIDUE ACCUMULATION STUDIES FISH - CATFISH AND BLUEGILLS BIRDS - WHITE LEGHORN CHICKENS MAMMALS - ALBINO RATS ANO BEAGLE DOGS MONS 090571 ASSESSMENT OF THE PERSISTENCE OF POLYCHLORINATED BIPHENYLS IN BIOLOGICAL SYSTEMS AROCLOR SEMI-CONTINUOUS ACTIVATED SLUDGE PRIMARY DEGRADATION STUDIES MOWS 090573 Semi-Continuous Activated Sludge Test Unit Stirrer MGNS 090574 MECHANICAL CYCLE SYNTHETIC SEWAGE AND AROCLOR (1 mg) ADDED MONS 090575 Semi-Continuous Activoted Sludge Degradation of Polychlorinated Biphenyls IOO Biphenyl a> O 80 - Aroclor 1221 CO 2: 60 - MCS I043^\ a> ao: % 2 40 Degradation Biphenyl Aroclor 1221 100.0 80.6 + 5.7 \ Aroclor VI0I6 O' a> MCS 1043 Q 20 - Aroclor 1016 6^ Aroclor 1242 O) Aroclor 1254 > 56.2 + 15.5 32.9+13.8 26.3+ 15.5 15.2 + 377 Aroclor ckw 1242 Arodor 1254 t Addition rote lma/48 hrs ____ 1____ 1____ L___ 1 11___ 1__ _i____ 1___ J____ 1____ 10 20 30 40 50 % Chlorine (w/w) mons 090576 Semi-Continuous Activated Sludge Degradation of Aroclor 1242 3 Elution Time (minutes) MONS 090577 BACTERIAL DEGRADATION STUDIES C ONC L US IONS RATE OF PRIMARY DEGRADATION INCREASES AS THE DEGREE OF CHLORINATION OF THE AROCLOR PRODUCT DECREASES BIPHENYL>AROCLOR 1221>MCS 1043 >AR0CL0R 1016>AR0CL0R 1242>AR0CL0R 1254 BIPHENYL, MONO-, DI-, TRI-, AND TETRACHLORO BIPHENYL HOMOLOGS UNDERGO PRIMARY BACTERIAL DEGRADATION HONS 090578 c AROCLOR RESIDUE STUDIES m m t m C Mows 090579 WHITE LEGHORN CHICKEN STUDIES PRODUCTS STUDIED OF ) CHICKENS) FEMALE MALE. NUMBER) OF ) SAMPLES) MUSCLE LIVER FAT EGGS CHICKS NUMBER) OF ) SAMPLES ANALYZED) MUSCLE LIVER FAT EGGS CHICKS 90 DAY ORAL AROCLOR 1242 AROCLOR 1254 AROCLOR 1260 AROCLOR 1242 200 80 40 16 40 40 40 ''-250 30 8 8 8 ,'<60 10 14 5 12 4 18 5 25 8 11 10 ES COLLECTED 'ZED 400 80 121 32 ORAL EXPOSURE CARRIED OUT BY INDUSTRIAL BIO-TEST LABORATORIES, INC. NORTHBROOK, ILLINOIS MONS 090580 RESIDUE STUDY OF AROCLOR 1242 ORAL EXPOSURE LEVEL IN WHITE LEGHORN CHICKENS 90 DAY ORAL HOMOLOG DISTRIBUTION PPM- PCBs 1 23 4 5 6 7 8 1 10 100 9 10 +THEORETICAL RESIDUE 1 26 .1 260 12602 - (2) (3) (4) (5) 6 --- - RESIDUE, 12 WEEK EXPOSURE 14 136 1312 - - (3) (4) (5) 6, - - - - RESIDUE, 30 DAY RECOVERY 9 77 749 (3) (4) (5) (6) tIF TOTAL PCB CONSUMED WERE RETAINED AVERAGE PPM IN LIPID - ALL TISSUES ( JELECTRON CAPTURE PEAKS GREATER THAN 5X OF TOTAL MQNS 090581 RESIDUE STUDY OF AROCLOR I25A IN WHITE LEGHORN CHICKENS 90 DAY ORAL HOMOLOG DISTRIBUTION PPM PCBs I 23 4 56 78 ORAL EXPOSURE LEVEL 1 10 100 9 (THEORETICAL RESIDUE 126 1260 12602 - - 3 (4) (5) (6) 7 - - RESIDUE. 12 WEEK EXPOSURE 38 362 3506 - - - 4 (5) (6) 7 - - RESIDUE. 30 DAY RECOVERY 17 164 1580 - - - - 5 (6) 7 - - +IF TOTAL PCB CONSUMED WERE RETAINEO AVERAGE PPM IN LIPID - ALL TISSUES ( )ELECTRON CAPTURE PEAKS GREATER THAN 5* OF TOTAL 10 - MOMS 090502 RESIDUE STUDY OF AROCLOR 1260 IN WHITE LEGHORN CHICKENS 90 DAY ORAL HOMOLOG DISTRIBUTION PPM PCBs 1 2 3 4 5 6 7 8 9 10 ORAL EXPOSURE LEVEL 1 10 100 tTHEORETICAL RESIDUE 126 1 260' 1 2602 - - - - (5) 16) (7) 8 - - RESIDUE. 12 WEEK EXPOSURE RESIDUE, 30 DAY RECOVERY 65 607 5909 - - - - 5 (6) (7) 8 26 232 2363 - - - . 5 (6) (7) 8 - - tIF TOTAL PCB CONSUMED WERE RETAINED AVERAGE PPM IN LIPID - ALL TISSUES ( )ELECTRON CAPTURE PEAKS GREATER THAN 5* OF TOTAL MQNS 090583 albino rat studies PRODUCTS STUDIED NUMBER) FEMALE OF RATS) MALE NUMBER) OF ) SAMPLES) MUSCLE KIDNEY LIVER FAT PUPS NUMBER) OF SAMPLES) ANALYZED) MUSCLE KIDNEY LIVER FAT PUPS 30 DAY ORAL AROCLOR 1242 AROCLOR 1254 AROCLOR 1260 115 115 18 18 18 18 " 18 18 18 18 " 2 YEAR CHRONIC ORAL AROCLOR 1242 AROCLOR 1254 AROCLOR 1260 500 500 33 33 33 33 33 33 3 GENERATION RAT R EPRODUCT tO N AROCLOR 1242 AROCLOR 1254 AROCLOR 1260 ''.20 \.20 - 10 - 10 90 DAY SUBACUTE ORAL AROCLOR 1221 60 60 7 7 7 7 7 7 ana TOTAL SAMPLES 144 198 20 COLLECTEO TOTAL ANALYZED 72 99 10 42 21 ORAL EXPOSURE CARRIED OUT BY INDUSTRIAL BIO-TEST LABORATORIES, INC. NORTHBROOK, ILLINOIS HUNS 090584 RESIDUE STUDY OF AROCLOR 1242 IN ALBINO RATS TWO YEAR CHRONIC ORAL EXPOSURE ORAL EXPOSURE LEVEL HOMOLOG DISTRIBUTION PPM PCBs 1 2 3 4 5 6 7 8 9 10 I 10 "TOUT +THEORETICAL RESIDUE 803 8037 80373 - (2) (3) (4) (5) 6 - - - - `RESIDUE, 3 MONTH EXPOSURE 6 23 90 - - (3) (4) (5) 6 - - - - `RESIDUE, 12 MONTH 9 37 155 - - (3) (4) (5) 6 - - - EXPOSURE RESIDUE, 24 MONTH 12 53 240 - - (3) (4) (5) 6 - - - EXPOSURE tIF TOTAL PCB CONSUMED WERE RETAINED `AVERAGE PPM IN LIPID - ALL TISSUES ( )ELECTRON CAPTURE PEAKS GREATER THAN 5X OF TOTAL MONS 090585 RESIDUE STUDY OF AROCLOR 1254 IN ALBINO RATS TWO YEAR CHRONIC ORAL EXPOSURE ORAL EXPOSURE LEVEL PPM PCBs 1 10 100 HOMOLOG DISTRIBUTION 12 3 4 5 6 7 8 9 10 tTHEORETICAL RESIDUE 803 8037 80373 - - 3 (4) (5) (6) 7 - - - `RESIDUE) 3 MONTH 13 94 679 EXPOSURE `RESIDUE. 12 MONTH 24 189 1471 EXPOSURE . . . 4 (5) (6) 7 - . . . 4 (5) C6) 7 - - - `RESIDUE, 24 MONTH 42 355 3038 EXPOSURE - - - 4 (5) (6) 7 - - - tIF TOTAL PCB CONSUMED WERE RETAINED `AVERAGE PPM IN LIPID - ALL TISSUES ( }ELECTRON CAPTURE PEAKS GREATER THAN 5* OF TOTAL MONS 090586 RESIDUE STUDY OF AROCLOR 12,60 IN ALBINO RATS TWO YEAR CHRONIC ORAL EXPOSURE ORAL EXPOSURE LEVEL PPM PCBs 1 10 100 HOMOLOG DISTRIBUTION 2 3 4 5 6 7 8 9 10 tTHEORETICAL RESIDUE 803 8037 80373 - - - - (5) (6) (7) 8 - - RESIDUE, 3 MONTH 18 134 970 - - - - (5) (6) (7) 8 EXPOSURE - RESIDUE, 12 MONTH 35 270 2099 - - - - (5) (6) (7) 8 EXPOSURE - RESIDUE, 24 MONTH 59 507 4338 - - - - (5) (6) (7) 8 EXPOSURE - tIF TOTAL PCB CONSUMED WERE RETAINED AVERAGE PPM IN LIPID - ALL TISSUES ( )ELECTRON CAPTURE PEAKS GREATER THAN 5* OF TOTAL MQNS 090587 Average ppm PCB in Lipid (Muscle, Fat, Liver) HUNS 090588 % Chlorine(%) BEAGLE DOG STUDIES PRODUCTS STUDIED NUMBER ) FEMALE OF DOGS) MALE NUMBER ) MUSCLE OF ) LIVER SAMPLES) FAT TOTAL SAMPLES COLLECTED 2 YEAR CHRONIC ORAL AROCLOR 1242 AROCLOR 1254 AROCLOR 1260 40 40 54 54 54 242 90 DAY SUBACUTE ORAL AROCLOR I4 14 7 7 7 21 NUMBER ) OF ) SAMPLES) ANALYZED) MUSCLE l TVFR FAT TOTAL ANALYZED 42 40 43 125 7 7 7 21 ORAL EXPOSURE CARRIED OUT BY INDUSTRIAL BIO-TEST LABORATORIES, INC. NORTHBROOK, ILLINOIS 0905d9 RESIDUE STUDY OF AROCLOR 1242 IN BEAGLE DOGS TWO YEAR CHRONIC ORAL EXPOSURE ORAL EXPOSURE LEVEL PPM PCBs 1 10 100 HOMOLOG DISTRIBUTION 123456789 10 tTHEORETICAL RESIDUE 519 5186 51865 - (2) (3) (4) (5) 6 - - - `RESIDUE, 2 TEAR EXPOSURE 2 6 12 - - (3) (4) 5 6 (7) (8) - `RESIDUE, 30 DAY RECOVERY 1 4 10 - - - - 5 (6) (7) (8) - *RESI0UE, 60 DAY RECOVERY 0.8 36 - - - - 5 6 (7) (8) - + IF TOTAL PCB CONSUMED WERE RETAINED AVERAGE PPM IN LIPID - ALL TISSUES { ELECTRON CAPTURE PEAKS GREATER THAN 5* OF TOTAL HONS 090590 RESIDUE STUDY OF AROCLOR 1254 IN BEAGLE DOGS TWO YEAR CHRONIC ORAL EXPOSURE ORAL EXPOSURE LEVEL PPM PCBs 1 10 100 HOMOLOG DISTRIBUTION 1 2 3 4 5 6 7 8 9 10 tTHEORETICAL RESIDUE 519 5186 51865 - - 3 (4) (5) (6) 7 - * * RESIDUE, 2 YEAR EXPOSURE 7 30 132 - - - - (5) (6) (7) 8 - - RESIDUE, 30 DAY RECOVERY 5 24 109 - - - 5 (6) 17) 8 - - RESIDUE. 60 DAY RECOVERY 4 20 88 - - - - 5 (6) (7) (8) - - +IF TOTAL PCB CONSUMED MERE RETAINED AVERAGE PPM IN LIPID - ALL TISSUES { )ELECTRON CAPTURE PEAKS GREATER THAN 5* OF TOTAL moms 090591 RESIDUE STUDY OF AROCLOR 1260 IN BEAGLE DOGS TWO YEAR CHRONIC ORAL EXPOSURE ORAL EXPOSURE LEVEL PPM PCBs 1 10 100 HOMOLOG DISTRIBUTION 1 2345678 tTHEORETICAL RESIDUE 519 5186 51865 - - - - (5) (6) (7) 8 RESIDUE, 2 YEAR EXPOSURE 8 63 388 - - - - ' (6) 7 (8) RESIDUE, 30 DAY RECOVERY RESIDUE, 60 DAY RECOVERY 7 60 363 - - - - - (6) (7) (8) 7 55 337 - - - - - 6 (7) (8) tlF TOTAL PCB CONSUMED WERE RETAINED AVERAGE PPM IN LIPIO - ALL TISSUES { )ELECTRON CAPTURE PEAKS GREATER THAN 5* OF TOTAL MONS 09059^  I Two Year Chronic Oral Exposure I in Beagle Dogs (at The I ppm Feeding Level) I I I I i i I i fl fl HONS 090593 WHITE LEGHORN CHICKENS ALBINO RATS BEAGLE DOGS EXPOSURE LEVEL (PPM) EXPOSURE PERIOD 1 .0 (FEED) 1 .0 (FEED) 1 .0 (FEED) 12 WEEKS 2 YEARS 2 YEARS CONCENTRATION FACTOR* 20 9 2 CONCENTRATION FACTORS DO NOT TAKE INTO ACCOUNT EXPOSURE PERIODS MOMS 09059^ CONCLUSIONS RESIDUE BUILDUP STUDIES FOR ALL. PRODUCTS THE PCB. RESIDUE LEVEL IN CREASED AS THE EXPOSURE LEVEL AND PERIOD INCREASED 0 RELATIVE TO AROCLOR 1260, THE HIGHEST CHLORINATED PRODUCT STUDIED, THE PCB RESIDUE LEVEL DECREASED EXPONENTIALLY AS AS THE WEIGHT * CHLORINE OF THE PRODUCT DECREASED RELATIVE LEVELS OF PCB RESIDUES FOUND WERE FISH>>>>>CHICKENS>RATS>DOGS RELATIVE PCB RESIDUE LEVELS IN TISSUES WERE - CHICKENS RATS DOGS FAT * MUSCLE>LIVER LIV ER>FAT = MUSCLE>KIDNEY LIV ER>FAT = MUSCLE FOR ALL PRODUCTS THE DOGS AND RATS EXCRETED AND/OR METABOLIZED 93 TO 9951 OF THE TOTAL AROCLOR ORALLY INGESTED CHICKENS EXCRETED AND/OR METABOLIZED PRODUCTS INJESTEO ORALLY AS FOLLOWS - 90% OF AROCLOR 1242 70% OF AROCLOR 1254 50% OF AROCLOR 1260 MONS 090595 CONCLUSIONS RESIDUE FALL-OFF DOGS AND CHICKENS CONTINUED TO EXCRETE AND/OR METABOLIZE PCB RESIDUES, INCLUDING PENTA AND HEXA HOMOLOGS, RETAINED WHEN PLACED ON PCB FREE RECOVERY DIETS DOGS > CHICKENS RELATIVE RESIDUE FALL-OFF RATES SHOWED DOGS: AROCLQR 1Z42>AR0CL0R 1254 >AROCLOR 1260 CHICKENS: AROCLOR 1242>AR0CL0R 1254>AROCLOR 1260 MOMS 090596 CONCLUSIONS RESIDUE STUDIES ALTERATIONS OF AROCLOR HOMOLOG DISTRIBUTION ALTERATION OF THE HOMOLOG DISTRIBUTION OF ALL PRODUCTS HAS OBSERVEO IN ALL STUDIES EXCEPT FISH LOWER CHLORINATEO HOMOLOGS PRESENT IN ALL PRODUCTS WERE PREFERENTIALLY EXCRETED AND/OR METABOLIZED ALTERATION OF THE HOMOLOG DISTRIBUTION INCREASED AS THE WEIGHT * CHLORINE OF THE PRODUCTS DECREASED (INCLUDING PENTA AND HEXA HOMOLOGS) AROCLOR 1221>>AROCLOR 1242>AROCLOR 1254 >AROCLOR 1260 DOGS>RATS>CHICKENS>>>>>FISH Hons 09Q597 WHAT HAPPENS TO PCBs IN THE ENVIRONMENT? By Dr. R. H. Munch Presented by W. B. Papageorge Because they can be detected by the same analytical methods, and because some suspect that they may have similar biological effects to DDT, polychlorinated biphenyls In the environment (PCBs) have become a cause of concern. It Is, therefore, Important to present data to show that PCBs do disappear from the environment. Probably the most effective way to do this is to compare what has been put Into the environment with what is found there now. This can be done In the following way: The commercial PCB products are mixture of chlorinated biphenyl homologs containing from one to ten atoms of chlorine per biphenyl molecule. If there were no degradation in the environment, or if all homologs degraded at the same rate, the ratio of homologs in "aged environmental samples" (samples taken at a distance from a known source) should be the same as that in the products Intro duced into the environment. On the other hand, if the homolog ratio in "aged environment samples" differs from that of material produced, some process must be operating in the environment to remove different homologs at different rates. Monsanto, the major U.S. producer, recently released data on its sales of the various commercial grades of PCB for the years 1957-72. Rest- of-world sales by other producers and production before 1957 probably represent a similar product mix. Using the Monsanto data and known homolog analyses of each of the commercial grades, the percentage of each homolog in the total U. S. production can be calculated. ' The other required datum is an estimate of the homolog distribution in "environmentally aged samples." Analysts experienced in this field generally agree that material recovered from such samples is similar to Aroclor 125** or 1260, the Monsanto trade name for mixtures of PCBs with chlorine contents corresponding to an average of five and six chlorine atoms per biphenyl molecule respectively (1-8). In order to present a conservative comparison and because most analysts cite Aroclor 1254, we shall use the homolog content of that material in our comparison. MOMS 090598 2 The homolog contents of the material produced in the U. S. from 1957 to 1971 and that of Aroclor 125A are tabulated below: Homolog 012. 345678 U. S, Sales 1957 - 1971 0.1 1.3 14.8 29.9 21.9 16.1 10.5 4.2 1.1 Aroclor 1254 L. 1 <L. 1 <L. 5 1 21 48 23 6 ND It is apparent that the homolog ratio of the material sold is quite different from that of Aroclor 1254. There must, therefore, be one or more processes in the environment which remove the lower homologs at much greater rates than the higher ones. The precision of the data is too low to permit accurate calculations of the relative rates of loss. However, it would appear that the homologs containing less than four chlorine atoms may be degraded at rates approximately thirty times those for the five and six chlorine homologs. Laboratory data which we hope to publish later show that the rate of bacterial degradation is an inverse function of the chlorine content for PCBs and might, therefore, be one of the degradatlve processes responsible for the relative decrease in the lower homologs. mons 090599 1) L. M. Reynolds, Pesticide Residue Analysis in the Presence of Polychlorinated Biphenyls Residue Reviews 2k, 27, 32, 41, 42, 44 (1971). 2) R. W. Rlsebrough, P. Reiche and H. S. Scott - Current Progress in the Determination of the Polychlorlnate.d Biphenyls - Bulletin of Environmental Contamination & Toxicology 4_, 192, 199 (197 ). 3) 0. E. Bagley, W. L. Relchel and E. Cromartie - Identifi cation of Polychlorinated Biphenyls in Two Bald Eagles by Combined Gas-Liquid Chromatography-Mass Spectrometry - Journal of the AOAC 251, 252, 257 (1970). 4) Albert C. Tas and Rudolf H. deVos - Characterization of Pour Major Components in a Technical Polychlorinated Biphenyl Mixture - Environmental Science & Technology 5, 1216 (1971). 5) Judith A. Armour and Jerry A. Burke - Method for Separating Polychlorinated Biphenyls from DDT and Its Analogs - Journal of the AOAC 21- 763, 765 (1970). 6) Ian Prestt, D. J. Jeffrerles and N. W. Moore - Polychlori nated Biphenyls in Wild Birds in Britain and Their Arlan Toxicity - Environmental Pollution 1^, 3, 15 (1970). 7) V. Zltko - Polychlorinated Biphenyls and Organochlorine Pesticides in Some Freshwater and Marine Fishes - Bulletin of Environmental Contamination & Toxicology 6, 464, 467 (1971). ~ 8) PCBs & The Environment - Interdepartmental Task Force on PCBs - Washington May, 1972 - COM-72-10419 - Table 6, P. 93- MONS 090600 WHAT HAPPENS TO PCBs IN THE ENVIRONMENT? 1. WE CANNOT DETERMINE IF PCBs DEGRADE IN THE ENVIRONMENT FROM THE TOTAL CON CENTRATIONS FOUND THERE. 2. THE PCBs ARE MIXTURES OF HOMOLOGS. 3. THEREFORE, COMPARISON OF HOMOLOG RATIOS IN "ENVIRONMENTALLY AGED SAMPLES" WITH HOMOLOG RATIOS IN MATERIAL PRODUCED CAN BE USED TO GAIN INSIGHT AS TO WHAT IS HAPPENING IN THE ENVIRONMENT. MONS 090601 HOW DO WE GET THE DATA NEEDED? 1. PRODUCTION FIGURES FOR ALL MONSANTO PCB PRODUCTS AND HOMOLOG CONTENT OF EACH PRODUCT ARE AVAILABLE FOR 1 957 71. WE USE THESE DATA TO CALCULATE HOHOLOG RATIOS FOR 1957-71 PRODUCTION. 2. EUROPEAN PRODUCERS MAKE SIMILAR PRODUCTS IN ABOUT THE SAME RATIOS AS MONSANTO. 3. PRODUCTION BEFORE '57 WOULD NOT AFFECT I HE FIGURES GREATLY SINCE PRODUCT RATIOS WERE SIMILAR AND PRODUCTION SMALLER. 4. ANALYSTS GENERALLY AGREE THAT MATERIAL FOUND IN "AGED ENVIRONMENT AL SAMPLES" IS SIMILAR TO AROCLOR 1254 OR IN RARE CASES EVEN TO AROCLOR 1260. MUNS 090602 HARVEY, MIKLAS AMD BOWEN OP WOODS HOLE OCEANOGRAPHIC INSTITUTE AROCLOR 1254 VS ENVIRONMENTAL MATERIAL CURVES HONS 090603 , COMPARISON OF THE HOMOLOG RATIOS FOR PCBs SOLD WITH THOSE FOUND IN AGED ENVIRONMENTAL SAMPLES HOMOLOG 0 1 234 5678 U.S. SALES '57 - '71 0.1 1.3 14.8 2S.9 21.9 16.1 10.5 4.2 1.1* AROCLOR 1254 <.l <.l <5 1 21 48 23 6 ND MO NS 090604 CONCLUSIONS 1. THERE ARE HARKED DIFFERENCES BETWEEN THE RATIOS OF HOMOLOGS IN PCBs FOUND IN "AGED ENVIRON MENTAL SAMPLES" AND THE RATIO OF HOMOLOGS FOR MATERIAL PRODUCED. 2. THESE DIFFERENCES. CAN BEST BE EXPLAINED BY ASSUMING THAT THE PCBs WITH 3 OR LESS CHLORINE ATOMS PER MOLECULE DEGRADE MUCH MORE RAPIDLY THAN THE HIGHER HOMOLOGS. 3. THE HOMOLOG RATIO DATA DO NOT GIVE INFORMATION ON THE RATE OF DEGRADATION OF HIGHER HOMOLOGS. HOWEVER, SEMI-CONTINUOUS ACTIVATED SLUDGE TEST DATA SHOW THAT THESE TOO DEGRADE BUT AT A SLOWER RATE. mqns 090605 MONSANTO PCB ACTIONS IN CANADA by D. Goodwlllle MONS 090606 MAJOR TRADITIONAL USES OF PCB O OPEN SYSTEMS PLASTICIZERS o SOLVENTS FOR CARBONLESS COPY PAPER(2) O CLOSED SYSTEMS DIELECTRICS HEAT TRANSFER INDUSTRIAL HYDRAULIC FLUIDS ^POLYCHLORINATED BIPHENYLS (2)N0 SALES IN CANADA HONS 090607 MONSANTO PCB SALES IN CANADA MUNS 090608 MONSANTO PCS ACTIONS PHASE-OUT OF PCB SALES WORLDWIDE IN ALL APPLICATIONS EXCEPT DIELECTRICS CONVERSION OF DIELECTRIC FLUIDS TO MORE BIODEGRADABLE PCB'S MONSANTO PCB SALES NORTH AMERICA DIELECTRIC APPLICATIONS 1969 1970 1971 1972 EST CANADA U.S.A. (in millions OF pounds) 3.24 37.0 4.44 40.5 3.36 28.4 3.30 33.0 SALES IN CANADA l 8 10 10 9 MQNS 090610 MONSANTO PCB SALES NORTH AMERICA NON-DIELECTRIC APPLICATIONS 1969 1970 1971 1972 EST CANADA U.S.A. (in millions of pounds) 0.83 30.0 0.96 33.5 0.22 -- 3.7 -- SALES IN CANADA % 2.6 2.8 -- 5.0 - MONS 090611 MONSANTO PCS SALES NORTH AMERICA CONCLUSIONS MONSANTO SALES FOR NON-DIELECTRIC USES IN CANADA ALWAYS WERE UNDER 3Z NORTH AMERICA TOTAL MONSANTO SALES DIELECTRIC USES IN CANADA ARE ONLY--10Z NORTH AMERICA TOTAL -------------- HONS 090612 EFFECT OF PHASE-OUT POLICY MONSANTO PCB SALES REDUCED: IN NORTH AMERICA BY 31 ' 0 34 M POUNDS IN CANADA BY 0.8 TO 1.0 M POUNDS MQNS 090613 PCB CHANGES IN DIELECTRICS By Dr. C. Paton 1 respectfully submit we have achieved a significant reduction in PCB output by our actions. Turning to the second phase of our actions, viz, the product changes in PCBs for dielectric use, I will first take a moment to explain the variation in blodegradabllity of PCBs. Slide 1: Degree of Biodegradation of PCBs. The product changes made in dielectrics are shown on Slide 2; PCB Product Changes in Dielectrics. Dealing first with capacitors: Slide 3: PCBs used in capacitors Note: (a) Penta-chloroblphenyl percentages include hexa- and higher homologs. Do not add both percentages together. (b) This slide shows a substantial decrease in pro duction of homologs of penta-chloro and higher over the years. Slide 4: Why convert to Aroclor 1016? Reasons were: (a) 9-fold reduction in penta-chloro and higher homologs (b) 10-fold reduction in hexa-chloro and higher homologs (c) Aroclor 1016 was the PCB product that could be introduced into the capacitor industry while still meeting Underwriters Laboratory's requirement on flammabllity. (d) Aroclor 1016 was selected because its electrical properties and in-plant processing performance most closely met the capacitor industry's requirements. Note: Our choice of Aroclor 1016 has since been borne out by industry experience which to date has shown no problems. MONS 090614 2 Slide 5= Capacitor Fluids: What Is Effect of Aroclor 1016? We have tried to show amounts of penta-chloro and higher and hexachloro and higher homologs which would have been produced (not entering the environment) for each of three possible capacitor fluids in 1972. Aroclor 1016 is obviously the PCB Involving least penta and higher chloro biphenyl production. Of obvious Interest Is the possible amount of PCBs entering the environment from capacitor failures. Slide 6: What is the Capacitor Failure Rate? Slide 7: Using the worst case (0.2# per year failure) we see that no more than one pound of hexa-chloro and higher homologs of PCB are likely to enter the environment If Aroclor 1016 is used at a rate of 0.6M lb./year. Turning now to Transformers. Slide 8: Note: Higher chlorinated PCBs are needed In transformers than In capacitors because the correct Hydrogen/Chlorine ratio Is vital in preventing formation of flammable, explosive a re-form gases. Slide 9: What is the Failure Rate in Liquid Transformers? Slide 10: How Much PCB is Affected? In Summary, Slide 11: We will continue our voluntary policy of no more sales world-wide except to dielectric users. We will restrict over 97% capacitor fluid sales to Aroclor 1016 only. This means penta-chloro and high production will be no more than 1.1%. Hexa-chloro biphenyl and higher will be even lower at 0.1%. We will eliminate Aroclor 1260 from transformer fluids and continue incineration facilities for scrap PCBs. We will encourage the dielectric industry through ANSI C-107, which represents both capacitor and transformer manu facturers and users, to enforce strict environmental control over PCBs. MOWS 090615 DEGREE OF BIODEGRADATION OF PCB'S BASED ON' DATA PRESENTED TRANSITION IN BIODEGRADATION OCCURS AROUND PENTA-/HEXA-CHLOROBI PHENYL DISAPPEARANCE OF ALL HOMOLOGS BELOW HEXA-CHLOROBIPHENYL OBSERVED PENTA- AND HIGHER PCB DETERMINED BY SPECIFIC GLC/MS TEST METHOD MOWS 090616 PCS PRODUCT CHANGES IN DIELECTRICS CAPACITORS 97% CONVERSION TO AROCLOR 1016 TRANSFORMERS ELIMINATION OF AROCLOR 1260 MONS 090617 PCB'S USED IN CAPACITORS MAJOR PCB USE PERIOD AROCLOR 1254 1930-1952 AROCLOR 1242 1952-SEPT. 1971 AROCLOR 1016 OCT. 1971 l PCB (PENTACHLORO- AND HIGHER 77.0 9.0 1.1 % PCB (HEXACHLORO- AND HIGHER 29.0 1.0 0.1 MOWS 090618 CAPACITOR FLUIDS WHY CONVERT TO AROCLOR 1016 ? 9-FOLD REDUCTION IN PCB'S OF PENTACHLORO- AND HIGHER O 10-FOLD REDUCTION IN PCB'S OF HEXACHLORO- AND HIGHER MINIMUM INDUSTRY TESTING REQUIRED MONS 090619 CAPACITOR FLUIDS WHAT IS THE EFFECT OF AROCLOR 1016? CANADIAN CAPACITOR FLUID SALES 0.6 M LBS/YEAR (AVERAGE) IF AROCLOR WAS l PENTACHLOROAND HIGHER PCBs WOULD BE* Z HEXA CHLOROAND HIGHER PCBs WOULD BE* 1254 462,000 pounds 174,000 pounds 1242 54,000 6,000 1016 6,600 600 THIS DOES NOT MEAN AMOUNTS OF PCB ENTERING THE ENVIRON MENT - REFERS TO PCB MANUFACTURE. HONS 090620 WHAT IS CAPACITOR FAILURE RATE ? INDUSTRY SOURCES CITE : 0.02-0.2% per year HONS 0906/1 IF CAPACITOR FAILURE RATE IS 0.2% PER YEAR (WORST CASE) PCB ESCAPE TO THE ENVIRONMENT* IS - AROCLOR 1242 AROCLOR 1016 ALL PCB HOMOLOGS PENTACHLORO- AND HIGHER HEXA CHLORO- AND HIGHER 1,200 POUNDS 108 12 1,200 POUNDS 13 1 * ASSUMES CANADIAN FLUID SALES OF 0.6 M POUNDS/YEAR MOMS 0906i^ . PCB CHANGES IN TRANSFORMER FLUID APPLICATIONS O AROCLOR 1260 BEING PHASED-OUT NOW O INCINERATION OF SCRAP PCB'S - 1971 NOTE: ASKAREL (PCB) TRANSFORMERS ARE HERMETICALLY SEALED UNITS MONS 090623 WHAT IS FAILURE RATE IN LIQUID TRANSFORMERS 1 INDUSTRY SOURCES CITE: UNDER 0.27. PER YEAR* ALL LIQUID TYPES - MINERAL OIL ANH PCB. HONS 090624 IF ASKAREL (PCB) TRANSFORMERS FAIL AT 0.2%/YEAR HOW MUCH PCB IS AFFECTED*? ALL PCB HOMOLOGS 6,000 POUNDS (ESTIMATED MONSANTO PCB TRANSFORMER FLUID SALES IN CANADA 3 M POUNDS/YEAR) WITH INCINERATION FACILITIES AVAILABLE, NOT ALL THESE AMOUNTS WILL ENTER ENVIRONMENT. HONS 090625 MONSANTO'S PRESENT PROGRAM TO PREVENT ENVIRONMENTAL POLLUTION BY PCB'S NO MORE SALES WORLD-WIDE EXCEPT DIELECTRIC USERS RESTRICT OVER 97% CAPACITOR FLUID SALES TO AROCLOR 1016 ONLY ELIMINATE AROCLOR 1266 FROM TRANSFORMER FLUIDS CONTINUE INCINERATION FACILITIES FOR SCRAP PCB'S ENC0URA6E DIELECTRIC INDUSTRY THROUGH ANSI C-107 TO ENFORCE STRICT ENVIRONMENTAL CONTROL OVER PCB'S . MOWS 090626 ANSI C-107 COMMITTEE ACTIVITIES By P. G. BENIGNUS MQNS 090617 PERSONNEL OF AMERICAN NATIONAL STANDARDS INSTITUTE COMMITTEE CI07 MONS 0906^8 ADMINISTRATIVE STEERING'COMMITTEE, CHAIRMAN ------------- PAUL G. BENiGNUS MONSANTO COMPANY COMMITTEE C107, CHAIRMAN ------------------- W. B, PAPAGEORGE MONSANTO COMPANY COMMITTEE C107, SECRETARY ------------------ AL M, SALAZAR NEMA CAPACITOR SUB COMMITTEE, CHAIRMAN ------ DR. AL POZEFSKY GENERAL ELECTRIC TRANSFORMER SUB COMMITTEE, CHAIRMAN -- EDW. L. RAAB GENERAL ELECTRIC HONS 090629 CAPACITOR SUBCOMMITTEE MEMBERS NAME N. R. CLARK ARNOLD S. DOTY R. D. McCLAIN KEN McGEE DR. E. H. MOORE E. G. HAMMER R. L. ROLLINS BUSINESS AFFILIATION UNIVERSAL MFG. P. R. MALLORY WESTINGHOUSE SANGAMO ELECTRICAL UTILITIES McGRAW EDISON JARD CO. ORGANIZATION REPRESENTED CERTIFIED BALLAST MFRS. ASSOC. ELECTRONICS INDUSTRIES ASSOC. (EIA) NATIONAL ELECTRICAL MFG. ASSOC. NEMA -- NEMA EIA HUNS 090630 TRANSFORMER SUBCOMMITTEE MEMBERS NAME BUSINESS AFFILIATION ORGANIZATION REPRESENTED F. R. LENGEFELD H. A. ONISHI J. P. MARKEY W. S. GROGAN W. C. REINHARDT H. R. ROWE A. L. RICKLEY DR. T. K. SLOAT UNION ELECTRIC CO. COMMONWEALTH EDISON EDISON ELECTRIC INST. ALLIS CHALMERS MOLONEY McGRAW EDISON DOBLE ENGINEERING WESTINGHOUSE ELECTRIC ELECTRIC LIGHT a POWER ELECTRIC LIGHT & POWER ELECTRIC LIGHT a POWER NEMA NEMA NEMA DOBLE CLIENTS IEEE AND ASTM HONS 090631 GOVERNMENT REPRESENTATIVES SERVING BOTH COMMITTEES NAME D. M. CRABTREE DR. KENNETH J. HOOD CHARLES C. TRAVIS AARON J. WOLOSHIN DR. STANLEY P. WASIK DR. JOHN DEUTRITZ, JR. WM. R. NICHOLAS organization represented DEPARTMENT OF THE ARMY ENVIRONMENTAL PROTECTION AGENCY GENERAL SERVICES ADMINISTRATION OFFICE OF ENVIRONMENTAL AFFAIRS NATIONAL BUREAU OF STANDARDS RURAL ELECTRIFICATION ADMINISTRATION DIRECTOR ENVIRONMENTAL RESEARCH TENNESSEE VALLEY AUTHORITY mons 09063.J INDIVIDUALS SERVING BOTH COMMITTEES NAME COMPANY AL 0. HAUSER H. A, ALSENTZER C. W. HART JULES S. LAPIDES LOUIS E. WAGNER P. WILLIAMSON ELECTRICAL UTILITIES ROLLINS-PURLE, INC. ROLLINS-PURLEj INC. GILBERT ASSOCIATES, INC. CHEM-TROL POLLUTION SERVICE ROLLINS-PURLE, INC. MONS 090633 OTHER AGENCIES NAME ALEX RODIN THOMAS G00DFELL0W W. FLOYD-JONES T. C. MANN C. S. MORGAN B. WHITAKER B. A, CANHAM C. C, EDWARDS R. SMITH E. L. ARMSTRONG H. R. RICHMOND C. L. KLEIN ORGANIZATION REPRESENTED AMERICAN PUBLIC POWER ASSOC. ASSOC. AMERICAN RAILROADS ASSOC. OF EDISON ILLUMINATING COMPANIES AMERICAN AUTOMOBILE MFG. ASSOC. NATIONAL FIRE PROTECTION ASSOC. UNDERWRITERS LABORATORIES WATER POLLUTION CONTROL FEDERATION FOOD AND DRUG ADMINISTRATION DEPARTMENT OF INTERIOR WATER AND POWER DEVELOPMENT COMM. OF RECLAMATION BONNEVILLE POWER ADMINISTRATION WATER QUALITY AND RESEARCH MONS 090634 OBJECTIVES OF ANSI CI07 SOURCE OF TECHNICAL INFORMATION AND ADVICE FOR FEDERAL, STATE, LOCAL AUTHORITIES AND ALL OTHERS CONCERNED. ENCOURAGE DEVELOPMENT OF SUITABLE DISPOSAL FACILITIES AND KEEP ALL CONCERNED INFORMED. SERVE AS THE ADVISORY GROUP FOR U.S. PARTICIPATION IN INTERNATIONAL ORGANIZATIONS: CEE, IEC, SIGRE. MONS 090635 SCOPE OF ANSI CI07 PROCEDURES AND GUIDES FOR SAFE USE MAINTENANCE AND DISPOSAL OF ASKAREL AND ASKAREL-SOAKED MATERIALS USED IN ELECTRICAL EQUIPMENT. HONS 090636 USE AND DISPOSAL OF ASKAREL FLUID AND ASKAREL-SOAKED MATERIALS CAPACITOR GUIDELINES AR0CL0RJ0I6 SPECIFIES EXCLUSIVE USE OF ASTM D 2233 TYPE D ASKAREL FOR CAPACITORS. LIMITS HIGHER BOILING HOMOLOGS TO O.W BY MONSANTO METHOD T-02302. MINIMIZE EFFLUENT STREAM CONTAMINATION ISOLATE ALL EFFLUENT STREAMS, USE SUMPS, CARBON ABSORPTION, LIMESTONE BEDS AMD SOLVENT EXTRACTION TO REDUCE PCBs. CONSISTENT WITH EPA GOAL BELOW O.Ol PARTS PER BILLION IN LAKES AND RIVERS. HONS 090639 SMALL CAPACITORS CONTAINING LESS THAN 2 POUNDS OF ASKAREL NOT FITTED WITH PCB WARNING LABEL DISPOSED AS HERETOFORE, INCLUDES BALLAST AND MOTOR RUN TYPE UNITS 090640 LARGE CAPACITORS CONTAINING MORE THAN 2 POUNDS OF ASKAREL LABELED CAUTION THIS CAPACITOR CONTAINS PCB, TO AVOIDPOSSIBLE ENVIRONMENTAL CONTAMINATION, IT SHOULD BE DISPOSED OF ONLY IN SUPERVISED DRY LANDFILL AREAS MEETING STATE REQUIREMENTS OR IN INCINERATION FACILITIES DESIGNED FOR DISPOSAL OF PCBs. HONS 090641 SCRAP ASKAREL FLUID TO BE COMPLETELY DESTROYED BY INCINERATION AT LEAST 2,000F AND HCL GAS NEUTRALIZED. SCRAP SOLID WASTE BURY IN SUPERVISED DRY LANDFILL. MUMS 09064* TRANSFORMER ASKAREL CAUTION LABEL ON ALL SHIPPING CONTAINERS AND ON ALL TRANSFORMERS. SCRAP LIQUID TO BE DESTROYED BY HIGH TEMPERA TURE INCINERATION. BURNABLE SOLID WASTE TO BE INCINERATED. NON-BURNABLE SOLID WASTE, TO BE DRAINED OF PCBs, WASHED OR SOLVENT EXTRACTED AND WASTE LIQUIDS INCINERATED. DRAINED AND WASHED SOLIDS HANDLED AS NORMAL SCRAP. MQNS 090643 CAUTION LABEL FOR ASKAREL TRANSFORMERS THE INSULATING LIQUID IN THIS TRANSFORMER CONTAINS POLYCHLORINATED BIPHENYLS (PCBs). CARE SHOULD BE TAKEN TO PREVENT ENTRY INTO THE ENVIRONMENT. IN CASE OF MALFUNCTION OR LEAKS, CONSULT THE INSTRUCTION MANUAL OR THE MANUFACTURER. MONS 090644 SUMMARY By W. B. Papageorge In summary, our observations, admittedly limited, both from our laboratory data and from reports of other Investigators, lead us to believe with considerable confidence that PCBs do degrade In the environment. The complexity of the commercial mixtures has, however, hampered the determination of the varying rates of degradation of all the possible isomers. Monsanto's sales actions have definitely reduced the amount of PCBs that could be Introduced into the environment. In those applications in which the use of PCBs is considered essential, namely transformers and capacitors, further actions will assure strict environmental control on PCBs. In transformers the elimination of the use of Aroclor 1260, along with proper handling during manufacture, use and repair and proper disposal of waste fluid by high temperature Incineration, should result in acceptable control. For the capacitor application the development of Aroclor 1016, which satisfied all of the Industry's requirements relating to dielectric characteristics and handling properties, as well as having Underwriters Laboratory flre-reslstance approval, permits the continued use of PCBs In this Important hermeticallysealed application but with a fluid that has a significantly lower content of the slower degrading Isomers. The use of this material, accompanied by proper handling and disposal of the scrap fluid by high temperature incineration, represents, in our considered opinion, a significant step forward in our efforts to control the impact of PCBs on the environment. HONS 090645