Document 6rNG15Ld8L2X5N4dnJrXRQ96

f 1 fi. sS 5' 7 i1 & POLYCHLORINATED BIPHENYLS A PRESENTATION TO THE ONTARIO HYDRO ELECTRIC COMMISSION i CANADIAN INTERDEPARTMENTAL WORKING PARTY ON PCBs 4 4 CANADIAN CAPACITOR AND TRANSFORMER MANUFACTURERS November, 1972 by ! MONSANTO CANADA LIMITED Ii. t 1 4 r i DSW 342257 !I STLCOPCB4083757 I HISTORICAL SUMMARY OF PCB ENVIRONMENTAL ISSUE i" By kt W. B. Papageorge | it i Polychlorinated biphenyls have been commercially available for over 40 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 9 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 & suiting in observable effects. In each reported instance the f existing evidence indicated that improper Industrial hygiene prac i tices were being followed. i During the late 1950's and 1960's increased interest in the pres % ence and effects in the environment of chlorinated hydrocarbon i pesticides resulted in the development of sophisticated analytical methodologies with capabilities of detecting these substances at extremely low levels of concentration. 1 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, i 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 ol* the early reports indicated that the polychlorinated biphenyls being identified represented mixtures of the higher chlo rinated isomers. L At this point, Monsanto launched a multi-point program aimed at 1 obtaining more information about polychlorinated biphenyls and ! their presence and impact on the environment. This program included the following: \ 1. Develop analytical methodology j 2. Conduct biodegradation studies I> qsW342258 STLCOPCB4083758 I1 ? * i L s 1 I.. ! * i . ft i.. . j s5 1 1 l i 4 i 3i I l | t i ! $ i L 1 i r I J i -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 fully with industrial, governmental and academic laboratories Studies performed throughout the world have resulted in the following 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. 4. 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 DSW 342259 STLCOPCB4083759 -3- i. . _ the effect on humans of low-level, long-term exposure, Monsanto | voluntarily instituted a worldwide program for terminating the l sale of polychlorinated biphenyls to those uses in which control of escape to the environment was impractical. DSW 342260 r I. STLCOPCB4083760 #t,\ ASSESSMENT OF THE BIOLOGICAL PERSISTENCE OJ? POLYCHLORINATED BIPHENYLS % > By Dr. E. S. Tucker i. Presented by W. B.Papageorge f- i The research I'will review today will focus upon one aspect of Mon- ` santo's efforts to understand the environmental impact and behavior of our polychlorinated biphenyl or PCB products. This research was initiated early in 1969 after development of the necessary PCB analytical methodology and subsequent confirmation of i Dr. Soren Jensen's identification of PCB residues in fish and birds 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 homologs with less than 5 chlorine atoms per molecule had been manufactured and used over the years. Now, before discussing our biological studies, I vrould like to * review for you the gross homolog composition of our Aroclor products ii* and then in a very brief fashion, try and illustrate to you the complexity of these materials and hence the complexity of the problem. In the first slide (#1) , is shown the most recent data on the weight % composition of four of our Aroclor products as a function of each I 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 PCE 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, I and so on. Aroclor 1016 is a special case in that while it contains about 41% chlorine by weight, its penta, hexa, and heptachloro biphenyl content has been significantly reduced with respect to Aroclor 1242, a product produced by direct chlorination, containing 42% by weight 1 chlorine. Please note that the penta, hexa, and heptach.loro biphenyl f homologs in Aroclor 1016 have been reduced by factors of about 8, 10, and 10, respectively, with reference to Aroclor 1242. As yon can also see, the chief constituents of Aroclor 1221 are the mono- and dichioro biphenyls, while Aroclor 1016 and Aroclor 1242 contain predominantly di-, tri-, and tetrachloro biphenyls, and f Aroclor 1254, tetra, penta, and hexachloro biphenyls. DSW342261 STLCOPCB4083761 ! -2- if f As I indicated earlier, this table represents our most recent I efforts at determining the homolog distribution of our PCB products and as such a number of you may have seen estimations of the homolog ! content of these products which are significantly different. The ! analytical methodology used is currently in a very dynamic state and our understanding of the contents of these products increases as t the methodology is improved. At this point in time, we regard these j. numbers as the most accurate ones currently available. In the next slide (#2) are shown examples of low resolution - packed f column electron capture chromatograms of Aroclor 1221, Aroclor 1242, 1 Aroclor 1254, and Aroclor 1260. This is what these products look like to a residue analyst using the most commonly employed detection i system. From these chromatograms, it can be readily seen that we are dealing t with multi-component products, which of course, increases the comi 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 i found in wildlife are most similar to Aroclor 1254 and Aroclor 1260 chromatograms. ' . 1 The next slide (#3) demonstrates that in reality, these materials are | J * t ^ j * j i even more complex than is generally realized. In the upper right portion of this slide is again shown a low resolution electron capture gas chromatogram of /^rcclor 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.O.T. column, If one carefully inspects this chromatogram,, our simple 1.5 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 (#5). For discussion purposes, they can be conveniently divided into two categories: "Primary Bacterial f 4 Degradation Studies", an area in which research on PCBs is just i beginning, and "Residue Accumulation Studies". Most of our bacterial degradation work has been centered around the fairly well known semi- I continuous activated sludge degradation test. i 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 ir eventually analyzed for PCB residues. ? 4 The prime objective of these studies is given on Slide #6. \ DSW 342262 i STLCOPCB4083762 r Slide #7. The semi-continuous activated sludge test procedure we 1 used to evaluate the primary bacterial degradation rates of the * Aroclor. products is the test method recommended by the Soap and r- Detergents Association for the evaluation of the biodegradability } of linear alkyl benzene sulfonate type surfactants [JAOCS 42., 986 * (1965) & 46, 432 (1969)]. I Primary. Biodegradation - Minimum alternation of the I 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 1 aeration, auxiliary stirring, a siphon for periodic removal of the supernatant and a septum for introduction of the test material. .^ 1 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. j The mechanical cycle employed is shown in the next slide (#9). | Each cycle is initiated by the addition of the synthetic sewage and * 1 mg of the PCB product being tested. 1 Since the PGBs 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 I sludge is obtained. I .. After about one hour of aeration an aliquot of the mixed liquor is i 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 5 analysis. At this point, the aeration is stopped and the sludge j allowed to settle, the sludge volume and pH are then checked to 5 insure that the unit is operating satisfactorily. Two-thirds of the supernatant is withdrawn and replaced with tap water; aeration is 1 ' then resumed. The cycle is re-initiated by the addition of the i synthetic 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 1 each cycle. Degradation testing of the Aroclor products shown in the next slide I (#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 > DSW 342263 STLCOPCB4083763 .\ f !i. -4- ri rates for b.iphenjl, /vroclor 1221, MCS 1043, a research material containing 30% by weight chlorine, Aroclor 1016 (41% chlorine), r' Aroclor 1242, and Aroclor 1254 versus the weight per cent chlorine present in each. The actual mean per cent degradation rates and 95% 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 chlorination 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. I We have also used this technique to study p,p'-DDT and have at this i 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 t 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 dichloro 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). 1 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. i i i.. .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 L 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 ^125, 1250, and 12,500 ppm. Next is shown the actual average level I 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 ^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 f excreted and/or metabolized. J S , DSW 342264 STLCOPCB4083764 -.5- On the right hand side of this slide is shown the homolog 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 ri i4 diet. The numbers across the top simply refer to the number of chlorine atoms per biphenyl molecule. As you can see, Aroclor 1242 contains dominant amounts of the di- through pentachloro- biphenyls and a minor amount of hexachlorobiphenyl. After 90 i days of exposure the dichlorobiphenyl was no longer observable and the dominant components were the tiri- through pentachloro biphenyl homologs. After 30 days on a PCB free recovery diet, the'hexaf chloro biphenyl is now a dominant component because of continued 1 excretion and/or metabolism of the lower chlorinated homologs. In the next slide (#16) are shown the results for the 90 day oral i 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 shown the actual levels found in the tissues after 90 days of continuous exposure and 30 days on a i . PCB free diet. In this instance, ^70-72% of the Aroclor 1254 s ingested was directly excreted and/or metabolized and after 30 $ days on a PCB free diet, M5% of the residues retained were, I excreted and/or metabolized. i The homolog distribution of the product and residues is shown on a 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 hexachloro biphenyls. The residue after 3 90 days of exposure did not contain detectable amounts of the tri- chloro biphenyls and the tetrachloro biphenyls were no longer a dominant component. The dominant homologs were penta- and hexachloro 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. i 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 I. consumed was directly excreted and/or metabolized and after 30 days on a PCB free diet ^40% of the residues retained were excreted 1*i and/or metabolized. I . As shown on the right, Tiroclor 1260 contains dominant amounts of penta-, hexa-, and heptachloro biphenyls and a minor amount of I octachloro biphenyl. The residues after 90 days of exposure and 30 i 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 day oral, 2 year chronic oral and a 3 generation rat reproduction exposure study with f Aroclor 1242, Aroclor 1254, and Aroclor 1260 and a 90 day subacute DSW 342265 STLCOPCB4083765 t ` * - r . ^ . ' "r . ' MA ! 6- i. oral exposure of Aroclor 1221. Approximately 1400 animals were i used in these exposure studios from which about 400 muscle, liver, L and fat samples were collected. Two hundred of these samples were analyzed for PCB residues. ' i i In the next slide (#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 4 `v*800, 8000, 80,000 ppm, respectively. The actual residues found in L 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 amounte of i 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. l 5 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 i 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 i demonstrates that 9.5-98% 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. St The next slide (#21) shows the the results for the two year exposure f* of Aroclor 1260 in albino rats. Again, the exposure and theoretical i- residue levels are the same and the residues found in the tissues after 3, 12, and 24 months of exposure are .shown. In this case i 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. T S In order to demonstrate the relationship between residue storage l t levels and the degree of chlorination of the product fed (slide #22). i I have plotted the average ppm PCB found in the lipid vs the weight per cent chlorine in the product fed. These data were taken from I our 90 day subacute albino rat studies with Aroclor 1221, Aroclor I 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 I relationship between the higher homolog content of an Aroclor product and the tissue storage level. DSW 342266 \ STLCOPCB4083766 fV 5 -7- | Our beagle dog studies (Slide #23) have consisted of a two year * chronic exposure of Aroclor 1242, Aroclor 1254, and Aroclor 1260 and a SO day subacute study of Aroclor 1221. In these studies, 108 I beagle dogs were used, resulting in the collection of 263 samples, i and the analyses of 146 for PCB residues. ! The next slide (#24) shows the results of one two year-study of f Aroclor 1242 at exposure levels of -1, 10, and 100 ppm. In this study, the theoretical residue levels are ^500, 5000, and-50,000 ppm I respectively. We have also shown on this slide the residue levels I 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 99.6% of the Aroclor 1242 consumed and after 60 days on l PCB free diets, 50-60% of PCB residue retained after two years of 3 exposure was excreted and/or metabolized. \ Aroclor 1242 contains dominant amounts of the di-, tri-, tetra-, and I pentachloro homologs and a minor amount of the hexa- homolog. The residue found after two years of exposure contained no detectable 1 levels of the dichloro homologs and dominant levels of the tri-, I tetra-, hepta-, and octachioro biphenyls. The pentachloro homolog, although dominant in the product fed, was not a dominant component of I 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-, t hepta-, and octschloro biphenyls. The trend toward excretion and/ ! or metabolism of the lower chlorinated homologs continued to the s extent that after 60 days on the recovery diet the hexachloro biphenyl . was no longer a dominant component, and the hepta- and octacnloro biI phenyls became the dominant constituents in the residue. 1- In the next slide (#25) are 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 i on PCB free recovery diets are again shown. i' . 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 J 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 I penta-, and hexachloro biphenyls remained dominant components, and 1 the heptachloro .biphenyls became dominant constituents. \. ] f j I 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 PC3 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. DSW 342267 STLCOPCB4083767 -8- The next slide (#26) shows the results for the two year oral exposure residue study of Aroclor 1260 in beagle dogs. 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 ^13% of the retained residues were excreted and/or metabolized. j . . i 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 * hexachloro 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 H diet, the hexachloro biphenyls are no longer dominant components of 1 the residue and it is now mainly the hepta- and octachloro biphenyls. ; l s j s | *' 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, s 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 i 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 I were, and are, still in better positions to carry out and evaluate I these types of studies. j We have done some very preliminary 21 day dynamic exposures of catI fish and bluegill fingerlings to some of our Aroclor products and it generally supports the conclusions which can be drawn from f literature data. ! The general conclusions which we draw from these residue studies are shown in the next three slides. jl* . i qsW 342268 . - STLCOPCB4083768 / m-.i ! Slide #29 - Build-Up - Conclusions y- Slide #30. - Fall-Off - Conclusions I 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. I E. S. Tucker I i I ss. i DSW 342289 ! 1 STLCOPCB4083769 I 5 i. Of CO I-- o _l CJ LO - LO o CJ o o Of V V < L 0> 1-- CO CO CO CM *J- CM a Zf o f z> iQ O I/O of o I-- CJ O' of i t o CL __1 cm O *d- O CM Of r-- ov co cr> LO 00 i-- 'd" CM O V o LU Of c Of o CJ <c CO LLl OX LU Of <c CO 0- CL oOf CO _l CO O CD CoJ Io-- o o o I/O 5 O Qi Oaf: I-- V CM Lf> CM V CO < II LJJ CJ CO Ixl O 5^ I-- < CO >- Zf CO oo. --~co o V 3: LU o of ^ Of LU o in_i -- 3 ------CO o(J CM ^2 O ovI ^ O CM Ctf r-- i-- CM uo co CM I-- _l ZO i c LU s CL CJ O 3= Of O Ixl >O. CQ * >- i' 1O CL CO i: i i o o. o s: I--I CO O f-- CM CO UO CO 00 o CJ l =fc= i i i DSW 342270 ? t STLCOPCB4083770 I i ? *s i Electron Capture Gas Chromatograms Elution Time (minutes) ? DSW 342271 i STLCOPCB4083771 CO <a> E a> E o LlI STLCOPCB4083772 I f ! I PCB PRODUCTS ARE NOT A SINGLE ENTITY, BUT COMPLEX MULTI i COMPONENT MIXTURES A 9 PCB RESIDUES FOUND IN WILD LIFE ARE DOMINANTLY PENTA-, HEXA-, HEPTA-, AND OCTACHLORO BIPHENYLS i i O PCB RESIDUE ARE MOST SIMILAR TO AROCLOR 1254 AND AROCLOR 1260 PRODUCTS l5 i ? ! DSW 342273 STLCOPCB4083773 { i l. i i. i PRIMARY BACTERIAL DEGRADATION STUDIES SEMI-CONTINUOUS ACTIVATED SLUDGE DEGRADATION RESIDUE ACCUMULATION STUDIES FISH - CATFISH AND BLUEGILLS BIRDS - WHITE LEGHORN CHICKENS e MAMMALS - ALBINO RATS AND BEAGLE DOGS f iI 1 DSW 342274 | i I STLCOPCB4083774 i | i t l i I. , i |I -A--S--S--E--S---S--M--E---N--T----O---F----T--H--E-----P---E--R--S--I-S---T--E--N--C---E----O---F' POLYCHLORINATED BIPHENYLS I IN BIOLOGICAL SYSTEMS ii I S' i I 4 1 i s f' I 5 DSW 342275 1 i *f STLCOPCB4083775 ! Ii k i i k I a 1 4 ARQCLQR SEMI-CONTINUOUS ACTIVATED SLUDGE PRIMARY DEGRADATION STUDIES 1t 9, I f f DSW 342276 Sf STLCOPCB4083776 1 Semi-Continuous Activated Sludge Test Unit t i i f i i Stirrer i i i t B DSW 342277 I' I STLCOPCB4083777 i MECHANICAL CYCLE r I SYNTHETICSEWAGE AND | ARQCLOR (Img) ADDED i ? i fi i DSW 342278 < STLCOPCB4083778 Semi-Continuous Activated Sludge Degradation of Polychlorinated Biphenyl's Aroclor 1254 DSW 342279 | i STLCOPCB4083779 !. ' Semi-Continuous Activated Sludge Degradation I of Arocior 1242 Elution Time (minutes) I OS\N 342280 f 1 STLCOPCB4083780 BACTERIAL DEGRADATION STUDIES CONCLUSIONS RATE OF PRIMARY DEGRADATION INCREASES AS THE DEGREE OF CHLORINATION OF THE AROCLOR PRODUCT DECREASES I BI PHENYL>AROCLOR 1221>MCS 1043 >AR0CL0R 1016>AR0CL0R 1242>AR0CL0R 1254 I *t, e BIPHENYL, MONO-, DI-, TRI-, AND TETRACHLORO BIPHENYL HOMOLOGS UNDERGO PRIMARY BACTERIAL DEGRADATION v3 i :m 1, DSW 342281 i STLCOPCB4083781 s it 1 f I. i1 i % \ J 1 AROCLOR RESIDUE STUDIES i& ii I 1 i i i i 0S\N i I ! i STLCOPCB4083782 tIl . . r i ! WHITE LEGHORN CHICKEN STUDIES i. 90 DAY ORAL AROCLOR 1242 f PRODUCTS STUDIED AROCLOR 1254 ** AROCLOR 1260 AROCLOR 1242 l i NUMBER ) OF ) CHICKENS) FEMALE MALE. 200 40 80 16 % MUSCLE ; NUMBER) LIVER OF ) FAT 1 SAMPLES) EGGS i CHICKS 40 40 40 ^250 30 8 8 8 0.60 10 i 5 | NUMBER) OF ) SAMPLES) ANALYZED) MUSCLE LIVER FAT EGGS CHICKS 14 5 12 4 18 5 25 8 11 10 i TOTAL SAMPLES COLLECTED 400 ? TOTAL ANALYZED 80 121 32 ORAL EXPOSURE CARRIED OUT BY INDUSTRIAL BIO-TEST LABORATORIES, INC. NORTHBROOK, ILLINOIS ~i a*. I r i 1 .I STLCOPCB4083783 i5 I II i *- a\ i r 04 II 04 CO 2 i ZD O' LU CO $ l--i Q VO VO VO VO O _J o GI--O *--l a in in in o o oo co o _i cf *3- e o $ O' o s in < o < CO co co co a QC QC LU GO Z LU u. O O CM CM c GO o t-- go o; III >--i LU ol I O' H- h- < 3 >- LU o O o> CM CM o O LU _J LU cc i o' LU C CD 3 I GO VO co CD ^ h-- UJ CO I-- LU O CM o vo c- LU Q s => a. GO --I C ui ol VO co Z _I LU CM sa;. Cl VO OO z OZD' er cq a. use CM O. Q- O CO CO LU o: ? LU LU 3 CM r-- . LU >e o o CO >>- < LU O I-- CD DC Ol-- <o: Ho- LU LU Vj_ > _l - LU +- * ' R E S ID U E EXPOSUR R E S ID U E RECOVER I ce a i _l LU <c > o Ul GO Q LU O --I ZC LU f-- OC ** | DSW 342284 i [ i STLCOPCB4083784 I oi i CD i 1 i sr i m Sii co 00 O 1i N O' LUe CO lO VO to to o to H Oo i lO LO in in o $ o C o ** i o in < o CO co I IQ 2= i< LU C/1 <C z lu zc L . ccl C* CM oO i--( ZD I-- i 1 < co -- in oc O LU KH lu cc t- t- i o< >- i1 < LU _I LU cc _j a: LU C to o LU i ____ | o T1 O' CM CD O 3 o o O CD O LO 00 in I CO SC i CM CO LU O <C CO LU m co ZZ> 0.0. o O CM C/1 I--l ` O- o VO vo 10 Z _J IU LU f j Q CM CO r- o OZ a: =3 O. t--I t-- a. ca a. CO 00 c_i z: c CM CO r-- CL CL. CL O _J z CO Z i LU C LU o -- cs a: X O I-- LU t-- Cl O LU LU LU R E S ID U E EXPOSUR R E S ID U E DAY RECOVER 3 t-t < LU * i CM o 4- i\ to < oo CO o. f--I LU >- X h- LU V i l = is. LU ZD cc a o *- UJ v> cc lu =C LU O -J i- cc +- DSW 342285 STLCOPCB4083785 : M;\ f i t is ta O I cn 1 i 1 oi CO CO co co l VO COCM r>. CO **-- '-- ' ^- cn LU Q Io L-- CO co LO LO *-- -- o* I CJ Q in LO LO LO o -J CO 3 o O 111 o I I o o tn oo co 11 az cnIj < of 2 lu to z uj <c x k CM i11 C to o o4 Ll. l-- co o; LU t--i LU a; l-- i- LU _J LU X _J DC >- Cl LU o o 1-- to co o a. o !-- a. CM O CM <-- o' ' CM r~ - CTl O CTl * LO o LO oo LO CO CM CM CO CM LU <C C3 3 i to o^ LU O <C s: lu zd O- Ca ul I--I Z _1 LU o ac O Z a. LO LO LO r-- CM LO CM CO o. o z: <c CL.' a o o. 9z CO -- LU t cn ! I: v I I ORAL LEVE T H E O R E T IC A R E S ID U E R E S ID U E RECOVER LU OC ` CO o o. X LU _l LU LU 3 CM LU Ll: DC a to o CO CL UJ X QC LU >< O o CO >- <C UJ (-- O' O Cf V-- f- ac o LU LU t--i c 4- * LU I DSW 342286 I I STLCOPCB4083786 ! i i CO i < C CM lO 00 II II CD 1^ CO II II i S iO in I CD = LU tO =C z lu n: CM I CM ? o' 2 I oc o LU I J-- c u LU QC o Z CO O IT) O CO i oN LO <t o o o CO DC O I-- CM to DC C X 00 c < u to CO LU CL o co t-*. co Of Q_ co cm co in LU f Ll. < LU ooo CC o >- Q_ O. co co cn CM a. c Oo CD >- 5 co Q C LU H- CD CD t CD CC h I-- CC c_> z CD O o s: z: s: CM !* LU LU U_ > _J --t C LU +- -K '' * c CO i-- CM Io >LU * LU * LU i ro caiu r3 LU DC CD CD LU Q LU CC ZD ZD o: o o --< Q LO --i O *C-Di OtO CD LO O Ql I > LU to CO Ql to Q- LO Ql. 5 Q LU SC LU LU X LU X LU X t O --I I-- Oi CC LU o; lu CC LU CO * * I LU 5 ce DSW 342287 { { STLCOPCB4083787 I CO I-- i i < O' L o cri i I 1 1 oo I 1 1 ! o CD N CO ____ <1 VO lO iO \o 10 -- 5-- /> .__,, Ul LO IT) to at -- "-- '-- ,__,, irt in O '-- Ii a. OJ X oo oo 1 1 1 s 111 < ex at 111 O os I _j u 111 1& uZ o o oo cn CO I oc o' X u < o 1". r*-. o oo vo oo o ,--. o r-- oo CO 10 1 I at < U_ u< CO o r-~ <X in o. o oo <T> 00 in t-- o i-- oo o >- a. CO f I o a. oo CO CM 5 r-- o r-- CJ 00 o CO L LU 3Z 31 OC 1-- h- 1-- Z Z zoo UJ o z: z: at z: _i CSJ oo CO CM oo o. 1--< *UJ A UJ LLi t3 i: Q ! i CO LU CX 4- * - Ii O RAL EX LEVEL THEORET R E S ID U E R E S ID U E EXPOSUR R E S ID U E EXPOSUR R E S ID U E EXPQSUR sail DSW 342288 STLCOPCB4083788 r iii. ?? \ CD < O' ? O O '. i OL f' CD i i CO CO CO oo < rN. ft CO -- .^ ,,--, ae O D >o to o CM a. X Q VO tt--o o Lf> to o _J o VO w LO ' t VO --" VO VO *-- ,___* . . . .____ in in in '-- ii o in i OL < o ac CO o zr i i i LU CO <X. O ec _J O cv, <C 00 i i i I-- to DC Vu DC I-- I-- oZ ? O' o DC . i i LU I LU DC -1 CSC LU C CO 3 <X u CO o cn 00 o 1-- cx> CO o CO cn o CO I o LU O CO ^ <C pN o CM S M uj IL. O DC <LU >- i/i CO CO o r^~ o r-* a. o CO CO r^ o r-- z: o 00 - *" CM LO O Q. CL. to --* Z _l LU O OC O ZO >- o! i i Q5 a. a. CO CO in o\ r-- o r-- co in co a. c_> s; a. cl. o o. h- CO ZJZ ni 3C H h- e LU o I-- CO Of O <C I-- co UJ i UJ Of co < o c_> Q_ i--i o z: co `LU o s: CJ i-- 111 o s: *3" CM * JjJ V- DC O 1--1 llJ 4- * --' R E S ID U E EXPOSUR R E S ID U E EXPOSUR 9 i i CO X LU _i __I LU > I-- LU LU ZD esc o O'--* LU to LU DC ID ZD o to 'O to O. LU i o' DC LU 0--1 ZH LU 1-- DC +- LUX CSCLU * * i 0SH/^289 if i STLCOPCB4083789 Average ppm PCB in Lipid (Muscle, Fat, Liver) f i i CO o o Q 1i 1I LU o> 1 i I 1 _l o 00 1 00 CO 00 i< v-- ,___, LU I! CD LU Of 3 I to OJ o Q. 1 r--. -- r>. w VO VO VO vo *-- LO in ----' _____ ,--. in i in i ?1 OJ X LU ------. __ ,, _____ CO CO t i CM 1 i i 11 i i t in C\1 o vo VO CO r-- r-- m VO vo CO 00 r-- in CL. I 1I5, Cl. cr> CM in CO o f 5. CO S i LU Q i CO I LU O' LU CC to o a. x _J LU a: > o: lu o _i DC >- ><C c c LU o o >o CM CO *>- *>- tT H E O R E T IC A L R E S ID U E *R E S ID U E EXPOSUR *R E S ID U E RECOVER *R E S ID U E 6 0 RECOVER DSW 342291 STLCOPCB4083791 I i! CO J 4 o oi 1ii Q I ii LU cn . i i _] | o _ __ oo i oo 00 00 -- < LU r-s. r-*. *-* ,__ ,, p>. '-- CD4 CO I--( - ____ oc co CO ^. CO CO ,___ CO i Hto LU I--t oc a LO '-- -- .'-- ___ _ in in LO -- '--1 in z> CD V) O ___ _ O --I i1i i4 in a. o s: Xo -- CNJ UJ CO 00 i 1 i | C < oc CM i1i of O %u ii1i oz oi o oc 1 X. in CM cn 00 o co CO o 00 o 00 r-- r-- t-- < u (/) CO in Q o CO O *3- o a. o 00 CO CM CM 1 Ll. < UJ r-- in oi O >- o_ a. cn P-. m * r-- r-- i5 in I% Q OC >~ >- c C' t I CO i LU !3 Q CO LU O' I +- * . * * ! i ORAL EXPOSURE LEVEL T H E O R E T IC A L R E S ID U E R E S ID U E , 2 YE EXPOSURE R E S ID U E , 30 D RECOVERY R E S ID U E , 6 0 D RECOVERY o DSW 342292 STLCOPCB4083792 L CO o o Q LU O < LU CD Of 3 to o O a. X O CJ < ee. o OL O _J o z 0 oc o a: < 1 u Of < LL oO $ CO LU O CO LU o' 111 CTV 00 CD l--l O' lO Hl/O- t--i Q CD O O DC CO CM o o 10 CO o o. O- 10 cc =in> o a. x _1 LU < D CC LU O _l 00 10 in in 10 00 in io oo m CT> in c o M I-- LU LU =3 oc a o *-- hi cn DC LU I-- DC 1 '___ 00 -- IX 10 1 1 1 1 1 00 00 00 CO 10 00 ac LU >CM LU LU OC ZD ZD o in --i o in cl uj X OC LU * 11 ___ . 00 00 -- __. (X I*'* ---- 10 \o 11 11 11 1 11 OO rx 10 CO CO CO 0 10 10 in rx rx >c a 0 CO >LU DC CD LU i--i >O in O LU LU OC OC * >< 0 O 10 m' lu ar CD lu a> H O CO CD IU LU OC DC * <I--' o o LU CO z lu *-- CD C in l-- in LU L-I OC h- 10 OC _J LU CD Q- in i--i Z --I o oz IH CO o 2: 0- O. Ol --I C LU 1-- CD o t I-- oc IU U. > -* <c +- * O' CD m < UJ OC CD J-- Q<c CD o oc CD IU DSW 342293 f i STLCOPCB4083793 Average ppm PCB in Lipid (Muscle,Fat,Liver) | I I Two Year Chronic Oral Exposure 1 in Beagle Dogs ! (at The I ppm Feeding Level) STLCOPCB4083794 I i % i i t. ^ EXPOSURE EXPOSURE CONCENTRATION LEVEL (PPM) PERIOD FACTOR* WHITE ! LEGHORN 1.0 (FEED) 12 WEEKS ! CHICKENS | ALBINO RATS 1.0 (FEED) 2 YEARS 20 9 . BEAGLE DOGS 1.0 (FEED) 2 YEARS I. i 2 CONCENTRATION FACTORS DO NOT TAKE INTO ACCOUNT EXPOSURE PERIODS 1 3 S Ii 1 r f k f i I i DSW 342295 STLCOPCB4083795 CONCLUSIONS * RESIDUE FALL-OFF e 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: AROCLOR 1242>AR0CL0R 1254 >AROCLOR 1260 CHICKENS: AROCLOR 1242>AR0CL0R 1254>AR0CL0R 1260 i iI DSW 342296 i STLCOPCB4083796 i *i i j WHAT HAPPENS TO PCBs IN THE ENVIRONMENT? By Dr. R. H. Munch Vs * Presented by W. B. Papageorge I I Because they can be detected by the same analytical methods, and ; because some suspect that they may have similar biological effects i to DDT, polychlorinated biphenyls in the environment (PCBs) 5 have become a cause of concern. It is, therefore, important to , present data to show that PCBs do disappear from the environment. i 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 5 homologs containing from one to ten atoms of chlorine per biphenyl j 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 i produced, some process must be operating in the environment to 1 remove different homologs at different rates. Monsanto, the . major U.S. producer, recently released data- on its sales, of the i various commercial grades of PCB for the years 1957-72. Rest- I of-world sales by other producers and production before 1957 8 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 I in "environmentally aged samples." Analysts experienced in this field generally agree that material recovered from such samples * is similar to Aroclor 1254 or 1260, the Monsantotrade name for \ mixtures of PCBs with chlorine contents corresponding to an average of five and six chlorine atoms per biphenyl molecule respectively f (1-8). In order to present a conservative comparison and because i most analysts cite Aroclor 1254, we shall use the homolog content * of that material in our comparison. I i DSW 342297 5 STLCOPCB4083797 f !t 1 i y- The homolog contents of the material produced in the U. S. from 1957 to 1971 and that of Aroclor 1254 are tabulated be-low: 'i Homolog 0 12. 34 5 6 7 8 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 ! 4.1 4.1 <4 5 1 21 48 23 6 ND 1 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 f of the relative rates of loss. However, it would appear that the i homologs containing less than four chlorine atoms may be degraded at rates approximately thirty times those for the five and six I chlorine homologs. Laboratory data which we hope to publish later j show that the rate of bacterial degradation is an inverse function of the chlorine content for PCBs and might, therefore, be one of * the degradative processes responsible for the relative decrease I in the lower homologs. I DSW 342298 I STLCOPCB4083798 1) L. M. Reynolds, Pesticide Residue Analysis in the Presence of Polychlorinated Biphenyls Residue Reviews 34, 27, 32, 4l, 42, 44 (1971). 2) R. W. . Risebrough, P. Reiche and H. S. Scott - Current Progress in the Determination of the Polychlorinate.d Biphenyls - Bulletin of Environmental Contamination & Toxicology 4^, 192, 199 (i97 ). 3) G. E. Bagley, W. L. Reichel and E. Cromartie - Identifi cation of Polychlorinated Biphenyls in Two Bald Eagles by Combined Gas-Liquid Chromatography-Mass Spectrometry Journal of the AGAC 53, 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 53, 763, 765 (1970). 6) Ian Prestt, D. J. Jeffreries and N. W. Moore - Polychlori nated Biphenyls in Wild Birds in Britain and Their Arian Toxicity - Environmental Pollution 1, 3* 15 (1970). 7) V. Zitko - Polychlorinated Biphenyls and Organochlorine Pesticides in Some Freshwater and Marine Pishes - Bulletin of Environmental Contamination & Toxicology 6, 464, 467 (1971). " 8) PCBs & The Environment - Interdepartmental Task Force on PCBs - Washington May, 1972 - C0M-72-10419 - Table 6, P. 93. DSW 342299 S STLCOPCB4083799 f i lI l I :' i WHAT HAPPENS TO PCBs IN THE ENVIRONMENT? | 1. WE CANNOT DETERMINE IF PCBs DEGRADE IN THE ENVIRONMENT FROM THE TOTAL CON- 5 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 S BE USED TO GAIN INSIGHT AS TO WHAT IS 1 HAPPENING IN THE ENVIRONMENT. I I { s 2,/V^00 OSNN j 1 STLCOPCB4083800 i s l l HOW DO WE GET THE DATA NEEDED? 1. PRODUCTION FIGURES FOR ALL MONSANTO .PCB PRODUCTS AND HOMOLOG CONTENT OF EACH PRODUCT ARE AVAILABLE FOR 1957 71. WE USE THESE DATA TO CALCULATE HOMOLOG RATIOS FOR 1957-71 PRODUCTION. I 2. EUROPEAN PRODUCERS MAKE SIMILAR 8 PRODUCTS IN ABOUT THE SAME RATIOS . AS MONSANTO. 3. PRODUCTION BEFORE '57 WOULD NOT AFFECT THE FIGURES GREATLY SINCE PRODUCT RATIOS WERE SIMILAR AND PRODUCTION SMALLER. i 4. ANALYSTS GENERALLY AGREE THAT MATERIAL FOUND IN "AGED ENVIRONMENT AL SAMPLES" IS SIMILAR TO AROCLOR 1254 OR IN RARE CASES EVEN TO f AROCLOR'1 260. ! %I ! i ! JI DSW 342301 i i f STLCOPCB4083801 ? I fW,< HARVEY, MIKLAS AND BOWEN OF I WOODS HOLE OCEANOGRAPHIC INSTITUTE AROCLOR 1254 VS ENVIRONMENTAL MATERIAL CURVES ?' i ft DSW 342302 i STLCOPCB4083802 Q __ 1 to O lU to __l CL. i/l s: CQ O to O- oc <c o lLu z LU to s OZ --i O h- qc i-- CC > z CD LU O _l Q O LU S CD o rn Z LU t--t Lu rD Oo u. o LlJ to to 1-1 o cc rc <c t- D_ s oc o -- co CM to m CD O _J o s: o DC CO CM in o f-- to r-- cn i-- CM cn CO CM CO CO Q to CO CM CO i-- CM in V CO LU r-- < to I to fs* tr> Q O _J O'd- O LD o: cm cr *- :M DSW 342303 STLCOPCB4083803 ? ff ' l df f5 ll f3 I f i ' CONCLUSIONS 1. THERE ARE MARKED 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. DSW 342304 STLCOPCB4083804 Ij s ! j I tti r 1 f 2t CD O CL CM QC t U- LU Q_ =C t O Q_ >- l CO D_ cO_> LU CO ? CO CO __I c_> --4 CO PCDD _ _J __ 1 >- < DC <=C cd DCOC oc CD <DCC- DC CD >- LU DC CO LU sc LU d: ct--uH PD 1. <CCD O *C>O~ LU ri---M\ ci di LU 1C--O s: SCOI LU 1-- Ct--Di DC 1-- CD CO s: D<CC t-- __ 1 t-=-c1 QC 1-- CD =C LU <c h- CD <C 2I CL1r O < CL LU l-- LU CO LU CO 1-- CO >CO CO <c 1 CL. > __ | CD CO >CO CD __ 1 L> Ui Q 1-- <c LU DC CD Q s----:i : CLUO QLU_ CD ___1 CD CD o i--i 2i--Ct QC _DC_DC1 CO LU __ 1 CD >- 1 <COc __ 1 --CQVD_ ,1 --^os 1v--_'1 CM O "0 I< .1 ? * DSW 342305 ! STLCOPCB4083805 MONSANTO PCB SALES IN CANADA 1965 66 r: i3 i. o QZ CM LU r^ M OJ DSW 342306 i STLCOPCB4083806 ! I !' 4 i tf 'i i i i CO __1 LU z o CsC =c CD - 11 O ? 1-- h-- O UJ iC--Di CO C1--D* CO Ct D i < CD QC __1 1-- ZD __1 QC CD LL_ CD5 1 O o 3: L__U1 CO Li--Ui LU CD __1 C--Dt QC 1-- CD CL a: f-- oo Q_ LU __1 C* O LU CD CD Li--Ui DD CD O CD X Q_ LU CD Q_ LJ- CO Li_ LU CD __1 < CU \-- Ci--D--i zd I-- O <c sr 3 CD i--i CD =a: CO QC | COi 1 LU Ci Di OO __1 OC CD LU LU > CD <=c Cl. zc Q_ CD CH--D1 1! Cl_ *=C CD CQ | *e I ! *$I f; DSW 342307 f jI | STLCOPCB4083807 MONSANTO PCB SALES <a: Q co =c UJ 2: --I <=c =C CD 6s? OO CD 1--I CD 1--I CD co 00 2: CD t--1 1-- <c *=c CD CD 1--1 1--1 oc ___ 1 LU Q_ g~ D_ <=c <C nr CD 1-- 1--4 oc QZ O 1-- 2: CD LU ___ 1 LU m OJ <C Q O LA =r CD m 2: a a - a CO ZD r\ O 00 rA O tA cr CM rA ~> Q. L_ O CO 2 O --1 <c _l Q --I =r =r CO 0 1--1 CM =r rA rA 51 _ - - <c fA rA rA CD 2 t-H OO LU CD CD I--1 CM CO r\ r^ CD 1--1 CD 1--1 cn 1--l 1C--D1 ! | |f ' 1 i ......... DSW 342308 STLCOPCB4083808 I I i i I | * CO 6^ >- CD ? <E i--I <C 4 CO I| LU < GO <C CD <=c CD sc =c CD LU cd <C st--:t <=C (CD CO <C LU CO *=c CD CD 0 <c CD --1 --cd <i--=c SC 11 cd oo 1-- CD CO o <--i ^ cd o CD 1-- LU LU CO CL 111 i--i --J <C re I s: co <C CD ___i LU CD 1--1 I--1 CD QC Ci Dt O CT CD 1 LU ce f-- cr z s: 1-- I-- oc o CD cd sc CD <=C sc re CD LU ___1 ___1 I or i-- cd or LU <c h---( y-- LL_ CD CD CD 1-- CO CO LU &-S --1 ND <C co or LU <c __1 CD <c i--< CO Cd f LU CD Q LU o 2: 1-- re 1-- s: cd sc =c <c re CO LU CO i-- I :s: cd CD LU Cd o CD 21 ^ 21 | i ? | oS\M 342309 STLCOPCB4083809 i i% - i, i. i * f- >O Li_ o O Q_ CJ LU O Ll_ I Ll_ LU LU CO < CL GO Q o Q_ GO . PQ NpQt CD Q_ pq NQ Lt_U> >- PQ PQ LU =C OP CD CO QP L__UI LU S <C <c CO PQ CD OP Q_ CD CD OO CD >-- PQ <C PQ <C <c CD CO e CD i r ! j DSW 342310 STLCOPCB4083810 :1 : Mil PCB CHANGES IN DIELECTRICS By Dr. C. Paton L I respectfully submit we have achieved a significant reduction in PCB output by our actions. Turning to the second phase of r our actions, viz, the product changes in PCBs for dielectric use, | I will first take a moment to explain the variation in biode* gradability 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-chlorobiphenyl 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? 1 Reasons were: i- (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 I introduced into the capacitor industry while still i meeting Underwriters Laboratory's requirement on flammability. (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. * DSW 342311 t STLCOPCB4083811 1 i: - 2 r 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 I than one pound of hexa-chloro and higher homologs of PCB are likely I to enter the environment if Aroclor 1016 is used at a rate of 0.6M lb./year. I. !. 1 Turning now to Transformers. Slide 8: I 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 arc-form gases. Slide 9: What is the Failure Rate in Liquid Transformers? Slide 10: How Much PCB is Affected? J In Summary, Slide 11: We will continue our voluntary policy of no more sales world-wide j except to dielectric users. We will restrict over 97$ capacitor 1 fluid sales to Aroclor 1016 only. This means penta-chloro and high production will be no more than 1.1$. Hexa-chloro biphenyl i and higher will be even lower at 0.1$.We will eliminate Aroclor j 1260 from transformerfluids and continue incinerationfacilities 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. I. DSW 342312 ! \ i l STLCOPCB4083812 S%I 5 J 1 CO CD CO 3: >ce CD CQ O a. CO ___1 CD >- cd cd LU ___1 LU CQ CD LU 2: DO CO HH s: CL CD CD sr .ll CD i--i i --i Ljl. --)-- CD CD CD LU ___1 > CD CL CL CD LU CD 1 DC I 1 |i O <=C CL CD CD <C ___1 CL DC LU CD CO DC CQ CD LU *-- CD LU CQ --CD CD ___1 CD i LU LU 1 ___1 ___I Q_ CO CD CD s: =L >- LU LU LU CD X DC CL 1-- 1-- LU LL LU LU a: CD t-- < LU CO LU CL pa DC X 1 l--l 1-- O CD LU C1--l4 CD CQ X CD DC CO CD S >--* '--^ DC CD __1 LU O CL =C CL CD CD $ o < t<--c a: CD oo Ci--Di LU CL 1----: CO *C^=O** DO CD CL CL CL <=C C__D_1 LU DO CL CD CL I <5 iC--Oi X LU z: <t C1 D4 i <c L1 L.4 f-- CD LU LU CL LU 1-- =c CD DC Ql CO CD ooi LU CO <c PQ i i CD e\ 4 I 5 1 I f ! DSW 342313 I i STLCOPCB4083813 M,l 0 il i f &i* f CO o QC to i--1 C--D1 CD u I---- o LU -J QC C__D1 CD CQDC UD CM H CSC C_D1 r=* III O~ O Cl <c o h-- 2: CD CODC =c LU CL CHDH CD CL Z CO CtC LU > m co CD o LU CceO: CD Q- e> CD 6-S 1-- cn OHH 1--- cCtOr LU <c >2--: s; QC CD S*--I4 __1 LU LU CD o: CO . Q-- <CCD <QCC 1-- I oiV ?<s 5 I i i j i DSW 342314 ij STLCOPCB4083814 1 03 *=c I X =c cd i UJ UJ ZJZ 1 rn i--i CD --i cCdd CD cn CNl H CD 5 CO 03 cd rc CD --I Q_ or cd O' o a.: H; <C 03 O h- X <Is s: <a; oo UJ UJ Q_ 1 DC w CD CD CD CD --i --" IX cn 1--| CLi oo t- -H IX 03 CD 3T < CD ____1 Q_ DC CJ cd I rx 03 cn O Ct--Di Cd Cd CNl i--i --1 LTV cn - rx cn T LU! CO9 CD UJ 3 O- UJ <--1 h- --i 1 CL. CD UJ - N3 CO 1-- C--O-i cn 1 CD I--1 CNl CD LO CO cn 1--1 ch u j Q- or CNl CO LO or 1--I CNl CNl CD i--1 i--1 r--1 ! ad cd cd 03 CD CD __ 1 CD __ 1 CD __ 1 Q_ CD CD CD I t CD Cd CD cd CD Cd <C <C Ie i f I DSW 342315 STLCOPCB4083815 f} s ii cd CD z s: =c *=c i ii CD o cp OP 9CO CD CD i __1 __1 pc CD pc CD gH- 3 =c =c 21--: X UJ o' 2i. -J UJ PC a. .fi ll UJ > QL LU CD CO LU CD CO z: o PD PQ CD o o _j! CD Cl. CL_ X u o --i i--* oZ O >- OL < C--D-4 1--- CD 1-- CD OL CD > PP3 a CD LU < UJ DP o DP CP) DP CD __1 OP _J UJ CD LU CD pc LU PC LU CD 1 CD 1 *--< CD i--i I cn PC i--1 DP i I ! i I DSW 342316 I ! STLCOPCB4083816 i 4 t i CO CD 1 PD CO OH CD CD a 1--4 OH Q_ * z > CD LU Z3 _l OH pq O LU i LU Q- 3CD Z1Z CD CD CD O LU ZC o- <XC 1----4 zc --i o CD CD CD CD CD UD h- ud LU ~ar CD 1--1 CO CD LU ~r~ CD ZH -I=XT CD "2^ l--l i--1 ___1 /--s <C i--1 OP <c LU LU CC CO CD h- CD <C CO ___1 CD Qi--i OH LU LU - CD CD . ZD > pa LU 4--4 OP ___1 -zz <C LL- 4 - _i CD OH CL_ 1-- 3Ll-- OH JC--D C<QCD_ <C CD u_ CD OH OH CD =C 1-- H1----4 >LU- CD CD LU LLU-- <nC_ <c CO P_D1 LU CD is: LU uz f-- <--a-:4 UD CD <z> C1 O4 =C 1 CO pd CD OH CD CL. * _zC_cD_1 OH LU LU pa C=Dc H-- DC 4C--D1 ZC i o LU CL. CD 6^ <C CO zZaD OQ_ O CD CD CD CD CD CDV CDN UD% CVJ UcDr L=nr UD U_ O CD <c IzC--O: LEID z: <c CD s: CD pa =c QCD_ z: <C LU 1O-- s: CO <c 1-- CD <c HzO:- OP LU LL- LU CO OH OL/"HJS tL--l_4 CD CPCD <COc cr LOTJV <--1 cCNrI CM r--i Ui--D1 Ci--D1 LU CD pa | 1 CO 1-- 44 Zt--C LsUz i s DSW 342317 STLCOPCB4083817 - - *i I i 1 lw 0 1i _ r i CJ UccJ <c f i :-usr! CO cn DC CO LU 1-- i i cc CD CD 'i CO OI C- O LU CO CD CD CD UJ LU CO l_i_l C<O rc CD Cl. Q_ *2=C --<cI 1-- LU CO i Q_ <an CD CD s: co PQ CD CL_ =C . LU LI_ CD 1Li-- . DQ CD LU I-- i C\I CD Z CD CD Cs! i--1 i-- QD LU <=c sz ^n an CO UJ CD LU <c <C =c on on 21 O : o i LU CLi CD CD CD O on s: <3: --4 Ll. CO O o 3 <\i 5i a -- i s { i*1 ! " I DSW 342318 ! STLCOPCB4083818 I L l I % 1 t LU CO * cc: =c i. h~ QC LU >- - < LU OC PQ c__5 c O' :z LU Q_ Q_ i QC CNI U I* i l O O ___I O' Li- QC CD CO2 :z-JJ 3 LU Q ___1 *=a: rD QP LU <1 <1 21 < Ll. or: UJ s; 1-- HH i 1-- CD CO COIt5 o CO LU LU Q_ CD >- oc t-- ZD t oQ CO h-l i o ZD >OC- C1--D-4 -J 1-- ___1 CO ZD ___I t Q ___1 2 *=c -- * 1 i f j$ . i I I I DSW 9 STLCOPCB4083819 i L LU LU CO oi m CL o CO CL CQ CD ___1 r Q_ CD QZ ii >- CD K- Q_ <C i--i f-- CO CD ad z: CD CO QZ CD *=c CD LU _1 LU s?" CO ztz ____1 t < <C Cd Cd CD <c CO CD CD ZD f-- LU LU CD z o5 01 CD *--i CO s: QZ LU CO DZ s: 1-- ~~i <C " LU 1-- z o0ii Cl- ___1 Od i i CD UJ c_> LU 1-- 1-- >- QZ i_ Cd M--4 01I X QZ ___1 1-- > LU CD CD >--i CO CL 1-- ad CD ZD LU _J LU CD i--t CD u_ <C CD LU 2d 1-- o H-H <C CD 1 -4 CD 13= Q_ CD - --* h z CL l QZ CD >- OJ r--I ad CD CD QZ i f-- i oz 1-- CO <c I-- LJ CD CO QZ X _J CD "Zd CD ____1 cd CD LU LU LU CD CO< LU CO CO CD QZ CD CD --J QZ > i LU CD LU CD LU CD Cd CD --* LU ___1 > i--1 <x. CD .L0U1 ; LUcl*Ii <c CD CD CD i--< LU CO C/5 i--t oz oLUz 1-- CD CSD ILU ___ r-H 1-- CD QZ -- O QC ___1 1-- CD LU 1-- <za:: co s--: C--D LU ZD z: l-- LU CD CD CQ =C \-- CD OZ Q_ ZD X CD CD QZ CO LU CD 2Z CD CO CD eLtUc Q<cZ --* ZD ____1 --1 LU LU CD CD CD i--1 1 >LU LU CD CD Oo e 01 ii ii LU 1 ! 5c DSW 342320 STLCOPCB4083820 to f i 1 | I 1 ANSI C-107 COMMITTEE ACTIVITIES .Ii i By P. G. BENIGNUS I ! * a fti i DSW 342321 \ \\ ! STLCOPCB4083821 fii ' . 1 9| : i % i iI I LU O :-- O i LU O ! $ Z LU Z Ll LU oi GO O I-- K cl z$ LU zCL CL Q ! oi LU Z t Z <i CJ < I-- CO ii g $ i r i t DSW 342322 f f ii STLCOPCB4083822 f ?( i I i i i h i CO >- LU >m 3 CD 3: >- C> O1 CO I 1 sr <c CC <c 3P op op CD Q_ CO Q_ QP CO 1-- 1-- s: LU 5: <c LU CO PQ CO 3 o CD CO LU LU <C LU l. LU co <c CO <c P3 Q_ __ 1 r>j __ 1 <c __ 1 CO LU DC LU CO *=E CO <c . - h~ D_ H-- CO Q_ __ 1 - __ 1 i i CD =c __ 1 CO DO 3: - =C PQ CO 3: <=c __ 1 <c cc LU - 3: __ 1 <z cc - LU 3= 3 =c CO - CO __ 1 LU OP LU PQ LU Q_ 51 3: SI <c 3: (=1 CD LU CD t LU 9 'i .? I-- 1 1 1 1 1 =c 3 51 < 1 1 1 1 1 1 <C 51 cc 1--t | OL 1 1 1 1 CC <c 1 HH 3 I-- 3 *=c 1 1 <C CO 13 CO 1 CO N iC--Ci 3 >cc LU > LU O < <c =c <c LU 1-- 3 CO N 51 CC 1--1 =c V-- LU CC CO LU 1-- fi----i 11----4 51 SI LU 3 LU SI CO LU CO CO SI CO 1-- h-- \ CO CO PQ r^s r^ 3 51 CO CO PQ CO 51 i--i i--i 3 CO CO CO CO CC CO LU LU LU cc 51 CD LU LU CO CC f f i 3i--i CC 1-- (-- 1H--H t1----H 11--1 CO o 3 CO LU 51 51 <c 3 LU SI 3 <C ff 1-- O CO *=c OP CO CO CO CO 1-- 5 i ! I ( 1 I i ii DSW 342323 STLCOPCB4083823 :: ,! =c ----( LU s_x - - <> ea <--> - O LU CD CJ CO CO CD CO CO CO w < <C CO LUij C CO =c LU - CD OP CO CO LU Q_ qp lu s: CD LU OP OP i 1-- <C LUI 21 l-- CO CD CD CO ro 1--4 < CD) OP ___1 d 1-- iX <r ___1 --i c_> r^j <. LU PQ CO ___1 CD LU LU <=t (=1 --t cd LU ___1 LU OP t--i CD <C i- I-- o LU OP d t--< 1-- CD 1-- CD - i QP LU hLU ___1 <c <c s: <c 11 I I--I t O LU d d lu 1X O CO o CD$ 2: CO CD ___1 1--H Z> CO 1--1 LU 1-- CD >LU OP LU h-- d CD CD d CO i--i <C --1 o CO ___1 CD co ___1 1----1 iii CO ___1 o 1--4 ___1 ___1 CD <C <=c cr <C ca CD LU - pa LU CO s: CD CD \----4 CD O' LU OP d S OP 3= CD <C LU - >--i <c 1-- <C o > OP 1-- CD <_> OP ea j-- CO CP LU CD OP d - LU <c ___1 O <C CD Q_ 3= CO LU SI --> o ! 1< LU 0. >- OP 1-- O CO i< CD t--H 3P (= O OP LU d t--4 o 3I OP ___1 LU - CD LU - C ___1 35T CO O LU s: o <c o CD rn OP 321 U LU m I OP - CD c OP ea - d LU OP CD - ___1 - 5 d <c 0*P LU OP i i { i Dsw 342324 i STLCOPCB4083824 f i !! i 1 is Q i LU Cd or or CO L-- LU LU LU O' d 3 ~sr - Ig LU CD o CD LU CO D_ o_ Cc i. LU CD CU o3 03 o3 D_ t 4 X LU 1-- 1-- 1-- Cd nr nr nr CD CD CD CO SI 1-- 1-- LU1 d it >i ii d CO CD ___1 ___1 ___1 LU <c i--< i--i 1-- (_D CD CD ___1 Q LUI i <C i--i i--i --i r^i or or or l-- 1-- 1-- CD nr <C LU c_> <_> CD <C a: <c ___1 LU LU? 1 I-- Wc LU LU LU si PQ LU QCD ___1 ___1 ___1 LU LU LU O LU QT LU LU LU i--i CD I-- - CD d 1-- i--i CD CO or 1 - CD d f-- CD CO --< 1-- CD CD fi O o <c CD H--1 Hj 1--- t Q <_> CD LU H--1 CO i--i or or d LU H--1 __ 1 or LU d LU CD LC Cd nr 1-- LU CD LU LU $i4 3 LC 1-- 1-- CD <c CD __ l LU __ 1 LU =c ;__ 1 =c iC--Oi d t 1 CO --> CD CD o COi CO __ I LU LU nr LU nr CO LU *^r CD >- LU CD LU d LU d I o: d--i CO CD o CO n <C LU i---- CD t--i s: CO ii __ 1 CD __ 1 cd CD _l PQ 1-- CO lu m d CD Q ___ 1 CD O c LU PQ m CD LU <=c SI > Q 3 cn o LiCO 3 1-- t-- Q =c LU or >- o LC HH >-- z^ =c LU __ 1 LU nr LU <c nr __ 1 CO LU CD 1C--Ot DU or CD CD d*--t LU DU CD SI <=c LU __ 1 z^ CD =c 5T" or CD LU or CD or I--1 or DU oni. < 1---- or *=c cc CO CD or __ i i-- LC 3= D3 or 3 <c a M.l DSW 342325 STLCOPCB4083825 r- 4 . ' I | Vi t4 1 CD HH 1 l-- CO1 CD LU 1-- >CD LU 32: CD HH 1-- CO Od t--- 4 <c CO =C oz f-- Ct--O- 4 2Z CD >- QZ 1-- 4----4 LU zz LU CD <C <c oz LU LU CODd 2 1--4 LU QZ CO CD CO CO LU l-- <c <C SI LU zn CO CD CD QZ i-- LU QZ o 1--4 __ 1 CL >- <=C <C 23 --J <c LU LU QZ sOd: <C 1-- CD LU 4--4 SI CD h*~ LU 1-- CO 21 CD i--i <c 1-- -Zd >LU 4 T=* h- =C SI LU f-- LU __ 1 * ^ l-- CD t--i LU m CODd CO 2 CD CD <C CD __ 1 T^*** <c 1-- 1-- Q_ LU Od ZD 1--4 CD > LU <C r^j CD 1--4 <c LU QZ LU __ 1 > LU 1--4 1--4 LU CD <. > 2 Od Od > LU COt* 1-- Od LU CD 1-- CO <=C 1-- z: LU CD CD LU CO LU O CD LU CO LU LU LU 3 3 OL u QZ LU CD __1 __ 1 QZ 2Z O s: s: __ 1 =C LU CD i-- CD <c LU 1-- LU CL Od <X. Od i--t Od LU CD !--- 4 5 __ 1 <C CD h-- LU LU Cl. > 2 LU i-- DC QZ CL LU s: LU LU <31 ZD 4----4 CD LU CD CD 2 Od CD i I LU o QZ D<z ~~> cd -- CD CO CLUL CLCUOLO <> ! LU LU QZ CD zrz D C4--O-4 > <QcZ h-- 24---:4 IS CO CD Q_ __1 11----4 QZ \C--D CO 3 o I-- CD <C QZ ZTZ 1-- LU 2 CD CD 2Z - >- LU LU CD __1 2Z 2Z zc CHDH CD - !>~ CD 2: CO ? LU LU i*Z __1 m QZ QZ <zec: QOZ <c ZD CD <c <c I-- CO > QZ CD Z3Z CD "O m Od ZD cn sz zs i t1 i DSW 342326 ? STLCOPCB4083826 ,1 i I i CO LU LU CJ <_> Od LU LlJ CO CO LU - - -\ 2!! i--i CO CO CO CD CD T ' ___I <C =3 1----1 "N > I-- ___I "\ I-- LU LU CD --I LU 20 --I 1 CD O --I ad od co Q_ od ___I =3 =3 CO 20 [ < CL CL < --I Q_ <3 I f OI l 1--I CO dc z: CO I-- 2 dc Od l-- 2CO: I-- *--1 *-- LU I 1--* ! 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O LU > LcUa zr CD --4 1-- sp<aa:: LU QP pa 1---- QP <C SI QP LU <c zr LU <c LU 3= __ 1 CD >- SI 1---- CD Q_ CD LU Q_ 11------1 <=c CD Hj PQ <C CD 00 ca CD h- LU DP __ 1 OO CD t--i 1-- CD =D PD Q_ DP LU LU ra <c 1--- 1 LI-- OP LU =0 __ 1 DpaP QP ' <x. - Q_ LU pa ca QP LU __ 1 __=c1 z=c LI_ O __ 1 --I m C3 > Cd CD z: Li_ 0 z: __ 1 l-- __ 1 CD pa QP LU QP LU z: LU <c CD - - <3: CD <C z Cd 3: Q_ <c 1<--c SI CD :z CD 1<--c --1 cd LU CD CD OO CD CD OO --1 LCUd CD 1-- OP LpUa DP LU (-- pa 0 3: CD PQ =C O<Oc OO <E =C <c z: m <C CD LI-- 3. CD __ 1 1 OO LU <a: z: l-H PQ CD Cd X LU LI-- Q CD CD CD <OOr LU z: "03 1 >pa- CD _L_L_1 z<c CD z<cr CD Cd SCDI OO DP LiZU <=c -- nr 3: s<~c nr zr CD OpOa *D=Pc LpUa m CD LU CD _*=_a:1 nt--r 13: I-- CD PQ PQ CD CD zr pa 0 z: QP CD 1-- * SI zr nl--r OO SQPI =c nr CD HQ-P4 --1 LU S__P1 hH s: 00 __ 1 - QP __ 1 - QP LU nr CD I {. j ; I ! . DSW 342328 STLCOPCB4083828 fi *\ f *=c GO Tgoc LU 1 < LU I--1 CD LU CD u_ LU hi----t ___1 s: to--i or i--i oc DC CD t-- <c CD LU <C Ll_ CD uu Q_ t-- o 2 LU CD CD 39 CD CD i--i <c GO 1-- DC CO > GO CD DC o_ <c Q-- LU GO Z3Z t--t - i < Q 1-- Sc CD __ 1 CD LU __ 1 GOCD - \ f __ 1 PQ CD DC o! tC--Di <C H-- CD =C LU 1i----< SC DC CD LU -- <C 2: CD CD CL. GO CO? SC <c DC CD GO GO LU SI LU i--i ZD CD DC *C--DH LU LU LU SC I--1 1--4 1-- h-H CD 1-- SI CD t-- *=c >DC ri ui * i __ 1 oc <c CD CD DC LU DC SC LU Q_ CD o GO >t <c CD O i--< 1---- CD Z > DC CD __ 1 CD CD CD UJ "0 OQ O zsz <c CD LU __ 1 1-- <c CD LU CD O __ 1 LU > LU CD > LU __ 1 CD ___1 =C LU CD CL = UJ DC LU <C __ 1 LU <C nr SI 1-- CD --< GO f-- <c CD LU ZD iC LU DC DC 1-- CD > LU ZD <C CD CD DC 1-- CD 1-- GO GO 2: LU <c LU GO SC 1 1 e9 ! i ? s! 11 I CEE I EC SIGRE. oS\N 3^2329 STLCOPCB4083829 f i SCOPE OF ANSI CI07 <a: GO __ t LU <c CD 1 t z QC <c LU z 1-- LU =c \-- s: z 1----t CD <c LU SI <c LU CD GO GO ZD 1 __ 1 .LU LU Li_ QC <C 1-- go Z QC <GOc LU SI CD Cl. Li_ CD 1--4 GO z<c ZD C3 LU LU CD __ i i--* LU __ 1 --i CD Q<Cc <C CD NC 1--4 CD z<=:c G<Oc QC 1-- CD LL- LU GO CD __ 1 LU LU QC ZD __=c1 CD GO t--i LU CD CD Q_ CD CD GO LU QC i--i GO Q_ CD ZD |. I OSNN342330 STLCOPCB4083830 t i f* I I I I; oLi_ Q LU < CO O -J Q CO < 1 or o UJ < --I UJ UJ j-- o' < < 2: 1 CO j< ! j DSW 342331 \ i STLCOPCB4083831 7* . \ CO LU LU vO Q O ZD oO o' O' oO o O < O' < CL < (J CD LU CM CL CD >- O hC PQ CM O ND CU I K'l LU CM DT CM CD CD i--i O nr GO LU GO <C <C GO LU GO GO CD CtC CD LU > >-- PQ CD GO <C CL ^r <=c CD CD CD X LU or CD CD I-- GO LU GO CD CD or __ I CD LU <c soz CL GO <GOc CD oS* 'i'j'2- STLCOPCB4083832 f I ! 2 1 f i * O C1--D4 1Q--_ Cd i--i - zz: f-- CD 00 CO PQ tot PQ CD Q_ _i__ iii 4 sr LU PQ CD CD PQ --> Cd OP CD <C LU LQU_ j < CD OP \ CD CO (-- CQO_ h-- S sr O<oP_c LU O O no CO Ci--Di r--1 t-- LU CD CD- M CO <C CD m Cd \-- 3: X CD < co LU 1 S<cI h-- LU PQ LUj LU zs.: Cd LU _1 O' 1-- CO >_1 =C CD * ! h~ CD CD 1-- CO sr <c C/D LU PD CL ZD sr UJ __i <c co LL_ nr op Ll_ CO 1-- LU LU CD -- > LU ZS. -- LU u pa op _i h- <=c lu ST Q 2: lu LU O 1-- <C H- I-- CO <C CO --CO U_ --I LU CO LU r LL U.i cd si l Ic--oI _--_I' <c_d> _<_n1 II - 0 i I 1f ji i | s I f DSW 342333 STLCOPCB4083833 lft* ! i s 1 ? I LU i <i. O' to i < C/D U_ O' o LU C/5 CO PQ LU 1-- i O VO <C 1_____ PD i--i PD s: t: a 1_____ ZD CD C_> Z Z zz LU oo < 3 Qu --* i i CU >- DP h<c LU is: OP z <CL CN z O< CD ZD PQ LU QP (_> CD Ol. 1-- DP LU CD ZET DP h-- I X 1-- LU CD i--i i s: ~=g to to CO CD PD <c LU <c LU 1-- PD 1-- LU 1-- C/D Oz z i--i CO CO LU CD <C CU 1_____ 1-- CO 1_____ CD i--i <c PD PQ < I-- z o u 3/V2^4 OSNN STLCOPCB4083834 s \ Q 2: CD KH CD 1---- LU =C DC It 'MH LU __ 1 s: <c LU DC C_> H- CD k--i LU z: >- PQ CO LU CK < =C CD >- __ 1 CD CD DC nr Q >DC Q Q y" 1-- CO CD MM*! LU CO LU CO CD =C O DC < CO!I __I o LU CD LU CL- => I-- CD CO CLLU CD OL1 < QC O __ I CL. CM SI CD I-- CD CO <c LU LU < QC O >DC =3 PQ PQ --I CO COI CD I-- I-- <C 4 I s * s j ! oS\M3A25 STLCOPCB4083835 I 1, CD CO 1---4 GO 1--- O'! 2: LU CD *--H OD 2Z ZD LU <C *--i OZ I 3X 1-- zr 1-- CO C3 ZD - z ? o' CD CD 1-- --1 i nz z: 1 OZ GO LU LU o LU zrz l_L. LU z 1-- OZ OZ CD UJ o =a; OZ 1-- COi coi. 2: Ll_ CD i--i ___i CO > ZD SI GO < <c LU z: < oi o'1 oz l-- C/3 LU CD CQ zrz CO CD 1-- Q_ CO zn CD o h- 1-- <c OZ I _! CO z: ___1 LU LU ___1 OZ --i >- --i < <t } LU O' CD LU >oz OZ o 1-- CD >--i zrz 1--- <C ZD Q_ z: LL. CD i--< LU CD ZZ3 i--i PQ i--i z: o __ 1 1-- 1-- *=c CD zz CD SI C/D < CD LU LU J-- > ZD LU --H -= LU LL. ZIZ 1-- <a: i--( OZ o_ __ 1 <c 1-- ___1 OZ oz Oo' CD CD CD CO s--zi ___1 zrz CD \-- Z LL. o __ 1 <a: Ll_ D- LU LU LU ___1 GO z: DC CD <C =c <c )-- Q_ 1-- CD SI 6 i i ! i I 1 ! DSW 342336 STLCOPCB4083836 i SUMMARY By W. B. Papageorge } ! In summary, our observations, admittedly limited, both from ! our laboratory data and from reports of other investigators, i lead us to believe with considerable confidence that PCBs do degrade in the environment. The complexity of the commercial t mixtures has, however, hampered the determination of the varying rates of degradation of all the possible isomers. jiI 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 i 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. If For the capacitor application the development of Aroclor 1016, which satisfied all of the industry's requirements relating 3* to dielectric characteristics and handling properties, as well j as having Underwriters Laboratory fire-resistance 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 s scrap fluid by high temperature incineration, represents, in 2 our considered opinion, a significant step forward in our efforts to control the impact of PCBs on the environment. I I DSW 342337 *\ STLCOPCB4083837 V. DSW 342338 STLCOPCB4083838 Ydd