Document wqpB718YmM6eK0DKkYVK3azjd

r COM72-1041t Polychlorinated Biphenyls and the Environment Interdepartmental Task Force on RGBs Washington D.C. May 1972 HONS 201841 /-/ S'SUOGftASmC OATA mux 4, T.il. nd Subudt t. Ns. ITF-PCB-72-1 PCBS AND THE ENVTHOfMENT 7. Author!*) t, PcrfoMiuflf 0tf*nkt(Jn Nm *1(4 A44r** Interdepartmental Task Fore* On PCBa ! SacieitM'a Acc*Hii Ns. 00H-72-lQlll9 ndfsTUiii 20 Hat . 72 y No*( P*rf*tai*| 0f|uiui>ss Aspt, It. P>*jsei/Ts*k/Vsfk Uh Ns. it. Cwn/Gn No. It Spntiri| Ntor i*tl AMrcn Depar Intents of Agriculture, Commerce, Health, Education* and Welfare, and Interior ; and Enriromental Protection Agency; plus other participating agencies. Ill Typ* of Kiyrn ft Ptti*4 Final TT tj, SupptoMmtcjr N Thie report is the product of a six month review of the chemical# known ae PCBa-- polychlorinated biphenyls--by five Federal agencies, with participation by other agencies. The Interdepartmental Task Foroe on PCBa had as its goal the coordination of the scientific efforts of the Ooverigwnt aimed at understanding PCBe and the strengthening of the Ooverment'e ability to protect the public from actual or potential hazards associated with thee. The task force Made nine findings, con clusions, and recossiendatione, prinarily pointing out that PCBe should be reetricted to essential or nonreplaceable usee which would minimize the likelihood of human exposure or leakage to the environmnt. Supplementing the 20-page report are eight appendices detailing current knowledge about various aspects of PCBe, including their use and replaceablllty; occurrence, transfer, and cycling in the envlroment; occurrence and sources in food; and PCBa effects on nan and animals. it. Ktf Sard* ,ad Document A ml, II*. 17*. Ducripm- ^Pollution, Chlorine aromatic compounds, Blphenyl/chloro, Environmental survey*, Insulating oil. Economic factors. Ooverment policies, Ttodcology, Public Health. 17k. Mtniifim/OeN-EaM T* !7t COSAT] FiiLd/Gftup I3B 6T 11. Afiilibiiny S<c*aifM IfttV, * urdif er. <tiIT" __ P`Wl_ASSirHD It N*. tf PM*. 192 1TM.-- PC 46.00 K l4frU*T* HONS 201*42 Tabla of Contents Page PREFACE........................................................................................................ 1 FINDINGS, CONCLUSIONS, AND RECOMMENDATIONS..................................... 2 I. PRODUCTION, DISTRIBUTION, AND USE OF PCBs......................... 5 II. CHEMICAL AND PHYSICAL PROPERTIES AND IMPURITIES..................................................................................... 10 III. BENEFITS, UTILITY, AND ESSENTIALITY..................................... 11 IV. OCCURRENCE, TRANSFER, AND CYCLING IN THE ENVIRONMENT................................................................................... lb V. A. BIOLOGICAL EFFECTS ON MAN {METABOLISM, TOXICOLOGY, AND RESULTS OF HUMAN EXPOSURES)............................................. 17 V. B. BIOLOGICAL EFFECTS ON ANIMALS OTHER THANMAN...................... 18 i MOMS 201043 Table of Contentsi Appendices Contents end Authors..*.*.......... ........................... 21 A. Chemical and Biysical Properties of PCBs..................... 22 B. Use and Replaceabillty of PCBs........................................Ill C. The Need for Continued Use of PCBs as Electrical Insulatint Liquids....................... 75 0. Occurrence* Transfer, and Cycling of PCBs In the Environment.......... ............................... 03 E. Occurrence and Sources of PCBs in Fbod.. .......... . 107 F. Human Directed Aspects of PCBs......................................... ............ 122 0. Biological Data on PCBs in Animals Other Than Man........................................................................................................... 158 H. Regulatory Action on PCBs................................................. ............ 173 HONS 201B4* ii Table of Contents (Continued) Figures Chapter I 1, U. S. Domestic Sales of PCBa by Grade.... 2. U. S. Domestic Sales of PCBs by Category Appendix A 1-6. Chromatograms of various representative PCBs, according to Armour........ ................ Appendix F 1. Storage of PCB-Derived Material in Tissues and Plasma............................................................ 2. Excretion of PCB and PCB-Derived Material in Feces and Urine.............. ...................... * Tables Chapter I 1. PCB Manufacturing and Sales Data From Monsanto Industrial Chemicals Co. 1957 Through 1971................................................ Chapter III 1.' Underwriters' Laboratories Plamnabillty Ratings....*............................................. Page 8 9 31-36 lljO 11*1 6 iii HONS 201845 Tables (continued) , Pass APPENDIX A 1. General Physical Properties of the Aroclor m nri nat.ari CffllROunda . .* 26 2. Relative Retentions, Hass Spectrometric Data on PCB Fractionated Sample.....*.*.*...*..,. APPENDIX B 1. Typical Properties of Liquids............ *...................... 2. Physical and Other Properties of Lubricating Oils, Engine Oils, and Hydraulic Fluids.............. . L7-50 3. High-Temperature Lubricant Specifications.............. 56 k. Some Properties of Puirping Fluids..........*................. .. 57 5. Decomposition Temperature Ranges of Several Gh will cal 01 mm* . ....................................... .......... . 60 6. Approximate Maximum Ccsipatibility, phr, of Plasticisers With Rasim t T** .,**,,..*.,., ^ 7. General Properties of Some Aroclors (PCB).......... . APPENDIX C 61 63 1. Composition of Different Liquid Chlorinated Bipheiyls..............................................**.*................ .. 2. Underwriters' Laboratories Flawaability Ratings 3. Alternate Insulating Fluids......................... *............. 77 76 80 HONS 201046 iv r" Tables (continued) page APPENDIX D 1. PCB Manufacturing and 3ales Data From Monsanto Industrial Chemicals Co. 1957 Through 1971........................................... 05-86 2. Concentration of PCBs in Municipal Sewage Treatment Plant Outfalls........ ............................... 88 3. PCB Concentrations in Industrial Effluents............. 89 la. Total Estimated Contribution of PCBs to the Aquatic Environment............. ................................... 90 5. Concentration of PCBs in Sewage Sludges.................... 91 6. A Sanpling of Measured Occurrences of PCBs in the Environment................................. 93-98 7. Accumulation of PCBs by Various Aquatic Organisms................................................... 100 APPENDIX E * 1. Positive Analyses of Random Food Sables............... 2. Positive Follow-Op Investigational Staples.............. 3. Summary of PCB Findings in FDA Total Diet Samples................. la. Objective Staples - CY 1971 Fbr PCBs.......................... Ill 112 117 120 MOMS 201047 v Tables (contiiriad) page APPENDIX F 1. Subjective Symptoms Ccmplained bp Tusho Patients................................................................................ 126 2. Oral Toxicity of Chlorinated Biphenyl*..;................ 127 3* Dermal Toxicity of Chlorinatad Biphenyls................... 128 b. Vapor Exposure Toxicity of Chlorinated Biphenyls.............................................................................. 129 5. Toxicity of Aroclors.......... *................................................... 131 6. Pathologic Changes Induced by PCB*..............................132-133 7* Residues in Tissues of Rats Orally Dosed With Aroclor 125b (500 mgAg)...........................................*........... 13b 8. Storage of Aroclors (In PPM) 2b-Hours After Oral Ingestion by Stcnaeh l\ibe............................. 138 9. Distribution of PCB-Derived Material Following 98- Dv Exposure to a Dietary Level of 1000 PPM Aroclor 125b......................................................................... 139 10. Distribution of PCB levels in Adipose of General Papulation as Shown in Analysis of Human Monitoring Survey Sables Since April 15, 1971............ Ib5 11. Experiments to Data Not Included in the Manuscript "Polychlorinated Biphenyl* 1 Distribution and Storage in Bod|y Fluids and Tissues of Sherman Rats"A. Curley, V. V. Bbrse, M. E. Grim, R. W, Jennings and R. E. Linder...........................................'............................ 150 12. Same Biological and Tojd.cological Effects in the PCBs............................................................................................... 153 13. Possible Phture Studies Involving PCBs, Their Individual Isosiers and Contaminants..................... ............ 15b vi HOMS 201848 Tables (continued) Page APPENDIX H 1. FDA Proposed Temporary Tolerances for PCB Residues....................... ............................................................ 178 ii HONS 201849 PREFACE On September 1, 1971, representatives of several agencies of the Federal QoVermont established an Inter departmental task force to co ordinate the scientific efforts of the Ooverment aimed at understanding the family of chemical compounds known as polychlorinated biphenyls (PCSs), and to strengthen the Government's ability to protect the public from actual or potential hazards from PCBs. On September 5 it was announced that the task force would "coordinate a government-wide investigation into PCB con tamination of food and other products". On September 13 the task force, made up of qualified specialists from a range of disciplines, held the first of a series of meetings. Appropriate spokesmen on various problems assoc iated with PCBs were assigned to prepare a series of background papers, drawing on the resources of their own and other agencies. The task force included operating unite of five Executive Branch depart ments! Department of Agriculture) Department of Commerce (Assistant Secretary for Science and Technology and National Oceanic and Atmospheric Administration)) Envirormental Protection Agency) Department of Health, Education, and Welfare (Food and Drug Administration and National Institute of Envirormental Health Sciences of the National Institutes of Health)) end Department of the Interior (Bureau of Sport Fisheries end Wildlife). The report which follows represents the results of the task force's re view end reflects the position of the operating agencies of the Federal Qoverrment which have major responsibilities concerning such chemicals as PCBs in food and in the environment. The task force had the advantage of some additional sources of information and review on PCBs. For exasple, dur ing the course of the study, the National Institute of Environmental Health Sciences sponsored an international scientific meeting on PCBs on December 20-21, 1971, at the Quell Roost Conference Center, Rougeaont, North Carolina. One hundred persona--from Government, universities, industry, and the pressattended. The proceedings of this conference soon will be published by the Institute. The task force also met from time to time with e group of scienti fic advisors from outside the Federal Government, which was already at work prior to September 1971 examining a number of hazardous trace substances, one of which was PCBs. The individuals who served on the task force included! Dr. John E. Spaulding end Dr. Harry W. Hays (Department of Agriculture), Dr. Robert W. Cairns and Dr. William Aron (Department of Commerce), Dr. John Ihickley (Siviroiznental Protection Agency), Dr. Lawrence Flehbeln, John R. Vfessel, and Dr. Albert Kolbye (Department of Health. Education, and Welfare), Dr. Lucille Stlckel (Department of the Interior), Dr. Edward J. Burger, Jr. (Office of Science and Technology), and Dr. TWrry Davies (Council on Environ mental Quality). Many. others participated in soma of the meetings and lent assistance in a variety of ways including authorship of background papers published as appendices in this report. The task force is grateful for this assistance. The task force will continue to assess new information that comes to its attention. 1 MOMS 201050 FINDINGS, CONCLDSIONS, AND RECOftENDATIONS Polychlorinated biphenyls (PCBs) have been used in the United States and elsewhere over the past 1*0 /ears, for many industrial and consumer applications. During the past three years evidence has aceustulated to indicate that PCBs are widely dispersed throughout the environment end that they can have adverse ecological and toxicological effects* The principal uses for PCB fluids are in the electrical industry. PCBs have sifterlor cooling, insulating, and dlelsotric properties and hencs ars widely used in various electrical devices. Transformers and capacitors filled with PCBs can be used in lneida locations where fail ures of oil-Insulated equipment would present a potential danger to life and property. Because PCBs are relatively nonflammable, apparatus con taining them is essentially free rtm the FH^ and explosion hazards associated with oil-insula t-'d and oil-cool'd lectrio devices. Stability at high temperatures is anothsr major factor in the attractiveness of these compounds. The principal advantage of PCBs over substitutes is the relative freedom from flraabillty in sane applications that previously had been plagued by serious fires. PCBs also give electrical equipment the critical advantages of reliability*. long life, and ccnpactneas. PCB impregnated capacitors, for example, are markedly more reliable and longlived, and 1/6 the size, 1/5 the weight, and 2/U the oost of comparable oil impregnated capacitors. Stall capacitors with PCBs have a use-life expectancy of 10 to 15 years, and large capacitors 20 to 25 years. PCBs in transformers ars replaced only every 25 to 30 years. PCBs have been discovered to have a widespread distribution in the environment, and sane environmental occurrences have been associated with adverse effects on certain forme of animal life. Beginning in 1971, the Monsanto Ccmpany, the sole U. S. producer, has reported taking volun tary actions to reduce the volant of PCB production and to limit its distribution to industries concerned with the manufacture of electrical apparatus. Similar restrictions haVe been put into effect by statute in Sweden and voluntarily in Great Britain. A large use of PCBs had been in carbonless duplicating paper. This use has been discontinued. The Food and Drug Adainiatration and the food industry have increased their surveillance to assure that PCBs are not used in food plants, products, or packaging. The task fbrea has reviewed all of the available scientific informa tion on various aspects of the PCB problem. It has found much data that it regards as inadequate end many questions that remain unanswered. Kit on the basis of available information, the task fores concurs on the following findings, conclusions, and reemnendationsl HONS 201551 2 1. PCBs should be restricted to essential or non-replaceable uses which involve minimal direct human exposure since theycanhave adverse effects on human health, there currentlytre no toxicological or eonlnyi. cal data available to indicate that the levels of PCBe currently known to be in the envlroment constitute a threat to human health, but additional experiments are underway to evaluate the impact of low level, long-term exposure to PCBs. 2. PCBe have been used so widely over such a long period that they are ubiquitous. Even a total cessation of manufacturing and use of PCBe would not result in the rapid disappearance of the material, and ultimate disappearance from the environment will take many years. The elimination of non-essential uses and prohibition of discharges from essential uses will result in gradual elimination from the environment, 3. PCBs were first identified as potential food contaminants in 1966. Three principal sources or routes of contamination of food have been identi fied, General^ environmental contamination has resulted in PCB residues in some fresh water fish. Prohibition of PCB discharges into water will result in the reduction of such residues. Another route occurs from the presence in food packaging materials of PCB residues, some of which migrate into packaged food. The FDA has proposed regulations for food packaging materials and foods to deal with this problem. The third route Involve# accidental contamination of food from leakage or spillage of PCBs into feed or directly Into food. The dietary intake of PCBs is of low order and does not preeent an imminent health hazard. To date, all of the high levels of PCBs encountered In human or animal foods havs been associated with acoldente, for which Govern ment agencies have exercised necessary regulation and control to minimize the distribution of contaminated foods. li. The sole domestic producer of PCBs, Government agencies, and key user industries are taking appropriate steps to cut off further introduction of PCBs into the food supnly and'to reduce the current levels of l-'CBs as food arid eWiromentai oontamlMnit. The Food and brug Administration j has acted, undsr the authority 0^ the Food, frug, and Cosmetic Act, to preclude the accidental PCB contamination of food. It has also proposed a prohibition on the use in food packaging materials of pulp from reclaimed and salvaged fibers that contain poisonous or delstarious substances that may migrate into the food if the contamination by such substances is deliberate or avoidable. It has proposed temporary tolerance* for unavoidable PCB residues in food packaging materials and in certain foods. The Department of Agriculture has acted under the Vholesame Poultry Act and other statutes to prevent accidentally contaminated foods from reaching the market. The major gap in the regulatory system to deal with PCBs is the absence of any broad Federal authority to restrict uss or distribution of the chemical, to control imports, and to collsct certain types of Information. The task force believes that such authority is needed, lhl* authority would be provided by the Toxic Substances Control Act proposed by the Administration and now pending before Congress. HONS 201852 3 S. Housekeeping la particularly important in the manufacture, use. and dlapoaal of PCBs. Under a program of limitation on nf flfflUj the electrical Industry will continue to be the principal ueer of PCBa) it, as well as Industries now holding inventories of PCBs, have a special responsibility for monitoring and controlling their wastes. In this con nection, the Environmental Protection Agency will restrict industrial liquid discharges of PCBs from PCB users. To keep levels in fish as low ae possible, and in any case below FDA's interim action level of 5 parts per million, concentrations in rivers or lakes from all sources should not exceed 0.01 parts per billion. 6. The use of PCBe should not be banned entirely. Their continued use for transformers and capacitors In the near future is considered necessary because of the significantly Increased risk of fire and explos ion and the disruption of electrical service which would result from a ban on PCB use. Also, continued use of PCBe in transformers and capaci tors pressnts a minimal risk of envlromental contamination. The Monsanto Compary, the sole domestic producer, has reported voluntarily eliminating its distribution of PCBa to all except manufacturers of electrical trans formers and capacitors. Pending passage of the Toxic Substances Control Act, the Federal Goverrment does not have the legal authority to Impose restrictions corresponding to the actions reported, by Monsanto. Although some Federal enforcement authority is available, the Federal Govarment does not have the authority to control PCBa at their source. 7. Most capacitors presumably have been disposed of in landfills. PCB containing material buried in soil la not expected to migrate but should remain In place. In the past, many fluids containing PCBs have been disposed of in sewers. More appropriate means of dlapoaal such as high-temperature (at least 970C) incineration muet be used Instead. 8. PCBs are manufactured in countries other than the United States. Importation of P<}!8s as a chemical or ai a componentIn products remains legally possible because the Toxic Substances Control Act has not yst become law. Electrical products lxported from abroad may contain PCBs. The task force looks to international agreements to bring about some multi-national understanding on the sale and use of PCBs globally. Im portation of PCBs for uses other than those singled out in the present pattern of voluntary limitations should be avoided by users. As an additional measure, the United States has asked the Organisation for Economic Cooperation and Development (OECD) through its Environs#nt Com mittee to make a special review of member states' national policies concern ing PCBs and also to identify products moving in International trade which contain PCBs. OECD, whose membership Includes all major Western industriali zed atates plus Japan and Australia, has been giving priority attention to the problem of PCBs over the past year. 9. More scientific information about PCBa is needed, and several Ooverment agencies are seeking it through research, fhe task force ~ recognizes that the scientific basis of much of our knowledge must be 1j HONS 201853 strengthened through research. The total exposure of a human being to a given substance from all sources--air, water, and food--must be considered, and Interactions of PCBs and other substances within and outside the body must be evaluated. Similar consideration must be given to the other body organisms. Current scientific knowledge gained from laboratory animal experiments is often Inadequate to allow reliable Interpretation of the data in terms of possible effects on man. The scientific basis for Interpreting such tests must be improved. The situation regarding PCBs is not significantly different from the problem of other toxic susbstances which cause concern when they come into contact with man, his food, and his envlronsent. Continuing vigilance on the part of Doverintent agencies, industry, universities, and maiy other agencies both within and outside the Govermant will be necessary to achieve an effective system for assessing and controlling the hazards of toxic sub stances, Including PCBs. The task force, by reviewing research needs and the present Federal research effort, has helped to Insure that these efforts of the agencies are well planned and coordinated. Certain OcnrerTinent laboratories as well as a number of non-Ooverrsnent scientists recently have embarked on additional research on PCBs, and the results will be coamunieated to the scientific public completely and pro^tly through normal channels such as meetings and journals. . I. PRODUCTION, DISTRIBUTION, AND USE OF PCBS Polychlorinated biphenyls (PCBs) were first manufactured comerclally in 1929. E|y virtue of their unusual chemical and physical properties, they achieved widespread use in a variety of applications. PCBs are now manu factured in Qreat Britain, France, Germany, the USSR, Japan, Spain, Italy, and Czechoslovakia, as well as in the United States. In the United States, PCBs have been manufactured by a single producer, the Monsanto Compary, and marketed*under the tradename "Aroclor". Table 1 gives a breakdown, by category of use and by type of PCB, of the totel U. S. production, domestic sales, and U. S. export sales from 1957 to ths present. Figure 1 and Figure 2 summarize these data for the years 1963 through 1971* Both production and domestic sales of PCBs roughly doubled between I960 and 1970. If one assumes a constant rate of growth of domestic sales since 1930, the cumulative sales in North America by 1970 would be of the order of 500,000 tons. (1) Corresponding data on production and use of PCBs outside ths United States are not available. Current estimates suggest that total U. S. production represents roughly one-half of the total world production. ' As can be seen In Table 1, the majority of the PCB material produced in the U. S. was marketed domestically. Between 1963 and 1971, the pro portion of the production which was exported averaged 13 percent. In 1971j the Monsanto Company reportedly undertook a variety of voluntary restrictions on the distribution of PCBs to various categories of Industries. Both HONS 201854 5 TOTAL PRODUCTION (For Domestic Sales) DOMESTIC SALES DOMESTIC SALES BT CATEGORY Heat Transfer Hydraulics/Lubricants mac. Industrial Transformer Capacitor Plasticizer Applications'2' Petroleum Additives Total DOMESTIC SALES BI PCB GRADE Aroclor 1221 Aroclor 1232 Aroclor 121*2 Aroclor 121*8 Aroclor 1251* Aroclor 1260 Aroclor 1262 Arcolor 1268 Total TABLE 1 PCB MANUFACTURING AND SALES DATA FROM MONSANTO INDUSTRIAL CHEMICALS CO. 1957 THROUGH 1971 (Thousands of Pounds) im 19H 1959 I960 37919 32299 26061 31310 35216 _ 1612 70li 12955 17028 - 1559? 151*9 755 5719 li099 3939 - 5SSST 2685 1569 5981* 161*99 1*573 -- into 2523 1559 7921 16967 621*1* - 355TC 23 196 16222 1779 U*61 7587 31 - 32299 16 113 1061*1* 2559 6691 5982 186 72 26061 256 260 13598 3386 6756 6619 359 102 31310 , 103 155 18196 2827 6088 7330 326 169 35216 NOTE: (l) Production amounts prior to i960 are not available. (2) Amounts for plasticiser applications prior to 1958 are not available. 1961 36515 37538 1962 38353 38063 1110 2X11* 6281 15935 9098 _ 37530 157 3915 1661 7981* 15382 8926 * 3801*3 96 261 19827 6023 6296 6560 361 158 37538 160 226 20656 3663 6325 6595 032 210 38063 MONS 201f55  U.S. PRODUCTION DOMESTIC SALES (LBS.) U.S. EXPORT SALES U.S. DGMSTIC SALES BT GATBOOBT Heat Transfer Hydraulic a/Lubricaota Rise. Industrial Traasfonaer Capacitor Plasticiser Applications Petroleist Additives 0.3. DOMESTIC SALES BT PCS (WADE Aroclor 1221 Aroclor 1232' Aroclor 12ti2 Aroclor 121*0 Aroclor 125U Aroclor 1260 Aroclor 1262 Aroclor 1260 1963 1*1*731. 38132 3617 TABLE 1 (cont -) 1961> 50033 1*1*069 Jj096 1*2 601*00 51796 1*231* 1266 6581.9 59078 6052 1967 75309 621*66 0121* I960 02051* 65116 11231 3269 76307 67191* 10621* 1970 1971 05051* 1*01,71 73061 37635 13651 9876 Prospect 1972 25-30 25-30 * 7 $82 391*5 1520 7290 15606 9101 929 1*371* 1692 7997 1951*0 10337 -- 1237 1*516 101*1 8657 2371.9 11696 -- 1766 1*58 1779 0910 28061* 131*81 - 2262 1.6L3 11*6 11071 29703 13361 - 2529 5765 1203 11505 29550 UiliOtt - 3050 0039 1079 12105 25022 161*60 11*39 3956 71*03 1627 13626 26?06 19537 - 31*60 161*3 570 11520 17305 3102 - - 25-30 * 25-30 a - - 361 13 16510 5013 5911 7626 1*11* 281* 596 13 23571 5238 6260 0535 iil*6 190 369 7 31533 5565 7737 5031 550 196 520 16 39557 5015 7035 5075 760 281* 1*1*2 25 U055 1*706 6696 61,17 01*0 207 136 90 1*1*053 l*09ti 8091 5252 720 200 - 507 273 l5loi 5650 9022 U*39 712 300 11.76 260 1*8568 1*073 121*21 1*090 1023 330 1600 211 21000 261 5600 1750 - t i 'fss HONS 201856 75,000 ,000 - 12*^2 + 12^ US DOMESTIC SALES (1 0 ' lb s ) 55,000 45,000 -- 35,000 -- 25,000 15,000 -- 5,000 -- llii 1963 1965 196/ YEAR |232' I____ Ug4=gsssT 122 l69 T971 FIGURE I.US DOMESTIC SALES OF PCBs BY GRADE n uppcrnMt curv* rapraaant* tha tatal **U frm Nlabat, I.C.T., and Sarofla, A.?. (I) 8 201457 75,000 r-- 65,000 -- U .S . DOMESTIC SALES (1 0 ' lb s ) 55,000 -- 45,000 -- ?5,000 25,000 -- 15,000 -- 5,000 |~s3 1 ijtib 1 19^ YEAR * 19^9 1 lull FIGURE 2. US DOMESTIC SALES OF PC3s by Catepory <** uppamost eurvo roproaontt th* total tilu.) From NUbat, l.C,T., and Saroflto, A.F, {I) 9 MOMS 201158 production and sales figures for 1971 were roughly half of those for 1970, when these voluaas were at their peak (Table 1 and Figures 1 and 2). Pro jections for 1972 indicate an even lower voltrae. Prior to 1971, about tiO percent of the PCB Material In the United States was used In applications where contaiment was difficult and losses into the envirorment were probable. These uses Included plasticisers, hy draulic fluids and lubricants, surface coatings, Inks, adhesives, pesticide extenders, and microencapsulation of dyes for carbonless diplieating paper. The remaining 60 percent of domestic sales was used mainly In electrloal applications (transformers and capacitors). In 1971, this fraction is ex pected to have readied approximately 90 percent of the total use, only about half of the total use in 1970. In terms of the grade or family of PCB manufactured, the lower chlori nated species have generally made tp. the majority of the products produced. Fran the figures In Table 1 It can be seen that Aroclor 12l2 and grades with lower percentages of chlorlmtion characteristically ccwpoeed one half or mors of the total production between 1963 and 1970. The largest categories of use of PCBs have bean in oapacitors and transformers and In certain "plasticiser* applications including carbonless duplicating paper. A large percentage of the production of Aroclor 121*2 went into these three categories of produots. (2) The major uses for PCBs prior to 1970 (In the order of lxg>ortance as a reflection of the volute of materiel used) were: Capacitors Plasticiser applications Transformer fluids Hydraulic fluids and lubrloants Heat transfer fluids II. CHEMICAL AND PHYSICAL PROPERTIES AND IMPURITIES Chemical and Physical Properties of'PCBs Theoretically, there are 210 possible PCB compounds, but only about 100 are likely to occur in commercial produots. The degree of chlorination determines the cfeamloal end physical properties of the Aroclorej the first two digits of the numbered Aroclor represent the molecular type, the last two digits tbs average weight percent of chlorine. Their physical stats thus varies ft cm colorless, oily liquids to mors viscous and increasingly darker liquids to, in the higher series, yellow and then black resins. The PCBs are not readily biodegradable. They resist breakdown by water, acids, and alkalis and have boiling points ranging from 278 to b7?C. Analytical Techniques Whereas in the past it was difficult to identify PCBs in the presence of other organoehlorlne cexpounds such as DDT and DDK, they can now be separated from interfering cexpounds and idantiflad and measured by means of thin layer and gas liquid chromatography at lavala lass than 1 part 10 MOMS 201859 per million in food end et significantly lower levels in air and water. Confirmation of their presence and molecular structure is possible by mass spectrometry* Various chromatographic columns and GLC detectors have been most useful in the analyses. Increased precision of residue detection in biological materials has also been made possible through the choice of chlorine specific detectors such as the microcoulcmstric detectors. Contaminants and Securities lbs starting materials used in synthesis of PCBs determine to a large degree the type of inpurity or contaminant in the cconercial product. The contaminant variation, of course, renders some divergence in the LD 50 values or other toxicologic response of the PCBs. Fractionated similes of sens PCBs of foreign manufacture have shown them to contain as contaminants the tetra- and psntachlorodibensofurane, the hexa- and hsptachloronaphthalenes. Further work is needed to ascertain whether additional Impurities or contaminants are present in the various U. 3. and foreign PCB products. Also, variance in biological response to the various PCB products should be corre lated with analytical data obtained on the actual or likely presence of con taminants . m. BENEFITS, UTHITT, AND ESSOfTlALITT The teak force reviewed the several categories of uses to which PCBa had been put in the past to determine what was known of their utility and to ascertain if alternate or substitute materials were available or whether any of the present applications were essential. The fbur major types of applications examined were* 1. Dielectric fluids for capacitors and transformers. 2. Industrial fluids fbr hydraulic, gas turbine, and vacuum punp uses. 3* Heat transfer fluids. ii. Plasticisers and miscsUansous us as. This review of utility was undertaken by the National Bureau of Standards The review was materially aided by information from the National Induetrial Pollution Control Council and Aram certain professional independent testing and evaluation associations. A major value of the PCB liquids is that those with four or more substi tuted chlorines per molecule are nonflammable as are their decomposition pro ducts, both vapors and arc-formed gaseous products. Thus thsy can b# ussd as fluids at tm^>*ratursa up to 700F without ths danger of explosions end firs. The major disadvantage of the PCBs is their toxicity sad environmental contami nation. The other ca^arsbls clsss of non-flm--able fluids is ths fluoro carbons, which typically have a lower vapor pressure end lower boiling point than the chlorinated compounds. 11 HONS 201860 Electric*! Uses PCBs are used in fluids (known *9 askarsls) for electrically insulating and cooling transformers when the transformers ars used in or near buildings. Being virtually free of fire and explosion hatarda, PCBs can be used where failursa of oilinsulated transformers would present a potential danger to life and property. PCBs also are superior to oils in reliability, in making small equipment possible, and in assuring long life and reliability to equip ment. Table 1 shows the flammability ratings of two PCBs compared to five other common materials. Table 1 Underwriters' Laboratories Flammability Ratings Fluid Flammability Rating Ether Gasolins Ethyl Alcohole Kerosene (100 P.P.) Mineral Oil Aroclor 12li2 and MC3 1016 '100 90-100 60-70 30-10 10-20 2-3 PCBs are used in transformers whersver fire protection is particularly important--for about 5 per cant of all transformers. Most of these transformers are located Inside public, commercial, or Industrial buildings--or on the roof tops of, or in close proximity to, such buildings--and require no special enclosures other than those necessary to prevent accidental hazardous mechanical or electrical contact of persons with ths equipment. The amount of Aroclor used in various types of transformsrs ranges from lO to 500 gallons (5l6 to 6,Jj$0 pounds) with an average of about 235 gallons (3,032 pounds). Curing 1968, ths last oomplets "normal" year for the electri cal industry, the total amount of PCBs used in new transformers or as replace ment fluid was approximately 1.3 million gallons (8.It thousand tons). The only present alternatives to Aroclor-insulated transformers are mineral oil-lnsulatsd transformers or dry-type transformers (either those open to ths atmosphere or those that are gas-filled and sealed). Mineral oils ars the preferred fluids when fire does not create a hatard. Cry transformers also can be used when space is available to install them. Fluorocarbon liquids require a special transformer design. PCBs are used in more than 90 psroent of ths electric utility (large power) type and small*r industrial type oapacitors mad* today. They are needed for safety, reliability, and long life, and to achiave sises compati ble with equipment and installation requirements. HONS 201861 12 Almost 80 million PCB-impregnated capacitors ere manufactured annually, most of them for first*time use. The principal types are high voltage power capacitors used primarily for power factor correction in the distribution of electric power| low voltage power capacitors installed in industrial plants at the load (typically large motors)} ballast capacitors to Isprove the efficiency of lighting systems; and small industrial capacitors for power factor improvonent in such equipment as air conditioning units, primps, fans, etc. Capacitors used in lighting and air conditioning applications contain 0.0005 to 0.09 gallons of PCB per unit. The largest power c^acitors contain about 6.7 gallons of askarel* The National Electrical Code requires that any installation of capacitors in which any single unit contains more than 3 gallons of combustible liquid shall be in a vault like that required for transformers. taring 1968, the last couplets "normal" year for the electri cal Industry, the amount of PCBs used in capacitors was approximately lb.b thousand tons. . Possible alternatives to PCB-loqpregnated capacitors are capacitors im pregnated with mineral oil or certain other liquids* Flammable fluids in capacitors used in buildings are not allowed by insurance companies and building codes* If codes did allow flammable materials in this use, replacement of PCBs in capacitors and transformers would require considerable time and money for re-engineering, manufacture, and application of substitute equipment, and lack of availability of PCBs for this equipment would cause a major and lengthy disruption in the nation's electrical system* Industrial Applications PCBs have been useful in hydraulic systems where leakage onto hot metal surfaces could cause fire, tat substitute fluids are available. Oaa turbines require lubrication at high tenperatures, PCBs can be used tat tend to be corrosive. Phosphate ester lubricants seem better In this respect* Chemical stability is more important than non-flammability for high temperature lubri cants. PCB fluids are useful in diffusion booster pups, tat non-flajmrtability is not especially imp or tant for diffusion pup liquids, and alternativa liquids are available. Heat Transfer Materials Fiaim&abie beat trensfar fluids present a fire hazard if they leak into a furnace or onto hot surfaces* The use of PCBs prevents this danger* In seme cases water is e suitable substitute at moderately high temperatures, and other satisfactory heet transfer fluids are commercially available and in usa. Plasticizers The PCBs are good plasticizers for use with adhesives, textiles, surface coatings, sealants, and copy papar. In soma cases the PCBs act as flra ratardants. There are no unique properties of PCBs for plasticiser uses, and equally effective alternatives are gensrally available (e.g., phosphate esters are often used as fire retardants). 13 HONS 201S62 IV. OCCURRENCE, TRANSFER, AND CrCLINO IN THE ENVIRONMENT Given the diversity of uses of PCBa end their chemical ehereeteriatics (greeter stability in the higher chlorine species), it is not surprising that the residues are widespread. While satisfactory quantitative estimates of the contribution of various pathways into the environment are not possible with existing data, there are enough data to be oertain that PCfis do reach the envlrorment at least from the following sources! -- Open burning or incomplete incineration (at usual temperatures) of solid wastes, municipal and industrial* Incineration at 2000F or above for two seconds will destroy PCBs, but poorly operated incinerators or open burning may result in PCBs bsing released to the atmosphere unchanged. -- Vaporization from paints, coatings, plastics, etc. (Nlsbet and 5aroHm, 1) estimate that as much as 20 percent may be vaporised. --. Municipal and scow industrial sewers (1 CBs present in treated as well as untreated wastes). Accidental spilla or improper wastes disposal practices. -- Formerly, direct application to the environment as ingredients of pesticides or as carriers for pesticides (such uses of PCBs are now prohibited). -- Dumping of sewage sludge, municipal and industrial solid waste, and dredge spoil at sea, -* Sewage sludges disposed of on land. -- Migration from surface coatings (paints, etc.) and packaging materials into foods and feeds. Probably the largest amounts of PCBs circulating In the envlrorment reach it through industrial and municipal discharges to inland and coastal waters. The recconendetion by the task force that 'biors scientific Information about PCSs la needed" Is illustrated by the sparsity of knowledge about PCBs in the environment. Only general statement! can be mads about how PCBs reach the envlrorment, how they reach target organisms, and how much Is present. Nlsbet and Saroflm (1) estimate that the total loss of PCBs into the U. S. environment over the last IjO years would approach 30,000 tons to the atmosphere, 60,000 tons to water and 300,000 tons to dumps. Of this total, remaining resi dues might be 20,000 tons from the air (which would be distributed on land or water), 30,000 tons in water, and perhaps 250,000 tons in duips. HONS 201*63 Hi Thousands of enviromental and biological samples have bean analysed for the presence of PCBs. One or more of the PCB compounds have been de tected in all environmental media, and in many organisms. Water The water environment is probably the principal sink and transport mechanism for PCBs. Calculations based on measured occurrences in municipal and industrial outfalls, in the receiving waters, and in the downstream reaches of the waterways demonstrate transport through the aquatic system. Measured residues in fishes from various environaents suggest accumulations at the downstream ends of the drainagewaye. There are few data on removal, disappearance, and sequestering of the substances in soils or bottom sediments of rivers, lakes, estuaries, or the ocean. Organisms Other Than Man _ PCBs being, like many of the organochlorine insecticides, fat soluble, are stored in ths lipids of animals. Also like the chlorinated hydrocarbon insecticides, they resist metabolic changes, and tend to be concentrated at succeedlngly higher levels in animals highar in the food chain. The higher chlorine PCBs are the most stable. . Occurrence and Sources of PCBa in Food The identification of PCBa as a potential food contaminant was first reported in 1966. Subsequent investigations. Including the development of analytical procedurss for PCBa in foods and their incorporation in Federal programs for monitoring the nation's food and feed supply for pesticide residues and other chemioal contaminants, established severe! sources from which foods may beccma contaminated with PCBs. Environmental Contamination of Food PCB residues in fresh water fish appear to be widespread geographically as a result of the environosntal contamination of lakes and streams. Depending upon the location of stapling and the species of fish, PCB levels generally range from 1 to 10 parts per million. Foods of salami origin, such as seat, poultry, eggs, and milk contain, in scats instances, low background levels of PCBs that may be attributable to environmental contamination. Industrial Accidents The widespread industrial uses of PCBe have resulted in a number of identified isolated accident# involving the direct contamination of animal feeds, which, in turn, caused human food to become contaminated. -- poultry and sggs became contaminated as a result of the leakage of PCB heat transfer fluid during the pasteurisation of fish meal (poultry feed component). 15 HONS 20I#64 * -- PCB residues in milk have resulted from the use of PCB in certain coatings on the inside walls of silos, which, in turn, contaminated the dairy feed silage. -- The use of spent PCB transformer fluid as a herbicide spray vehicle allegedly contaminated dairy.cattle grazing areas thereby causing residues in milk. -- The grinding of bakery products along with their PCB-containing wrappers for use as poultry feed is suspected to have caused contamination of fowl. These incidents, as well as others during the past several years, represent localized sources of contamination* Federal, State, and Industry actions pre vented most of the contaminated foods from being marketed. Food Packaging ,, A significant percentage of food paper packaging materials contains PCBs and has resulted in the migral1 :-n of low levels to the packaged food. This source of food contamination was identified in 1971* The origin of PCBs in packaging materials is not fully understood. Recycled waste paper containir^ PCB carbonless "carbon" papea. is the prime source of PCB in paperboard pro duct. Virgin paper products, however, have also been shown to contain PCB residues, probably as a result of the paper manufacturing processes. Data on current production of food packaging materials indicate that the levels are decreasing and are controllable so that the potential for PCB contamination of packaged foods can be minimized. Dietary Intake National monitoring data, and in particular FDA's total diet studies, indicate that the human dietary intake of PCBs is of a low order. Fbr example t the dietary intake expressed as mg/kg body weight/day, and based on food consusption approximately twice as high as the normal diet, was less than 0.0001 in FT 1971 and 0.0001 in the first-half of FT 1972. As a point of reference, from 1965 to 1970 dietary Intake of DOT was 0.0007 mg/kg body weight/day. Other investigations further disclose that except for unavoid able background levels in certain food#, the PCB contamination of food can be significantly reduced or eliminated through appropriate controls. Man and the Ecosystem In air and water away from Immediate sources of waste discharge, levels of PCBs are low -- a few mlcrograms per cubic meter (parts per trillion; ppt) in air and less than a part per billion (ppb) in fresh water; soil or bottom sediments contain a few parts per billion, up to several hundred parts par million (ppm) near some industrial outfalls; from tenths of a ppm to tens of ppm in fish and up to hundreds of ppm in some fish and birds near the top of the food chain. To illustrate these relationships, 1/8 of an inch is about MONS 201865 16 on4 trillio'nth of the distance to the moont end e pert per million Is about $ steps on a walk from Washington to San Pranolsco. Man, who Is at the top of a food chain, may also have PCB residues In his body fat. Analyses of tissue residues from 688 persons from three States showed two-thirds to hare detectable residues, but only one-third contained residues of 1 part per million or more. PCBs have been shown to accumulate in fish and aquatic invertebrates to levels of IS,000 times that present in the water, and to be accumulated from concentrations as low as O.Co parts per billion (the lowest concentration for which experimental data are available). Thus, to keep levels In fleh as low as possible, and in any cass from reaching the 5 parts per million established by FDA as an interim action level for safety as food, concentrations in water should be less than 0.07 cart oer billion, or to allow some safety factor, 0.01 ppb. This level in water should be sufficiently low that fish and shellfish are not themselves adversely affected. Esd. sting data suggest that the principal route of-PCBs through the environ ment is from waste streams into receiving waters, downstream movement in the waterways in the water and on sediments, accumulation from the water by aquatic organisms, and transfer to birds and mammals (Including man) through residues in fish that are eaten. Another route to man is through migration of residues to foods from PCB containing packaging materials. A third route to man may have been absorption through the skin from handling carbonless carbon paper. Ihete exposures are being rapidly diminished since PCBs are no longer used in carbonless carbon paper. Presumably most of the PCB residues in paper made from waste paper also cams frora used carbonleee carbon paper, which is no longer used in making food packaging material. V.A. BIOLOGICAL EFFECTS ON MAN (METABOLISM, TCQCICXOOr, AND RESULTS OF HUMAN EXPOSURES) Human beings occasionally have been exposed to high levels of PCBs. Sene exposure has been the result of occupational exparlence or of accidental con centrations in food as in the accidental contamination of rice oil in Japan ("Yusho" episode). As far as can be determined, the number of exposed persons in these cases has been limited. Another source of contamination and exposure (although at a lower level) has been fleh containing PCBs. Samples of human fat have been examined to a limited extent for the pre sence of PCBs. As a result of this limited sampling, it has been concluded that some persons carry a'body burdtn of PCB in their fat tissue. In contrast to the ubiquity and levels of ECT end its metabolite, DEE, in humans in this country, the current levels of PCBs do not appear to ba as uniform in distri bution. At the levels in which they ere found, PCBs do not appsar to present an imminent hazard. 17 HONS 201*66 The acute toxicity of commercial PCBs In experimental animals appears to be low. In the case of the human exposure with the Tusbo episode, the average dose to that exposed population was calculated as 2 pa. From this incident, it was estimated that the minimum dose necessary to produce posi tive clinical effects was 0.5 gm. With a sufficiently high dose it is possible to distinguish a number of toxic actions of PCBs and their contaminants In manuals. Alterations in the functioning of the liver have been observed in a number of species, and these are attributed to PCBs. It is likely that other conditions, such as chloracne (severe skin eruptions), liver damage, and hydropericardium (accumulation of fluid in the sac which surrounds the heart) may be caused by a contaminant, chlorinated dibenzofuran. The limited mammalian chronic studies of the Monsanto Company indicate no evidence for carcinogenicity. The possibilities of embryotoodcity and mutagenicity, however, are poorly studied and, hence, are ill-defined. Because of the possibility of human ^xp^vure to PCBs, the task force recommends the following additional studies! 1. Toxicological evaluation of a select number of representative, purified PCB isomers as well as purified trace contaminants such as the chlorinated dibenzofurans. 2. Definitive mammalian elaboration of the kinetics, absorption, dis tribution, metabolion, and excretion of the technical PCBs as well as a num ber of key isomers and the chlorinated dibensofurans. 3. Elaboration of the subcellular and Intracellular actions of the technical PCBs as well as a number of representative isomers and chlorinated dibenzofurans. it. More definitive epidemiological studiee of the PCBs with both more representative population sampling and standardization on the basis of lipid content of the' tissuee. ' V.B. BIOLOGICAL E7TECTS ON ANIMALS OTHEl THAN KAN The significance of PCBs to wild animals depends primarily upon the sublethal physiological effects of these substances rather than upon their lethal toxicity. They have accumulated in all portions of the natural environmental complex in a manner predictable from their high solubility In fat and their resistance to degradation. PCBs can ba lethally tcocic to some fish and aquatic invertebrates when concentrations in the water are parts per billion or less. They ere metabo lized and excreted very slowly by these organisms. MOMS 201*67 18 I r They are only moderately toxic to birds and mammals) lethal levels are similar to those of DOB. PCBs say have contributed to direct mortality of eome adult birds in the field* but not to an extent to affect populations. In sublethal exposure* PCBs are physiologically aotive and induee enzyme activity. Direct effects on reproduction have been sham for chickens, but not for dicks, quail* or doves. Sene studies tentatively suggest the possibility of subtle behavioral effects and of interactions with disease organisms or other environmental chemicals. Pull evaluation of actual or potential effects in the environment is harpered by the conplex nature of the mixtures that across PCBs* and by the Inclusion of contaminants In these mixtures. As experimental studies have been conducted with the unaltered products * as sold* the remit* may not properly reflect the effects of the components as they exist in the environment. Although fully'conclusive data are not Liable* the evidence for toxic and physiological effects indicates that the PCBs must be viewed as potential problems at present environmental levels. HOMS 201568 19 FOOTNOTES 1. Nisbet, I.C.T., and A.F. Sarofin, "Rates and Routes of Transport of PCBe in the Enviroment". Paper delivered at International Scientific Keating on PCBs sponsored by the National Institute of Environmental Health Sciences, and held at the Quail Roost Conference Center, Rougemont, North Carolina, December 20-21, 1971. (Environmental Health in Perspective (in press) 1972.) 2. Data supplied by the Konsanto Company. HONS 201869 APPENDICES Content* and Authors Pm Chemical and Physical Properties of PCBa H. F. Kraybill Food St Drug Administration Department of Health, Education, and Welfare 22 Use and Replaceabllity of PCBs Martin a. Broadhurst National Bureau of Standards Department of Coranerce Lil The Need for Continued Use of PCBs as Electrical Insulating Liquids ' Electrical and Nuclear Sub-Council National Industrial Pollution Control Council Department of Connerea 7? Occurrence, Transfer, and Cycling of PCBs In the Environment John L. Buckley Environmental Protection Agency (with assistance of Edward draining, EPA) 83 Occurrence and Sources of PCBs In Pood John E> Spaulding Department of Agriculture John R. Weasel Food St Drug Attaintstration Department of Health, Education, and Welfare 107 Human Directed Aspects of PCBs 122 Lawrence Fishbeln National Institute of Environmental Health Sciences Department of Health, Education, and Welfare Biological Data on PCBs in Animals Other Than Man Lucixle F. Stickal Bureau of Sport Fisheries and Wildlife Department of the Interior 158 Regulatory Action on PCBa Terry Davies Council on Environmental Quality ' Executive Office of the President 173 21 HONS 201S70 APPENDIX A Chemical and Physical Properties of PCBs Table of Contents I. Chemical and Physical Characteristics II. Problems in Analytical Chemistry - Comparison of Methods II.1 Separation II.2 Quantitation m. Contaminants, Impurities, or Other Chemical Moieties in PCBe Tables l - Oeneral Physical Properties of the Aroclor Chlorinated Cabounds 2 - Relative Retentions, Kiss Spectrcmetric Data on PCB Fractionated Semple Figures 1-6. Chromatograms of various representative PCBe, according to Armour 23 27 27 29 37 26 37 31-36 HONS 20IS71 22 APPENDIX A Chemical and Physical Properties of PCBs I. Chemical and Physical Characteristics The PCBs (trade name Aroclore In the United States, unknown in Soviet Union, Phenoclor In France, Colphen in Germany, and Kanachlor in Japan) are manufactured in the United States primarily by Monsanto Chemical Company. There are also suppliers in Europe and Japan. Because of their unique chemi cal and physical properties the PCBs have been widely used in paints, electri cal transformers, condensers, non-inflammable oils, adhesives, plasticizers, heat transfer systems, hydraulic fluids, caulking materials, printing inks, and many other uses where the nonflammability and heat resistance properties are useful. Monsanto Chemical Company, reacting to the conoern about extensive erwiromental contamination by the Aroclors, have recommended discontinuance and curtailed uses in equipment or products which inAdrc^tcntljr letd to con-- taminatlon of the environaent (food products, potable water supplies, and as an air pollutant). Presumably the history of the polychlorinated bipheiyls started in 1930 when an industrial use of non-flammable oils was introduced for electrical transformers, condensers, and paint. It was probably not un til the mid-sixties that an awarenaas of the envlroxaental contamination came about with the realization that after tiO years use of the Aroclors, there was as extensive a problem of contamination as with the organochlorine pesticide DDT. Swedish scientists drew attention to the faot that PCB has been found in fish and birds in thsir surveillance in 1966, and soon this alerted Investigators in other countries to the problam. Surveillance of total diets by PDA failed to report any PCB in fruits and vegetables. Perhaps the accumulation of PCBs in environmental substrates or living organisms can be associated with the particular chemical and physical proper ties of these aeries of synthetic chlorinated aromatic compounds. For exanple, the nonenvir omental degradability or biodegradability accounts for it as s residue in many media and for its persistence. Like DDT, closely related structurally, it will enter the organism, be stored in the depot fat, and thus be transferred through the food chain at increasing conosntrations. The basic structure of PCBs is shown below where x represents ary number of possible positions for chlorination leading to about 210 possible combinations, of which 102 are probable. (Midaark, 1), who made this calculation in developing XX XX criteria for these limitations, noted that the criteria were based on com pounds containing five to ei>t chlorine atoms per molecule and the number of chlorine atoms per ring differing by not more than ona. The Aroclors may consist of chlorinated blphsiyls, chlorinated terpheryls, or a mixture of these compounds. Invariably, although a specific numbered Aroclor may represent a molecular type and degree of chlorination or wei>t percent of chlorine, the product is a mixture of coeqpounds In a series such as 1200, 2500, LliOO, and 5U00. The first two digits represent the molecular typo, 23 MON5 201*72 and the last two digits give the weight percent of chlorine. For example! 1200 - chlorinated bipheynla 2500 - blend of chlorinated biphenyls ana chlorinated trlpheryls (75t25) hliOO - blend of chlorinated biphenyls and chlorinated trlpheryls (60tli0) 5hOO - chlorinated trlpheryls Thus Aroclor 12U2 would be a chlorinated biphenyl containing t>2 percent chlorine. These biphenyls produced by Monsanto range frae 21 to 68 percent chlorine. To refer back to the existence of many possible isomers, it is of interest that Aroclor 1260 would show the presence of 11 isomersj five containing six chlorine etams, five containing seven chlorine atone, and one containing eight chlorine atoms (2). Begley, et al,(3) studying Aroclor 125b, observed 18 distinct conpounds. However, as previously stated,the num ber of conpounas present or identified by mass jpectrographic studies is much less then theoretically deduced. The polychlorinated biphenyls which are chemically inert were described in the literature beck in 1881 by Schmidt and Shults (l) but aohleved by 9waim Company in 1930 and fully developed for industrial use in that year. During tha hO-year era, 1930-1970, it was discovered that Aroelora could be used to extend the effectiveness or lethality of organoohlorine insecticides such as chlordane, aldrln, and dlaldrin In pestloldal formulation, thus enhancing tha possibilities for proliferation into the environment (5)* Additionally, there ware Indication that PCB had a synergistic effeot on linden (6). Tha Aroelora, ae previously stated, are chemically inert, making them ideally suited for certain industrial uses. They are not hydrolysed by watar and resist alkalis, acid, and corrosive0chemicals. Sines they are not volatile, their boiling points rangd frem 278 C for Aroclor 1221 to 1*51C for Aroclor 1268, They are stable to long heating and can be distilled et ordinary pressure without any carbonisation or deoespoeition. Aa might be expected, since they are lnoluble in aqueous media, they are quite soluble in hydrocarbon solvents* It is belisved that PCBs ere more stable than DDT ana metabolites and, aooordingly, resistant to blodagradablllty or biological decomposition. Die proximity of the aromatic rings probably accounts for the lack of degradation of transformation as with DOT, which has an athana linkage intervening the'aromatic nuclie. PCBs and formulations thereof have e wide range In viscosity and physi cal state, from colorless moblle-llke oily characteristics to yellow-green clear mobile oil, to light ysllow viscous oil, to litfit yellow soft sticky raein, to white powder, to light yellow deer brittle resin, to yellow trans parent sticky"resin, to clear yellow-amber brittle resin, to a black opaque brittle resin. Other properties such as low solubility in water and high dielectric constants msks them versatile for industrial uses. Many of those WHS 201973 2h PCS properations have strong adhesive properties, and it is this use in bonding of paper and cardboard in certain packages for food, plus reuse of printing paper in manufacture of grayboard, that has led to a few problans of contamination of certain food pro&icts. A rather couplets compilation of these properties is listed in the attached table from a roport by Monsanto company. 25 HONS Z01S74 V" 00!BUI rUTIICJLl PMMRB Of BIB a*mocctlo* cphmorhjiumttob oooorraoorwa*i l?ri,.........................................................*......... Osier......................................................................... Ac UK* * KuJMJb 'nf*. ROM per Oe.)............ Cstfflfl*rt of MtMlm. iril*r 1721 Celeries* nettle *11 $0 N**. {n*l O.OUi o.cpon ur-w*?) mioi d.mhj Four** per fills* . iyC CTT0F).................. DUlllUtl?? Jltnf* . ASTK ttiTO (Hod.1 corr. C............................................................... Iveperetl*'' La** * 1 * 1STJC 0*4 Ned. it .........................................................| mi. 10CC.........................................................t hri. fleeh Fain . Ci<r*lr.4 M*n Cup................ *0 Pt-* Fein * (lirtlvd C*e tap...*..,.. *C r i.iti-i.m ITS*.110* 1.0 u 1.5 lblj-lfoj )*> IW* Xtf* Peur - iflM 0-FT..........................*0 fr7*m *i r Crnula 1/Hlir un PreetlMlly Mlsrlecf Mill lU SO *U. . <**) o.oib 0,0007) <2f *100*0 1.1TO. 1.1*0 ttwiiro io. n a*o,in* 1*0 u 1.5 *: ic vs -no * uo* -.* ItfUt 12fc2 Frsetteellf elerltea NiMl* *11 50 Nil. 0.010 0.00044 <?5*- *e> " l.iti.i.m <n*/i5.*e) u. Ireelor ltbl eUarlm N 11014 F*Ua> pen, lMPt nebtt# U 50 Nu, (mu dreelee 17B U*i peUav TtHM Ml 90 Hu. <m*> 0.010 i.SSBfi I.liOS-l.Uf II.dk o.no --e.asau " <-* l.w-i.m str/is.rt) i. *0*-)T* ).o U ).4 0.0 be 0,b 1T*.1*0* **'15* J.o 4* b.0 0.0 4* 0.) 1.J6-1*** nr-** 1.1 te 1*1 0*0 4* 0* -- ' Rene Rene Areeler 1740 110*4 7*1 lev ten euttp rttle fo mi. unul o.ou (20*.100*C| I.Stt-l.W <*0*/H.S*Cl II.50 m'w1 o.f M o.l 0.0 U o.l Pens Rene -1* -T* 1M* 19* so* & krutini rotni . um t-ii.................................*e 1- - -- Fefrertlee Indet - D-llr* * J<TC,,.. *............* 1.UT-1.41I l.iiaa.Ut 1.427*1*42* ftMMitr ajrk.lt iiriwul JWf (N.rtl *t. U tt-Ml mrr <fk.k*e> jo-n *-* * Jt'kl . *-js iocr [ e-w Ui-n MMI teapereUlr* fir* ptm* <*f u ktiutf Oral L&f^ret* (eppr**,> . sf/Rf mo* Still XLD * rabbit* af/k| * 2000* eetinliliMd 01*0 biro* *1240* tooo* 6650* .Till. .1160. NJndiluMd wpimiuri4 m SOt ulit, in writ *!#3JI/JI In tn *11 tOf Nlit, lit *m nl> . 1.610-1.111 *-n T>-0 1*5-1*0 1.615-1.6U u-u MO-MO ltee-ifoo 11,000* th* l240e 11,900* -1240* 42000* fff 100 Min. In writ Ml* 1.647-l.M* 72*7* JfOO-hfOO - 10,000m 1240** 20QQ*e HONS 201*75 VH1 iW U|hi ua**r tl r*k* irielH iJ06 4liu u fr-toit* piNf SO MW, (ABU) Q.Qlli m------------ i.itM'Si U-w l.f DU. A (wlM) 0.05 D.HSM (to*.ioo*<> l-dobl.JLl (rtVJ5*C) U.M 0,5 to 0.6 9,0 U 9.1 t. *. 0.1 to 0.} 0.0 to 0.06 ton* Nor* tor* JS"-*1 ff* tom , UMlm Utf Li#w*n*, lMT* fertUlo rtoln 2 to. m Mton) O.OJ (i?3s*c) <*/ 13-n (Won' ____________1, - 0.2 to 0.) o,o to 0.01 ton* ; irtlr 5kU toll* franto Mn* ilto PMlt 2 toe. to (mlton) 0.05 t k a. fe. 0.3 0.01 # sfr ArMlor 5U0 Qmi, TUw> krlUU r**t* , ...i hpltui PMtn i toe. VI (mIIm) o. 4.4W (t**.|k*C] ISS^1 1 ' ..i.k te*3k> in5**> *#*.) m I a. M. 0.0) i.f t* t**rl-.ft to..) m tom 0.3 to 0.) torn ton* ;- 600-1*0 <i*r Ut)D0*n *1260m 10ffOQw ;J1NN 14.000** tOOOM AHM V0 <IQC0M *.no* ^TUM *noott - )U0 HONS 201B76 I II. ?roblama In Analytical Chemistry - Comparison of Methods II, 1 Separation One of the primary end early problem* In the Identification of the polychlorinated biphenyl* (PCBa) was that of posaible interference in the QLC determination of arganochlorine pesticide*, where the PCB occurred along with the pesticide residue. Curing 1969 and 1970, various investigator* worked on methods for separating PCB from pesticides (7-lb). An excellent treatment of the subject of PCB as a contaminant in the environment, as related to its detection in the presence of other compounds, is covered by Jensen (15). Jensen (15) in his review, has shown that seme of the earlier studies of DDT an! DDE in human fat by GELC must have been inordinately high. He first identified some QLC peaks in wildlife in 196b-66 that were not recon cilable but later identified chromatograph peaks from human fat that were not attributable to DDT or metabolites of DDT, which were more nearly com parable to peaks ascrlbad to PCB. The possibility that thase peaks could be attributed to naturally occurring constituents in fish eaten by man was dis carded when it was suggested that these eame peaks could ccme from environ mental pollutants. TO further establish the then uncertain composition of the chemicals causing the false DDT peeks, Jensen (l5) separated out one of the chemicals by QLC and subjected this fraction to mass spectrometry. The mass spectro metry data showed compounds with molecular weights of 32b, 358, 392, and b26. The molecular weight differences or differences of 3b mass units suggested one lees chlorine atom per position on a carbon atom. In essence, through calcula tion, he deduced that these unknown chemicals could only be polychlorinated hydrocarbons, in this case having 5> 6, 7, and 6 chlorine atoms in the molecule. He verified hie conclusion by introducing a synthetic or known PCB into the mass spectrometsr. He also found that PCS standard chromatogram matched those with the same retention tinea as observed in various sespies he analysed, 1. e., eagles, fish, or othar wildlife. It is Interesting to point out that failure to recognise such inter ferences led to spurious results and,data and obviously led to tha over estimation of DDT in our envlronmsnt, in man, in wildlife, and aquatic organisms. Jensen (15) referred to PCB as a new pollutant, but, as stated earlier, PCB was with ua in the environment since 1930 and thus it would be an old pollutant only recently correctly identified by appropriate analytical chemistry. In earliar work in the identification of some organochlorlne pesticides such as p,p'-DDT| o,p-TDR (DDD), lindane, dleldrin, aldrin, heptachlor, and lindane, some unidentified spots and peaks in TIC and QLC interfered with the detection of these pesticide! chemicals. Jensen (15) in hie work extracted the compounds from biological aaaples and, by ^propriate cleanup of some con taminants, identified the pesticides and PCBs by thin lprer and get liquid chromatography followed by mass spectrometry. In 196b, Jensen used TLC to separate the fat soluble chlorinated hydrocarbons from the rest of the saapla. 27 HONS 201*77 r For peeticid* an*ljsis, the common detector is tho slactron captura detector. For sensitivity, one can determine 1-vela at the plcogram range. However, this detector, not specific for chlorine, also gives an answer for oxygen containing compounds. Although the response here is much lower, this can be counter balanced if the level of o^gen containing impurity is some what higher. This system has certain Inherent disadvantages in that two different compounds ean have the same retention time and thus be detected as one compound or the recorded peak does not need to contain chlorine since, as indicated above, the detector is not that specific (15). However, by using different columns with variant properties, one can Inject a sample into tho instrument and thus secure a good separation. To farther demonstrate whether a compound which is responsible for a certain peak contains chlorine, one ean concentrate the sample and analyze by a less sensitive chlorine specific detector such as the microcoloumetrlc detector. This, therefore, enhances the specificity in this residue analysis. When Jensen (15) analyr human fat ft " by use of two columns, he was able to separate from human fat the two "DDT" peaks into four peaks. Two of these peaks were similar to those for o,p and p,p'-DDT, but two of the peaks were unidentified. As indicated earlier, he thought these peak* were due to naturally occurring components, which would be found in the fish consumed, such as pike. He was able to rule out this premise by treating the sample with alcoholic KOH and H2S0(i which would chemically alter DDT but not the more stable or inert polychlorinated bipheryl. Jensen simultaneously noted that samples of pike from a certain region, containing the then unidentified component, were correlated or associated with an area of extreme pollution. Similarly, eagles that fed on pike showed this unidentified component in their tissue. The com pound in the eagles had the same retention time as the pike, thus confirming that this was a problem of biological magnification rather than the mere occur rence of a natural biochemical entity. Another speculation was that metabolites of DDT could explain the appear ance of unidentified peaks. Interestingly enough, these same peaks were found in an eagle sample collected in 191} (prlbr to use of DDT in Sweden), thus im plying that the DDT metabolites were not the potential unknowns. In addition, mercurials were considered, but the occurrence in water, fish and pheasant* did not correlate or show a consistent pattern. A method for the separation of polychlorinated biphenyls from DDT and its analogs has been developed by Armour and Burke of FDA (16). Identification by means of a combination of high resolution gas chromatography and mass spectro metry has been carried cut by three Independent laboratories in Sweden (17), Holland (2) and the United States (3) in addition to those named above. There is a need to measure PCBe at extremely low levels of the order of 1 part in 10 or less. Accordingly, the method must be both specific and highly sensitive. Hence gas chromatography, using electron capture detection, has bsen extensively used with occasional identification and structure con firmation by gas chromatography mass spectrometry. This involves such steps as (a) sampls preparation, (b) extraction of PCBe, (c) removal of interferences, (d) concentration, and (e) final gas chromatography and measurement. HONS 201878 28 Some biological samples require nore extensive pretreatment then for water or effluents from industrial plants. The measurement of PCS concen tration of effluents Is a simple procedure involving chromatogram of sasple and then chromatograms of standard samples developed from known PCBa. For more accurate analysis, calibration graphs can be developed frcm known speci fic peaks in the standard samples (15). In the following charts (Figures 1-6) some chromatograms of the various representative chlorobiphenyl Aroclors are presented according to Armour (18). Some additional points might be mads relevant to separation and quantita tion of PCBs. First of all, in ssparation, the methods used prior to quanti tation of residues in samples containing PCBs and chlorinated hydrocarbons fall essentially into two categories * la) those which necessitate destruction or alteration of one or more of the compounds and (b) those whloh do not. Psakall and Linear (19) have described in detail the procedures used for separation. p Briefly, the first group requires nitration (HHO* + H^SC^) treatment at 0 C for 5 minutes, which destroys or alters maqy of.the orgamochlorlne pesti cides i thus PCB is lsft unaffected along with "t and 91C. Some workers such as Armour and Burks (l) reported that cotqplex chromatograms resulted after nitration* which could not be related to the unreaeted DDT-PCB mixture. Thus, nitration was not pursued as a practical means of separating DDT and PCB for further analyses. Saponification with alcoholic NaOH or KOH will dehydrochlorlnate some pesticides such as Perthane* Toxaphene, DDD and DDT to their respective Ole finic compounds (20). Perhaps the more desirable technique allcws for special separation of many chlorinated hydrocarbon pesticides from PCB. This Involves using various columns and solvents. Another procedure is to use a series of differing polarity columns in the gas chromatograph at the time of determination (21). II.2 Quantitation Koeman, et al (2) measured residues in Japanese quail by using one of the peaks in a phenachlor EF6 mixture as standard. Rlsebrough (22) quanti tated relative levels of PCBa by assuming that each PCB coepound produced the same peak height with the electron capture detector as the same amount of weight by p,p'-DDB. After adding the heights of the individual peaks, the total was multiplied by a factor derived from measureewnte of standard solution# with EC and MC datectors. Jensen and oo-workers (23) reported concentrations of PCB as the sum of all PCB components and based the esti mation on several detection systesis such as mass spectrometry end EC and MC detectors. In spite of all these techniques, these investigators consider the method epproxlmate and correct only within a factor of 2. There are other modifications of techniques, but with all the quantita tion methodology available, relative estimates of concentrations of PCB are MOMS 201879 29 QAS CHROMATOGRAPHIC CONDITIONS Figures 1-6 Columns; (1) 10$ DC-200 on Chronosorb V HP (2) 15$ QF-l/l0$ DC-200 on Chronosorb V HP 6 ft x Lum id. 200C 120 Nj/nln. ' Dstsotori slsetron capture (tritiumJ 200C one nanogran heptacblor epoxide causes one half scale recorder deflection MONS 201880 30 f Figure 1. Aroclor 1221 101 DC-200 HONS 2018B1 1 Aldrin pp'DDT Figure 2. A. Aroclor 1242 10% DC-200 TIME(MINUTES) n MOMS 201882 Figure 3. A. Aroclor 1254 101 DC-200 r^tmtrrfmWfTTwnwmwT,,,wrwww|,w 0 *10 tt * 20 29 SO 99 40 49 90 Aldrin pp'MJT B. Aroclor 1260 10X DC-200 rwwiT'n'iT rT'iT^T'^TTT^'i i rr rv nri i i i i i m i i it*1 r i r i"i i i i 0 9a K> 19 a 20 29 90 99 40 49 90 Aldrin ppW TffT 99 C. Aroclor 1262 10X DC-200 r Aldrin 1^ I I I WIH I I I I I I I | I | I |J | | l I I | | I I II I I IJ I II l"l"l ^ a 20 29 30 35 40 49 90 99 PP'UOT ____________ _ HONS 201883 Figure 4. Aroclor 1221 15X QF-1/1QX DC-200 Aldrin HONS 201884 B. Aroclor 1248 15% QF-1/101 DC-200 I r r-i- in i o fp'cor1* TIM E< MINUTES) HONS 201885 36 HONS 201886 only approximate. At auch time, when om la abla to synthesise the individual PCB components comsor&y found In th* snvlronwnt and Idratify than In tarna of Individual peaks, than tha aatlnatlon remains, a* stated, a relative concentration. However, for noat biological aaaaasnant work, tha oorract ordar of magnitude and accurata ralatira ancunta of PCS provide tha requisite in formation for tnla purpose. - III. Contawlnanta. Inpurltlaa. or Other Chemical Holatlaa la PCBs In tha analysis of tha polychlorinated biphenyls, ona rasountara a problem similar to that of tha polyehlorcphenols ana 2,U,5-T In that oartaln contamlnanta or impurities prevail. Ibaaa i^mritAss arise from tha baalc starting oatariale or ooraoutvie uaad in tha aynthesle and alao trm tha pro cessing conditions used In tha chlorination procaduraa. In thla reapact, tha aariaa of confounds identified through CfcC and aaaa spectrometry are semewhat similar in nature to the epee tram of dioxins found in working with chlorinated phenols, haxaehlorcphene, 2,U,5-T and related synthetic organic chemicals. It has bean noted In tha bloaeeay of various Arodors for toxicity, usually tasting on chickens, that there was a variance in toxicity of oartain PCS preparations. Since tha occurrence of lesions resembled those of chick edema in birds fad PCS, thla prated a operative study between three cexpounds, Fhenoclor DP6, Clcphan A60, and Aroclor 1260 by Foe at al in 1970 UM. In this study, *ha apsolflc PC8s wore fractionstad, analysed, and bloassayed using tha chlok embryo assay. These studies revealed tha presence of certain polar ooqpounde which ere present as Impurities in tha various PCBe and thus explain tha variance in toxicity of certain coontrolal PCB preparations. In Table 2 soma of tha retentions and aaas spectr cmetric data of soma of the peaks identifying the presence of soma dlbeneofurana, chlorinated napthalenea, and aaaoolatsd chlorinated biphenyls are indicated, proving the presence of i^urltlee. Table 2 Relative Retentions. Mass Soeotrometrio Data on PCB Fractionated Samole Peak No. Rslatlva Retention Mass Nos. and No.- of Cl atoms oar mol Identity of Ccapouad 1 l.UO 3Qb (Ji Cl) Tatraohlorodibenaofuran 2 1.56 332 (6 Cl) Karachior onqpthalana 3 1.7b 358 (6 Cl) 392 (7 Cl) Hexaohl a roblphe iqrl Haptechlorobiphanyl it 2.U2 * 338 ( 5 Cl) 392 (7 Ci) PentachlorodibanjofUran Hep tachlor oblpheiyl 5 3.1* 366 (7 a) Hep tachlor onap thalene 37 HONS 2017 Thus far, the dlbenzofitrani, the chlorinated napthalone* and chlori nated dlpehnyla appear to be the major contanlnants or iapurities dotoeted in -various PCB samples. It Is not unlikely that other chemical aoietiea will be characterized as further identification work proceeds, these con taminants arise, as previously indicated, by method of manufacture and the procedure for distillation of PCB, In which NaOH can be uaed. Through this NaOH treatment at elevated tenderatures, sequentially polychlorohydroxybtphenyls are produced and then, through loss of hydrochloric acid, the diberuofuran derivatives result (25). The chlorinated napthalenes are far less toxic than the chlorinated dLbon-.v>furann (26). Thus, one might expect, with the varying ratios of impurities with variant toxicities in different PCB staples assayao for biological effects and toxicity, that the end result will depend on such factors In examining various cornerclal PCB preparations. MON* 201BB* 38 FOOTNOTES 1. Widmark, 0. 1968 - OECD Report - Sweden. 2. Koeman, J. J., Ten Noeverde Brauv, M, C. end de Vos, R. R. (1969) Nature 221 1126-28. 3. Bagley, 0. E., Reichel, W. I. and Cromartie E. (1970) J. Assoc. Office, Analytical Chemistry 251-261. 4. Schmidt, H. and Schulte, 0. (1881). Ann Cbem. 207. 336-3lili. 5. Sullivan, W. N. and Hornstein, I. (1953) J. Scon. Entomol 1, 158-159. 6. Tsao Ching Hsi, Sullivan, W. N. and Hornstein, I (1953) J. Econ. Entomol ij6, 882-884. 7. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918, July 1, 1969, Armour, J. and Burke, J. 8. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918A, July 23, 1969, Armour, J. and Burke, J, 9. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918B, Sept. 30, 1969, Davenport, J. E. 10. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918C, Oct. 13, 1969, Armour, J. and Burke, J. 11. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918D, Jan. lit, 1970, Armour, J. and Burke, J. . 12. Laboratory Information Bulletin, FDA FSCS/ACFC No. 9l8E,Mar.ll, 1970, Armour, J. and Burke, J. 13. Laboratory Information Bulletin, FDA FSCS/ACFC 1157, June 17, 1970, Westfall, J. E. and Febringer, N. V. 14- Armour, J. and Burke, J. JAOAC , 761-768 (1970). 15. Jensen S. (1970) PCB Conference, Nat'l. Swedish Environment Protection Board, Research Secretariat, Dec. 1970, Solna, Sweden. 16. Armour, J. and Burke, J. (1970), IA0AC, July Edition. 17. Widmark, 0. (1967), JAOAC 0, 1069. 18. Armour, J. (1970) FDA Laboratory Information Bulletin No. 9l8f FSCS/ACFC, pp. 1-17- HONS 201889 39 r" 1?. PeakaU, 0. B. and Linear, J. L, (1970) Bio Science 20, No. 17, pp. 998-961*. 20. Archer, T. E, and Crosby, 0. (1966),'Bull Environ Contan Toxicol 1, 70-75- ~ 21. Simons, J. H, and Tatton, J. (1967) J. Chromatogr. 2J, 253-255. 22. Risebrough, R. W.' (1969), Chemical Fallout, Q. C. Borg and M. W. Millar (Ed.) 23. Jenson, S., Johnels, 0. A., Olsson, J. and Otterllnd, 0. (1969), Nature 221*, 250. 21*. Vos, J. G., Koanan, J. J., Van der MaAs, H. L., Tan Noavarda Brauw, M. C., and DeVos, R. H. (1970), Fd. Cornet. Toxicol 8, 625-633. MOMS 201090 1*0 APPENDIX B Use and Raplaceability of PCBs Table of Contents I. Dielectric fluids A. Capacitors 1. Advantages and Disadvantages of PCS in Capacitors. 2. Replacaability of PCB in Capacitors. 3* Extent of Capacitor Use. ' B. Transformers 1. Advantages and Disadvantages of PCB in Transformers. 2. Replaosability of PCB Transformers. 3. Extent of Transformer Use. Z*l li3 63 SI II. Industrial Fluids For Hydraulic, Oas Thrbir*, and Vacuum Pung> Uses. A. Hydraulic S3 B. Oas Turbines C. Vacuum Pump Applications m. Heat Transfer Applications se A. Advantagss and Disadvantages of PCBs an Heat Transfer Fluids. B. Replaceability of PCBs as Heat Transfer Fluids. IV. Plasticiser and Miscellaneous Uses. A. Adhesives 59 B. Textile Coatings C. 9urface Coatings ' D. Sealants E. Printing F. Fire Retardant ana Flame-Proofing Compositions* 0. Miscellaneous Applications. til MOMS 201891 APPENDIX B Use and Replaceability of PCBs Table of Contents (Continued) ** V. Summary...................................................................................................... 66 Tables ,, 1. Typical Properties of Liquids.................................. U5-U6 2. Physical and Other Properties of Lubricating Oils, Engine Oils, and Hydraulic fluids........................... L7-50 3. High-Temperature Lubricant Specifications........................ 56 li. Some Properties of Pumping fluids................................... 57 5. Decomposition Temperature Ranges of Several Chemical Classes....................................................................... .6 Approximate Maximum Compatibility, phr, of Plasticizers With Various Resins......................................... 60 61 7. General Properties of Some Aroclors (PCB)....................... 63 HONS 20i li2 APPENDIX B Use and aeplaceabllity of PCBs I. DIELECTRIC FLUIDS _ Dielectric (electrical!/ insulating) liquids are iag>ortant to the electrical industry for filling agents or lmpregnants in transformers, capacitors, and other devices. Besides their electrical functions, the liquids may also be used for cooling art arc quenching functions. De tailed discussions of dielectric fluid applications are available (l-L). A. CAPACITORS Generally, industrially important capacitors use liquid impregnated cellulose paper as a dielectric. The required properties of the liquid aret 1. Non-flammability (important for preventing fires, particularly in indoor uss). 2. Dielectric constant matching that of paper. A good matah reduces electric field inhcnogeneities, increases dielectric strength and lifetime, and allows deoreaae in capacitor sice. 3. Low dissipation factor (reduces energy loss and destructive heat ing in a capacitor;. Li. High dielectric strength (prevents breakdown and allows decrease in capacitor site). High chemical stability (increases capacitor lifetime and stabili zes its performance). 6. Low vapor pressure (increases physical stability). 7. Inert decomposition prodicts in an electric arc (prevents explosion or corrosion following breakdown). 8. Low toxicity of the material and its dacomposition products. 9. Low cost* ' 1. Advantages and Disadvantages of PCB in Capaoltors The PCB capacitor liquids, commonly called askarels, are mixtures of chlorinated biphenyls and chlorinated benzenes. Several standard mixtures are specified by ASH (5). The askarel capacitor liquids and their de composition products are non-flamable. Thus their use in capacitors greatly reduces firs and explosion hazards. This characteristic permits economies where safety codes require fireproof enclosures for cspacltors containing flsmsbls liquids. The dielectric constant or the askarels is high compared to other common dielectric liquids. Doubling the dielectric constant of the dielec tric allows a reduction by half in the area of the cepacitor electrodes, and a significant saving in the oost of construction and installation. The dielectric constant of askarele closely matches that of the capacitor paper. HONS 201893 1*3 The askarels are adequate with regard to dissipation factor and dielectric strength and have good chemical stability and low vapor pres sure. The breakdown products, in particular HC1, have the advantage of being non-flammable, but are highly corrosive. Oils dictates the use of special corrosion resistant materials inside the capacitors. The major disadvantage of the aakarels is their suspected toxicity. In ordinary capacitor usage the askarels are used in closed systen to pre vent contamination from moisture. This practice also prevents the askarels fran reaching the envirorment. However, when electrical failure occurs, sealed capacitors can leak and are ordinarily discarded. 2. Replaceability of PCB in Capacitors Capacitors can be made dry or with gas dlslectrics. Dry capacitors have Inferior electrical strength to liquid-filled capacitors and, tor comparable performance, must be made larger. ,, The major disadvantage of alternative capacitor liquids is their flammability. When comparing flash point data, as in Table 1, askarel flash points comparable to those of other capacitor liquids are sometimes listed, ASTM states that these are not true flash points but are pseudo-flash points which differ noticeably from the flash obtained on combustible materials, and such a flash point la not indicative of a fire haaard (5). The require ment of non-flanmability for most capacitor uses is critical, and capacitors with flwnnable liquids are forbidden in many casts by the National Electrical Code (6). In other cases replacement of askarel capacitors with flmable capacitors requires use of fireproof installations (6). The fluorocarbons are one group of non-flammable liquids which are used for some dielectric applications (1;. The ones listed in Table 2 have low dielectric constants and could not directly replace aakarels without increas ing capacitor size. The fluorocarbons have low toxicity but the decomposi tion products may be toxic (l). They are generally mors volatile than aska rels and are considerably more expensive. The fluorocarbons are a possible replacement for PCB liquids for capacitor use, but no fluorocarbon liquid is known to be available and acceptable for this purpose. Besides the problem of flamubllity, possible PCB replacement liquids generally lack either a sufficiently hii dielectric constant to keep capaci tor size down or a sufficiently high dielectric strength. Bbr example (see Table l) the silicones have the disadvantage of a low dielectric constant whereas the organic eaters often have poor dielectric strength. Some sili cones deteriorate rapidly under electric arcing (7). The acceptance of a PCB substitute is a cosplex process involving not only users but also various regulatory groups. In most of the electrical industry, regulation is non-governnental, and tha primary regulatory influ ence cones from Underwriters Laboratories, who test products and decide on their suitability (8). In addition, control over electrical materials is MOMS 201B94 Uu Vecautp. VIS K*C I14C M-IM'C VinM|. CL 1S*C sivc M-IM'C FlaiKppa* can a*. *L *?:4it* Nifr. KOM/gm Pane paaif. C SfMciPc paily, IU"C 1>C CaaTrfi (lU/hWUCPJ__ Mn pa* at TMi mm, t VahtDtp. !#* laIwW 1' (IW cm) CAtMMlaLM Ml W Ml w*c _ _____ tr m_____ _ IMkMi hMr. M Hi __ Il*r" Mmli._)_M_*C_ Va mum iMiHWi. Pw-ta______ IMMM* MM UM scr in 14V C* -*s.* M* MMi MMU* W 11.5* .Ml' f1>CMar M ir jr n 1M a* r -MV MW* MM* 0.070* >ir MM" TYPICAL PMPtffTE$ Of LIQUIDS OH-----------Pipe itaip am* atm 4 4 nr 11*5* 0T Ml' Ptp* caWt * liMM 1.100- 1>1" P00*r 0M* l?*` 1* i* r -nr * a KIT r --nr M* Mia* OtMMI* rwr 0.072* 154* 1' - *4M* Mora MV oor -71' .nr MI4 mi' >30- >w >15- >11' .Ml" Ml Ml" POMS'* III" P.PM5'* >r.r-~ >iiicr - flpMMr ;oo.oog2,200* mi* 01* i.r ' w mi- >15" m* .MS'* Ajklrib -- <0*42 3001 51 5102 02-42 III14 HW-/5X) * si 1007 44-40 40 <i* 144.1' ) 4W It 49 m 45 1 H 4 <! Is 3.2 1 *.K 1*5.3* i i' i4?r <4mi* 0.010 men 0010 mjr 515 ma ? CtC mu --35.5 -140 -7 0 i<?0 1.1* 0MT1 MI m* >51 s 110 MTS 0.00* 240 0 >55 iJ 1.30 MM* MW 5150 >35 > >45 0.00070 0057 J4S.0 >11 II > 54 MOM' 0.554 v*S5 n Ml Ml Ml Ml Ml HONS 201895 -FtoVfOGH'tOfft (UFA0 CJjQ TYPICAL vncpwlj. SUS. 25"C 37.0*C n-i'c -/! ViKBilf. a, *C JT.*C 99-100`C |#M Of, *c Aciftr, nin KM/m fou |M|. *C 13t too Baa -10.7 -/Ml -10 0 -114/-oa Sprtik ranty. li.4*C 75*C Caf afcon.ix/nl'C Iffenitf cipQk. IfirLlUBcHta'K't/iBl IBTU/hr!ttt*X*F,'(IU 01 imy print at 740 att *C VvUlkfHj. n#8 tan DiHrc MM' l4.7S4oal IHtnoa BBMMt. 40 H ir Hi Id* Hr' ]J \.m .0017 o<m 177.0 too lit 190 i.u/t.ia . I.M/1.14 .MMirMMO 0070/0.040 aao/7747 70/10 101/1.41 101/1.43 OivipHiairtacMr, M Ht ' 10* Ht ir hi Villi rtwlWtK. ihir.-(9 <0.0003* <0.0003 <0.0003 miv` <*L*0*04 <0.00004 -/>4rt0" 6.U IM M 10.5 --100.0 1.79 1.77 AO14 --90 6.996 0-00003 0-00*54 0.001 1011 13 *4) >1i*r IA4 1.04 1.67 1717- <3.4003* .00013" <00003 <0.0003 A0001** Oalfl** U10" MtOPEItntS OF UOUIDS--caatawd jonbACS -- OMkUic *! 6tft?f Sm6 Tri* SttnU Cm(t AtcUorf* Oil Slurllt 3bO 137 9 100 60 29 >30 710 200 140 5* >113 100 500 900 140 >171 96 291 40 7 147.3 -11 --52 7 -HO -- 21 4.4 71.7 0.979 .00047 0.066 6.9T1 0.471 6*59 6.99S 0.00041 00447 6.6606 6 ooeoo* C.0*057 0.007 oooo 0-161 6.105 i%* ' 13 <134,* n 71 1.73 1.7J on 1.73 7 71 1.71 <0.0001 <0.0001 <4 0001 3.00003 >laic=r >1110** Tmr* J.79-' 0.04* laio" i.sr*' 17 0.0047* 6.61 000011 o.jaio" InlO* ---- ----- Butyl Batyl Srtncrtr HapMA- nau Tftrft Iwfcirjl OWaU 46 61 6 175.6 -10 0 16 205.9 -17* t 4.4 5.1 - 4.1 661 0 014 7.014 ooooii 0.0011 66065* It 10* <HlO" tlMcn* GJ)uf S6c*t Ettcr 6m Fl/iJ 122 195 118 107 0 0<.1-5564m1 1 1159 0.607 0.00047 .666645 -60045 .660527 0 0*0 194-204 >171.1 2r 2 45 41 2.45 0CJ5* CQ*MX tilV' ` ''CFCF.O'.CMFCF. ` Cf. a astm moo I U1 QU < astm on 4 AST* t * ASTM 0077. SurAtfHy *f MTT hr 4*4 racavty )h MA ncafeh to--4 MlMm KaMJ In UMt 4a4 am km BrlcramaA f ASTM 0444 *STM 0474 0 W*-M h 44 15 ( MiapM IB A 30 I" nCJOrr at .SO* tar M Ml. 1 ASIM IKA4 I as:m im 1 r km afltr 40 Mi. at M0*C B 100 HI * ASTM 014* * 10'Mt ASTM 0130. I HONS 201896 Teb1e 2 P`.ysteal and Other Properties of Lubricating Oils, Engine Oils, and Hydraulic Fluids rivia. Oiwlcil C1*M or tmna Nanwf 44 (4ilf) tca-sm HLO-7217 IUU RMt) M1L>H-4003S MIL-O-34o4(0*m Mvtl J-U) WmkI Oil < m " - fcpfcrt--1 a m 09 * " * VlnKUn, 1*0 <WMl M*ml Oil mm +m . m o KhrltM ciycet Oljreal !U;lm ClfCl * 301 SltfT (tita'lcfc 211 " " 3t0 " - in ||m toimaii) lm 901 (Si*U) Veto MM IM Vc M u-il lew U'404-1 NnpNflit* MOO " * MU " lUJ - 1110 * 1130 Olfcel 0 ttawOtyool m * l* m SO Ohtaf^Olywl < *MUI** 1ht*r-011 kiltU* NI|Ufl*M Clywl m m m o TrUfyl WiHnti Imt * m mm m <* mm vikmIo. c* 100*9 HOT Specific Cmit? (Wttr>l) run Mm *r 13.1 IM -- -- 14 ttlacral Oil* }. M ** *- 3.13 0.04 0.00 -- ** 0.00 *430 *440 ** -- 30) 114 * f ** 0.14 t* ia.2 * *- -* 0.92 ** " 390 23) -* 193 oil--U --< fctw CIf--U I.J 19.4 1.1 *) 43.2 43.2 41 91.4 34 10.1 -- -- * *14(130*9) 23.1(130*9) 29.0(130*9) -* 31 * - -- -- 140 *- 230 -- 1.043 -r 1.013 1.033 -- 1.01 # ** 0.93 * ** _ 433 -- 300 *- 310 -- ** Fir* 9ulat t -- -- -- 430 -* -223 133 mm 300 400 323 -- Au(oi|nirln4' IhfUiMo Tep*r*tur* Tap'ratart *r *r 443(3) 400(3) -4*4(30) 700(27) 102. 4*200) 470( 30) 437(4) 431(2) ** 440(10) 723(30) *420(331 -- -- 034(30) 0( 30) 90)( 30) 147(3) -- -- 130()U 10*01) 743(30) 143(20) 433(34) 132(20) ** -- --- --- > *- ** U.l 13.0 12.2 49,a 42.0 3.9 1.20 303 410 >1100(31) * 0.0 1.143 303 440 1020,130(10) 4.1 1.143 -- 400 >1200(31) 3.0 1.13 403 490 1020(3) 4.0 1.143 490 4M >1200(31) NONS 201697 Tku2 (Cwt rinU CWriul tU t CanaaniaO HIL-H-lf4l7(TVp 1) Trlcf|l nw*fk*( iriKt;i Trltaanpl FlutfliiK *c PrOml r-4 Caliataaha 110 (Shall t.P.ft.) Mital (30 (MhmM*) Triaryl Iheaphata but N *i a frlaIkyl IbifUta bear N a lhaaphala btaa-CkUllatla* Ijiiarathna ' V taaaphata btaa *a r Plaaal 241 M-MmijI tahacata Fla ml 1U Plaaal 173 Ncaal n 1-lMattrl Mipata ' H-lwbcpl M(Ht( hlytatar Hlt-L-7404 (0-40-11. bM 4040) Ichacata-allpata Mtatir fclL-t-7404 (1-10)4) 41-7-achalhuyl bkacata HU-1-41364 (0-40-7. IP-4330) Trtaathylal rnpua btaa Klt-L-4136 (0-40-17) a a a* HIL-L-4136 (0-40-13) IIIt-t-4116 (0-41-17) HU.-L-4I364 at aa aa HU3-34-S0I (Tnan, 11-1*34) Maatar TP 4331 (Oy.>nfti() Trlnathylal Paapaaa beat P/0 (taaa 4173) Myaaul 700-40-34 TrInathpalfrapaan Tai- filaatirltl PtapMa lataa m m 4t palarpaawta HL0-M-404C 00-34-144 00-34-374 Tatra PoOaayl Ulna Olphaayl 4l-a-4a4*crl 31 li 0cta4acyl trtactyl Sllaaaa _ _yi*<aaltT. ca 100*r110*T Spatlflt Crtvlty (Vatrr-I) Plaah taint *T Flra Aaiiol to11 tool' ftaampaalctea taint Tcaparatura Taaperatata p-y ** 31.3 -* *44.4 30.4 43.4 M.i fhaaMata tatara (Cent) ** 4.11 ** -- 3.0 `* 1.17 0.424 *- 1.34 3.4 l.3 4.4 1.143 7.4 1.123 11.7 4.44 14.3 130 1M 11.30 13.1 14.4 13.44 13.71 14 -* -- -* -- - a*4 Dtbaatc Act* Catara 3.31 1.77 3.34 101 0.411 0.416 0.410 1.013 3.1 3.3 3.4 3.43 3.41 3.34 -- -* * * -* -- 3.1 0.47 - -- -- *0.47 1.0* 0.431 * m ' *- - 470 ** 403 -* -- * * 430 743 430 473 433 443 340 470 340 470 410 *30 400 **S 413 *40 3*0 670 *37 *40 ** -*34 473 433 *13 *70 373 440 333 *73 310 433 *73 -* 310 -- -- -- 1040< 14) 1110(17) 3*3(13; 1*4(11) 11*4(3) 1100(31) 1014(3) 4/3(1!) >1300(31) .. 660(*6) *340(13) a* -- ** 711(11) n* -- 7. *44(7) 733(30) 7M, *41(7) -* -- -- 3400(31) 714(1) 703. *07(30) 711. 100(30) .. ** () 373(13) *630(24) a. .. ' -* *410(1*) ** -7*4(30) 404(H) 34.31 37-1 17.3 fiisss 4.37 4.1 3.74 * 333 IS -- 330 304 *- 310 344 773(17) *40(11) 740(17) 430(13) 3440(13) *- HONS 201899 Tatla 2(Caat) ruu . HU>-34*3SZ uo-3e-4io HLoot-tu ALO-37-7 .Cfcaalcel Claaa ar Caamaat - OcMtacrl trlAaeyl Sllaaa OaAecyl trlOecyl Ollaaa IMwrl dactyl Sllaaa Tatra aaeatyl Sllaaa ----- ***>. ta ioot HOT Syectdc Cicvlty (llcter-l) 71.1 10.4 11.1 77.10 Silence (Cent) 4.0 3.0 1.0 4.11 -- -- *- *Urh Salat a M 33) 310 34) Sira Saloc *F 373 373 34) 400 Tatra (I-ethyUicayl )|1 Uaata trail s.r.i Oraalta 0100 Onalla Dll Itg-M-U) (baaaate N>U) Mt-M'IM (aelUegcfcceS, Mm Varat lata 1-M Vartllufca F-44 hw Contat HO tw Caralag MO tw CdTtii yoo lw Caralag 330 lav Caralai TOO av Caralag 710 M-37-70 M0.}).Mt (Cl 01400) M0-97-M) (Cl F-30) Flaerelvhe M SyAraal 4-700 Arechlar-1140 Aterhler-1241. Arachlar-1134 Scfcyl kaiyl Slllcata (l*atlrlkai|rl) Slllaata SlllcSOata bea- r S3t Otaalta S 1R flaaal SlllcSSata btSOar Hllwt "* WHsics -- 31.79 14.) * -- -* -- 11.14 s.u -- -* o* .* *- SlllcN aaa FalyaatAyl illaaaaa hliaathfl II laaaaa hlr>tfc|l SIlaaaaa Slllcaaa Fair (aeebyl. fkaqrl) Illaaaaa Methyl Ikeayl Slllcaaa Ml Methyl Ifceayl Slllcaaa (SC 1M) ylae 901 7 ASlyete J1 3) 11.0 10.7 44.7 09 ta S7 l.S no 01.s u 17 -- ** ** ** -* *- 13.3 1.04) 1.043 ** -* *- 1.003 -- 1,111 a Tatracayraata btaaaaataS SI1 laaaaa aaS Mrnattai OlerteateS Slllcaaa Chlcceyheayl Methyl Slllcaaa -- -* blytrlflaarachlareechyleae 3 -* 1.00 ChlarlaataS NyCracarbea 47-S 9.0 1.41 VacrachlaraSlfhaayl 43.0 J.t 1.41 TrIchlaraSlphaayl 17.7 -- OilarlaataS SyOrecarhea ** -- a* *- - - 3S3 440 370 430 340 4)3 313 430 313 440 390 440 330 440 140 ** 1)3 MO 470 000 303 313 330 -- ** -* 300 710 -a ** * 330 400 300 ||M 330 433 ---- Aatalgaltlaai^ hcwpriltla Iay<iitH taftntari *r *r 7)0(17) 730(17) 730(17) 740(17) -- 3?0(U) 714(1) 710(30) 714(1) 703(1) 714(1) 700(31) 700(31) 040(30) 410(30) 700(31) ** 740(30) ** -4 4)0(10) a. 7400(31) >40()l) ** aVHM) -- 300(13) 413(30) 704(1) *- 1103(11) 1100(31) *1103(11) 1130()t) <v 1003(11) 3*4(13) 430(30) >413(31) * 4* 4 HONS 201899 Tati* 2 (CmO rut* 01-11* (Nmumm, INI) NCS-21) (Haauata) (> (RM*iM) a*-4KE *P-*3 w-JNI JM w`m no-o-H MA-U-l) Ml (Oita Hrt>a**o) Tlacaiita. ca Cl ar Caaaaal---------- 100*? 110*r f**Cltl Cravltv (UatCT-l) 3 Blag Ibliptaayl Ittar iraaatl* Beta* Ola (Qianyfluai) taaaaaa Bla<a>ptMaaoah*aol) Beta* Bla(o-pfc*aiypfcaa)rl) Other a-lla<a-*taa*fpt*!) B*aaaaa BtafttaaaayphaoaKy) taaaaa* Bla la-|o-|liaaaajiOa>--y)|tayy Bcaar Oaaaftaayl trlybaa*t*U trl la ftaaaay taaa Tilftaagtaaltctla Tatraatlt Octyl flaaraaayl Itaaftaaltrllata Irwtlc EUwri 30) 13.1 23.1 ** *0.* MXSOO'F) .l) * ).* 1.31(400*7) 1)1 11.7 o 13.4 *.aK*oo*n l.ixM'r) It*ta*oattrllea .. ** * -* -- 1.10 l.lf .. ---* -- -- " 71aab Is tat *r sso *20 -- HI )U 5*0 5*0 a -- 71 ra hi at *r 4*0 SIB SO) 4*0 460 -- - . 4utol *nl(ioD^/ Drtapotl tlaa Taytrahift Tcapvratara r *r 111200) 114(50) 10*5(17) 1040(17) 10)0(17) 1130. 1030(7) 1030(17) >030(30) 473 *42(303 *'0)3(17) `allltll) 70(17) 70(26) 773(13) 00(11) 10(30) *03(30) a Utl all Umi>I til M all, cflldir - , ll#t --Ofciao - * , aplaOla m.J.Maa Ml Ntaaral aaal all 4lln ail hla all ria* all Bayaaaa* all aala all aytaaa all Thai all Tuln|*i<l Oil l.t.l. aa. 10 lata all 1.1.1. la. M lata alt - <i W3 33(*7) -- -- I.D *35 535 020(47) -* -- -- <1 * ))) X7) -- ** -- <1 MB 370 ** -- ** -- <1 1*1 WO - a -* -- 1.117 4)9 - 20(47) -- -- -* 170 2)3 *- - *- -- 0.*l 4)7 ** H(47) ** ** -- 1.11 *11 *- 430(47) * -- -- O.M ' 171 in -- -- -- -- O.IIJ 323 330 34(47) * ** -- 0.11-1.1 24* ** 4W(47) -* ** -- 0.113 540 -- 31(47) -- * .. O.M 9)2 * (47) -- * -- 411 S)(47) 340 wo 7hxie) V- 410 * 770(10) 1/ Aacalaaltlaa aaO lraf*iu aa taaparatar* 4ata laa ralaraacaa *lta4 to paraaOita**. Tlacaalty, pacific bmUt, float aalat. aa* (Ira falat 4ata aalaly (n* aaaOafa lltacatava. $/ Igaltlaa a14*aca4 to alaltla flaaa nfl fat ao4a*Tlaa4 aaWaa i*aca wOw praam# ilaa aa aaal. taraaa a< Hlaa* lata (Bala 1, *. S. 7. aal SO) a** *ttala*4 aalat raactlaa aaaaala >100 cc. fftlaaa llac*4 aa aaaaala <113 < HONS 201900 exercized through companies which insure against fire, utilities which supply electrical power, and building codes. 3. Extent of Capacitor Use Almost all industrial capacitors contain PCBe. In 1966 95 percent of the U. S. production of capacitor Uquids (2.h6 million gallons) were PCSs (9). Two important types of capacitors are phase correction capaci tors on power lines and ballast capacitors for fluorescent lighting. Non ballast Industrial capacitors produced in 1967 had a value of $112 million (10), and fluorescent leap ballast capacitors produced that year numbered 21.7 million units with a value of $15*5 million (l0), In 1970 there were 5^0.9 million ballast units produced with a value of $163 million (ll). These ballast units are in extensive use inside buildings whare non flammability is iiqportant. Phase correction capacitors are necessary on power circuits to correct for the Inductive loading of much electrical power equipment. The amount of phase correction capacitance is ordinarily specified in kilovolt asp ores of reactive current or levers. Most power capacitors are rated at from 1/2 to 25 Wars to that the number of capacitors la very roughly the kvar value divided by 10 (12). Aa exasplee of the extent of power capacitor use, TVA has 2-l/Ii million levers (13)* and a power company serving suburban New Jer sey has 3*6 million kvars on their power linee with 1/2 million kvars on order (lb). The value of these capacitors la roughly $5 per kvar (llj). More than 20 million kvars of power oapaeltors were produced In 1970 (16). The procurement lag for these capacitors is 1-1/2 to 3 years, and esti mates for redesigning new systans range from 3 to 10 years, according to power company representatives to ASTM Ccemittee D-27 (lb,15). Extensive re-designing is anticipated if dietribution capacitor a were required to use presently available non-PCB liquids. Askarel capacitors have been developed to the point that failures are considered negligible (13, 15). Several private sources reported extensive efforts to find replacements for PCB capacitor fluids, but none reported having a good substitute* B. TRANSFORMERS Most power transformers contain a liquid to electrically insulate and remove heat from the core and windings. The properties required of these liquids are: .I 1. Non-flammability (required for indoor use and desirable in remote location use). 2. High dielectric strength (prevents breakdown and allows transformer size reduction)* 3. Low viscosity (promotes convective heat transfer). b. High chemical stability (allows higher ten^erature operation and reduces degradation of the transformer). SI HONS 201901 5. Compatibility with other materials 6. Inert deccn^osition products (reduces fire dancer and damage to other materials following breakdown). 7. Low toxicity of the liquid and its decomposition products. 8. Low coot. 1. Advantages and Plaadvantages of PCB in Transformers The PCB transformer liquids, ccawonly called askarels, are mixtures of ohlorinated biphenyls and chlorinated benzenes. Several standard mixtures for transformers (differing from the capacitor askarela) are speolfied by AS7M (17). These liquids are used to overcome the fire and explosion hazards present with transformer oils. For moat power transformer applications where oecaslonal explosions and fires do not endanger life and property, mineral oils are still preferred. However, for distribution transformers which are located near congested areas and in buildings, aakarel and dry-type transformers are re quired by electrical codes (6). Other advantages of tha askarela include * l. their superior chemical stability, which eliminates the sludge formation canmon in mineral oils, 2. a high dielectric strength, which reduces electrical failures, and 3* suitable viscosity. The disadvantage of the transformer askarela include! 1. a poorer resist ance to impulse voltages end production of highly corroeive HC1 during aroing, 2. a tendency to image common insulating solids inside the transformer, 3. probable toxicity, end b> higher ooet (about $1.60 per gallon compared to $.25 per gallon for mineral oil (15, 10). 2. Replacsabllity of PCB in Transformer! Askarsl transformers cost about 1.3 times as much as oil transformers, and dry types cost about 1.5 times as much as oil transformers. Thus most users prefer to use the oil type where possible. This preference for oil transformers accounts for the fact that 96 perosnt of transformer liquids in use in 1968 were mineral oil (?). However, fire underwriters will not accept the use of oils, silicone, and other flamaable liquids for indoor transformers, fry-type transformers can be used indoors, but are generally larger in size, require more copper and iron, and are somewhat more expensive, as shown above, fry-type transformers could possibly replace askarsl trans formers in many cases. No currently available liquid which will replace askarela In existing trine formers is known. Possibly, non-flunable fluorocarbons could be de veloped as a suitable fluid, similar in Jj^ortant properties to the askarels. Fluorocarbons are currently in use as convective end evaporative dielectric coolants. One main disadvantage of the fluorocarbons is their high volatility and high cost (about bO times the cost of oil and 6 times the cost of askarels (18) ). 3* Extent of Transformer Use In 1967, 1.7 million liquid-limneraed distribution transformers of 500 kva and smaller, valued at $350 million, were produced (10). These Include askarel-filled transformers placed under streets to serve 1 - b city build ings. These transformers can fail and cause fire damage if filled with a 52 HOMS 201902 flammable liquid. An annual report on such failure! la compiled by the Edison Electric Institute (1?). II. INDUSTRIAL FLUIDS FOR HYDRAULIC, GAS TURBINE, AND VACUUM PUMP USES A. HYDRAULIC Hydraulic fluids are liquids used as force transmitters (20, 21). The characteristics of a good hydraulic fluid are (20)i 1. High lubricity (lowers heating and increases lifetime of moving components), 2. Stability (increases lifetime of use). 3. Appropriate viscosity and high viscosity index (21i). It. Low pour point (necessary for material to flow at low temperatures (25). 5. Compatibility (prevents interactions with other conponents, for .example, rubber seals). 6 Good heat transfer (reduces local heating and large temperature gradients). .7. High bulk-modulus (Important for extreme pressure applications). 8 Low volatility (necessary to prevent malfunctioning due to "vapor lock"). 9. Low foaming. 10. Low thermal expansion. Aside frcn the implication of a more con stant volume over a wide temperature range, a low thermal expansion isplies a high viscosity index and the constancy of certain other properties with respect to temperature. 11. Good demulsibility. 12. Inhibitor (necessary to prevent oxidation of metals or rusting). 13. Oood fire resistance (very Important in high tenperature environments). III. Low density (desirable in transportation, particularly airborne, applications). 15. Good dielectric properties (reduces arcing or short circuiting should the fluids come in direct contact with electrical components). 16. Non-toxicity (reduces the danger to human beings tram rupture of hydraulic equipment or inproper disposal and to maintenance personnel during transfer of these fluids). Since most commercial hydraulic fluid mixtures are proprietary, it is difficult to obtain information with respect to their conpositlon. The results from inquiries with respect to PCB content have been somewhat contradiotory. No definite knowledge Is availible that PCBs are present in commercial hydrau lic fluids. Since composition specifications of these fluids are usually not available to the public, PCB content should be established by chemical analysis. PCBs are useful in hydraulic fluids as lubricating additives in extreme pressure applications (26) and as pour point depressants. Although it is true that the pour point of oils may be lowered by extensive dewaj&ng, the use of additives is much cheaper. There are other inexpensive additives which are often used for these applications and which anpear to be adequate. For HONS 201903 53 example, TCP (tricresyl phosphate) Is chemically stable aa an additive In lubricants, and, although quite toxic, it is more biodegradable than the PCBs. An important requirement for many applications of hydraulic fluids is good heat and fire resistance (27). Table 2 (28) gives the ignition charac teristics for a large number of lubricants; however, in view of the propriety stated earlier, there is no detailed specification of the compositions of those fluids which are given the brand names* PCBs have excellent fire resistance characteristics. Die flash and fire points given in the literature for the pentachlorobiphenyls are attributed to the burning of residual contaminants (29). At very high tenperatures, however, PCBa with higher chlorine content may emit phosgene (a very toxic gas) in the presence of oj^gen.. <No evidence is available that high chlorine content PCBs are being used here). Aircraft hydraulic fluids are an exanple of an application where exoellent heat and fire resistance are necessary in view of moderately high operating temperatures and frequent accidents involving ruptured hydraulic consonants in the proximity of hot metallic surfaces. Also the flbarglas acoustic blankets in the Jet engines beoome soaked with leaking hydraulic fluid within aa little as one year of use (30). Fire resistance in phosphate ester type hydraulic fluids has been related to PCB content (31). Phosphate ester hydraulic fluids have been used extensively for commercial aircraft (32). According to one manufacturer, no PCBs are currently being Incorporated In these fluids, PCBs have been assumed to be useful as "snuffers" in that they tend to extinguish a fire supported by other constituents. The market value of used phosphate ester type hydraulic fluids is suf ficiently high that they are being recycled (33). The recycled products are said to satisfy the same specifications as the uncycled fluids. Considerable research is being done in connection with fire resistant hydraulic fluids for military aircraft. Some of the hydraulic fluids being tested do not contain PCB additives^ but do contain TCP. It is possible that under appropriate processing, ^CBs may be replaced by TCP and perhaps certain other additives to obtain satisfactory lubrication. In naval applications current research includes development of water based hydraulic fluids (3b), which would not contain PCBs. lhe boiling points of these fluids are too low to permit their use in aircraft. It is possible that PCBs ara also used in phosphate ester and other halogenatad hydraullo fluids for industrial applications at high tsmperaturss. The requiremanta here are similar to, but not as stringsnt as, those for air craft hydraulic systems. B. GAS TURBINES The characteristics of a good gas turbine lubricant are similar to those of hydr aullc fluids except fbr the additional requirement of lubricity at high rates of shear (35). Particular emphasis is placed on heat resistance, high HONS 201904 $h viscosity indax, low pour point, ind oxidation and foaming resistance. Sample U. S. and U. K. military specifications are given in Table 3 (36). Usually, dibasic acid esters containing appropriate additives meet the atova requirements. In the case of the turbcprops, the same lubricant is usually used for both the turbine and prop-drive gear. PCBs would seem to be useful as additives In gas turbine lubricants, but there is no evidence that PCBs are currently used for this purpose. Research along these lines has been done, and there is some indication that some PCBs have on occasion been added to gas turbine lubricants. The objection to PCBs and other chlorinated hydrocarbons is that they tend to be corrosive at the high temperatures reached in gas turblnss. This corrosion is accelerated by decomposition of the PCBs and the forma tion of hydrochloric acid at high temperatures. The corroslvenees of PCBs is a major deterrent against their use in these lubricants. TE? also has the desirable property of reacting with metallic surfaces at high tenperatures to form a protective coating. Jet engines are run for approximately 18,000 hours (37) betwesn over hauls. The lubricants are not usually diangsd during this period! however, the appropriate "oil level" is maintained at frequent intervals. Immediately before engine overhaul the lubricant is drained and discarded. Unlike the situation with respect to hydraulic fluids used in commercial aircraft, there appears to be no general recycling facility for gas turbine lubricants (37). As a result of their Increase In acidity and viscosity during use, recycling of gas turbine fluids would demand expensive redlstlllatlon and reblendlng. C. VACUUM PUMP APPLICATIONS (22, 23) Both mechanical and dlfltoion pusp applications require fluids of one highly fractionated component. Accordingly, additives generally are not used. However, PCBs ere used in pure form as a diffusion pusp oil in commercial applications. The characteristics (38) of a good diffusion pusp fluid aret 1. Relatively high vapor pressure at operating tenpsratures. 2. Low vapor pressure at room -and lower temperatures. (The vapor pres sure imposes a lower limit on the ultimate vacuum). 3. Heat resistance (prevents cracking or molecular degradation at operating tenperatures). b. Narrow vapor pressure rangs and freedom from contaminants such as absorbed gases and liquids with higher vapor pressures. (This requirement often implies the necessity of a narrow fraction). $, Oxidation reslstancs (important because air may enter a diffusion pump during operation either accidentally or through slow leakage). 6. Nonhydroscoplc (absorbed water Increases pimp maintenance and may contaminate the vacuum system). 7. Compatibility (must be compatible with pusp and vacuum system components), 8. Stability in the presence of the vapor being pulped. Sane of the pertinent properties of many diffusion pump fluids are given in Table b (39). The stability, oxidation resistance, appropriate vapor pres sures, and, In particular, the relatively low cost of PCBs make them a desirable choice for many industrial applications. Although the ultimate vacuum using $$ HONS 201905 s.- Table 3 Htgh-Tamperature Lubricant Specification* Viscosity, os at !r.'10F too F 2!0F 100 " F - SO K -tOF Viscosity atabillty lost tamp Vis change In 3 hr Vl after 3 hr, ca Vis nftsr T2 hr, oa Vis at -tOF aftsr 13 hr Shear stability at 313F I'our point, 0 F Flash point, 0 F Spontaneous Ignition temp, F Vapor pressure at 500 F, mm Hg Evaporation lose teat temp % Lons 6-1/2 hr nt 29,5" tig 'A Loss 0-1/2 hr nt 9.3" Hg Specific heat. liTU/lb/F at 100F Spaelfio heat, UTU/tb/F at 300 F Rubber swell, T2 hr Rubber ewe!], !6ft hr I'ortming sequence 1-2-3, max vol l-'onmlng collapse lima, max, min Csar scuff at ltiF % reference Lear scuff at teat tomp, * refereaoe Gear fatlgua, hr to failuro Mlte-L-IS** Q 1.0 min * Report * - -3F 6% max .1.000 max 2t,000 max -T3 max 423 min T30 min 400F 13 max -* - 12-25* at 400 F - 100-23-100 ml 5-3-3 36 min (3 aides) Report (400 F) Report (400F) MtL-L-irua 1,0 min Report Report 13,0.00 max - -30 F 6* max 13,000 max 17,000 max -40 max 300 min Raport 3.0 max 300 F 10 max Raport 0,33 min 0.43 min 12-23* at 300 F 100-23-100 ml 3-3-3 100 min (8 atdea) Haport (300F) Report (300 F) or:Kit itsr 2.0 min 3.5 max * mm 13,000 max -63F -- Raport + 2* KV/210 F 300 min TS2 min -- 392'/ Report ee am -- * 13-23* at 138 F 100-23-100 ml 3-3-S 100 min (392 F) (Raf. oil at 230 F) HOMS 201906 56 i Table 4 Sob* Properties of Pupping Fluids Apiceoa A Apicioe ft ApkzoaftW AptttoeC ApiciwO Apczaa FW Coo*od 10 Cwni 20 ptMtulxtt OFI-clbyl hnpl Di-2-clhrl hexyl Di'iuqji pldiUa Tn-cmH phuplu* Tn-xyknyt pheiptlXr Gljccrol M*wd cfeloriaMod Midxpedtcdaidrlo* riuM f^oprittt/p AiBdn'ftM' * * tm w m m f* m Octail OctotlS Kuod-iO VUcot-20 NxecoiMO VacodAO -- ArocSor I34| Comdorl ClopfccS A-40 Arador 1234 Edens ffnmlfr laid A CkalnfMn MdekHnodw * 00 m" m ,, ** *t mm C.H.lCTXfc.H^, C.HUCOOC.H1,)b CJBUCOOCJi,,A C.HUCOOC.H.0. (CHA^HLkFO. 1KCH,)jC.H. ,PO. (CH/JHAOKOH) Appras. CaHeCU AfvnQiHA SUomc D.C or MXTOl SdioM D.C m ** D.C or M S. 704 * laceiuw YiaooO-lO Owndorn Clopfccp A-50 Aiato'W Coe>xlcx 10 o. V AT. bid E \Mc1bji p. /pJ.SiOHCTI^,SiO!^CHASi ^TEuMUpehpieKeaprIl UlanwoHiciXbWSrtlrla-d-e--us "wd S-nSfkd)rpha>ylcfjMl1 H* Soffit /lex* t'/radar grmtilr (rSMMap.) (tfrrn'd Apfmx VucMity pour pom. {ptMtisiokrs) {or frttt'mf mi 20'C t**i) 'C Appro t. boJnig point mt 1 imri *C Estinuttcd troc l opo-jr prasmt (ftrr) 414 4a 0*71 0*71 210 211 4n 574 0-MO US 445 0-473 111 MO DO 091 400 OK 191 111 in 1-044 Ml 0911 119 194 <n 0911 W 49 -12 100 -12 291 -9-1 H -12 147 --21 110 -09 19 -71 71 -- S2 24 -54 190 220 IO*(70'C| )* 10- *(2I`0 225 -I0T(WC) 221150 4 io-*iiox) 1 I0-'(20 C) its 150 6S-J*kI010-* (lO'O Itf 1-1*10*' W'O 102 1-5* I0-* <`0 204 ,I4-'<!0'0 215 lO'tW'O 41* 0971 US Kt 117 414 tt 1-14 124 m 1-41 140 30 191 105 140 1110 400 -7 215 Id'JK'C) 219 J*10(2**CJ 243 in SO* 10 '(15*0 117 1 SxIO'WrC) ac t-M IM* >4000 10 ISO **io-*oo*o 5)0 570 444 544 447 2004 1-071 1-099 1-046 I-09S 1-191 114 194 2T7 214 24) 241 -- 1* 40 47 170 (25*0 2300 (25*0 IIS -40 -M -H -IS 4-S -U9 171 104 22) l0*fO 254 2*5 i i*irf 127 iiKio-(iro HOMS 201907 PCBs is limited by their relatively high vapor pressure at Low terperatures, their use at high boiler p-essures nakos possible operation with poor fores vacuums Hence thny are useful as booster punp fluids. In this respect the vjpor pressure-tosporature properties are closely matched by amyl phthnlats. Except for certain applications where alternative liquids may be incom patible with the vapors being pushed, the advantage of using PCBs diffusion pump oils appears to be moetly an economic one. Other fluids miy often be preferable through considerable more costly. TCP ie used as a commercial diffusion pump fluid and is also inexpensive. Its vapor pressure CL9) is lower than that of the PCBs making It less desirable in booster pumps, but in many applications TCP may be a suitable replacement. PCB diffusion pump oils can be decomposed after usu by lnclnnration. This service ie availeble mainly for disposal of Askarel transformer fluids contalng PCBs. III. HEAT TRANSFER APPLICATIONS Heat transfer fluids are used to absorb thermal energy from a source and by cooling or changing phase, deliver heat to a place of utilization. The re verse process, using a fluid as a coolant, requires similar fluid properties. Summaries of heat transfer fluids and applications are available (hi, h2). The properties required of heat transfer fluids are (Ll) as follows! 1. Suitable density and expansion coefficient, 2. High heat capacity or heat content (Increases amount of heat trans ferred during cooling or phase diange). 3. High heat conductivity (increases heat transfer). L. Low viscosity (necessary for fluid flow through system). S- Physical stability (will not have unpredictable phase or property changes). 6. Chemical stability (will not degrade, oxidize, etc.). 7. Radiolytic stability (will not suffer damage from radiation If present), 8. Low cost. 9. Low surface tension (radices fluid flow and heat transfer between fluid and surroundings). 10. Low corrosion (reduces damage, to metel parts of the system). 11. Low flasnabllity (reduces fire and explosion danger). 12. Low to:d city. Electrical properties, refractive index, appearance and odor may be considered for acme applications. A. ADVANTAGES AND DISADVANTAGES OF PCBs AS HEAT TRANSFER FLUIDS The main advantage of the PCBs as hast transfer fluids ii their firs resistance. This property if of primary importance where there is a possi bility that fire from high temperature leakage could endanger life and pro perty. The other advantages of PCBs are low pour points and viscosities and good thermal stability tp to 600F. PCBs are relatively Inert and have ex cellent electrical properties, which makes them valuable for cooling trans formers. The cost is relatively low. Disadvantages of PCBs include possible 58 HONS 201908 toxicity, a tendency to decompose to form highly corrosive HC1, a lower decomposition temperature than some alternate liquids (1*3) and relatively poor radiation resistance (1*1*). B. REFLACEABILITT OF PCBs IS HEAT TRANSFER FLUIDS Increased risk from fire and exploeion is a major disadvantage with most PCS replacement fluids. Other non-flasmable fluids are > 1. fluoro carbons, which have low toxicity, high thermal stability, and in spite of high cost are used as convective or evaporative coolants (1), 2. water, which is quite corrosive, has a high temperature limit of 37tC end requires extremely expensive high pressure system for Its use above the atmospheric soiling temperatures and 3 molten ealta and metals which, because of their resistance to radiation damage, are useful in reactor applications. Several liquids are more stable at high temperatures than the PCBs. Table 5 (1*2) shows the decomposition point range of liquids in e variety of chemical classes. Few of these liquids ere non-flamable, however, as can be seen from Table 2. The ph^rrhate eaters, : 'i-mes, end aromatio ethers have high fire points (around 600F), but they am flammable and it la not clear how high the fire point must be for a fluid to be safe In e high tem perature system, especially in the event of leakage into a furnace. The details of speolflc heat transfer applications ere necessary to evaluate the suitability of PCB replacement fluids. IV. PLASTICIZER AND MISCELLANEOUS USES * A plasticizer is a material incorporated in a plastic to increase its workability and flexibility (1*5,1*6). The addition of e plasticiser may lower the melt viscosity and flcxt temperature (increasing the ease with which the plastic can be made to flow),or lower the elastic modulus (making the plastic softer) (1*6). Plasticizers are generally non-volatile liquids or low-melting solids. A major requirement of a plasticiser is that it have high compatibility* (mixes will to form a homogenous competition with useful properties) (1*2) with the material being plasticised. Figures ere given in Table 6 for the compatibility of some comon plasticisers with sons cannon synthetic thermosetting or thermoplastic resins (1*5). Other properties which are important when considering plasticizers are specific gravity, refractive index, color, odor, moisture sensitivity, vapor pressure (volatility), boiling range, stability (to light and heat) toxicity and oost (1*7). Of course, the properties of the final plasticized material are of prime Importance. Certain plasticizers provide formulations with specific properties such ae> 1. phthalate eatara - general purpose. .2. adipates and osslatss - low temperature flexibility. 3 highly aromatic esters - fast processing, strain and extraction realstance. ]*- epoxies - heat stabilization during processing. 5. phosphate esters and PCBe - fire retardant materials. * Xha information in this section about specific uses wee obtained from Chemical Abstracts (1928-1969) and patent claims. The Task Force has no knowledge whether or not specific applications are In current production or use. * Note that the term "compatibility", used here, has a meaning very different from Its use earlier in this appendix. In the earlier ease, compatibility meant that two materials could coexist without either being affected by the other. The present meaning is quits the opposite. 59 HONS 201909 Decomposition Point Range (*F) Over BOO 700-800 600-700 500-600 Table 5 U?) Chemical Clan Unaubatituted Polyaromatic compounda Unsubatituted Polyphenyl ethera Unaubatltuted Aromatic aminea Unaubatituted Aryl allicataa Unaubatltuted Aryl allanea Unaubatltuted Aryl boratea Lower alkylaromatlc athera Aromatic phoaphatea Aromatic aulfonea ' Aromatic ketdiK Sillconea Halo-aubatituted aromatic ethera Halo-aubatituted Dolvnhenvla (including PCB'a) Alkyl boratea Alkyl aillcatea Higher alkylaromatlc ethere Highly refined mineral oila Fluorinated eatera Neopentylpolyol eatera Sebecate eatera Methyl aryl eatera Aliphatic tertiary amidee HONS 201910 60 Table 6 . Approximate Maximum Compatibility, phr) of Plasticizers with Various Resins pul>(*yl cMnrklr) pjlytrmyl rrluu) Hjr(i^Mnc (MuriO:) pobStflM ttbyfcibshii tdiluv Htlrtic luBulim wI-.It wbulm iul<n baljnu dUiulrl n3-l* li|k flfRItt-bcliilinii Climbiurr pm1 (in ls.d |4Um srjlit n^m Oyd im wlmnr ImnUlyik ma pJjfmmkw _ asrib ml nnymn nWsr * TkabmHt MmsiIii (1. 1 TtabmHl Urn* CirMe C.p Tradammt bksi4llmC>. Flihilaif* Adi|li' llufilrltrl nuKJ.1 gtycubic* 1' la!_rol4' OXlrir- cm lr* Muiflkl i > = a | I 1! 1 a II:s1 i s 1 | f ib2l i $ Xm3 I 1 " A a | C "ii -- i S' 51 "C r~ (5*.* h iS5-.San _ T. 5 >< 3 1 S ll v iftv* 3 j_ * # a ?! 0 3 J * i r* /. ? if C4As o jHl E <2 1 o JH4 m Cn. E Co * O M Z. O o *1 f#5 >C.S "3 (31 i JB 1 g E 0* 7 * JL n l >i ran MO I0U iso 100 100 so JO MO MO ICO SO 20 too ion 100 in llW mo 100 40 ) 17 40 IMl 100 100 1 I ion i 1 40 10 i 40 100 1" 75 100 II n 5J 1 100 jfl `to 1 71 so n 31 10 IS 71 IS M 70 71 71 so 71 7j 10 35 so 20 NO m so M0 IS m 103 31 30 11 SO MO IS 3U 1 SO 10 10 in 100 ion ISO 100 MU as in too HO * 140 iso .ill 71 71 10 33 1 1 < it ino n 75 75 100 00 ISO 100 .. IOC as 100 X 31 71 M0 IW in lun ino WO M0 ICO 100 ion 100 114 no SO 100 10 oo 1 1 | 10 1 1 IS IS <n 10 in SO 1 1 i i 1 | to J 1 100 HO so so IS 100 31 so so . s <31 31 ISO so too urn 1 | 100 1 so K so 30 2* 100 XI 100 as WO M0 SO MS 100 100 n So U 10 100 100 100 *0 ii 100 mu w SO so so 30 is 30 30 IS as so SO so IS IS t> 21 ii 10 31 30 1 1 t IS 1 1 IS 10 31 10 30 40 i 1 10 40 1 1 * 1 1 11 1 1 1 1 l 1 1 HI i1 40 so 1 1 MS 10 21 Si 73 IS 1 31 IS NO 100 r. SO 7l* | 1 l 11 Zi H au 1 31 30 10 ia 31 31 M 31 31 i~i 1 .Ml | 1 10 li ii * IS 30 11 30 1U 1 1 IS 3B l 3S 1 At a. 10 10 i 11 i 1 3* 1 1 10 31 | 1 IS 31 31 la 21 31 31 50 V, 33 so SO 30 11 31 ii i 1 SO 111 to ii 3". so X i ao SO ii 21 7S 31 r> 31 an 30 31 10 IS 70 so TO hi 30 SI is 31 33 15 1 | 1 i 1 i. 1 1 1 1 1 11i 11 10 VO 1 i Si 31 n r. M 13 * 11 I* IS 31 31 31 31 ii 13 11 30 10 21 ii m too 4* u SO in> 91 u so 40 as SO 10 21 so 33 SO SO SO 10 HONS 201911 PCBs are attractive aa plasticizers because of their high consistability factor. They have been made with a wide range of properties, as shown in Tabls 7 (L8). The PCBs are permanently thermoplastic, chemically stable, non oxidizing, non-corrosive, have excellent solvating powers, and are fire re sistant (L18, 149). They are not normally attacked by aoida, alkalinsa, or water. They are insoluble in water, glycerol, and glycols, and are soluble (at the lower chlorine contents) in organic solvents (I18). The main disadvantages of PCBs are their possible toxicity, and relatively high cost. A. ADHESIVES An adhesive is a substance capable of holding materials together by sur face attachment (Si, 52). The major types of plasticised resin adhesives are emulsion, hot-melt, delayed tack, solution, pressure-sensitive and adhesive primers and coatings. Almost every thermoplastic resin is used individually or in resin blends as a hot melt adhesive. This necessitates a wide range of plasticizers. Of special value are the solid plasticizers. They plasticize the resin while hot and while the bond is being formed, but solidify at lower temperatures to overcome the problem of excessive softness (53) Among those solid plasticizers used aret o,p-toluenesulfonamide, N-cyclohejqrl-p-tolunesul- fonamide, triphenyl phosphate, and dipheiyl phthalates. The more resinous chlorinated polyphenyls would also be included in this category. Hot melt adhesive compositions based on phenolic resins are used in brake linings, clutch faces, and grinding wheels. Reactive plasticizers, such as the toluene- sulfonamides, are employed because they Improve the flow properties by reducing the viscosity of the phenolic resins (5li). They help the resin wet the fillers and abrasives. Chlorinated polyphenyls and aryl phosphates (non-reactlve plasticizers) also improve flow properties of phenolic resins prior to curing as well as imparting some flame proofing characteristics to the composition. PCBs have also been used In laminating adhesive formulations Involving poly urethanes and polycarbonates (55-57) to prepare safety and aoouatlcal glasses. The laminates have improved strength and resistance to delaainatlon over a broad temperature range, and inyroved sound-absorption and energy dissipation properties. ` Polyarylene sulfides, treated with chlorinated bipheryls, are enployed to laminate ceramics and metals (58, 59). An ethylene-propylene copolymer blended with ?CB has been used in a hot melt adhesive having inproved toughness and re sistance to oxidative and thermal degradation. It has excellent adhesion to polyethylene films (60). Similar adhesives, used to bond polyethylene to Itself or other plastics, were prepared from styrene, alpha-methylstyrene or methyl methacrylate (61) Vhshpble wall coverings and upholstering materials, made from films of polyvinyl chloride, are claimed to be improved by the addition of PCB to the adhesive formulation (62). PCBs can also be applied in the pre paration of polyvinyl alcohol adhesive compositions which are used to manufac ture envelopes (63), in self-adhering films (6L), and in preparation of coatings of pressure-rupturable capsules for adhesive tape (65). B. TEXTILE COATINGS A textile coating for ironing board covers can be formed from a mixture of chlorinated biphenyl, cellulose acetobutyrate, and aluminum metal particles (66). PCBs also can be used as a de-lueterlng agent for rayons (67, 68). Poly-elphaoleflns, (i. e., polypropylene) films, when coated with a mixture of PCBs, UV 62 MONS 201912 Table 7. General Properties of Some Arodors (PCB) Material Pw aail ffflflr ferity Distillation ranee.* *C(cmr) Flash point.* c Firs point.' *C Pour point,4 c Softening point,* *C n Vne.-jsile/se*! -I7.ST 9S `J*C AfucLit 1231* Arudor 1232 Arnclor 1213 Amdorl240 Arodorl?54 Amrlnr 1280 AndurlSK) Arwclor 1265 Ancle I27u AndtfMS AndcrUll Amdor MOO Arwclur 2105 enlorlwa, iwliilt oil 1.192-1.19! (25/15 VC) almost c.iturie*^ 1.270-1.23# aiWIntf (35/16 5*0 atmoot culurlm, 1.391-1.392 mohilo oil (25/15.5*C} jnlknr-inn Unlad, 1 105-1.415 mobile oil (5/15.5*C) light ytllnw, viaroue 1 41*5-1.605 oil (#5/15.5*0 tight yellow, soft. 1.535-1.50# sticky, row (90/13.5*0 light yeII.nr. Sticky, 1.572-1.5SI clear mis (90/15.5*0 while to ofi-wbite 1304-1811 powder (25/25*0 white crystalline 1.914-1 DOO powiicr (25/2'>*<.) 1 #70 brittle resin (25/25*0 yellow. transparent. 1 470 Sticky resin (25/2=1*0 dear. ydlow-to-wm- 1 .CTO bar, Isrittl* resin (25/25*0 Uwk,n|iW)SI, 1.734 brittle min (23/25*0 275-320 141-150 290-325 152-151 325-366 178-130 340-373 190-196 305-390 bom 3S5-I20 305-425 435-450 non* 450-400 230-320 (4 mot Hg) 213-300 (4 mm Ilg) 210-335 (3 mm Hg) aoa* 247 mom aoM 17# crystals at 1*C 233 -35.5 1.#17-1.#15 l.C20-!.22 14-51 30-31 ."i-;2 notM -19 1.#27-1.#29 #2-92 34-35 non* -7 1.C30-1.C3I l-2!0 30-37 acme 10 1.039-1.041 1590-2500 44-4S aooa 31 1. #47-1 619 72-79 mom 35-33 1.#301-1.C517 SC-100 nom 150-170* IHM1 249-300* mom 00-6# 1.#04-1.067 >JJ0 40 40-$* 90-150 (i:W*Ci 300-401 09-105.5 1.090-1 GC5 mom #0-72 * ASTil D-A) (nu|j|il>. * Cleveland *tprw cup * Cleveland upen cap: nuns WialM fin; p>nut tip t boiling temperature. * ArfTS! D-lC. * ,UT)1 K4#. ' Say Wt rnivcml VST.M 1)-S#. * Lust tiro digits irvlieatc approximate ehL.fi ar rout cut, ie, .ln<c.W 1131 r.*u`.3;n* abo-i* 31 \ V* rev. * Bold |wu( > avIidiOcaliun. HONS 201913 light absorbers, end antioxidants show increased stabilization to oxidative degradation on closure to sunlight and weathering (69, 70). Polyamide (nylon-type) yarns were found to be flame proofed when treated with PCB (71). Chlorinated biphenyls can also be used as Ingredients in some sealing formula tions employed to waterproof canvas (b8). C. SURFACE COATINGS In paints and varnishes, the hard resinous PCBs impart Increased hard ness to films, and the softer resins give flesd-bility (u8). The role of thcso materials is similar to the oil, except that thsy do not oaddize and lose flexibility on aging. In nitrocellulose lacquers, PCBs either alone or in combination with other plasticizers and resins insert increased weatherability, luster, adhesion, and decreased burning rates (1*8, 72). Some comparison studies have been made recently, on the affects of various plasticizers upon the overall properties of paints and varnishes made from acrylic latexes (73)* Films plasticized with tricresyl phosphate (TCP) had better stability, tensile strength, and adhselon than did film plasticized with dibutyl phthalate or PCB (73) F'ar varnishes prepared from polyvinyl chloride formulations, and plastlclzsd with aither di-butyl phthalate or PCB, the films plasticized with PCB had better overall properties with or without pigments {TiO^) (7b). PCB and other plasticizers can be used in combination with poly (organoslloxanes) to prepare film casting solutions, These polymeric films could bo employed in electrical coatings, insulating tapes, and protective lacquers (75-77). Plastic vessels, 1. e. bottles, manufactured from polyethylene, polyvinyl chloride, polyvinylldene chloride or similar resins coated with an epojqr lacquer (which contains PCB) make the vessels pliant. Impervious, and resistant to aromas, acids, and alkalis (73). Paints .it ltomlc energy Installations are needed for (a) contaminated areas, (b) tolerance to high energy radiation, and (c) to meet clean condition standards. Paints for (a) should be glossy and smooth and should not transmit contaminants. For this purpose, the vinyl polymers are preferred over epoxy lacquers. The best plasticisers for use in this area are claimed to be the PCBs (79). The extent, if any, of thair use in this application is unknown. The PCBs are usually compatible with epoxy resins, and they give good final hardness and Impact resistance equal to the unmodified resin (80). They also aid in the acceptance by the resin of larger amounts of fillers. 8ojqr resins in combination with PCB can be used as protective coatings for metals, i.e., encapsulating electrical capacitors (61), for ferrite magnet cores (82) (ussd in computers), for corrosion resistant resistors (83), for plgmsnted metal coatings (8b, 85) for winter camouflage coatings (86), and for pipes and blocks (87). MONS D. SEALANTS Sealing and caulking cmnpoaltiona Include a wide range of compound* which can bo uaad to seal joints or voids against water and wator vapor, air and other gases, dust, sound, vermin, heat and oold (88), Specialised applications require resistance to certain chemicals or atmofphsrlo environ ments. PCBs can he used ar.plasticisers in tha formulation of putties from copolymers or sthylene-vinyl acetate or styrene (69). The products are non hardening, and resistant to moisture *nd frost and show good weatherability A non-sticky, non-hardening putty was also prepared from polyaulflde mix tures which mnploys PCB as the plasticizer. This putty gave good bondiim to building materials and had good sxtrudabillty and ahm>* retention (90). Elastic pavement or concrete sealing co^ositlone, used for traffic markings, were prepared from coal-tar-polysulfids mixture* which are plasticised with PCB (91). A sealant, effective for concrste end asphalt applications, can be formulated from a mixture of polysulfide, chlorinated rubber, and polyiso cyanate, and plasticized with PCB (92). E. PRINTING ,, Chlorinated biphenyls have been employed as oart of the formulations used to prepare pressure-sensitive record (93, 9b) and colored copyii^ papers (95, 96, 102, 103). They have been used to coet papers used in thermogr^hle duplicating procease* (97-101) as well as in xsrographlo transfer proceseee (10L, 105). Solvent-free printing on polyolefin plastic* can be accomplished by heating a mixture of low molecular weight material, chlorinated biphenyl or terpene resin, and suitable pigments end djras. Durable print# can be mad* on the surfao# of the polyolefin at the time of their thenwplaetlo shaping (106). Printing pistes, hard enough for hlgi quality letterpress printing, and suf ficiently flexible for us* as flexographlo plates, osn be prepared from com positions containing a liquid rosin euota as epajy, polyester, urethen, acrylic or viryl with an exeese of curing agent and PCB as tti* plasticiser (107). The extent, if any, of currant uses of PCBs in printing application is unknown. F. FIRE RETARDANT AND FLAKE-PROOFING CCMP0SX1T0KS When PCBs ar* used as plasticisers, they impart a oertaln degrse of non flammability to the objects as described previously. However, for increased effectiveness in flams retardant ^plloatlons, the PCBs osn be Mhrtxed with various ratal oaids*. Seme flam* retardant oopoaition# based upon thee* mixtures tret polyolefin yarns (108)} organepciysUogcaM sealants (109)} thermoplastic poly (hydraxylathsrs) (110)} fireproof panele made from starch whioh can be used for does*, floors, callings, and partition* (ill)} poly amides (112)} and In fireproof flberboard* (113). Rigid polyurethane foams (llL-116) and hardboard oospositioo* (117), tfien treated only with PCBs do not show any significant increase in flam* retardanoe. 0. MISCKLAMWJ3 APPLICATIONS Tha wide rang* of chemical anl physical properties exhibited by the PCB# (see Tables 6 and 7) make them desirable for an assortment of rtaoeUaneoue uses. Some of the mors interesting and non-conventional uses ar* a*. follomt 65 HOME 201915 1. Catalyst carrier for poljmsrizetion of olaflna(llfl). 2. Conversion of watsr-permeabl* toil to a non-permeable etate Soil la made non-peimable by applying to the eon a corpoeition ooiw sisting of an ethoaylans-baeed rsein* polyamide* casphor, and PCB ae olaaticizer. The aowoeition tie* a deneity creator than water, and it harden under water It can be applied to river banks* where it flows down the bank* and after hardening, prevente penetration of water (soil erosion-'' etardant) (lid), . 3. Combined ineeetioide and baeterlcide fbmulatlone. The com* position contains aldrln or dieldrin, naphthalene hydroearboos* malethien mathoxychlor, lindane* oblordans* ttrpineol, and chlorinated blphenl as * active agents (120). 1*. Inhibitors of nlorobial growth in enamel clay formulations (121), 5* Plastlo sound lns^Uhtlng nmteriale for railway oars (122). 6. Plastic (PVC) decorative articles which give theiapreesion of internal scintlllatlan (123). 7. Increasing the density of oarbon plates by impregnation with PCB (I2li). 5. Graphite electrodes with low thermal expansion coefficients and high bending strengths (12$). ` 9* Increasing the ooke yield from ooal pitch. The coke is very hard* dark* and brilliant (126). 10. Aa a metal quenaher or twparing agent for eteel* alloys, and glass (127, 128). 11. As an aid to fusion outting of staaked metallic plates without ad herence* The cutting Is done with an sleetrio are or os^-gas torch (129). We find no evidence that PCBs are indigeneable to a particular plaatldzer or mlaoellaneoua application. In moat of the formulations and composi tions cited* there were usually altarmtive plaetictzsra included in the citation (see Table 6) which did not appear to be detrlmentel to the applica tion, 7, SUMMARY Ths major value of the PCB liquids la that those with four or more sub stituted chlorine per molecule are non-flaaeaable as are their deommsosltlon produots. Thus they oan be used as fluids at tsa^sratursa ip to 700P without ths daiger of explosions and lira. The major disadvantage of the PCBe la their possible toxicity danger. Tbs other oc^arabls class of non-fleaMhle fluids are the fluorocarbons which typioally have a lower vapor pressure and lower boiling point than the chlorinated oomounie. PUBa ar* used in fluids (known as asktrela) for electrically Insulating and oooling transformers when ths transformers are used in or near buildings. Kinsral oils ere ths preferred fluids when firs doss not create a hazard. Dry transformera can-also be used but are larger and mors e^ensive. Fluoro carbon liquids require a special transformer design. Fluorescent light bal last capacitors snd phase correction oqpacitore utilise the high dlaleotrlo constant of the PCBe to effect algnlfloant reduction In capacitor siae and cost, Fsw suitable fluids hkre s oc^arably high dlaleotrlo oonetant. Flanabl* fluids ere not allowed by lneuranoe oo^aniee and building oodea In capacitors used in bulldings. Replacement of PCBe in cqpaoiters and 66 M0N$ 201916 transformers would require considerable time and money for reengineering, manufacture, and application of substitute equipment* PCBs are useful in hydraulic ayatana where leakage onto hot metal sur faces could cause a dangerous fire. Hydraulic fluids can also be Bade with phosphate esters which are toxic and which will burn at high temperatures. Replacement of PCBs in some hydraulic systmaa could increase loes of life due to fire. Oas turbines require lubrication at high tanpentures. PCBs can bs used but tend to be corrosive. Phosphate ester lubricant* seem better in this respect. Chemical stability is more Important for high temperature lubricants than la non-flammability. PCB fluids are useful in diffusion booster puaps to produce moderately high vacuums with relatively poor fore vacuums. Non-flammability is not especially laportsat for diffus ion punp liquids, and with a few possible exceptions alternative liquids are available. FIamiable heat transfer fluids present a fire haaard if they leak into a furnace or onto hot surfaces* Hie use of PCBs can prevent this danger. In some cases water is a suitable substitute at moderately high tsoperatures. Other heat transfer fluids are commrdally available and in use. Replace ment of PCBs is satisfactory in same, but may be dangerous in other heat transfer uses* The PCBs are good plasticizers for us* with adhesives, textiles, surface coatings, sealants, and oopy paper* In some oases the PCBs act as fire retar dants, There are no particularly unique properties of PCBs for plasticizer uses, and equally effective alternatives ere generally available (e.g. phos phate esters are often used as fire retardants). Die extent of current use, if any, in such applications has not been determined. MOHS 20191? 6? FOOTNOTES 1. Directory/Encyclopedia lama, Insulation/Clrcults, Vol. 17, No. 7, June/July (1971), p 17. 2. Encyclopedia of Oiomical Technology, 2nd Edition (l961i). 3. Dielectric Haterlale and Applications, A, R. Ton Hlppei, ed. Technology Press of MIT and John Wiley and Sons, Inc. N. T. (I951i), pp 156, 189, ai, 221. Li. Insulating Materials for Design and Engineering Practice, F. M, dark, John Wiley and Sons (1962). 5. Astin D2233-70 Standard Specification for Chlorinated Aromtlo Hydro carbons (Askarels) for Capacitors, American Society for Testing and Materials, Phil. Pa. ' 6. National Electrical Code Handbook 10th Ed,, 1957 McGraw-Hill, 7. Insulating Materials for Design and Engineering Practice, F. M, Clark, John Wiley and Sons, p 2Li6, (1962), 8. Chemical and Engineering News, October 18, 1971, p 16. 9. National Industrial Pollution Control Council Report oh the Use and Disposal of Electrical Insulating Liquids, U. S. Oovemaent Printii* Office, Washington, D, C., June, 1971. 10. 1967 Census of Manufactureres, Connsrce Publication MC67 (2)-36A, Electrical Measurement and Distribution Equipment. 11. Fluorescent Lamp Ballasts, Summary for 1970 Commerce Publication Series MQ-36C(70)-5, Septaaber (1971). 12. Dielectric Materials and Applications, A. R, Ton Hlppei, ed. Technology Preee of MIT and John Wiley sad Sons, Inc., N. T. (195b) p 197* 13. PrlTate communication. L, E. Stalth, Special Engineer Transmission Maintenance and Test Branch, Tennessee Valley Authority, Chattanooga, Teim. lLi. PrlTate ccmraunleatian. Herbert C. Erckaan, Public Service Electric and Gas Co., Maplewood, N.` J, 15. Private communication. Earl Morrison, Chief Chemist. Los Angeles Department of Power and Water, Los Angeles, California. 16. Private'communication. Anthony J. Nesti, National Electrical Manu factureres Aasoc., 155 E. Lilith St., N. T. N. T. 10017* 17. ASTM D2283-71 Standard Specification for Chlorinated Aromatic Hydro carbons (Askarels) for Transformers, American Society for Testing and Materials, Philadelphia, Pa, 68 HONS 201918 18* Private communication. E, L. Raab, Manager, Insulation Systems Section, Power Distribution Div,, General Electric Co., Pittsfield, Mass. 19. Report on Power Transformer Troubles, 1969, Edison Electric Institute Publication No. 71-20, (1971). 20. "Introduction to Hydraulic Fluids", R. E. Hatton, Rheinhold Publishing Co. (1962). 21* "Synthetic Lubricants", R. C. Gunderson and A. W. Hart, Rheinhold Publishing Co. (1?62). 22. W. Espe, Materials of High Vacuum Technology, Vol. 3* Pergamon Press, (1968). 23. "High Vacuum Punping Equipment", B, D, Power, Rheinhold Publishing Co. (1966). - 2b. Viscosity' index. A high V. I. means a low viscosity-testerature coefficient, . 25. The pour point is related to the lowest teiperature a liquid can be poured from a container. ASM D 97-66 Standard Method of Test for Pour Point! American Society for Testing and Materials, FtHla., Pa, 26. Boundary lubricant additives cling to metal surfaces facilitating good lubrication at high pressures. See ref. 21, pp lb-21, 27. "Fire Resistance of Hydraulic Fluids" ASTM Special Technical Publication No. b06 (1966). 28. "Review of Ignition and Flammability Properties of Lubricants", J, M, Kuchta and R. J, Kato, Bureau of Mims Tbchnioal Rsport AFAPL-TR-67-126 (1968). 29. ASTM D901-70 Standard Methods'of Testing Askarels. Secs. 18, 19. 30. National Bureau of Standards Rsport of Tests No. TO 10210-2158* FR 3695. 31. See for exai^l** Ref. 21, p 133. 32. Reference 21, Chapter b. 33. Phosphate eater type hydraulic fluids are being reayoled byi Eppi Pre cision Products, 227 Burlington Are., Clarendon Hill, HI. 3b. See for emsnplet A. M. Dobry, E. A, Glass, and A. Zletz, roved Non-flammable Hydraulic Fluid", Bureau of Ships Rsport M67-lb (1967). 35. Ref, 21, Chapter 5. 36. Ref. 21, P 235. 37. Private cocmurdcatlon, R. K* Crothers Maintenance Division, Federal Aviation Aekninistration. 69 MOWS 201919 38. Ref. 22, Chapter 18. 39. Ref. 23, p 66. . LO. Ref. 22, pp 352-353. hi. W. J, Danzlger, "Heat Transfer Media Other Than water". Encyclopedia of Chemical Technology, 2nd Ed., Vol. 10, pp 8L6-861 (1965), 12. Paul L. Gelringer, Heat Transfer Media, Rheinhold Publishing Co., N. T. (1962). h3. Ralph L. LaMar, "Thermal Stability of High Tenperature Fluids and Fluid Intermlxture3,t U. S. Army Weapons Consand Teehnioal Report DA#lC02bii01A106 (1967). hh, L, Mendeloorn and R. L. Miller, "Radiation Resistance of Capacitors Dry and Inpregnated" paper # E-9, Conference on Electrical Insulation and Dielectric Phenomena NAS-NRC (1971). L5* J. R. Darby and J, 1C. Sears, "Plasticizers", Encyclo. Poly. Sci. and Tech., 10, 275 (1969). L6, ASM D 883-69a Standard Nomenclature Relating to Plastios, Aaer. Soc. For Testing and Materials, Phlla., Pa. L7. Cene Wilde and David Press, "Raaticixera", Modern nasties Sncyelo., iS, W8 (1968). h8. H. J. Hubbard, "Chlorinated Biphenyls and Derivatives", Encyclo. of Chsm, Tech., , 291 (l96ii). Lt9. R. H. Kosher, "The Technology of Coated end Proceaeed Papers", Raaaden Press Division, N. 7. p 368 (1952). . 50. Ref. h9, p 2li0. 51. ASTM D 907-70 Standard Definitions of Terms Relating to AAiesivee, Amer. Soc. for Testing and Materials, Phlla. Pa. 52. Irving Skeist "Adhetive Conditions* Encyclo. Poly. Sol. and Tech., Vol, 1, Inter science Publishers, N, T. p Ia82 (l96ii). 53. Ref. ii9, p 286. 5U. ibid, p 292 55. V. E. Hamilton and J. M, Roeeland, 3. African. 67 0lt,865 (McDonald Douglas Corp.) (1966). 56. ibid, ft. 1,519,535, (1968). 57. Brit. Patent l,lli8,0t*7 (Douglas Aircraft Co.) (1969). 70 HONS 201920 58. Harry Smith, U. S. Patent 3,395,132, (Dow Chemical Co.) (1968), 59. Davdd A. Frey, U. S, Patent 3,380,951 (Dow Chemical Co.) (1968). 60. T. P. Flanagan, U. 3. Patent 3*220,966 (National Starch and Chemical Co.) (1965). 61. R. P. Cox, J, L. Wagner, and R. J, Sere, 0. S, Patent 3,117,000 (E. I. Dupont de Nemours) (1969). 62. P. Ruckstuhl, Qer. (East) Patent 1|0,927 (1965). 63. P. Prumier and J. Duthu, Fr. Patent 1,1*82,172 (1967). 6L. P, Rucketuhl, Qer. (East) Patent 37,967 (1965). 65. H, J, Elchel, U. S. Patent 2,988,1*61 (National Cash Register Co.) (1961) 66. 3. 0. J. Velthoren and H. J. Wlenjes, Neth. Patent 109,025 (1961*), 67. EMI Kline, U. S. Pater,t 2,077,699 (E. I. DuPont de Nemoura) (1937). 68. ibid, U. S. Patent 2,07,',700. 69. 0. Liatner, U. 3. Patera 3*1*58,1*71 (Johnson and Johnaon Co.) (1969). 70. ibid, 0. S. Patent 3,277,01*6 (1966). 71. Brit. Patent 1,133,050 (8. I. DuPont de Nearaura) (1968). 72. R. J. Jenkins and R. N. Foster, Ind. Big. Chen. 2^, 1362-1365 (1931). 73. N. V, Maiorova, M, I. Karyakina, 7. A. Kargin, Z. Ta. Berestneva, L. P. Malysheva, Lakokrasoch* Mater. IKh Prlnen, 3, 17-19 (1969). (Cf. C.A. 71. 623251 1969). 71*. S. 7. Yakubouich, N. Ya. Qiebkova, 7. A. Zubolmk, and P. V. Kotlov Lako krasoch. Mater. IKh Prinsn 1*6 (1966). (C.A. 6, 1882Of, 1966). 75. D. P. Spalding, Fr. Patent 1,353,506 (Co^>agnie Franealse ThomsonHouston) (1961* ) 76. Brit. Patent 1,020,053 (General KLsctrlc Go.) (1966). 77. D* P. Spalding, U. S. Patent 3,288,71*3 (Oeneral ELeetrie Co.) (1966). 76. E. Kamp and Karl Jahn, U. 9. Patent 3,393,087 (Monsanto Co.) (1968). 79. H, Wells (Atomic Energy Res. Establishment, Harwell, England) J. Oil Color Chemists Assoc. 1*8, u) 28 (1965). 80. Ref. 1*9, p 293. 81. Francis J. Whilby, Brit. Patent 1,138,976 (Standard Telaphona and Cables Ltd) January 1966. 71 HOMS 201921 82. Robert S. Helms and Dianas J. Walsh, U. S. Patent 3,279,91*5 (IEK Corp) October 1966, 83. Theo A. Helens and Jan Kunnen, U, S. Patent 3,109,751* (North Anerlcan Phillips Co.) November 1963. 8L. Fritz F, Freltay, Herman H. Halter, and Lothar Kluth, U. 3. 3, R, Patent 157,031, September 1963. 85* Margarete K. Helmholtz and Waltraud H. E. Helmholtz, Qer. Patent 1,156,922, November 1963, 86. Fr. Patent 1,358,681* (KommanditbdLaget Svenske Farginduatrl Landin and Co.) April 1961*. 87. Irvin J, Steltz, Ger. Patent 1,279,262, October 1968 88. Charles T. Ralrdon, "Sealants" Ehcyolo. Poly. Sd. and Tbch., Vol. 12, p 1*18 (1970) Interscience Publiritsrs, N, I. 89. Societe Civllle Plorillo, Fr. Patent 1,1*02,991, June 1965. 90. Thiokol Chem. Corp, Neth, Patent Appl, 6,606,31*9, November 1966. 91. J. M. Pachuta, ft. Patent 1,566,1*13 (Thiokol Chem. Corp.) May 1969. 92. Edvard 0. Mlllen, Fr, Patent 1,521,786 (Thiokol Chem. Corp.) May 1969. 93. Barret K, Oreen and Rdbert W. Sandburg, 0, S, Patent 2,51*8,361*-5 (National Cash Register Co.) (1951). 91*. ibid, U. S. Patent 2,51*8,366 (1951). 95. S. Kimura, T. Kobayaehi, 5. Ishlge, Fr. Patent, 1,51*5,51*5 (Hodogaya Chem. Co., Ltd.) November 1968. 4 96. A. Corredor Oarole, Span. Patent 31*5,296, November 1968. 97. Brit Patent 1,01*7,512 (Minnesota Mining and Mfg. Co.) November 1966. 98. Richard Own, U. S. Patent 3,315,596 (3M Co.) April 1967. 99. Buck Stricklin, U. S. Patent 3,360,367 (3M Co.) December 1967. 100. Martin Hepher, Brit. Patent 966,053 (Kodak, Ltd.) March 1965. 101. A. 0. Gulko, U. S. Patent 3,l*Ol*,99lt, October 1968 102. S, Ancar, Brit. Patent 1,025,757, April 1966. 103. R. Oda, H. Fuju, H. Morlga, and S. Dotani, U, S. Patent 3,369,007, June 1966. 101*. Brit, Patent 1,11*9,265 (Xerox Coi>) April 1969. 72 HONS 201922 I 105. B. B, Jacknow, J. H, MoricoteL, and F. M, Palermlti, S. African Patent 6,803,560 (Sank Xerox, Ltd,) January 1969, 106. Hans J. Lena, Oar. Patent 1,199,290 (Hoechst Fabweke) August 1965, 107* Daniel L, Goffredo, 0. S. Patent 3,269,306, August 1966, 108. Brit, patent 1,126,1*76 (Johnson and Johnson Co.) September 1966, 109. Charles A. Berridge, U. S. Patent 3,151*,515 (General Electric Co.) October 1961*. 110. R. H. Snedeker, U, S. Patent 3,1j05,199 (Union Carbide Co.) October 1968. 111. D. Lurie, Fr, Patent 1,529,506, June 1968. 112. w, F. Busae, U. S. Patent 3,1*18,267 (E. I. DuPont de Nemours) December 1968. ,, 113. R. O* Quinn, U. S. Patent 2,030,653 (International Paper Co.) February 1936. 111*. H. Picchota, Kunstoff-Rundschau, 1 (1*), 191 (1965). 115. Paul E, Burgess, Jr., Carlos J. Hilado, and William R. Proops, Space Mil, Appl. Cell. Plast. Syst. Amu, Conf. Cell. Plast, Dir., Soc. Plast. Ind., 12th, 1967, 3-C-1-3-C-10. 116. Carlos J, Hilado. Paul E. Burgess, Jr., and William R. Proops, J. Cell. Plast. ^ (2), 67 (1968). 117. T, ULrata, H. Abe, and I. Fukui. Ringyo Shikenjo Kenkyu Hokoku, 1967, No. 200 155, Cf C. A. 22 12779u (1969). 118. H. V. Coover, Jr., and N, H. Shearer, Belg. Patent 652,653 (Eastman Kodak Co.) Deoeober 1961*. 4 119. Hans Schumann, Gar* Patent 1,296,1*58 (Deutsche Soleay-Wbrke) June 1969. 120. Rene Michael, Fr. Patent 1,532,115, July 1968. 121. H. T. Imp, Jr.. T. L. Statler, and E. E. Hueliar, Mitt. Ver. Dsut. Qnailfachleute l (5), 1*5 (1966). 122. Rolf Bremer, Eberhard Rhelnhold, and Hermann Fiebig, Oer. (East) Patent 66,712, My 1969. 123. Belg. Patent 696,620 (Establishment Mareohal) October 1967. 121*. Brit. Patent 1,159,220 (Sigri Elektrograpit) December 1967* 125* R. B. Trask, and Mark J, Smith, Fr. Patent 1,520,177 (Air Reduction Co.) April 1968. 73 HONS 201923 126 Fr. Patent 1,299,631*, Julj 1962, 127. Hth. Ptnt Appl, 6,1*11,169 (Monsanto Co.) Mar oh 196$, 128, ibid, 6,1*01,1*71* (Monsanto Co.) August 1961*. 129* K, Sato, U. 3. Patent 3,1*68,726, Septenfcer 1969. MOMS 201924 71* APPENDIX C The Need For Continued 0 se of PCBs As Electrical Insulating Liquids I. II. HI. Table of Contenta How are PCBe Used by the Electrical Industry? The Need for PCBs in Transformers A. Mineral oil-insulated transformers B. Dry-type transformers ,, The Need for FCBs in Capacitors A. Mineral Oil 1. Size 2* Reliability and life 3. Safety B. Other Liquids 1. Castor Oil 2. Dibutyl sebacate 3. Silicone fluids Page 76 76 79 IV. Environmental Protection 01 Tables 1. Composition of Different LiquidChlorinatedBiphenyls 76* 2. Underwriters* Laboratories FlammabilityRatings 3* Alternate Insulating Fluids 77 SO Il MONS 201925 f 75 APPENDIX C The Need For Contimid Use of PCSa Aa Electric*! Insulating Liquids I. HOW ARE PCBa USED BY THE ELECTRICAL INDUSTRY? (1) The principal use of PCB fluid in the electrical industry is in trans formers and capacitors (both large and small) as an Insulator and coolant. Transformers are devices for converting electrical power from one voltage and current level to another, and the conducting parts of these devices must be separated from each other by a suitable Insulating medium. . Capacitors are devices for storing electrical energy through the physical separation of charged metal surfaces by an insulating medium. Because of the nonflammability (Table 1) of Aroelors (the trade name of Monsanto), their vapors, and their arc-formed gaseous products, trans formers filled wltti PCBa are relatively free of fire and explosion haterde and may be used in locations where failures of oil-insulated transformers would present a potential danger to life and property. In addition to Im proving the safety aspect of capacitors, Aroelors also have the advantages of reliability, long life, and small size. Table 1 Underwriters* Laboratories flammability Ratings Fluid Flaambility Rating Ether 100 Gasoline 90-100 Ethyl Aleohol ' 60-70 Kerosene (100 F.P.) 30-10 Mineral Oil 10-20 Aroolor 12l2 and MCS 1016 2-3 II. THE NED TOR PCBs IN' TRANSFORMERS PCBs are used in transformers wherever fire protection is particularly important -- for about peroent of all transformers. Most of these transformers are located inside public, commercial, or industrial buildings) on the roof tops of such buildings or in close proxi mity to such buildings, end require no special enclosures other than neoessary to prevent accidental hazardous mechanical or electrical contact of persons with the equipment. See Table 2 for some liquid chlorinated blpheiyls. 76 MOMS 201926 TABLE 2 O^ositAon of Different Liquid Chlorinated Biphenyla Couponsnth - given i3 < - 1221 1232 Monsanto Aroclors MCS 1063 12li2 MCS 1016 12$L 126o" Chlorine Biphenyl Mo no-chlor ob ipheiyl Di-chlorobiphenyl Trl-chloroblphenyl Tfetra-chlor oblphenyl Penta-chloroblpherpl Hexa-chloroblphenyl 21 32 111.6 56.5 26.9 w55 l.ti2 .06 32 .Oli 22.2 7lt.li 3*3 Ii2 .02 .72 15.6 51.5 22.5 6,7* 1(2 .02 1*8 .93 19*1* 61(.5 15.0 ^ 55 .16* 51i 60 60 70 Includes higher than pent*-chlorinated lacaaors. HONS 201927 The amount of Aroclor used In various types of transformers ranges from liO to 500 gallons ($16 to 6,L50 lbs.) with an average of about 235 gallons (3,032 lbs.). During 1968, the last complete "normal" year for the electrical industry, the total amount of PC8s used in trans formers waa approximately 1.3 million gallons (8.1* thousand tons). Hie only present alternatives to Aroclor-insulated transformers are mineral oil-insulated transformers or dry-type transformers (either those open to the atmosphere or those that are gas-filled and sealed). A. MINERAL OIL-INSULATED TRANSFORMERS 1. If one disregards safety considerations, there are no technical reasons why mineral oil-insulated transformers could not be directly sub stituted for PC8 insulated transformers. The size of the unit would be unchanged; the weight and cost would be less. 2. But one cannot disregard safety considerations, which are often embodied in legal codes. Obviating the safety hazards Involves serious economic and space constraints, that would occur either by the use of protective vaults, or use of insulated buses (with the transformer located outdoors). Either solution, if space is available, could cost $,000-$$0,000 per transformer. B. DRY-TYPE TRANSFORMERS . In most locations, dry-type transfozmers (either those open to the atmosphere or those that are gas-filled and sealed) could not be directly substituted for PCB-insulated transformers. There are several restrictions to such a direct substitutiont 1. The reliability of dry-type transformers is less than that of comparably rated liquid-Insulated transformers. An Edison Electric Insti tute survey of failures in network transformer banks showed a 7 percent per year failure rate for dry-type unite compared to 0.2 percent for liquid- insulated units. ' 2. Furthermore, liquid-insulated transformers have a much greater overload capability. Many liquid-insulated units can sustain a 100 per cent overload for 8 hours and a 200 percent overload for 2 hours. These transformers are able to maintain continuity of electrical service during periods of ta^orary malfunction of related equipment. 3. Some dry-type transformers ars larger by 10 to 30 percent them comparably rated liquid-insulated units, and most are expensive. b. Dry-type transformers are noisier by 5-10 db than are liquid- insulated transformers. 5. Open dry-type transformers, which are cheaper than sealed drytype transformers, cannot be used in certain corrosive or hazardous atmospheres, s.g., on furnaces or on electrostatic precipitators near hot stacks. Clearly there is no substitute for PCB-filled transformers where fire protection is required. MONS 201928 78 in. THE NEED FDR PCBs IN CAPACITORS PCBs are used in more than 90 percent of the electric utility (large power) type and smaller industrial type capacitors made today. They are needed for safety, reliability and long life, and to achieve sizes compatible with equipment and installation requirements! The principal types of PCB-impregnated capacitors and their applications are high voltage power capacitors used primarily for power factor correction in the distribution of electric power) low voltage power capacitors Installed in industrial plants at the load (typically large motors)) ballast capacitors to improve the efficiency of lighting systems) and small industrial capacitors for power factor Improvement in such equipment as air conditioning units, pumps, fans, ete. Almost 80 million such capacitors are manufactured annually, moat of them for first-time use. Capacitors used in lighting and air conditioning application! contain 0.005 to 0.09 gallons of PCB per unit. The largest power capacitors contain about 6.7 gallons of askarel* The most popular site contains about 3.1 gallons. The National Electrical Code requires that any installation of capacitors In which any single unit contains more than 3 gallons of combustible liquid shall be in a vault like that re quired for transformers. During 1966, the last caplets "normal" year for the electrical industry, the total amount of PCBs used in capacitors was approximetely H4..I4 thousand tons. Fosaibls alternatives to PCB-impregnated capacitors are capacitors Impregnated with mineral oil, or certain other liquids. A. MINERAL OIL 1* Size The single most important property of e liquid to be used in a capacitor is its dielectric constant (the ratio of its ability to store electrostatic energy relative to air). The dielectric constant of the capacitor-grade PCB (Aroclor 121*2) is 5.65 t&lle that of mineral oil is 2.25. (See Table 3) Reverting to an oil-paper dielectric system would Increase the average capacitor volumn(size) by approximately 600 percent the weight by 500 percent, end the coet by approximately 1(00 percent. At the present levels of demand for capacitor STAR, there would be a shortage of electrical grade paper and a shortage of capacitor factory facilities further tending to increase the cost to the utility, and ultimately to the coDimr# 2* Reliability and Life . PtJBs are thermally and oxidatively more stable than mineral oils, and discharges, which can occur in capacitor*, are less likely to generate gases from askerele than from mineral oils* The chemical stability of PCBs in the presence of capacitor tissue end pleatie films end the favorable stress distributions between solid and liquid have made it possible to desi^i low-coet capacitors with a life expectancy of more than 10 years life in lighting applications and more then 20 years In electric utility applications. In each application the first-year failure rates are lese than 0(2 percent. This level of life and reliability bad not been achieved prior to the introduction of PCBs. 79 HONS 201929 Table 3 Alternate Insulating Fluids flop* Significant Properties of Osrtain Candidate Insulating Fluids to Replace Aroclor 12li2 Fluid . Aroclor 12l*2 Aroclor PCS 1016 Aroclor MCS 10i*3 Mineral Oil Dielectric Constant, e'r. at 25 C 5.85 5.85 5.7 2.25 Cleveland Gfc>en Cup Flaaaabilitj Flash Point -C - Fire Point 191a 191 160 Hl5 333 319 2lili 150 Cost Density t lb 1.38 1.36 1.26 18 16 16 .9 3 HOMS 201930 3. Safety The relative non-flasmability of PCBe significantly reduces the fire basard that sight otherwise accospany those failures that result in rupture of the ease* B. OTHER LIQUIDS . 1. Castor Oil. The dielectric conetant of castor oil is U*S, and this material la useful as an impregnant in D.C. energy storage capacitors. However, A.C. capacltore filled with this liquid have relatively short lives and are not vcy stable under A.C. discharges and in the presence of water derivable from the celluloslc paper. 2. Dibutyl sebacate. This ester is especially useful in high frequency parallel plate capacltore because of its low, flat loss charac teristics over a broad frequency range. In this type of construction the liquid ia the sole dielectric material. When used in conjunction with paper,this ester is elso unstable* _ 3* Silicone Fluids. These materials have a dielectric constant of 2.7 and would generally be subject to the seme disadvantages as mineral oil. In the interest of achieving a higher degree of environmental compatibility the capacitor Industry switched during 1971 from Aroclor 12U2 to Aroclor MCS 1016, from which the higher-chlorinated persistent fractions have been substantially removed. 17. ENTISOtKENTAL PROTECTION The advantages to the public in terms of safe, reliable, and efficient electrical equipment made possible by the use of PCBs have been documented in the body of, and especially Appendix B to, this report. It is elso clear that there are no present or prospective substitutes for these materials, and that the functions they perform are essential. Thus the continuing need for PCBs in closed electrical system applications is con clusive. The electrical Industry well understands, however, that continued use of these materials requires unusual protective measures. These measures were the subject of rsoemendation* made by a previous NIFCC BubCouncil report (The Cat and Disposal of Electrical Insulating Liquids. June 1971) end are judged to be well on their way toward impleMtrtaiion i witness the introduction of the new capacitor dielectric, the provision of facilities for the iaoineratlon of liquid and solid wastes,,and the instructions* to operating personnel and users regarding the need for cars in waste diapoeal, an activity now being further formalised and strengthened by ANSI's committee CIO7. The annual residual leakage to the environment from the continued use in transformers and capacitors has bow eatlmated between one pert in a thousand and one in ten thousand of the easting environmental PC8 burden. 1. The above paper was prepared by the Electric and Nuclear Bub-Council, National Industrial Pollution Control Councilt Chairman, D. C. Burnham, Westinghouae Electric Corporation; Tics Chairman, Fred J.Boreh, Chairman and Chief Executive Officer, General Electric Company; Mmaberet A. P. Fontaine, President and Chairman, The Bendix Corporation; Raymond H. Olesecke, MOMS 2Q19B1 8l President and Chief Executive Officer, McQraw-idison Companyj C. Lester Hogan, President and Chief Executive Officer, Fairchild Camera and Instru ment Corporation) Robert v, Sarnoff, Chairman of the Board and President, RCA Corporation. 82 HONS 201932 APPENDIX D Occurrence. Transfer, and Cycling of PCBs in the Environment PCBs have been in use for more then four decades, not only In the United States but throughout the developed world. They were not recognised as environmental contaminants until (Jensen , 1) in Sweden identified a series of unknown peaks on gas ohromatograms of pesticide analyses as these sub stances. These first identifications were in fish and bird tissues; examina tion of other samples soon revealed that PCBs were widespread in biological materials. Existing data suggest that although the greatest concentrations of residues are found in the vicinity of industrial and municipal areas in the Northern Hemisphere, residues exist in areas remote from civilisation and in both the Northern and Southern Hemispheres. Data on sales of PCBs are available only for the United States from 1957 1971, with sales reaching a high of 36,OCX) tons in 1970, Table 1. Sales doubled 1960-1970; assuming the same growth rate from 1930 to 1970, about 500,000 tons have been sold in the United States. Data from outside the United States ere few. It is estimated that Japan manufactured 13,000 tons per year (2). PCBs are also produced in Waat Germany, the United Kingdom, Spain, France, Italy, Russia, and possibly new producers in Bretil, Argentine, India, and East Qermany. Assuming that the United States used half of the world total, world pro duction would have been about one million tons--approximately half the estimated total production of DDT. Monsanto1* 1971 sales dropped to half the 1970 level, and 1972 sales ere expected to be 12 - 15,000 tons. Prior to 1971, wben Monsanto (the sole U.S. manufacturer) curtailed sales to non-closed system uses, about bO percent was used in plasticizera, hydraulic fluids and lubrioants, surface coatings, inks, pesticide extenders, and micro-encapsulation of dyes for carbon less duplication paper--uses that potentially result in environmental contamina tion. If the same percentages held worldwide, 1*0,000 tons might have been used in ways that could easily reach the environment; accidents and careless disposal practices would have increased this amount considerably, perhaps to 50,000 tons or more. (Nisbat and Sarofla, 3)provid#d rough estimates of the loseas of PCBs to the North American environment in 19701 1500 to 2000 tons to th* atmosphere (mostly Aroelor 125b to 1260 from plastics and 12l*2 from burning dumps); 1*000 to 5000 tow to fraab and coastal waters (Aroelor 121*2-1260); 22,000 tons into dumps and landfills (mostly Aroelor 121*2). Other losses were judged to be small, but often locally significant. The total loss to the North American environment from 1930 to 1970 was estimated to bei Atmosphere - 30,000 tons Water - fresh and coastal - 60,000 tons Dumps and landfills - - 300,000 tons The total of 390,000 tons is within a factor of two of the estimate above of 500,000 tons that might have reached the world environment. They further 81* HONS 201914 TOTAL PRODUCTION (For Domestic Sales)'H DOMESTIC SALES DOMESTIC 3ALES BT CATEGORI Heat Transfer Hydraulics/Lubricants . Misc. Industrial Transformer Capacitor .. Plasticiser Applications'^ Petroleum Additives Total DOMESTIC SALES BT PJB QRADE Aroclor 1221 Aroclor 1232 Aroclor 12b2 Aroclor 12b8 Aroclor 125b Aroclor'1260 Aroclor 1262 Arcolor 1268 Total TABLE 1 PCB MANUFACTURING AND SALES DATA FROM MONSANTO INDUSTRIAL CHEMICALS GO. 1957 THROUGH 1971 (Thousands of Pounds) 1957 1958 19^9 1960 37919 32299 26061 31310 3521b 1612 70b 12955 17028 - 5559? 23 196 18222 1779 bb6l 7587 31 - 32299 1519 755 5719 1L099 3939 - 5535T 16 113 lObbb 2559 6691 5982 18b 72 26061 2685 1569 598b I6b99 b573 * 5I5IO 2523 1559 7921 16967 62bb - 352IE 251* 21*0 13598 338b 6751* 6619 359 102 31310 . 103 155 18196 2827 6088 7330 326 189 3521b NOTE: (l) Production aiaounts prior to I960 are not available. (2) Amounts for plasticiser applications prior to 1958 are not available 1961 36515 37538 1962 38353 380b3 bno 211b 6261 15935 9098 - 57515 157 3915 1681 798b 15382 892b - 55655 9b 2bl 19827 b023 629b 65bO 361 158 37538 lbo 22b 2065b 3b63 6325 6595 b32 210 380b3 MOMS 201935 u.s. FHcoucnoa DOMESTIC SUES (LBS.) U.S. EXPORT SUES D.S. DOMESTIC Sims BT CATBQOKT_________ Heat Transfer HydrauUcs/Lubricwts Misc. Industrial Transformer Capacitor Plasticiser Applications Petroleua Additives ao> u.s. Domsnc sales BT PCB GRADE Aroclor 1221 Aroclor 1232 Aroclor 121t2 Aroclor 121)0 Aroclor 1251) Aroclor 1260 Aroclor 1262 Aroclor 1266 m. Ut73li 36132 361)7 TABLE 1 (coni.) 126k 50033 LD069 1)096 1965 6OI|0O 51796 1)231) 6501t9 59070 6052 1967 75309 621.66 012li I960 02051i 65116 11231 1969 76307 67191 10621) 1970 1971 05051) 1(01*71 73061 37635 13651 9076 Prospect 1972 25-30 n 25-30 ? 502 39L5 1520 7290 15606 9101 929 1)37U 3692 7997 195W 10337 1237 1(616 lOlil 0657 2371)9 11696 1766 1)250 1779 0910 20001) 131)01 2262 L61i3 11)26 11071 29703 13361 - 2529 5765 1283 . 11505 29550 11)1(01) - 3050 0039 1079 12105 25022 161)60 1U39 3950 71)03 :fc-27 12P20 26/00 19537 -' 3600 161)3 578 11526 17305 3102 - . 25-30 m 25-30 m - 361 13 10510 5013 5911 7626 Ui) 26b 596 13 23571 5230 6200 0535 U6 190 369 7 31533 5565 7737 5631 55 196 520 16 39557 5015 7035 5875 760 201) lil)2 25 1)3055 l)70b 6696 61)17 01)0 287 136 90 1)1)053 1)891) 8091 5252 720 200 507 273 L5li0i 5650 9622 U39 712 300 11)76 260 60588 1K>73 121)21 1*90 1023 330 1600 211 21000 261 5000 1750 * 300 300 LOOO _ 6000 600 HONS 201936 estimated that one-third of the PCBs released to the air and one-half of those released to water have now been degraded. The PCBs in dunps probably have undergone less degradation. Given the diversity of uses of PCBe and their chemical stability (greater stability in the higher chlorine species), it is not surprising that residues are now widespread. While satisfying quantitative estimates of the contribution of various pathways into the environment are not possible with existing data, there are enough data to be certain that they do reach the environment at least from the following sourcest -- Open burning or incomplete incineration (et usual tamperatures) q of solid wastes, municipal and industrial. Incineration at 2000 F or above for two seconds will destroy PCBs, but poorly opsrated incinerators or open burning may result in PCBs being released to the atmosphere unchanged. - Vaporization from paints, coatings, plastics, etc. (Nisbet and Saroflm, 3) estimate that as much as 20 percent may be vaporized. -- Municipal and some industrial sewers (present in treated as well as untreated wastes). Tables 2 and 3* -- Accidental spills or improper waste disposal practices. -- Formerly, direct application to the enviroment as ingrsdients of pesticides or as carriers for pesticides (such uses are now prohibited). -- Dumping of sewage sludge, municipal end industrial solid waste, and dredge spoil at sea. -- Sewage sludges disposed of on land. -- Migration from surface coatings (paints, etc.) end packaging materials into foods and feeds'. Probably the largest amounts of PCBs circulating in tha eaviroraant reach it through industrial and municipal discharges to inland and coastal waters. Tables 2, 3, and li present data on such discharges. Based on Ifcble ii, we can estimate 6,000 tons per year may reach these environments. In addition, PCB residues occur in sludge from municipal sewage systems. Table $ presente results of analyses from several such sludges. Sewage sludge is disposed of by incineration, landfill, spreading on the lend, and dumping at sea. Four million tons per year reach the Atlantic Ocean and Oulf of Mexico, which would Include only 10 or so tone of PCBe (li). Analysis of the waste water from the effluent scrubbers of three sludge incinerators showed no detectable residues of PCBs (level of sensitivity 0.1 part per billion), suggesting that most PCBs had been destroyed by incineration. The total amount of PCBs con tained in the sludges would not be more than ^70 tons per year. MONS 20193? 87 TAILS 2 CONCXNTMTION OF KJS IN MUNICIPAL SIVACI T1IATHENT PLANT OUTFALLS Coll act ion Site Collection Data Aroelor Compound Detected (ppb) Flow par Day Hgd 1/ Eat. PCB Dlachargad par day (lba.) Ohio Miami River Dayton 1-19-71 0800 to 1-20-71 0800 1234 17 48 6.2 HamlIton 1-19-71 0000 to 1-19-71 2400 1248 10 6 0.6 Source of Data EPA Unpb. Data fF Middleton 1-19-71 0800 to 1-20-71 0800 HD* II Wlaeonain Milwaukee River Wait Band 3-26-70 Fradonla Saukvllla Grafton tt tf if 1234 1234 1260 1234 0.23 0.12 0.13 0.04 1.4 0.1 0.1 0.8 0.002 0.002 0.002 0.002 velth 4 Lae Ft t California laat Bay (San Franclaco) 12-70 1234 ' 3.1-3.a 153 4.2 Schmidt, at el, <71 San Franeleco Terminal Island Orange County Hyperion White Point rl It It ` it 1234 1254 1254 1254 1254 3.8-3.8 3.8-12.8 0.21-0.64 0.16-0.37 76 31.5 9.3 130 340 350 1.2 0.7 0.4 0.7 213 II It tF tf It Richmond ND* - San Dlago ' Oxnard HD - Not Detected HD* - - KD* * 1/ ngd * Billion gellone par day * (8,000,000 Ibe./day) "M MOMS 20193# TABLE 4 TOTAL ESTIMATED CONTRIBUTION OF PCBS TO THE AQUATIC ENVIRONMENT Municipal Outfalls Asiurett 150,000,000 sewered population x 130 gallons sewage par parson par day x 8 pounds par gallon of sewage " Approxlmataly 160 billion lbs./day. With concantratlon of 0.1 ppb In sawaga, 16 lbs./dy; With concantratlon of 10 ppb In sawaga, 1600 lbs./day. [Nota that only tha Whlta Point outfall and Dayton (largely sarvlng Industrial conraunltles) axcaad tha 10 ppb concantratlon] Annual contribution would not axcaad 300 tons from this source, avan If tha avaraga concantratlon in municipal sourcas was 10 ppb. Industrial and Othar Sourcas Baals for Estlmatai Concentrations In tha Great Miami Rlvar of 5.8 ppb and flow rata of 728 cfs yield aatlmatad.dally carriage to tha Ohio Rlvar of "'>'95 lbs. par day. Contribution from tha sawaga treatment plants at Dayton (6.2 lbs./day) and Hamilton (0.64 lbs./day) account for 6.8 lbs. ('--7% of tha amount present in tha rlvar). In tha Milwaukee Rlvar, tha aatlmatad discharge of PCBs to Lake Michigan^ based on a concentration In tha water of 0.15 ppb (Velth and Lea, 1970) and flow rata of 500 cubic feat par second, Is'v 0.5 lb. par day. Contributions from the sawaga treatment plants at West Band, Fredonle, Seukvllle, and Grafton, total 0.002 lbs./day, (about 0.41 of tha amount present). Extrapolation! Tha Great Miami Rlvar drains a heavily Industrialised area and represents something near tha upper limit of PCBs to be expected in municipal discharges. The Milwaukee Rlvar Is less Industrialised. If one asaumaa .that municipal sources contribute on tha avaraga not more than 5X of tha total, tha annual contribution from othar sourcas would be on the order of 300 x 20 6,000 tons par year. 90 MOMS 201940 Collection Site California Hyperion (LoS'Angeles) Bars tow TABLE 5. CONCENTRATION OF PC3S IH SEWAGE SLUDGES Date Aroclor Detected Concentration (ppb) Sludge per dry tons/day Est. PCB Content Day (lbs.) Sourc e 12/70 1234 7/21/71 1254 85 (78.5-92.1) 20,000^ 1400 1.4 3.2 .004 Schmidt, ct. al. , (13) EPA Unpublished date Ohio Dayton (Miami River) Little Miami (Cincinnati) Mill Creek (Cincinnati) Lebanon (Turtle Creek) Sheyler Run 1234 1254 1234 1234 1234 103,000 32,000 12,700 2,300 3,200 47.9 20.2 88.3 1.0 - 10.1 1.3 2.2 .005 * EPA Unpublished data t 11 fl fl tl it 11 t| tl t 1* tl Virginia Lorton 1254 1,200 h r r* Indiana Indianapolia 1254 3,800 126.1 1.03 1 M 41 _1/ Thie number is based on outfall discbarf and represents a relatively dilute sludge. The estimated FCB content in lbs./day is the important figure here. Assumptions! Each million gallons of sewage contains about l ton of sludge. The dally output of sludge, then is 130,000,000 sewered population x 130 gal. sewaga per day " 19,300,000,000 gallons ocr day and 19,300 tons of sludge per day. At 10 ppm of FCBs (highest larval found), the dally output would be 19,300 tons x 2000 lbs. - 39 million lbs. x 10 ppn ** 390 lbs. per day, at 1 ppm, 39 lbs./day. These would be respectively 70 end 7 tons/year. MONS 201941 57 f*r the largest quantities of PCBs nust end up In dumps and landfills. As noted above, open burning will doubtless release sone PCBs to the atmosphere. Little is known about concentrations In landfills, degradation, leaching or vaporization. Much of the material here will be In sealed containers, and win be sequestered or only slowly released to the envlroment. Analyses of stagnant water close to a Swedish landfill were below the level of detection of b parts per billion, suggesting little leaching from such sources (5)* PCBs are known to have reached the envlrotment or man's food supply In a variety of other ways, no one of which Is Important as a source of envirormental contamination, but each of which may have serious consequences locally. Spent transformer oil containing PCBs, used as an herbioide carrier, contaminated dairy cattle grazing area and resulted In residues In milk. Silo paints containing several percent of PCBs are thought to have migrated Into silage, and In turn resulted In residues in milk (6). A leak In a heating element used in pasteuri zing fish meal resulted In contamination of poultry feed which, In turn, resulted in reduced hatchabillty of eggs In some chicken flocks, and residues in excess of the PDA interim action level in some eggs and meat (6). In Japan, rice oil contaminated from leakages during heat treatment resulted In poisoning of hun dreds of people and the only known disease attributable to PCBs. Residues in packaging materials have contaminated the foods they contained} presumably, most of the residues came from recycled paper which had Included "carbonless" carbon paper with relatively high PCB levels. Virgin paper products have also been shown to contain PCBs, and their source of contamination is not well defined at this time. There are other cases of food contamination in which the source of the contaminant has not been Identified. Fran the sediment measurements, we can crudely estimate the burden In sedi ments underlying Inland waters in the continental United States. There are about 58,000 square miles of such sediments. Assuming sediment has a specific gravity " *.5j residues are In the top 3 inches} the weight of 3 inches of sediment la 62.b (vt. of a cubic foot of water) x 13,560 sq. feet/acre'll,600,000 lbs./ acre, or/\sl billion lbs. per square mile (1.6 million x 6b0). At 10 parts per billion, the PCB burden would ba 58(000 sq. miles x 10 lb,/sq. mile 580,000 lbs. At 100 parts per billion, the PCB burden would be 5,800,000 lbs. -- 290 to 2900 tons. The higher estimate Is leas than 1/10 the amount Nisbet and Sarofim (3) estimate may be present in freshwater and coastal sediments. I. OCCURRENCE IN THE ENVXRONfENT Thousands of samples from various parts of the envlroment have been analyzed for PCBs. Table 6 presents selected data on occurrence in air, water, sediments, and various living organisms. In air and water away from iimnediate sources of wsste discharge, levels are low--a few nanograms per cubic meter (parts per trillion, ppt) in air and marine waters, and less than a part per billion (ppb) In fresh water} soil or bottom sediments contain a few parts per billion, up to several hundred parts per million (ppm) near some Industrial outfalls} from tenths of a parts per nillion to tens of parts per million in fish and up to hundreds of parts per MOMS 20i*2 92 Air Precipitation Suapaidtd Forticulata 3 Water 'CABLE 6. A SAMPLING OP MEASURED OCCURRENCES OF PCBS IN THE EHVlROMtEKT tuition No. Samples Date Aroclor Compound Dateeted Concentration (ppb) Source of Data Remarks United Klngdoa Florida Sweden 4 U. S. cltiaa I960 N.S. 1971 N.S. 1970 N.S. 1968-1970 N.S. Datec tad but not quantified Below level of quantification Praaeut In snow -- 27-230 ppm on suspended solids Tarrant and Tatton, 1968 USCS- Unpbl. Smithsonian Inst. CFSLP- 1970 EPA- Unpbl. Quantification questionable Croat Hlanl Elver, Ohio 19 11/70 1242 Ohio liver Elf Samlco Eivar, Rise. Pastlfo Rivar H1k< 2 Oconto Eivar Wise. Milwaukee Eivar 10 11/70 - 11/70 4/71 Smr *71 1254 ii 11/70 4/71 Smear *71 1254 ii t* 1970 1242 1260 ND to 15.1 -X " 5.7 EPA- Unpbl. NO <0.01 t ti Velth, 1972 3 snaplas above Dayton below level of detec tion. Mean of 16 smqtlas 5.7 0.31 0.38 <0.01 0.43 0.16 <0.01 It ff r* n II 0.03-2.07, x 0.29 Vaith and Lea , 0,02-0.13, x 0.08 1970 HONS 201943 i Water (continued) Ssdtnunte Location Mo. Smples TABLE 6 (Continued) Date A roc lor Coapound Detected Cone ent ration (ppb) Source of Data Green lay, Wiac. Lake Michigan South Florida Etcanbia Elver A ley, Fla.' Irish Sea ` 1234 Sumer 1970 4-7/71 M.S. Fall *69 1234 ID/49 M.S. 0.04-0.07 0.013 <0.01-0.02 HD to 40.1 <0.01 Veith, 1972 Velth, Faraonal Cowunlcation USGS, Unpbl. Duke, at. al. 1970 Holdgata, 1970 11 lakes in Pennsylvania 1971 M.S. <10-50 USGS, Unpbl. 7 locations In S.E. Florida 4 locations In Waat Central Fla. 6 locations In S. Florida Escaabla Bay, Florida 1971 1971 /69 /69 1/69 M.S. M.S. M.S. 1234 1234 1234 10-3200 <10-20 ft / tv 10-1300 9 aaa. of 486,000 1700 <300 Duke, at al.. 1970 t Remarks a of 12 saaplcs ^ ni. off 12 river souths. Data con sidered good to within + 501 Near Indus trial outfall 6 al. from outfall HONS 201944 Biota Marine Plankton Location No. Samp Lies North Atlantic TABLE 6 (Continued) Date A roc lo t Compound Detect ed Cone entration (ppb) 1971 N.S. i 200 Zooplankton Irish Sea 7 10/69 N.S. 10-30 Invertebrates Mustals M h Oysters 11 M Irish Sea Baltic Saa Stockholm Archipelago (about 200) 10/69 40 1965-1968 IS * N.S. N.S. Kscaabla Bay, Fla. 18 1971 1254 ft 2 1970 *1 11 2 1969 1 Florida S 1964-1970 M Georgia 12 1967-1970 It 3. C. 3 1965-1969 Blue Crab Crabs 19 Shrlap Norway Lobster Florida S. C. Bscanbla Bay, Fla. m Irish Saa 10 33 2-3/70 1969 1969 1969 N.S. 1254 1254 50-500 4300 (1900-8600) 5200 (3400-7000) 650 (100-1400) 840 (710-970) 1050 (1000-1100) 1400-2700 2000 Present but not Ouantlfled rt <100 1000-7000 1500-2500 10-100 3 Source of Data Remarks Harvey Nesbit 6 Sarofim, 1972 Holdgate ^n Nesbit & Sarofim, 1972 VI Jenson, et al., <69 H BPA- Gulf Breeze, Unpbl. rt IV i i* it it hike, at al., '70 If It Holdgate 1970 in Nasblt A Sarofiw, 1972 HONS 201945 it ii t t i (W iote (continued) nh No. Staples TABLE 6 (Continued) Date A roc lor Coapound Detected Concentration <PPb> Source of Data Rer.arks Karine (species North not stated) Atlantic Herring 98 10 species Baltic Boa Stockholm Archipelago Irish Sea Bey of Fundy Gulf of Me. 18 4 134 1971 N.S. 1963-1968 <8 If 1969 1971 n 1234-1260 100 Harvey Nlsbet 6 Sara fin, 1972 6800 (300-2300) Jansen, et al., '69 3100 (3300-8300) II 10-2000 70-1340 M Zitko, at al., 1972 Rstoerlne Menhaden It freshwater Florida H 8/70 10/69 1234 1234 6700 7300 8FA- Gulf Breexe Lab., Unpubl. M nationwide flsh-pestlclde aonltorlna 1969. At leant mat (lsh at 67 of 30 uapllni atatlons contained mere than 100 ppb of KBs (the lower Halt of detection). Level* tanged fraa <100 to 14,800 ppb. Henderson, at el., 1971. 1970. (bily 1 flab of 40 tOTpled contained leaa than 1000 ppb. Tha highest 20 fish averaged 36,000 ppb, ranging fraa 9600 to 213,000 ppb. Fish fraa tbe Ohio River and tbe Hudson River contained the highest residues-- 4 fish fraa the Ohio averaged 80,000 ppb; one fish fraa the Hudson River centalaed 213,000 ppb. Other waters in the top half Included tha Tatoo Rlvar, Allegheny River, Delaware River, Capa Fear Rlvar, Mississippi River, Missouri River, end Lake Ontario. (St*llli end Meyer, 1972) 201946 i I TABLE 6 (Continued) Location Biota (continued) No. Samples Bird* - Lend Starling* Continental 11. g. 124 Date A roc lor Compound Detected 11-12/70 N.S. Woodcock N.S. - Nothart) U. S. Bald Bagla 25 atatas 69 Bird* - Water CulllMOt Eggl Baltic Saa 9 Fall 1971 N.S. 1966-68 N.S. 5/6S White-tailed Eagla Stockholm 4 Archipelago 3/65-6/66 Heron fl 4 Doubia-creitad Bey of Fuad? Conorant (egg*) Abdominal fat Herring Cull Bay of Fundy Fat 4/67 19717 16 1254 1254 1254 Concentration (ppb) Source of Data Remarks x 660 (50-24,300) Bureau of Sport Fisharies A Wildl., L'npubl. 4000-9000 69 Not quantified ir 250,000 14,000,000, 8,400,000 17,000,000 / 9,400,000 17,200 52,000 75,000 Jensen, at al., 1970 (22) ri Jensen, ct al., 1969 (19) Zitko, et al., 1972 (20) If 96 MOWS 201947 9icta (continued) Manvels - Sea Cray Seal Location Baltic Sea Mo. Samp ice 2 Grey Seal Man Fiesta Stockho la Archipelago 3 South Carolina 723 Hi lk Fat Sweden California Germany 22 - Germany - United States 235 229 18S 36 TABLE 6 (Continued) Date A roc lor Compound Detected Concentration (ppb) 9-11/68 5/68 N.S, N.S. 30,000 30,000 1968 1254-1260 ' 43X of eanpla* up to 29 x 40 x 60 a 100 5700 N.D. <1000 1000-2000 >2000 ' Source of Data Rnr.arks Jensen, et al., 1969 (19) n Fink lea, et all, 1971 (23) IH) Waetoo, et al., 1970 (21,) Rleebraugh & Brodlne, 1969 ( 2$) Acker end Schulte, 1971 (26) Yob*, 1972 (27) -- Unknown N.S. Hot specified N.D. Hot detected L HOMS 201948 million in some fish and birds near the top of the food chain (1/8 of an inch is about one trilllonth of the distance to the moon; and a part per million is about 5 steps on a walk from Washington to San Francisco). Man, who is also at the top of a food chain, carries residues ranging up to 2 parts per million or occasionally more. II. BEHAVIOR. IN THE ENVIRONMENT ' A. Ai - The relative importance of the atmosphere as a transport mechanism is not known, Vhile PCBs have been identified in air, the residence time, transformations, and movement from air to land or water surfaces through fall out or rainout, or return to the atmosphere are virtually unknown. There are at least two observations that suggest substantial aerial transport) data on residues in fish in Lake Minto in a remote part of northern Quebec (7), and residues in woodcock which feed almost exclusively on earthworms, which in turn pick up residues from the soil. Only by invoking aerial transport can we account for residues in arotio lakes or in more or less wilderness areas of the North where woodcock summer. Niebet and Sarofim (3) suggest airborne PCBs will have been adsorbed on particles and have a relatively short resldsncs time_ thus most will have been redeposlted on the U. S. continent, but some will have reaohed the oceans. B. Water and Sediment - The water environment Is probably the principal sink and transport mechanism for PCBs. Calculations based on measured occurrences in municipal and industrial outfalls, in the receiving waters, and the down stream reaches of the waterways demonstrate transport through the aquatic sys tem. Measured residues in fishes from various enviroments suggest accumulations at the downstream ends of the dralnageways. There are few data on removal, disappearance, and sequestering of the sub stances in soils or bottom sediments of rivers, lakes, estuaries, or the ocean. Table 6 includes some data that indicate presence in bottom sediments, and sug gest that sediments may be a major reservoir of PCB residues. Work by Nlimo and his colleagues at Oulf Breeee (8) has shown that at least pink shrimp and fiddler crabs are able to take up PCS residues from this source. Fiddler crabs and pink shrinp exposed to clean flowing sea water in aquaria containing sandy silt with initial residues of 6l parts per million (dry weight basis) of Aroclor 125li accumulated an average of 80 * 25 parts per million in the whole crab and 2ti0 parts per million (one pooled sanple) in the hepatopancreas of the shrimp. Accumulation was much less, 17 1 9 parts per million and 6.1 parts per million, respectively, with silt initially containing 30 parts per million. Some accumu lation took place 3*2 0.9 parts per million (in crabs) and 1,1 parts per mil lion (shrimp hepatopancreas) from silt initially containing 2.5 parts per mil lion. The same investigator* have shown transfer of residues from sediments to overlying water. Effluent water from the aquarium with 6l parte per million Aroclor in sandy silt contained 3*5 parts per billion) from the aquarium with 30.0 parts per million in silt, effluent water contained 0.5 parts per billion. III. EXPOSURE AND BIXOOICAL ACCUMULATION Experimental work on biological accumulation by individual species of vertebrates and invertebrates has been conducted by a number of laboratories in the United States and elsewhere. Table 7 presents selected data that demon strate accumulation factors of up to 75,000 in whole organisms, and in the 99 HONS 201949 TAIiLE 7. ACCUMULATION OF PCBS BY VARIOUS AQUATIC ORGANISMS Specie* Aroclor Compound Exp Time Environmental Concentration (ppb). _ Residue (ppb) Concentration Factor Source CatfUh 1248 1254 60 da. 60 13.3 4.1 958,000 312,000 72,000 76,000 Stalling And M*yer, 72{7) 11 Uluegl 11 1248 60 4.9 312,000 63,700 IS 1254 60 6.8 87,000 12,800 It Fiddler Crab 1254 Plntc Shrimp 1254 30 30 3.5 0.5 3.5 0.5 ' 80,000 17,000 240,000 6, 100 23,900 34,000 69,000 12,000 It IS s 11 HOMS 100 hepatopancrsaa of pink shrisp. The date reported in the preceding section demonstrate that pink shrirp are able to accumulate PCS residues from "environ mental levels as low as 0.5 parts per billion; and Table 7 shows accumulation by fish from levels as low as 1 part per billion* FVidence from envirormental samples (Table 6) suggests uptake of PCB residues from exceedingly low environmental concentrations. Thus the plankton samples from the North Atlantic contain something like 200 parts per billion, yet PCB levels in marine waters are believed to be exceedingly low--certainly less than 0.01 parts per billion. PCBs, like many of the organic Insecticides, are fat Suluble, and are stored in the lipids of animals. Like the insecticides, they resist metabolic changes, and tend to be concentrated (at least to some extent) st succeedingly higher levels as they pass through various steps in the food chain. The data presented in Table 6 suggest that there are two components of movement through the biota. One is the familiar pattern of food chain accumu lations . The other involves direct uptake from the envlroment by various trophic levels; e.g., soil to earthworms; water to phytoplankton, tooplankton, larger invertebrates, and fish. The fish and plankton data from the North Atlantic reported by Nisbet and Saroflm (3) are consistent with the hypothesis, in that plankton residue levels are higher than fish levels, suggesting direct accumulation rather than food chain transfers. So, too, is the evidence from feeding studies reported by Stalling and Mayer (?) that suggest accumulations of no more than a factor of 2 over dietary intake levels in fish. It seems reasonable that food chain transfers are the principal route of accumulation in warm blooded vertebrates, and possibly in the highest levels of carnivorous fish. Conversely, direct envirormental uptake is probably the most important for aquatic invertebrates and fish. That humans are exposed to PCBs is evident from the data in Table 6. There are a number of possible routes * air, water, food. Pish end shellfish through uptake from water would be expected to provide the principal continuing source in the diet. Sampling of fish to keep those containing more than the FDA interim action level from the market is carried out by PDA and the various States whsre fish are known to have substantial PCB contamination. Other foods have been found to oontain PCB residues, but these residues are for the most part traceable to accidents; e.g., residues in eggs and poultry whose diet in cluded fishmeal contaminated by leakage of PCBs from processing equipment (Monsanto reports they no longer sell PCBs for this purpose); residues in milk traoeable to silage stored in silos painted with PCB-containing paints; residues in dry food packaged in PCB-contaminated packaging materials. Aside from the occurrences traceable to incidents such as the above, residues have been found in only 1j79 of 15,000 food settles by PDA during November 1969-June 1971 (200 of the li79 were followups on staples found to contain PCBs). In the PDA diet studies during FT 70 and 71, only 22 of 720 composite samples contained PCB residues * It is clear that only a small fraction of the D. S. food supply contains detect able levels of PCBs. HONS 2Q19S1 101 Other routes by which men me/ be exposed, or may have been exposed, include breathing of PCB-containing house dust and dermal uptake from carbon less copy paper or PCB-containing Inks. One sample of house dust from Michigan was reported to contain 200 parts per million of PCBa (10), Carbonless "carbon" paper was reported to contain 2-6 percent of PCB Kanechlor 300 (11)j experiments with this paper demonstrated that PCBs rubbed off when handled, and that even after washing the hands, approximately two-thirds of the PCBs still remained on the skin. Dermal uptake through Intact skin has been demonstrated In the rabbit, guinea pig, and rat, and presumably would occur In man. IV. DISCUSSION PCBs occur widely In the environment. It seems reasonable that by far the largest amount Is present In dumps and landfills whare it is thought to be more or less sequestered from the rest of the envlroment. It Is clear from environmental samples that smaller but significant amounts are present In the terrestrial and aquatic envlromenta. Much smaller total amounts are present In the biota, but levels in some organisms in soms places are sufficiently high to cause undesirable biological effects. The residues present in soils and bottom sediments are potentially available for transfer to the biota, directly or through movement to water and uptake by aquatic organisms. A relatively small amount of PCBa is required to contaminate a large part of the biota (for axanple, 10 tons would be sufficient to contaminate the en tire U. S. population to a level of 1 part par million). Organisms can accumu late residues from remarkably low environmental concentrations. PCBs have been shown to accumulate in fish and aquatic Invertebrates to levels of 75,000 times that present In the water (up to 200,000 times in selected tissues), and to be accumulated from concentrations as low as 0.06 parts per billion* Thus, to pre vent levels in fish from reaching the 5 parts per million established by PDA as the interim action level for fish as human food, concentrations In water would have to be less than 0.07 parts per billion, or, to allow some safety factor, 0.01 parts per billion. This level should be sufficiently low that fish and shell fish would not be adversely affected. Monsanto has taken a number of voluntary steps to reduce the amounts of PCBs reaching the envlronaent--both through restricting sales for such uses and by providing a disposal sarvica for its customers. (Dbring the first year after this ssrvice was announced, more than 500,000 pounds accumulated awaiting disposal in tha 10,000,000 pounds-par-year incinerator being constructed (3). Despite these steps, substantial amounts of PCBs are still reaching the environ ment. Ihey are prssent In detectable levels in virtually all municipal sewage effluents. Effluents from many industrial plants such as paper mills, appliancs manufacturers, electrical aquipmant manufacturers, and cbamical industries, in cluded higher levels than municipal sewage. As the restrictions continue, a decrease In residues should occur through gradual exhaustion of existing stocks and uses. - Wien the restrictions become Ailly effective, the principal source to the aquatic envlronnant can be expected to be that part of the electric equipment manufacturing Industry and the electric utility industry that requlrs these valuable materials because of their fire resistance and dialactrlc.properties. HONS 201952 102 The effluents from such installations should be regulated and closely moni tored to assure that no more than 0.01 parts per billion results in the re ceiving water. (So, too, should the manufacturing and disposal facilities of Monsanto.) Oood housekeeping should permit this level to be achieved. An educational campaign aimed at users to assure proper disposal will also be necessary--so long as the materials are referred to as transformer oils, cutting oils, hydraulic oils or fluids. etc., care in disposal will be hard to assure. After all, oils in moderate quantities aren't regarded as trouble some substances. V. RESEARCH NEEDS AND OPPORTUNITIES 1. Data provided by Kuratsune and Masuda (11) suggest that PCB-containlng carbonless copy paper may have been an lnportant soured of PC8 residues in man. An epidemiological study, Involving a group of regular users of such copy paper (airline ticket salesmen; clerical workers; etc.), would shed much light on this question. 2. The detection of high levels of PCBs in house dust by Price (10) suggests that inhalation may be an important source of PCB levels in man. Both the question of occurrence in dust and of respiratory uptake from such dust should be explored, 3. Residues of PCBs have not been determined in soils, though by infer ence they must be preeent. A set of sauries from the program of pesticides monitoring in soils should be analysed for PCBs; the set should be drawn with care to illuminate distribution patterns in, near, and remote from industrial areas. Li. Data on pasticldes in air are unsatisfactory. A few samples, in cluding both vapor and particulates, should be collected from industrial areas and analyzed. If the methodology proves satisfactory, a small-scale survey should be undertaken to determine the importance of the atmosphere as a trans port mechanism. 5. The presumption that PCBs do not move to ground water should be tested. The volume of water in this reservoir, coupled with its relatively long residence time, suggests that even very low levels of contamination may be significant. 6. Dumps and landfills are thought to be the principal reservoir of PCBs but there are virtually no data on behavior of PCBs in these locations. Shall scale sampling should be undertaken to determine the concentrations brought to dumps, the fate of PCBa from open burning, and into leachate and gases from sanitary landfills. Degradation in place should also be investigated. 7. The presumption that submerged sediments contain a large amount of PCBs should be examined. Such questions as vertical distribution, degradation movement, transfer of water, should be explored as well as the current distri bution of residues beneath inland and inshore marine waters. S. The reported finding of PCB residues on the order of 0.2 parts per million in marine plankton of the mid-North Atlantic requires elaboration. 103 MONS 201953 PCS content of plankton from equal volume* of water In inshore and mid ocean water*, a* well a* sampling of the surface film in both areas, would be informative. 9m Carbon filter samples going back to the mid-1960's are available from some fresh water locations. If a satisfactory analytical method can be worked out, samples Arom a few locations with continuous records should be analyzed to provide some data on trends that might be useful for correla tion with manufacturing data. Pish smnples should be considered for the same purpose. HOMS 201954 lOt FOOTNOTES 1. Jansen, Soren. 1966. Report of a new chemical hazard* New Scientist, 32i6l2. 2. Isono, N. 1970. Jlahu Koza, 1 (l)t60, 1 (It)*58 (in Japanese). 3. Nisbet, Ian and Adel Sarofim. 1972. Rates and routes of transport of PCBs In the Environment. Environnental Health in Perspective. 1, (in press). L. C.E.Q. (Council on Environnental Quality). 1970. Ocean dumping! A national policy. Washington, D. C. 5. Lidgett, R. A. and H. A. Vodden. 1970. PCB -- the eriviromental problem pp 88-96 in PCB Conference, Wenner-Qren Center, September 29, 1970. Stockholm! National Swedish Environment Protection Board. 6. Acker, L. and E. Schulte. 1971. Vorkonanen von chlorieten biphenylen und hexachlorobenzol neben chlorierten insektisiden in human milch and menschlichen fettgewebe. Naturwiss, 57*197. 7. Rlsebrough, Robert W., and Brock de Lappe. 1972. Accumulation of poly chlorinated biphenyls in ecosystems, Environnental Health in Perspective. 1, (in press). 8. Nimmo, D. R., P. D. Wilson, R. R. Blakman, and A. J. Wilson. 1971. Polychlorinated biphenyl absorbed from sediments by fiddler crabs and pink shrimp. Nature, 231*50-52. 9. Stalling, Ekvid and Foster L. Mayer, Jr. 1972. Toxicitles of PCBs to fish and environmental residues in fish. Environnental Health in Perspective. 1, (in press). 10. Price, Harold A. 1972. Occurrence of polychlorinated biphenyls in humans. Environnental Health in Perspective.' 1, (in press). 11. Kuratsune, Masanorl and Toshito Masuda. 1972. Polychlorinated biphenyls in non-carbon copying papers. Environnental Health in Perspective. 1, (in press). 12. Velth, 0. D. and 0. F. Lee. 1970. A review of chlorinated biphenyl con tamination In natural waters. Water Research, 1:265-269. 13. Schmidt, T. T., R. W. Rlsebrough, and F. Cress. 1971. Xrput of poly chlorinated biphenyls into California coastal waters from urban sewagm outfalls. Bull. Envlr. Contaa. & Toxicol., 6(3)i235-2l3. Ill. Duke, T. W., J. I. Lowe, and A. J. Wilson, Jr. 1970. A polychlorinated biphenyl (Aroclor 1251) In the water, sediment, end biota of Escambia Bay, Florida. Bull. Environ. Contamin. Toricol., 5*171-180. 15> Tarrant, K. R. and J. O'G. Tatton. 1968. Organochlorine pesticides in ralnwatsr in the British Isles. Nature, 2l9t725-727> MOMS 201955 105 16. Smithsonian Institution, Center for Short-Lived Phenomena. 1970. S, W. Sweden snow pollution. Event 19-70, Item 876. 17. Veith, 0. D. 1972. Chlorobiphenjrls (PCBs) in Wisconsin natural waters. Environmental Health in Perspective. 1, (in press). 18. Holdgate, M. W. (ed.). 1970. The seabird wreck of 1969 in the Irish Sea. Unpublished report (with supplement). Natural Environment Research Council. Referred to Nisbet and Saroflm, 1972. 19. Jensen, S., A. 0. Johnels, S. Olsson, and 0. Otterlind. 1969. DDT and PCB in marine animals from Swedish waters. Nature, 22L*2ii7-250. 20. Zitko, 7., 0. Hutzinger, and P. M. K. Choi. 1972. Contamination of the Bay of FUndy - Gulf of Maine area with polychlorinated biphenyls, poly chlorinated terphenyls, chlorinated dibenzodioxina, and dibensofurane. Environmental Health in Perspe ,;ve. 1, (in pr-'esj. 21. Henderson, C., A. Inglls, and W, L. Johnson. 1971. Organochlorine insecticide residues in fish. Fall 1969 National Pesticide Monitoring Program. Pesticide Monitoring Journal, 5(l)*l-ll. 22. Jensen, S., A. 0. Johnels, T. Odsjo, M. Olsson, and 0. Otterlind. 1970. PCB - occurrence in Swedish wildlife. Presented at PCB Conference, Wenner-Gren Center, Stockholm. Sept* 23* Finklea, John F., Lamar E. Priester, John P. Creason, Thomas Hauser, and Tom Hinners, 1971 v. Polychlorinated biphenyl residues in human plasma esqsoae a major urban pollution problem. Read before the American Public Health Association, Minneapolis, Minnesota. Oct. M tt 2h. Westoo, G. and K. Noren. 1970. Levels of organochlorlne pesticides and polychlorinated biphenyls in fish caught in Swedish water areas or kept for sale in Sweden, 1967-1970. Var Foda, 22i93-1Ii6. 2%. Risebrough, R. and V. Brodine* 1969. More letters in the wind. Environment, 12116-27* 26. Acker, L. and E. Schulte. 1971. Vorkonmen von chlorlaten bipherylen und hexachlorobensol neben chlorierten insektlziden in human milch und menschllchen fbttgewebe. Naturwiss, 57*ii97. 27> Yobs, Anne R. 1972. Levels of polychlorinated biphenyls in adipose tissue of ths general population of the nation. Environs* ntal Health in Perspective. 1, (in press). MQNS 201996 106 APPENDIX E Occurrence And Sources Of PCBa In Pood Table of Contents I. II. m. IV. V. VI. VII. VIII. n. FDA Pesticide Surveillance Program FDA Total Diet Studies ' USDA Sampling Programs Other Regulatory Programs Sources of Contamination Results of Surveillance Sampling Programs Industrial Accidents A. Poultry B. Meat By-Products C. Milk Paper Food Packaging Special Surveys Tables 1. Positive Analyses of Random Food Samples 2. Positive Follow-Up Investigational Samples 3. Suimary of PCB Findings in FDA Total Diet Samples li. Objective Samples - C7 1971 for FCBs Page 108 109 109 109 110 no 113 116 118 111 112 U7 120 MOMS 201957 107 APPENDIX S Occurrence and Sources of PCBs In Food Residues of polychlorinated biphenyls (PCBs) as potential food con taminants were first identified by(Jensen, l) in fish from various Swedish waters. Other early interests in the occurrence of PCB residues in foods were directed to PCB Interferences in the determination of organoehlorine pesticide residues, particularly DDT and its analogs. (Wictaarck, 2). In 1967 the Food and Drug Administration initiated a methods development project to determine the analytical behavior of PGBs and to devise a means of separating PCBs from chlorinated pesticides in the regula tory analysis of food. Experiments demonstrated that PCBe are recovered and detected by the FDA methodology routinely employed for multiple residues of organoehlorine pesticides at a sensitivity of detection approximately onetenth that for p,p'DDT. For example* using FDA's standard!ted procedures the limit of detectability for p,p'DDT in butterfat is about 0.15 parts per million, while for PCBs it is aboit 1.5 parts per million. Further investi gation lad to a procedure,(Armour end Burke, 3} that separates PCBs from organoehlorine pesticides after Initial saipla extraction and cleanup, and permitting separate determinations of the groups of chemicals. This procedure is designed for use with the FDA multiple pesticide residue procedure as the basic analytical method. The analytical method, along with the PCB-separation stap, has application to a wide variety of food end animal feed comnoditles and many types of envlrotnental substrates. In July 1969, FDA field laboratories were provided with the analytical Instructions for saparating and determining PCB residues in foods. Sines all objective food sables collected under FDA's pesticide surveillance programs are examined for chlorinated pesticide residues, the advances in analytical methodology facilitated analysis for PCBs in food. The food surveillance pro grams formally incorporated examination of all sables for PCBs and reporting of results in November 1969. Hie United States Department of Agriculture in corporated similar procedures in its staling programs for meat and poultry in January 1971. , The objective sampling programs represent the beslc Federal activity for monitorinx the Nation's food and feed supply for pesticide residues (Duggan and Cook, L). Hi* main components of these programs are as follows* I. FDA PSSTICIDB SURTOLtANCB PROCRAM # This program is designed to gather information on tha extent of pesticide '(Including PCBs) contamination of foods and faade on a geographical basis through ths use of a statistical sampling plan. Sasplsa are collected at shipping points to facilitate co^liance action when illegal residues or potential residue problems are encountered. FDA field offices select coaaaoditles grown or processed within their areas. Sampling is based on possible residue problems, volume of production, and other related factors. Commodities may include Aresh fruits and vegetables, dairy products, shell eggs, grains, fish, animal feeds, and processed foods. The limits of detect ability as applied to objective senplee is about 0.3 - 0.5 parts per Billion PCBs in non-fatty foods and about 1.5 parts par miUlom PCBs in tha fat for fatty foods. MOWS 201958 106 II. FDA TOTAL DIET STUDIES The total diet program la designed to determine the levels of pesticides, PCBs, and true heavy metals in the dietary intake on a geographical and seasonal basis. Market basket samples, representing the two-week diet of a 15-20 year old male -- which is approximately twice that of the normal diet -- are collected at retail stores, bimonthly, in five regions of the United States. Food items are cooked or prepared for table-ready use by dieticians and are divided into 12 food class composites, such as dairy products; meat, fish and poultry; and leafy vegetables. Each composite Is analyzed for a variety of chemical contaminants, including PCBa. The limit of detectability as applied to total diet ccstposites is approximately 0.05 parts per million PCBo. When abnormally high residues are detected in any composite, follow-up analysis is made of the individual food com modities of the composite to determine which food ie contributing the excesaive residues and to detsrmlna whether compliance action is warranted. III. USDA SAMPLINO PROGRAMS ' The Consumer and Marketing Service, USDA, has primary responsibility for sampling and analyzing meats, poultry, and broken egg products for pesticide, environmental (PCB), and othar chamical or biological con taminants The USDA program involves all federally inspected slaughtering plants (about 1,200) and egg breaking establishments (about lhO). The instructions for sampling request that the agricultural producer of the animal, bird, or eggs, be named eo that tha State of origin will be known. This facilitates follow-up if a violativa sample is found and identifies those samples which originate from the sane fern. Inspectors are Instructed to collect objective samples ftom different agricultural producers* The time of sampling and tha plant location are determined on a random basis, by computer, for this program. 17. OTHER REQULATORT PROGRAMS In addition to thaaa routine sampling activities, FDA and USDA laarn 6f PCB contamination of foods in other ways* As part of their enforcement responsibilities, they conduct in-plant establishment inspections; condupt special investigation* and surveys to determine the cause and extant of specific PCB problems; and maintain close contact with State officials and Industry who also monitor the occurrence of chemical contaminants In food. When required, there is also a selective phase to these sampling programs and investigations. Selective sampling Is used to determine the extent of violations when a violative sample is encountered or a report of possible harmful residues is received by the responsible agency. An increased number of samples is taken In the suspected area to determine 109 MONS 201959 the extent of the problem, end the degree of regulatory control required to safeguard the wholesomensse of the food aupply end to correct the problem. The selective program hea been uaed to control apecific PCS lncidenta. V. SOURCES OF CONTAMINATION Because of their widespread induatrlel epplicetiona, their chemical stability end persistence, end their ubiquitous presence in the ecosystmn, it is not unexpected that PCB residues here been detected In e variety of food commodities* Several sources of contamination have been Identified. These can be generally divided into three categoriesi 1. Environmental contamination - background levels of PCBe In fish from contaminated lakes and streams. 2. Industrial accidents - isolated incidents Involving direct leakage and spillage or contact of PCB fluids and other PCB containing materials on animal feeds, feed Ingredients or food. 3. Food packaging materials - PCB migration ta foods packaged in PCB contaminated paper products. Identification of these categories is not intended to Imply that all positive PCB findings in food and other materials have been successfully traced to any one of the three sources* Samples have been reported where the cause of the PCB residue was not clearly defined,'and one could only speculate aa to the source of the residue. Since examination for PCB residues was incorporated into the routine sampling programs of FDA and USDA, thousands of objective samples have been analysed. Additionally, numerous investigative surveys and selective samplings have been conducted to respond to specific "accidents" and other problems associated with PCBs in food* VI. RESULTS OF SURVEILLANCE SAMPLING FROORAMS Since November 1969, FDA has analyzed for PCB residues all raw agri cultural commodities and other food classes sasqaled under its pesticide surveillance program. More than 15,000 saaple examinations had been completed aa of June 1971. A total of 279 of the objective samples was reported to contain PCBe (Table l). An additional 200 food sables, collected as follow-up sables of suspected lots because previous analyses indicated a potential problem, were also found to contain PCB residues (Table 2). PCBs were encountered most frequently in fish, with 317 of the total positive samples (It79). The levels in fish reported in Tables 1 and 2 Indicate that most residues are between 1 and 10 parts per million. The Department of the Interior and others have gathered extensive amounts of data on PCB residues in fish, and it appears that the occurrence of PCB reslduea in fresh water fish la widespread geographically. Residue levels are related to location (highest in waters near industrial and metropolitan centers) and the species of fish (high or low fat, and feeding habits). In order to control the interstate shipment of fiah containing excessive reslduea of PCBs, FDA (February 1970) established 110 HONS 201960 TABLE 1 iaNr ficuin M rtAi.'SUs Itw-nfM'f IH^ thr^.'Ji JkiH" 19 P| (IS,000 SMftn Antijputl '--tl prlr tt t'it Coast TtroUd H;fc K*l locit*t> Spit (la|fpf) Avr*c* ppm la ttlet flab Laa 4a(tlta 2)<.l-l.M).tl Niaaaapalla lb* Orlaaaa mi Tarfc l(.12-J3.1t)17.l (T.t. nf.t* )!* Saa ftbaclaca run *r Pra*Mt Chaaaa* Mlb 1* t(S.U-.M).l* Shall Ifta !<.)>.) !(.. hM* Wf fnhicl Saattla Eaaaaa Cltr 4tUa*a altlaaaa aataa MftU 1(I.W).W 1(.JJ).J1* lU.MH.N 1(T).W 1(T) 2<.M-.t7>.H 3(t-T.M Alcana ClalHMl Mt f*)i.rr 4(.-.24).14 2(.1}'1.U>.44 ttftlt allaa Tacal Mlht 49<l>tS*U.I.M 1M 4 4<.4*-l.M)t. 1 7 M V f tab Wlti H tatl* la m. Sarin Qyatara Hlac. Hlllat lie* !<.> ft in ua.Mi Ua.t lit ) S1U|* 1 {-!> tlla ChiIh 1(11.J) 12(t>T).tt CraWat !(.) Cat FaW 1 (*.*) ab l(*.7p> U Tatal Paaltiva 411 fiatata > 14 ) 1 11 It 4 .4* 1 1 Jt 2 V* HONS 201961 IftfiLE 2 tMilH Ititrltl Lm Mb* M Jl<4.1-*.#>1.1* ruk r hMt ) (Inn* rutrrivF na au-ot unnicwiwu smna foll'Vtrd k Y'ttl ( iMivili'd rCI IrtliiM IhmAw If* Umtt J> 1*71 h*itm <tl (>m-w) Inotf ft* HI lk* Mil 4ta r r iiMt ortYc HIM. Ttlll TNltlri All iiMtt 74 IIWMilli In HIM w Tick MM Mm !(.]}> Trig Us* !{.*> M J 1 ta hMM bWlli MM '*r Kl.MH.M !<.>. 91 i(i.-i.7J)i.M s 1 Mill UlMM KM) I(4.k*-tt.M)U.7 IMkiM.KM.il %1 Mil UT) * t* Inin Mfili KUI4.)I. i iw hM 77).M* 9 J hlMtt U<i.04.Ml.U II Uw TNll NilUn U1 41 *1 M I J *5T f*4 Mi *MMt *tMM Latl. 1* an, ^>li >mm M HOMS 201962 an interim action level of 5 parts per million in the edible portion of the fish. The surveillance data for milk and manufactured dairy products also show this claes of food to have a relatively significant incidence of positive findings. For the most part, the PCB sources were traceable to localised "industrial accidents" which are described elsewhere in this report and were not always present as environmental contaminants. The occurrence of PCBs in milk does not appear to be widespread nationally. Although no PCBs were found in fresh fruits or vegetables, residues were reported in potato by-products used for animal feed. The source of contamination in this case has not been established. The FDA total diet studies for Fiscal Tears 1970, 1971, and 1972 (first-half only) included PCB analysis for 75 market baskets representing 900 composite samples. Theas analyses showed 5k composite samples to contain PCB reaiduea ranging from a trace to 0.36 parte per million (Table 3). Twenty-six of the positive samples were present in the neat, fish, and poultry composite, and nineteen in the grain and cereal composite. Findings in other food class composites were at lesa than 0*05 parts par million, with no consistent pattern of PCB occurrence. These studies indicate the dletarv intake of PCBs la of a low order. Expressed as mg/kg body weight/day, the PCB level for FT 70 was lees than 0.0001 and 0.0001 in FT 71 and FT 72. The objective phase of the USDA. sampling program for meat and poultry during 1971 detected PCBs in 161* of the b,175 samples analysed. There were 25 sauries positive in the 2,b0lt samples collected from cattle, swine, calves, and sheep with a range in the positive results from .1 parts per million to 3*0 parts par million. The poultry samples reflected the contaminated feed supply in the Southeastern United States and in the l,60it samples analysed, there were lliO positive with an analytical range of 1 parts per million to over 15 parte per million. The three poultry classes, young chickens, fowl, and turkeys, all had between 7-9 percent sanples positive for PCBs with a range of 1 parts per million. Only two samples were over guidelines established by JDA.. VH. INDUSTRIAL ACCIDENTS The following isolated Incidents of avoidable PCB contamination of food led to the actions described to remove the contaminated food from the market. A. POULTRT 1. New fork State Incident. The Campbell Soup Company, Camden, New Jersey, noted In Dftcember 1970 surveillance data excassive PCB residues in chickens rrown In New Tork State. State of New Tork placed a quarantine on the three counties involved and pretesting of all fowl was mandatory before slaughter. Analysis Indicated PCBs in poultry fat varying from a non- detectable level to 26.6 parts per million. FDA advised the State of New Tork and USDA on February 1, 1971, that FDA would not object to the 113 HONS 201963 distribution of poultry containing laaa than 5 parts par million, this level was applicable to the edible tissue on a whole tissue basis or to the separate fat removed durinf slaughter or processing and intended for use as a food or feed ingredient. The regulatory control action extended from December 1970 until August 1971) when all aArmies submitted for testing prior to slaughter were found to be below the 5 parts per million guideline. To support this control activity and determine disposition of the fowl scheduled for slaughter the following samples were analyzed for PCBe: 1,566 dozen eggs, 196 feed, and 5,790 chicken samples. Most of the analytical work was done in the New Tork State chemical laboratory. On the results of these sanples, li*0,i*50 chickens were killed on the farm and buried, 75,7LO chickens were passed for restricted slaughter, and 1*09,000 chickens were released for normal slaughter. The alleged source of the PCBe in this incident is believed by State officials to be plastic bakery wrappers. Bakery goods were used as a feed ingredient for the poultry and the plastic wrappers which may have contained high PC3 levels were ground with the bakery goods. 2. East Coast Terminal Incident (FDA Actions). The Monsanto Chemical Company informed FUA in Juiy 1971 tlr-t large amounts of fish meal might have been contaminated with Aroclor 12h2 leaking from a heating system during pasteurization of fish meal at East Coast Terminal, Wilmington, North Carolina. Aroclor 12k2 was used as the heat exohange fluid. PDA inspection revealed PCB contamination'of processed fish meal on hand at the firm. Investigation indicated the leak began in April 1971 and continued through July. The fish meal on the premises was embargoed and the firm Initiated a voluntary recall of fish meal processed since April 1971. An estimated 12,000 tons wers distributed. Over 2,000 tons were recalled. Individual fish meal samples examined contained from U* to 30 parts per million PCB. PDA also initiated follow-up sampling of fish feeds, catfish from fish farms, and eggs when the contaminated fish meal was Implicated. USDA was Informed when Investigation indicated eggs were being distributed to coranerclal egg breakers. As of September 1971, 22i* samples of eggs had been analyzed with 71 containing residues in excsss of 0.5 parts per million. PDA seized 3 lots of eggs. The samples representing these lots contained from 0.7 to 1;9 parts per million PCB. PDA seized 5 shipments of fish feeds that were manufactured from contaminated fish meal,. These seizures were in the States of Louisiana, Georgia, and Mississippi, and were on feeds that contained from 0.6 to i*.5 parts per million PCB, In addition, a shipment of the contaminated fish meal from East Coast Terminal that had not been recalled was seized. The analysis of this seized product showed level* In axcsss of 3$Q parts per million PCB. Catfish sampled from coemtercial fish farms contained leas than 3.0 parts per million PCB. MONS 201964 Ill* 3. East Coast, lamina! Incident (USD* Actions). The Meat and Poultry Inspection Program, USDA, waa notified by Holly Farms, Wilkesboro, North Carolina (July 1971) that poor hatchability had alerted then to a problem in their poultry operation. The cause was PCBs in the poultry ration, Tbe contaminated feed ingredient was the fish meal from one supplier in North Carolina. The USDA objective surveillance program had recent reports of PCBs in poultry fat from the southeastern United States The Food and Drug Administration informed USDA of the confirmed PCB contamination problem on July 19, 1971. The 5 parts per million guide line for poultry was reaffirmed. The list of primary consignees, received from FDA, showed the c ontamlnated fish meal had been distributed throughout 10 southeastern States. USDA required all poultry coming to market from this area to be either pretested or tested after slaughter before marketing. This program is continuing with owner's certification now being accepted since the source and feed distribution channels have been identified. e The Poultry Division examined 900 lots of broken eggs, and 123,750 lbs. of product were removed from the market. The Meat and Poultry Inspection Program has examined samples from over 5,17it flocks of broilers, fowl, and turkeys during this time. One producer had to destroy over 88,000 broilers. The present trend in PCB levels is downward, and the contamination is subsiding. Therefore, an effort is being made by U3IA to test all re maining flocks that were exposed to the contaminated feed so that the pre testing requirement can be discontinued. Any chicken or turkey flocks identified aa having violative levels of PCBs by this final testing program will remain under surveillance until disposed of by slaughter. It, Minnesota Incldwt, USDA notified FDA in August 1971 that USDA and Swift and Company had found excessive PCB levels in turkeys. Investigation indicated that the PCB residues found in the turkeys were caused by the feed. In addition, it appeared that the fat used as an ingredient of the turkey feed was the source of the PCB. The suspect fat used by the feed mill was received from a processor in Minnesota. It was found that the fet being manufactured at that time contained negligible levels of PCB* The_ source of the PCB levels found in the tarkeyw was not established. USDA. surveyed turkey flocks for PCBs in the immediate geographic area, which included parte of Minnesota, North Dakota, and South Dakota. There were lZiO flocks tested, and no residues of PCBs were found ebove 2 parts per million (fat basis) except in the original grower's flocks, where PCBs were present at levels up to 20 parts per million (fat basis). This one grower has been required to pretest all flocks prior to slaughter. Today the PCB level (fat basis) is approximately 1 part per 115 HONS 201965 million. Approximately 1 million turkeys approaching market weight were withheld from market until residue levels were reduced to less than 5 parts per million. 5. Oklahoma Incident, on August 20, 1971, USDA informed FDA of excessive PCB findings in chickens in Mississippi during routine sampling. Investigation revealed that the birds came from a grower in Oklahoma and the feed from a mill also in Oklahoma. PDA analysis of eggs and feeds from these firms showed no PCBs. .6 California Incident. USDA examined turkeys after slaughter in warehouse storage in California. PCBs were found In the amount of l.hl to 28.0 parts per million in the fat tissue. There were 100,000 pounds of turkeys detained until testing was completed. The turkeys had originated from flocks raised in four counties in California. Hie source of the PCBs could not be determined. B. MEAT BY-PRODUCTS . National By-Products, Inc., Mason City, Illinois Incident - On July 28, 1971, FDA inspection of this firm revealed that PCBs were used in heat treatment equipment. Sampling showed the pasteurized meat meal to contain PCBs. The firm initiated recall of the contaminated product. C. MILK . 1. West Virginia Incident. In July 1969, FDA's Baltimore District found PCBs in milk samples collected in the routine food surveillance program. Baltimore District investigated possible routes of contamination, and by February 1970, the investigation pointed to spent transformer fluid used as a vehicle for herbicide sprayed along power right-of-ways in the Martinsburg, West Virginia area. Through this route, PCBs contaminated dairy cattle grazing areas. The dairy farms involved were taken off production by State officials. 2. Ohio Incident. In April 1970, the State of Ohio notified FDA's Cincinnati District of unidentifiable residues in milk. FDA identified the residues as PCBs and advised the State of a guideline of 0.2 parts par million (whole milk). The State of Ohio and FDA investigated the problam and determined that the dairy farms were using a PCB-containing sealant in slloa that migrated to the silage. The State of Ohio banned milk from seem producers and destroyed an undetermined amount of milk. 3. Florlda-Oeorsia. Incidents. The States of Florida and Georgia reported findings of PCBs in milk to FDA's Atlanta District in August 1970. A PCB-containing sealant in silos was found to be the source of contamination in this incident. FDA found approximately 11 percent PCB in the silo coating. VIII.PAPER FOOD PACKAGING FDA first learned of the PCB food packaging problem in July 1971. The total diet market basket samples showed low level PCB residue in a grain and cereal composite (Table 3). The PCB was traced to the Shredded Wheat HONS 2019*6 116 117 TABLE 3 - SUMMARY OF PCB FINDINGS IN FDA TOTAL DIET SAMPLES Pood ClaM Conpoeltes PI 1970 30 Market SaSketa 360 Conpoaltea Positive Saage (PIN) I Dairy Products II Meet, plah, Poultry III Crain and Cereal Products IT potatoes T Leafy Vegetables VI Legtatt Vegetables VII toot Vegetables mi Carden Fruits n fruits X Otis, Pats l Shortening XI Sugar b Adjuncts XII leverages l T* 3 0.02-0.03 >. 1 0.08 FT 1971 30 Market baskets 360 Conpoaltea Positive Kangs (PON) -- Id T-0.15 b T-0.36 TOEAU 5 a. Trace (generally less than 0.05 PP PCB) b None detected 18 1/2 PY 1972 IS Market baskets 180 Ccmposltea Positive Range (PPM) lT 9 T-0.08 IS T-0.10 lr -' - lT - 2T 2T * . 31 HONS 201*6? packaging material was identified as the source of FCB in the food* ttie manufacturer of the packaging material used about 95 percent recycled paper to manufacture paperboard containers. FDA analysis of different types of the firm's paperboard shoved PCB levels ranging from about 2 to *33 parts per million. Various types of packaged food products, some of which used this firm's paperboard, were also analyzed as part of FDA's investigation. Nine samples of the 28 packaged foods examined contained PCBs in the food portion. As a result of this limited investigation, FDA initiated a nationwide survey in September 1971, to determine the extant of the PCB food packaging problem. The survey Included analysis for PCBs in all paper packaging components and the packaged food portions of 15 different.representative food categories. This survey was completed in late December 1971. A detailed statistical analysis of the results of the survey Is currently being compiled. Sixty-seven percent of the packaging portion of the samples contained PCB residues as high as 33& parts per million; 19 percent of the food portions of the samples contained FCB residues, with an average PCB concentration of 0.1 parts per million. The maximum PCB level found in food was $ parts per million. The FDA survey, as well as other studies by the paper and food industries, show a significant correlation between the presence of PCB residues in the food component and the packaging component. The mechanism of PCB migration from the packaging to the food probably occurs through both the vapor phase and abrasion or physical contact. The Level of PCB contamination is dependent upon many factors -- levels of PCBs in the packaging materlala, type of food, length and conditions of storage, and others. The extent of migration of PCB from paperboard packaging to the food contents is being investigated (Trout. 5). There is also significant correlation between the presence of PCB residues in packaging and the presence of recycled paper components in the packaging. The occurrence of PCBs in recycled paper materials is attributed primarily to the recycling of the so-called "carbonless" carbon paper (contains 3-5 percent PCB -- use of PCBs for this purpose has been discontinued) and to a lesser degree,, the use of certain printing inks. PCB residues also were found in sens packaging components that appeared to be composed entirely of virgin paper material* This source of PCBs probably occurs in the packaging manufacturing processes. Industry has taken steps to reduce the levels of PCBs in food packaging materials by avoiding the recycling of carbonless carbon paper. Although it is not know if this practice has bean instituted industry vide, data provided by the (k'oeery.Manufacturers of America, Inc., does reflect a change. For example; recycled board manufactured during the period June 1970 January 1972 shows that only 18 percent of the sables contained lees than 5 parts per million PCB; the same type of recycled board manufactured from November 1971 through January 1972 shows that 95 percent of the smnples to be below 5 parts per million PCB. IX. SPECIAL SURVEYS FDA is currently conducting a national survey to determine the extent and levels to which complete animal feeds are contaminated with PCBs. MOMS 201968 118 The survey covers feeds for cattle, sheep, swine, chickens, turkeys, and other miscellaneous animals. The survey results available to date show that less than percent of the complete animal feeds sampled contain PCBs* Levels range from non-detectable (less than 0.1 parts per million} to a maximum level of 0.6 parts per million PCB. Another investigation survey was recently initiated by FDA to survey the milk sudd1.v on a State by State basis to determine the extent of PCB contamination of milk intended for bottling and manufacturing use. Rseults from this survey are not available at this time. The results of tissue sample studies of several domestic anlmels and poultry are shown in Table b. HONS 201969 119 TABLE h - OBJECTIVE SAMPLES - CY 1971 for PCB's SUMMARY PPM - fat Basis ANIMAL AND POULTRY TISSUE CY 1971 Class N.D. .01-.1 .11-.50 .51-1.5 1.51-3.0 3.01-5.0 5.01-7.01 7.01-15 Over 15 Animals 2379 1 9 11 4 Poultry 1664 4 25 53 23 4 5 15 11 Animal Number of or Samples Poultry Analyzed PCB RESIDUES IN ANIMAL AND POULTRY TISSUES COLLECTED IN OBJECTIVE PHASE DURING CY 1971 Number of Samples with A Residue Percent of Samples with A Residue Number of Samples Exceed ing Guidelines Percent of Suples Exceed ing Guidelines Cattle 722 9 1.2 0 Ca Ives 66 4 6.1 0 Swine 1436 7 0.5 0 Sheep 1B0 5 2.8 0 Young Chickens 1637 127 7.8 2 Mature Chickens 69 5 7.2 0 Turkeys 88 a 9.0 0 Ducks 10 0 0.0 0 4208 165 3.9 2 0.0 0.0 0.0 0.0 0.1 0.0 0.0 0.0 0.04 HONS 201970 120 FOOTNOTES 1. Jensen, S, (1966), New Scientist ^2, 612, 2. Widmark, 0, (1967), J. AOAC 0, .1069 3. Armour, J. A. and Burke, J. A. (1970), J. AOAC 762-763, h. Duggan, R. E. and Cook, H. R. (1971). Pesticide Monitoring Journal , 37--1*3 5. Trout, P, E. (1971). Grocery Manufacturers of America "PC8 Workshop", fovember 17, 1971, HQNS 201971 121 APPENDIX T Human Directed Aspects of PCBs I. II. III. IV. V. 1. 2. 3. li. 5. 6. 7. 8. 9. 10. Table of Contents Pge Introduction 12b Toxicological Aspects 12b A. Human Episodes B. Animal Toxicity C. Contaminants in Polychlorinated Biphenyls Epidemiological Aspects lbb Studies in Progress lb6 Summary and Conclusions Tabies Subjective Symptoms Complained by Tusho Patients 152 126 Oral Toxicity of Chlorinated Biphenyls 127 Dermal Toxicity of Chlorinated Biphenyls 128 Vapor Exposure Toxicity of Chlorinated Biphenyls 129 Toxicity of Aroclors . 131 Pathologic Changes Induced by PCBs 132-133 Residues in Tissues of Rats Orally Dosed with Aroclor 125b 13b Storage of Aroolors (in PPM) 2b-Hours After Oral Injeetlon by Stomach Tube 138 Distribution of PCB-Derlved Material Following 98-Day Exposure to a Dietary Level of 1000 PPM Aroclor 125b 139 Distribution of PCS Levels in Adipose of Oeneral population as Shown in Analysis of Human Monitoring Survey Samples Since April 15, 1971 lb5 122 MOMS 201972 Tables 11. Experiments to Date not Included In the Manuscript, "Polychlorinated Biphenylsi Distribution and Storage in Body Fluids and Tissues of Sherman Rats" - A. Curley, 7, w. Burse, M. E. Qrim. 12. Some Biological and Toxicological Effects in the PCBs 13. Possible Future Studies Involving PCBs, Their Individual Isomers and Contaminants Page 150 153 15b List of Figures ' 1. Storage of PCS-Derived Material in Tissues and Plasma 1L0 2. Excretion of PCB and PCB-Dsrlved Material in Feces andUrine lbl HONS 201973 123 APPENDIX F Hunan Directed Aspects of PCBa I, INTRODUCTION The salient aspects dealing with the chemistry and toxicology of the polychlorinated biphenyls have been suimarlzed previously In a number of Status Reports of the FDA (Kolbye, 1; Burke and Fltzhugh* 2f Cook, 3). Additional literature reviews have stressed the chemical and biological aspects of the PCBs (Peakall and Linear, Li National Swedish Environment Protection Board, 5i Reynolds, 6i Zitko and Choi, 7j and Flshbein, 8). The major objectives of this report are to review the current status of the toxicologic (acute and chronic), carcinogenic, teratogenic* mutagenic, metabolic* biological, and epidemiological aspects of the PCBs that are of greatest relevance to man and, based on the above, to cite areas of suggested future research that will more definitively relate to the human aspects of the PCBs. II. TOXICOLOCHCAL ASPECTS A. HUMAN EPISODES ' Compared to the chlorinated hydrocarbon pesticides* definitive aspects of acute* sub-acute and chronic toxicity still remain rather poorly known. Chloracnogen effects were reported as early as 1936* following Industrial exposure to the PCBs*(Schwartz* 9, 10, 11) Jones and Alden, 12) Meigs, et al., 13). Occupational chloracne* however, has not been a problem with recent usage of the PCBs. Approximately 10 cases of fatal intoxication involving persons who handled or were exposed to chlorinated biphenyls or naphthalenes in their occupations have been described (Fllnn and Jarvik* lL) Greenburg, et al., 15) and Drinker, et al.* 16). lit all cases histological examination revealed liver fatty degeneration* necroses and cirrhosis. It is Important to note that chlorinated naphthalene (as well as chlorinated dlbenzofurans) have been recently Identified in two corniercial polychlorinated biphenyl samples (Pheno- clor CP 6 and Glophen A60), (Vos, et al.* 17). Human intoxication with the heat exchanger Kanachlor LOO* a Japanese manu factured PCS with ii8 percent chlorine and containing as its main components* 2,L* 3*, L1-, 2*5*3'* L'-* 2,3*ii*L'- and 3*l4*3Mi'-tetrachlorobiphenyl, and.2,3,1*3', L'-pentachlorobiphenyl,(Saeki, et al.* 18)* was reported in Western Japan in 1968. More than 600 people were eventually affected following the consumption of contaminated rice oil containing levels estimated to range from 2,000 to 3*000 parts per million PCBs (average of about 2*000 parts per million). These levels were derived from the known organic chlorine content of the rice oil related to the known organic chlorine content of Kanachlor LOO. Exposure levels to the oil were calculated to approximate 15*000 milligrams per day. The lowest reported figures allow an estimate of a minimal positive effect level at 3 milligrams PCB per day over several months. However* the average doses associated with signifi cant disease in the 'Tusho" incident were much higher and were in the range of 30 milligrams/day. (Kolbye, l). 12L MONS 201974 The clinical aspects associated with "Yusho" included: chloracne, blindness, systemic gastrointestinal symptoms with Jaundice, edema and abdominal pain. Chloracne is very persistent with some patients showing evidence of it after three years. Table 1 lists the subjective symptoms of 89 male and 100 female Yusho patients. New-born infants born from poisoned mothers had skin discoloration due to the presence of PCB via placental passage. (The dark skin discoloration re gressed after a period of 2-5 months). Oingival hyperplasia with pigmentation was seen in several cases. Decreased birth weights ware also noted but no evidence could be obtained in regard to the possible retardation in physical and mental activities of the babies (Yamaguchi, et al., 19). Die akin of still born infants showed hyperkeratosis and atrophy of the epidermis and cystic dila tion of the hair follicles. Residues of PCB have been found in fetal tissue (Kojlma et al., 20 ; Inagami et al., 21). The components of Kaneclor LOO with longer retention times have been detected in sputa and fatty tissues of patients (Kojlma, 22). Serum triglyceride levels were higher than 300 mg/ml in 60 out of 396 subjects investigated before the end of 1969 (Uzawa et al., 23, 21:). Among the incidence of hyperglyceridemia (triglyceride>300 mg/ml) of the six decade groups (age 0-9, 10-19, 20-29, 30-39, L0-l:9, 50-), that of the first decade group was the highest while that of the third decade was the lowest. The mechanism of the hyperglyceridemia was suggested to be possibly due to an observed decrease in post-heparin lipolytic activity and impaired plasma triglyceride removal (Uzawa et al., 2u). Cholesterol and phos pholipid concentrations were increased while lecithincholesterol acyl transferase activity was decreased. In female patients plasma lipoprotein lipase activity was decreased (Uzawa et al., 2ii| Nagel et al., 25). Nearly 1:0 percent of the examined patients exhibited an elevated excretion of steroids with the 17-ketosteroids (androsterone, etlocholanolone and dehydroepiandrosterone) found to increase in males and to decrease in females (Nagai et al., 25). Examination of autopsy tissues of two YUsho fatalities revealed the presence of chlorobiphenyls in all of examined organs, especially mesenterial fatty tissues, skin and bone marrow (Kikuchl, et al., 2o). Kojlma, et al.,(20) found PCBs with longer retention times (probably pentachloro- and higher chlorinated biphenyls) in autopsy tissues and it was assumed that their presence might have been responsible for the observed long duration of the intoxication symptoms. B. ANIMAL TOXICITY Early studies of acute oral, dermal and vapor exposure of the polychlori nated biphenyls have involved in many cases mixtures or compounds of undefined specifications and hence have been, difficult to interpret unambiguously. Tables 2-b describe the oral, dermal and vapor eiqoosure toxicity involving a number of chlorinated biphenyls and the results would suggest that the toxicity of these compounds is proportional to their degree of chlorination. These investigations have primarily focused on liver damage. The toxicity of 11 Aroclors in terms of oral LD^q (rats) and skin MLD (rabbits) is sumnarized in Table 5. a. Sublethal and acute effects: Analogously with the chlorinated hydro carbon pesticides, the moat important effect# are long-range sublethal effects. The pathologic changes in various organs are summarized in Table 6 illustrating some interesting differences between mammals and-birds. For example, the most MOWS 201975 125 TABLE 1SUBJECTIVE SYMPTOMS COMPLAINED BY YUSHO PATIENTS3,b Symp tom Dark brown pigmentation of nails Distinction of hair follicles Increased sweatlnq at palms Acnellke skin eruptions Red plaques on limbs Itchlnq Pigmentation of skin Swelling of limbs Stiffened sole and palm Pigmented mucous membrane Increased eye discharge Hyperaemla of conjunctiva Transient visual disturbance Jaundice Swelling of upper eyelids Feeling of weakness Numbness In limbs Fever Hearing difficulties Spasm of limbs Headache Vomlting Diarrhea * Male X 83.1 64.0 ' 50.6 87.6 20.2 42.7 75.3 20.2 24.7 56.2 88.8 70.8 56.2 11.2 71.9 58.4 32.6 16.9 18.0 7.9 30.3 23.6 19.1 Female X 75.0 56.0 55.0 82.0 16.0 52.0 72.0 41.0 29.0 47.0 83.0 71.0 55.0 11.0 74.0 52.0 39.0 19.0 19.0 8.0 39.0 28.0 17.0 3Elghty-n1nt male and 100 female patients diagnosed before October 31, 1968 were examined. . bFrom a report of "Yusho, A Poisoning Caused by Rice Oil Contaminated with Chloroblphenyls", Kuratsune, M., Yoshlmura, T., Matsuzaka, J. and Yamaguchl, A, Fukuoka Acta Med.. 60[6] (1969) 513. HONS 201976 126 TABLE 2. ORAL TOXICITY OF CHLORINATED BIPHENYLS. Chi orl ne . % atom 42 3 42 3 65 7 Anlml 1 Guinea Pig Rat Rat i Dose Effect 69 mg/anlaal t doses 1 week apart 139 ag/anlml 25 dally doses 50 ag/anlmal every second day Death In 11-29 days. Liver damage. (Hiller, 1944) (53) All animals survived. Liver damages. (Hiller, 1944) (53) : , 1 1 i ! j 501 dead within i 35'days. Severe liver damages. ' (Bennett, eta]* 1938) f j : i 127 HONS 201977 TABLE 3 DERMAL TOXICITY OF CHLORINATED BIPHENYLS. Ch1<Drfne 1 atoms . 42 iii 3 1 1 i 42 3 3 l AnInal Guinea pig Rat Rabbit Dose 34.5 mg/dally over 11 days Effect All animals died within 21 days. Liver damage. Miller, 1944) (53) 34.5 mg/dally over 25 days All survived. Minor liver changes. Skin affected. (Miller, 1944) (53) 86 Mg/day with 2-day Intervals for 7 appli cations and 172 *g/day with 2-day Intervals for 8 applications i All died between 17 and 96 days. Liver damages more pronounced than in rat or guinea pig. (Miller, 1944) (53) 128 HONS 20197B 129 TABLE 4 VAPOR EXPOSURE TOXICITV OF CHLORINATED BIPHENVLS. Chic>rine X atoms 42 3 Concert ration mg/a3 8.6 830 Dally exposure time (hours) 7 42 3 54.3 5 6.83 660 5.4 410 7 7 54.3 5 55 7 1.5 115 0.57 0.93 7 16 8 Exposure niaaber 17 84 83 150 Exposure period (Days) Symptoms 24 No effect on cats, rabbits, rats and mice. Poor growth in guinea pigs. (Treon, 1956) (55) 122 No effects on animals as above, Treon, 1956)(^ 121 Liver cell Injury. Increased liver weight In the rat. (Treon, 1956) (55) 213 / Histological changes In the liver in the rat. (Treon, 1956) (55) 37-134 42-143 Advancing liver damage. (dMnett. ft ij-. 1936). _________________lai MONS 201979 striking findings in mammals are alterations to the liver, whereas fluid in the pericardial sac, kidney damage and reduced spleen are found in birds. The FDA has conducted a subacute feeding study (lasting up to 90 days) in rata with dosage levels of 25, 75, 150, 300 and 500 parts per million of Aroclors 12and 1260 and including sacrifices at 5, 15, 30, 60 and 90 days (Burke and Fitzhugh, 2). Liver weight to body weight ratios increased at all levels. Dose-related increases were also found in liver aniline hydrojqrlaae and nitroreductase activity at all levels with the magnitude of the increases approximately the same at all time levels fo* both Aroclors. Aroclors 12$U and 1260, in contrast to many chlorinated hydrocarbon pesticides, did not stimulate liver allesterase activity, (Mlshlsunl, 27) studied the effects on mouse and monkey liver of chlorinated biphenyls (1*8 percent chlorine, equivalent to three to four atoms of chlorine per molecule, with a trace (0.01 percent) naphthalenes. Oroups of 30 female mice were given a dosage level of 0.2 ml rice bran oil containing 1600 parts per million or 0.5 percent PCS in olive oil by stomach tube each day for L to 26 weeks resulting in marked liver enlargament. (Light microscopy revealed only slight liver changes, but electron microscopy disclosed marked alterations in the liver cells.) A similar study with eight monkeys (5 cyncnolgus and 3 squirrel) given chlorinated biphenyls In dosage levels of 1.1* to 16 mg/day in their diet for 1*0 to 1*8 days showed both liver cell enlargement and fatty degenera tion. The major abnormality reported for the administration of chlori nated biphenyls to mice and monkeys was an lncreaae In the amooth endo plasmic reticulum In the liver cells. The metabolism and distribution of Aroclor 1251* In normal and carbon tetrachloride-treated Vlstar strain rats have been studied by (Qrant, et ai,, 26). Residues of Aroclor 1251* (following oral administration of a 500 mg per ml corn oil solution of Aroclor at 500 mg/kg) were found in all tissues analyzed with fat and blood having the greatest and leaat concentra tion, respectively (Table ?) Aroclor 1251* was found to potentiate the toxicity of carbon tetra chloride In a manner similar to that reported for DDT (McLean and McLean, 1966; Cawthorne, et al., 1970), The studlea (Qrant, et al., 28) suggest that the liver is the main site of Aroclor 1251* metabolism since rats with carbon tetrachloride damaged livers were unable to metabolise this mixture of chlorinated biphenyls as rapidly as rats with normal livera. Aroclor 1251* significantly Increased the size of the liver and also the peroent lipid in the liver. The same study revealed that the component! of Aro clor 125tt with the shorter OLC retention times, presumably with the lowest chlorine content (Bagley, et al., 29), were metabolized to a greater de gree than those with the longer retention times. This effect is In agree ment with the studies of Phenochlor IP6 fed to Japanese quail (Koeman, et *1., 30). Yoshimura and co-workers,(31) studied the effects of a elngle 2.0 ng/ mouse dose of polychlorinated blpheryls of the KC-liOO type. The concentra tion of PCB in the skin one day after ingestion was twlca as high as that in the liver. Although tetrachloroblphenyls were almost completely elimi nated from the tiseuea in 3-1* weeke, email amounts of penta- and hexachlorobiphsnyls wars still detectable after 9-10 weeks. 130 MONS 201980 TABLE 5. TOXICITY OF AROCLORS*. Aroclors 1221 1232 > 1242 1248 1260 1262 1268 4465 5442 5460 2565 Oral LDg, eg/Kg (rats) 3980* 4470* 8650* 11,000* 10,000b 11,300* 10,900* 16,000* 10,600* 19,200c 6.310c Skin N.0 ng/Kg (rabbits) wH H >2000* >1260* >794* >794* <3169* <2000* <1269* >1269* >1260b >1260* <2000* <3160* >2000* >2500c <3160* >1260* <2000* >7940C >2000C <3160 *Uid1 luted. bAMnistird as 50X solution In com oil. cAiM*1stered t) 33.3X solution In com oil. f *R)A Status Report on the Chenlstry and Toxicology of Polychlorinated Biphenyls (PCS) or Aroclors as of June 1 . 1970. HONS 201901 TABLE 6. PATHOLOGIC CHANGES INDUCED BT PCBs. Treatment Anlaal Lifer Kidney 51 rale oral dose Guinea Pig of 69 eg (421 Cl) Rat Rabbit S11 droplets Essentially through lobules, noraal slight to aoderate central atrophy, focal necrosis noted In a few anlaals 300 ag dally for Rat 6 days (651 Cl) Cells swollen, hyal ine granules present, aost died within few days. 50 ag dally for up to 6 aontbs (651 Cl) uM Rat Enlarged (331 weight Increase), large maber of hyaline globules In cytoplasa. Several died during experiment. 25,50 1 100 ppa In diet for 15 days (21*681 Cl Aroclors) Rat Increase In weight, effect Increasing with Increasing chlorine content. Aroclor 1232-101, 1242-121, 1254 141, 1268-241 at 50 ppa. 100 ppa In diet 200 ppa In diet 400 ppa In diet 800 ppa In diet (Aroclor 1242) Chicken No effect (It effect Enlarged 8 Mottled Damaged Daaaged Pericardii* i Other Peritonei* Observable Changes No noteworthy Adrenals, spleen, 6 changes pancreas showed no noteworthy changes. References Miller, 1944 (53) ' Slight ttydroperIcardi i* Nydroperlcardl i* Hydroperlcardli*, hydroperl tonci*. Enlarged Bennett, et al., 1938 (51.) Bennett, et 1L-, 1948 (5b) Street, et al 1969 (56) McCune, et. al_,, 196F (57) HONS 201962 TABLE 6. (Coiit'd.) PATHOLOGIC CHARGES INDUCED BY PCI*. Treatment Anlaal Liver Kidney 200 4 400 PPM In diet for 3 Meeks (42%, Aroclor Chicken No changes noted Paleness at 200 ppa, extensive heanrrhage, and enlargaent at 400 ppa Various doses (54% Cl, Aroclor) uWH 400 ppa In diet for 60 days (60S Cl*) Bengalese No weight changes Finch Chicken Centrolobylar necrosis (coapd. 1 4 2). Liver 1 weight Increased froa 2.76 g/IOOg to 4.31g/1Q0g (coapd. 3). Fatty degeneration. Height was 32.4% of brain weight for controls and 53.5% for those dying froa PCB poisoning. Tubular dilata tion, coapd. 1 4 2). Rare with coapd. 3. Pericardii* 4 Other Perltoneua Observable Changes References Increased fluid Paleness of pancreas. Flick, et In pericardial enlargaent of adrenal ah, 1955 sac at the high- and saall apleen at ($) er concentration.low concentrations. At higher concentrations pale c reaa-colored pan creas, adrenals heaorrtiaglc. Slight weight increase, a few showed liquid In pericardial sac. Presst, et. ah, 197(T (59) Hydroperl cardlua Increased porphyria, coaeon with spleen saall with cowpds. 1 4 2. reduction of red Rare with coapd. pulp and atrophy of 3. white pulp (coapd. 14 2). Spleen de creased froa 0.l4g/ lOOg to 0.136g/100g. (coapd. 3). Vos and Koeaan, 1970 (1.2) *Phenoclor OP 6 (epapd. 1). Clophen AGO (ceapd. 2) and Aroclor 1260 (coapd. 3) Mere used. Differential effects noted under coapd. ntabers. All chickens died on coapd. 1 and 2 within 60 days; only 15% Mortality on coapd. 3. HONS 201903 TABLE 7. RESIDUES IN TISSUES OF RATS ORALLY OOSEO WITH AROCLOR 1254 (500 mg/kg)*. Group Blood Testes Heart Spleen Kidney Brain Liver L1verd Fat Residue found (ppm, wet tissue) 1 23 4 1.96a 0.23b 19.22 * 0.59 24.16 1 2.84 29.17 3.44 31.14 2.09 39.98 5.91 115.66 1 10.55 1868.14 166.63 996.16 t 98.58 0.42 i 0.07 4.30 t 0.44 5.83 1 0.53 5.82 1.17 11.20 1.76 4.01 0.31 18.85 1 1.65 -- 672.66 + 155.12 ,3.85 l 0.46 33.18 1 1.35 62.40 4.37 36.60 1 4.39 57.38 i 3.91 41.91 + 3.30 796.47 64.96 6137.64 t 556.06 900.46 106.16 0.25c 5.62 6.17 -- 11.08 5.96 18.79 -- 1149.05 aMean of five values. ^Standard error of the mean. cS1ngle value. dPpm on a fat basis. ' *Grant, 0. 1.. Phillips, W. E. J. and Villeneuve, U. C.t Bull. Env. Contam. Toxicol., 6 (1971) 102. (Jl) - HONS 201964 13li Stract and co-rworkers (32) studied the effects of diets of 50 parts per million to 100 parts per million of 10 Aroclors ranging in chlorine content and 21 percent to 68 percent fed to rats for 15 days. Their effect on sleep ing time induced by hexobarbital, in vitro rates of aniline hydroxylation end demethylation of p-nitroanisole, and the rate of excretion were ell found to be increased with increasing chlorine content. Aroclor 1221 (50 parts per million) reduced hexobarbital sleeping tine by 11 percent, whereas for Aroclor 12L8 and 1268 the figures were 35 percent and L8 percent, respectively. Liver weights were also found to increase with increasing chlorine content of the Aroclors. The storage of dleldrin was decreased in relationship to the chlorine content. For example, with Aroclors containing 60 percent chlorine, or more, the storage in adipose tissue was reduced to the levels found in untreated con trol animals. The induction of PCBs of hepatic microsomal hydroxy1sting enzymes has been demonstrated in the American kestrel (Peakall and Linear, li), and pigeons (ftisebrough, et al., 33)* Fujita, et al. (66) studied the enhancement of the liver drug-metabolizing enzyme system in the rat by several individual chlorinated biphenyls. The most potent inducer was 2,3', bb', 5-psntachlorobiphenyl and the effect Induced with a single dose of 3*3* ,b,b'-tetrachlorobiphenyl was found to persist for 6 weeks. Vllleneuve, et al. (3b) studied the effects of PCB administration on micro somal enzyme activity in pregnant rabbits. The no-effect level of Aroclor 1251* for enzyme induction in the pregnant rabbit is between 1.0 and 10 mg/kg body weight when administered for 28 days during gestation. Aroclor 1221 did not in duce any enzyme activity in the dose, fetus or placenta, so its no-effect level must be considered higher than that for Aroclor 125b. Placental transfer was shown to occur for both Aroclor 125b and 1221 but does not cause any changes in the bio chemical or physiological parameters measured, e.g., total amount of Vitamin A stared per liver, protein levels, aniline hydrojqrlase enzyme activity, serum cholesterol, no effect in reproductive processes. The drug-metabolising enzymes aniline hydroxylase and amlnopyrins-n-demethylase were both Induced by 10 mg/kg Aroclor 125b> Ito and co-workers (35) found that the administration of PCBs to rabbits in creases the total lipid, triglyceride, and cholesterol content of liver and de creases the total liver phospholipid content. (The concentration of serum tri glycerides was abnormally Increased). Kimbrough (36) described some aspects of ths toxicity of Aroclor 125b and 1260 in Sherman strain rats. The acute oral LD0 for Aroclors 125b and 1260 in adult rats was greater than b and 10 grams/kg, respectively. The salisnt features of the subacute feeding and reproduction study in both male and female rate can be summarized ae fbllowsi - - 1. Feeding 500 parts per million of Aroclor 125b and 1260, respectively, to both male and female rats over a period of about 2b0 days resulted in Isss weight gain as well as lowered hematocrit. 2. Some malr rats fed Aroclor 125b at a dietary level of 100 parts per million (approximately 5 mg/kg per day) developed porphyria. Porphyria was also found in female rats fed Aroclor 125b at the 20 parts par million level and in both male and female rats fed 100 parts par million Aroclor 1260. 135 HONS 201985 3. Liver changes found with both Aroclor 125b and 1260 include accumulation of fat, inclusions within the liver cells and as-called margination (also found with chlorinated hydrocarbons). li. Kale rats fed Aroclor 1260 at a dietary level of 100 parts per million on up had larger and heavier livers. In the females the liver weights were not significantly Increased at aiv of the dietary levels that were tested. 5. Adenofibrosis was found ini (a) 1/10 males and 6/10 females at the dosage level of 100 parts per million Aroclor 1251 in the diet for about 8 months; (b) in 1/10 female rats at 100 parts per million Aroclor 1260 in the diet fo" sbout 8 months; snd (c) in seversl male rats at 1000 parts per million Aroclor 1260 in the diet for 8 months (none at 500 parts per million)* The adenofibrosis consisted of fibrosis in the livers concomitant with a proliferation of cells which is con sidered by seme to represent proliferated bile ducts. 6. Two bladder cancers in rats fed 100 psrts per, million of Aroclor 1260 were slso found and the significance of this finding has not been fully assessed at this time. 7. A definite effect on reproduction was produced by feeding 100 parts per million of Aroclor 125b* The first breeding was performed after 76 days on the treated diets and resulted in less offspring. The offspring at weaning were smaller and the survival was decreased compared to control animals. An increase in the liver weight in the generation of the weanlings at a dietary level of 20 parts per million Aroclor 125b was also found. 8. A dosage of Aroclor 1260 equivalent to 100 mg/Kg/day during the 7th and 15th days of pregnancy reduced the survival and timber of young. Ourley and co-workers (37, 36) studied the distribution and storage of PCBs in body fluids and tissues of Sherman rats followlngi (a) a single oral dose; (b) repeated dietary intakei and (c) after discontinuance. The salient findings of this study could be sumaarised as follows 1 (1) following acute or chronic administration of Aroclor 125b or 1260, residue amounts can be detected in all bo$r tissues, fluids and excrement. (2) Pronounced changes in the gas chromatograms or mass spectroscopic total ion current traces between the Aroclor atandards and components observed in the fat and urine suggest possible metabolism or differential absorption. (3) Rata given single oral doses of Aroclor 125b at 1600 mg/Kg or of Aroclor 1260 at 3200 mg/Kg had essentially the same levels of residue in their tissues after 2b hours (although individual variation was high). (b) At the same dosage level rats store more PCBs than DOT. (5) No significant differences were apparent in the storage of PCBs by male or female rats when fed the same dietary levels with PCBs stored primarily in adipose tissues. 136 moms 201986 (6) Toxicity of the Aroclors apparently increases with decrease In chlorine content suggesting the enhanced reactivity and/or leee stability of some isomeric chlorobiphenyi' in the mixture. (7) Rats fed Aroclor 125b at 100 parts per million for 56 days and untreated food for 71 days showed gradually increasing residues during dosage while the ex cretion trend was quite erratic. (0) Aroclor 125b administered at a dietary dosage of 1000 parts per million for 93 days resulted in deaths of 9 of 10 male rats and 6 of 10 fancies with deaths commencing on the 35th day. Although the survivors appeared normal, there was no weight gain after 77-QL days. Table 8 illustrates the storage of Aroclors 125b and 1260 in plasma and tis sues after oral ingestion by stomach tube at levels of 1600 mg/Kg and 3200 mg/Kg, respectively. Table 9 depicts the distribution of PCB-derived material following 98-day ejqjosure to a dietary level of 1000 parts per million of Aroclor 125b. Figure 1 shows the storage (mean cone. v. time) of PCB-derived material in tissues and plasma* Figure 2 shows the excretion of PCB and PCB (mean cone. v. time) derived material in feces and urine. Die distribution of PCB in rats dosed with PCBs has been studied with the aid of X-ray fluorescence analysis. PCB residues were found mainly in the skin, and to a lesser degree in muscles, intestines, livers, pancreas and lungs, and the GLC patterns of PCB varied from tissue-to-tissue (Sekita et al., 39). . The intestinal absorption in the rat of a number of isosMric chlorobiphenyie has been studied by Albro and Fiihbeln (bO). PCBs having from one to alx chlorine atoms per molecule wars very well absorbed snd/or metabolized when the compounds were fed in a single doae between 5 and 100 mg/Kg body weight. No significant difference in excretion rates (e.g., retentions) wars observed over the molecular weight range 116*5 to 289, suggesting that diffusion may not be rate-11mlting for the uptake of these compounds. (khan similar testa were performed using aliphatic hydrocarbons, a clear relationship between percentage excreted in the feces and molecular weight was observed). Less than 10 percent of the amount fed were ex creted in the feces (over a b-day period) indicating a high degree of absorption and/or metabolism of these confounds. b. Long-term studies The chronic PCB studies of Monsanto with Aroclors 12b2, 12$b, and 1260, e.g., two-year albino rat and baagle dog, three-yaar rat reproduction ae well ae the twenty-five week chicken, have been completed and a copy of the results sent to the FTtA. As of this writing, the full report has not been evaluated* However, Elmer Wheeler of Monsanto has verbally touched on the highlights of thsse studies supplementing information pravlously reported in the FDA Status Reports of the PCBs of Juns, 1970, and December, 1970, as wsll as reported by Kspllnger and co-workers (bl) and discussed with the Interdepartmental PCB-Task Force at a meeting in khshlngton on September 15, 1971. These results can be briefly summarized as followsi MOMS 201967 137 TABLE 8. STORAGE OF AROCL0RS (IN PPM) 24-HOURS AFTER ORAL INGESTION BY STOMACH TUBE. Aroclor 1254 (dosage level - 1600 mg/kg) PUsm Mean SE i 24.03 8.08 Brain , Mean SE i 138.00 36.41 Fat Mean SE 1146.9 574.5 Liver Mean 141.20 SE 47.80 Kidney Mean 274.03 SE 30.47 Lung Mean SE 65.91 29.48 Niscle Mean SE 80.29 67.58 Aroclor 1260 (dosage level - 3200 ng/kg) 15.79 0.99 145.17 t 23.50 930.0 i 426.6 236.1 116.3 328.5 114.9 t 105.17 21.13 37.00 22.37 HONS 201988 TABLE 9. DISTRIBUTION OF PCB-DERIVED MATERIAL FOLLOWING 98-DAY EXPOSURE TO A DIETARY LEVEL OF 1000 PPM AROCLOR 1254 Males (ppm) Plasma Mean . 17 SE 1 6 Fat Naan SE 1 11278 5742 Kisde Mean SE i 155 117 Lung Naan SE 78 23 Brain Mean SE i 111 14 Kidney Mean SE 1 56 9 Liver Naan SE 155 30 Females (ppm) 18 5 8431 579 753 721 52 20 94 21 54 24 210 13 Males Females p >0.50 p >0.50 p >0.20 p >0.50 p >0.50 p >0.50 p >0.20 HONS 201989 kmo Figure }. Storage of Pf.B-Oerived Material in Tissues and Plasma- tOr I S U u r i ! i i O Fat ' Uver Kidney Muscle A Brain " A Plasma iU U MONS 201990 MEAN CONCENTRATION (ppm) Figure 2. Excretion of PCB and PCB-Derlved Material in Feces and Urine. HONS 201991 (1) Aroclor I2b2 is the least toxic of the Arodors tested in two-year rat and dog studies. Aroclor 12b2 was negative at 1, 10 and 100 parts per million levels. ' (2) Rats fed compounds 125b or 1260 had increased liver weights at 100 parts per million, but not at 1 or 10 parts per million with no other effects having been observed. (3) Dogs fed 100 parts per million of 125b or 1260 did not gain weight as well as the controls. Animals were sacrificed at 3*6 *nd 12 months and revealed no abnormal tissue histology. (b) In the rat reproduction study, there was decreased survival of pups at 100 parts per million of 12b2 or 125b, and decreased mating indices with 12b2 at 100 parts per million were also observed. Ho adverse effects were found at any of the three levels of 1260 or at 1 or 10 parte per million levels of Aroclors 12b2 and 125b. In regard to the 25-week chicken study, there were no effects found follow ing feeding with Aroclor 1260 at 1, 10 and 100 parts per million levels. There was anorexia, loss of body weight, decreased thickness of egg shells, and poor hatchablllty of eggs from chickens fed 10 or 100 parts per million of 12b2 or 100 parts per million of 125b. There were no effects observed for Aroclor 125b at the 1 and 10 parts per million levels. Oral feeding studies with Aroclor 12b2 were repeated at the 2, b end 6 parts per million level and decreased hatch- ability was observed at 6 parts per million. A rat teratology study of Monsanto following FDA protocol in which 35-65 mg/Kg of PCB is administered has produced no effect. In regard to the mutagenesis study of Monsanto (Dominant Lethal Test), two dose levels of Aroclors 12L2, 125b and 1260 are being used, e.g., 500 and 1000 mg/Kg. As of the fourth week since mating, no adverse effects have been found. It is of interest for conparison to recite the reproduction studies of the Atlanta Laboratories of the FDA (FDA Status Report, Decmaber, 1970). Wean ling male and female rats were fed diets containing Aroclor 125b at dosage levels of 0, 100 or 500 parts per million for 67 days and then pair-mated. The rata fed 100 parts per million were comparable with the controls in numbers of litters and pups per litter. However, 76.8 percent of the pupa in the 100 parts per million group survived to weaning compared with 95*5 percent of the controls. The mean body weight of the 100 parts per million group at weaning was 31.b and that of the controls was 39.2 gm. Only two of ten females fed 500 parts per million of Aroclor 125b had litters (1 and 7 pups, respectively), and these pups died within 3 days after birth. In a similar study with Aroclor 1260 no difference In reproduction was found between the controls and the 100 parts per million group. C. CONTAMINANTS IN POLYCHLORINATED BIPHENYLS (Vos and Koemah, L2) reported a significant difference in toxicity between three commercial PCB preparations (Clophen A60, Phenoclor DP6 and Aroclor 1260), despite the marked resemblance of the gas chromatograms and the suss spectra lb2 MONS 201992 (Koeman at al., 30). One hundred preeent mortality, centrolobular liver, necrosis and abdominal edema were found only in chicks fed the samples of Clophen A60 and Phenoclor DP6. Hydropericardium was recorded in nearly all chicks fed these PCBs and only rarely seen in chicks fed with Aroclor 1260. Porphoryia was found as a general PCB effect in chicks as well as in Japanese quail and rats (Vos and Koeman, 1(2). A subsequent study by Vos and co-workers (17) revealed the presence of tatra- and pentachlorodibenzofuran as well as hexachloronaphthalene in Phenoclor DP6 and Clophen A60, but not in the Aroclor 1260 sample. Since hydropericaidium occurred occasionally in chicks fed Aroclor (Flick, et el*,1(3). Vos and co-workers (17) felt that this could possibly be indicative of small quanti ties of a toxic factor in this preparation. Dermal toxicity studies in rabbits of technical PCB samples which contain an average of 60 percent chlorine (Phenoclor DP6, Clophen A60 and Aroclor 1260) as well as fractions containing tetra- and pentachlorodibensofUran have been recently described by Vos and Beems (bli). PCB-induced' skin lesions were hyper plasia and hyperkeratosis of the epidermal and follicular epithelium following application of 118 mg of the three PCBs (5 times per week for 36 days) in the back skin of adult female New Zealand rabbits. HlStopathology of the liver in cluded centrolobular degeneration, centrolobular liver cell atrophy, focal necorsia and cytoplasmic hyalin degeneration. PCB-induced kidney lesions were hydropic degeneration of the oonvoluted tubulea and tubular dilatation with the preeence of casta. Definitive hyperplasia and hyperkeratosis of the follicular epithelium of the ear skin were seen after the topical application of fractions of Phenoclor and Clophen (eluted from chromatographic columns with 2$ percent diethyl ether in hexane) while the fraction from Aroclor caused a minimal hyperplasia and hyper keratosis of the follicular epithelium. Other affecta elicited by the dermal application of the PCBs Included thymus atrophy and lymphopenia as well as ele vated excretion of fecal coproporphyria and protoporphyria. From the response of the back skin and the liver of the rabbit to the three PCB mixtures, and from the response of the ear to the 25 percent diethyl etherhexane fractions, it was concluded that there were definite quantitative differen ces in toxicity, at least between the samples that were used in the above study (Vos and Beems, Uii), and the prior studies (Vos st al., 17). The extant to which these samples are representative of the normal commercial output has not been established and emphasises the difficulty in the evaluation of toxicity data of PCBs in which the samples may differ in the amount and nature of toxic ispuritles. Vos and Beams (LiU) also raised the possibility that since PCB is a porphyrogenic chemical, it is possible that the skin lesions in man due to PCB may be due to a combination of ohloracne and acquired porphyria cutanea tarda. It is important to additionally stress the toxic nature of the polyehlorodlbenzofurans. Fbr example, tri- and tetrachlorodibentoftran in a single oral dose of 0.5 - 1.0 mg/Kg caused severe and often lethal liver necrosis in rabbits (Bauer et al., i*5)* The related compound 2,3,7,8-tetrachlorodibenso-p-dioxin HONS 201993 m (which ha* been identified a* a contaminant in 2,b,5-triehlorophanol and 2,b,5-T) caused a lethal liver necrosis in the rabbit after a single oral doae of 0.05 0,1 mg/Kg, and when applied to the ear again in a dose 10 times lower than that found to be effective in the case of chlorinated dlbenzofuran, resulted in chloracne. Vos and co-workers (Lb) calculated a maximum dose/egg of 0.2 ug pentachlorodibenzofuran (obtained from Clophen A60) that caused 100 percent embryonic mortality when injected into the air cell of chicken eggs. (The analogous effect was obtained with 0.05 ug hexachlorodibenzo-p-diaxin.) (Higginbotham et al., 60). The relationship between the toxic nature of PCB and the chick edema factor 1,2,3, 7,fl,9-hexachlorodlbenzo-p-dioxin has been described by Tlick and co-workers (58). III. EPIDEMIOLOGICAL ASPECTS Flnklea nd co-workers (L6) compared both polychlorinated biphenyl and chlori nated hydrocarbon pesticide residues in 723 plasma samples collected from healthy volunteers (not occupationally exposed to pesticides) who resided in Charleston County, South Carolina. PCB residues were found in L3 percent of the samples ranging up to 29 parts per billion. DDD and disldrin residues wars found in 8b and 63 percent of the people, respectively, and p,p'-DDT and DDE residues were almost universal. PCB residues wert intermediate in concentration (e.g., lass than half those of p,p'-DDT and DDE but six or seven times those of o,p'-DDT, DDD and dieldrin). Maximum levels of PCB, p,p'-DDT and DDE were similar, exceeding such values for the other tested residues. The prevalence of PCB residues varied remark ably over race-residence groupings, being greatest in urban residents and rural whites. PCB residues were rare (L.l percent) in rural blacks. Rural blacks had ae arithmetic man of 0.3 parts per billion, urban blacks, 1.9 parts per billion, urban whites 2.3 parts per billion and rural whites 3.1 parts per billion, respec tively. Urban exposure to the PCBs was suggested to be via polluted air and con taminated water. (PCBs in suspended particulates have already been found). Aspects of the determination of PCBs in the adipose of the general population of the U.S.A. to date have been summarized by Dr. Tobs in a preliminary report in the Human Monitoring Survey (originally established by tbe-Pssticidss Program of the DHEW, now Division of Pesticide Cosminlty Studies, EPA). Table 10 depicts the preliminary sunaary of distribution of PCB levels in adipose tissue of general population (as analysed I9 three laboratories) in the analysis of Human Monitoring Survey samples sines April 15, 1971. A total of 688 samples were analyzed of which 235 (3b.2 percent) were nsgetlve for PCBs and b53 (65.8 percent; were positive for measurable amount of PCBs by TLC| of these 229 (33-3 percent) contained trace to <1.0 parts par million and 188 (27.3 percent) contalnad v2.0 parts per million PCBs. The Aroclor formulation most frequently encountered is 125b with-Aroclor 1260 also well represented in human tissues (Enos, b7). (Aliquots of all samples in which measurable amounts of PCBs were found will be analyzed by mass spectroscopy at the Perrin# Primate Laboratory for future confirmation). The correlation of PCB information In this study with age, sex, geographic distribution or diagnoses has not yet been completed. These samples were collected In late 1968 and 1969 and the sties of the positive samples.were located In the following states 1 Michigan, New York, Minnesota, California, Massachusetts, Georgia, Kentucky, Illinois, North Carolina, South Dakota, Ohio, Louisiana, Delaware and Arkansas. ILL HONS 201994 TABLE 10. DISTRIBUTION OF PCB LEVELS IN ADIPOSE OF GENERAL POPULATION AS SHOWN IN ANALYSIS OF HUMAN MONITORING SURVEY SAMPLES SINCE APRIL 15, 1971. (parts per million, wet tissue basis) Michigan No. % Florida No. % Colorado No. % Samples Analyzed 144 100 274 100 270 100 Total No. X 688 100 PCB Levels Negative Trace--<1,0 ppm 1.0 - 2.0 ppm >2.0 ppm * 12 8.3 181 66.0 42 15.6 235 34.2 64 44.4 44 16.0* 121 44.8 229 33.3 55 38.2 40 14.6 93 34.4 188 27.3 13 9.0 9 3.3 14 5.2 36 5.2 Actual decimal reading .05. 11*5 MOMS 2I*9* Dr. 0. J. Lot* (6l) of EPA has reported that 72 *t of specimens (blood, urln*, and hair) collected from >6 workers occupationally exposed to burning automobiles or refuse dumps and from an equal number of controls are to be collected and analyzed for PCB levels. It Is of Interest to note the analysis of PCB In human adipose tissue. Biros and co-workers (bfl) examined two human adipose tissue samples by combined QLC-mass spectrometry and found substantial quantities of PCBs ranging from pentachlorobiphenyl to decachloroblphenyl and Including at least lb Isomers and chlorine homo logs. The samples were estimated to contain 200 parts per million and 600 parts per million total PCB, respectively, as determlnad by electron-capture gas chroma tography. IV. STUDIES IN PROGRESS Curley and co-workers (37) have described results In a study with Aroclor 125L to determine placental transfer, rates of excretion In milk and consequent tissue distribution and storage levels In fetuses and weanling rats following oral dosage to the mother dally on tha 7th through the 15th day of gestation at 10 mg/Kg, respectively, by stomach tube. Table 11 lists the experimental protocol for tha above studies, this Is summarized as followsi Fetus Analysis? Samples were taken by Caesarian section on the 20th day of preg nancy, The mean concentrations of Aroclor are given for the respective dosages as parts per million. Controls - 10 mg/Kg 50 mg/Kg Mother 1 0 l.b2 2.b2 Mother 2 0 1.2b 2.90 Mother J 0 1.1b 2.93 Mother 1 Mother 2 Mother 3 10 mg/Kg Wt. at onset (gas) 25b 265 258 Age (days) 90 90 90 Mother 1 Mother 2 Mother 3 50 mg/Kg 2b2 2bb 26l lb6 90 90 90 HONS 201996 Tissue Analysis: Samples were taken from 21-day-old male and female weanling rats. The concentrations In the tissues for three animals are given In ppm. Controls 10 mq/Kq 50 mo/Kn Males Liver <0.05 Females <0.05 Mean X S.5. t Males 4.06 3.28 2.70 3.35 0.39 Females 2.85 8.28 4.11 5.08 1.64 . Males 17.36 25.56 11.80 18.24 4.00 Females 21.63 12.02 15.99 16.55 2.79 Controls 10 mq/Kg 50 nn/Kn Males Females Males Females Males Females Brain <0.08 <0.08 Mean 3 S.E. t 1.96 2.28 2.24 2.16 0.10 ' 1.94 2.72 1.24 1.97 0.43 10.16 5.44 7.47 7.69 1.37 10.48 3.89 6.75 7.04 1.91 Kidney <0.04 <0.04 Mean X S.E. i 1.52 2.42 1.14 1.69. 0.38 1.54 2.19 2.32 2.02 0.24 7.53 6.73 6.70 6.99 0.27 2.41 2.25 4.10 2.92 0.59 Milk Analysis: Milk samples were taken from suckling rats 11 days after the last dose to the mother. Concentrations are given In ppm. Controls 10 mq/Ka Range Mean S.E. 0 0 16.48 - 24.90 20.60 tl .59 45.80 - 100.29 66.35 8.36 Ar 7-70-G4 HONS 20199? U7 The results of a study with Ar 1260 show consequent tissue distribution and storage levels In weanling rats following oral dosage to the mother dally on the 7th through 15th day of gestation at 50 mg/Kg by stomach tube and Is summarized as follows: ~ Note,: One female and one male taken from each of 3 litters 1 Tissue Sex Mean (3 animals) Kidney M F 7.38 5.44 Brain M F 7.53 7.76 Liver M F 12.80 16.13 Weights of Mothers 284, 264, and 288 gm. Mean weight of Mothers 278 gm. S.E 2.56 1.41 1.04 ' 2.54 1.72 6.75 Additional residue studies completed Include the following: Experiment No. Tissue Mean ppm (4 animals) tS.E. Ar-7-70-812 Fat Liver Kidney Muscle Brain Plasma 778 9.9 S.1 1.22 6.96 1.6 72.4 1.16 .95 .104 .68 .311 When compared to males at the same dosage level for an equal amount of time, Student's t-test shows significant difference In brain and liver storage. When these data are compared to data from male rats on the same dosage for an equal amount of time, the Student's t-test shows significant differences for brain and liver storage. U8 HONS 201998 Experiment No. Ar-7-70-812 Tissue Fat Liver K1dney Muscle Brain Plasma Mean pom (3 animals 1 1022 14.6 2.8 1.2 9.3 2.1 *S.E. 127 0.69 0.21 0.11 0.57 0.43 When these date are compared with 8 mo. study test for significant difference shows p < 0.05 for liver only. Experiment No. Ar-7-70-812 Tissue Fat Liver K1dney Muscle Brain Plasma Mean ppm (3 animals) 820 22.5 4.7 2.9 11.2 3.0 S.E. 216 2.51 .24 .96 1.71 0.78 When these data are compared with 10 mo. study t-test for significances show p < 0.05 for liver and kidney. Experiment No. Ar-7-70-B10 Tissue Fat Liver Muscle Kidney Brain Plasma Mean ppm (4 animals) 274 2.2 .32 .60 2.6 .42 iS.E. 48 .10 .06 .05 .50 .06 lJi9 MOMS 20It99 TABLE 11. EXPERIMENTS TO DATE NOT INCLUDED IN THE MANUSCRIPT, "POLYCHLORINATED BIPHENYLS: DISTRIBUTION AND STORAGE IN BODY FLUIDS AND TISSUES OF SHERMAN RATS" - A. CURLEY, V. W. BURSE, M. E. GRIH, R. H. JENNINGS AND R. E. LINDER. (37) Experiment No. Ar 7-70-812 Ar-7-70-B12 Ar-7-70-B12 Ar-7-70-810 Ar-8-71-B No. of Rats Sex Age at Onset of Experiment (days) Wt. (Gms) Dosage/Route 4 (analyzed) F 30 224* TOO ppm in Diet for 247 days *B.l mg/kg/day 3 (analyzed) F 30 224* 100 ppm In Diet for 300 days *B.1 mg/kg/day 3 (analyzed) F 30 224* 100 ppm in Diet for 366 days *B.1 mg/kg/day 4 (analyzed) F 30 240* 20 ppm in Diet for 280 days *1.6 mg/kg/day A study to determine placental transfer, excretion In milk and consequent tissue storage In weanling rats of Aroclor 1254 when the compound Is given to the mother rat during organogenesis. Ar 7-70-G4 The effect of Aroclor 1260 upon reproduction In female rats when the compound Is given during organogenesis. *Average weight of group and average rate of food consumption for group. HONS 202000 Mink reproductive studies sre being csrried out by Ringer, Johnson end Hoopingerner f 1*9) of Michigan State University involving the initial feeding salmon containing 15 parts per million PCB or 10 parts per million each of Aroclor 121*2, 1251* and 1260 was fatal to mink which appear to be extremely sensitive to PCB. Reproductive failure in ranch mink fed Coho salmon and other Great Lakes Pish (possibly containing PCB) have been reported by Aulerich, et al. (62). Courtney and Chernoff (65) of the Perrine Primate Laboratory are studying the teratogenicity of PCBs. No effects have been observed in rats (CO-1 strain) given a variety of Aroclors at a level of 200 mg/Kg. Mixtures of PCBs and DDT have been found negative as well in the above strain of rats. Studies involving individual isomeric chloroblphenyls as well as conmereial PCB mixtures in in-bred strains of the rat will also be undertaken. Wilson and Sharp (63) of the National Institute of Environmental Health Sciences are studying aspects of the interaction of beef brain (Na4>K4') ATPase with the polychlorinated biphenyls. Enzyme activity was inhibited by $0 per cent in the presence of Aroclor 1221 or Aroclor 1251* at PCB concentrations in the range of 8-12 parts per million at 37. Under similar conditions 2.5*10"5n ( 9 parts per million) DDT also inhibits the beef brain enzyme by about 50 percent. The PCB- and the DDT-sensitivity of the (Na*HC*) ATPase are similar whether the enzyme is obtained from beef brain or from fish (blue gill) brain. On a parts per million basis a commercial preparation of 3-chlorobiphenyl is about as inhibitory as Aroclor 1221, whereas biphenyl, l*-chlorobiphenyl and 2, Lt-dichlorobiphenyl were less Inhibitory. The technique for exposure of the (Na^+K^jATPase to the Aroclor preparations was found to influence the degree of the enzyme inhibitory response. Beef brain (Na^+K^ATPase responsiveness to commercial PCBs has been demonstrated to simulate several aspects of enzyme responsiveness to DDT. Young (50) of the Virginia Polytechic Institute is studying PCB levels (in feces and urine samples) of pre-adolescent girls fed diets typical of low income families. PCB levels in paper bags, lurking tags, turkey fat, heavy fowls, eggs and poultry feeds are aleo being aaaessed and have been found in all but two samples with concentrations ranging from 0.063 parts per million to 1*.56 parts per million. The possibility of the PCBs exhibiting isnunosuppressive effects is being further studied by,Vos (5l)> The leucopenla, the reduced number of germinal centers in the spleens and lymph nodes, the atrophy of the cortex of the thymus (Vos and Beems, li*), and the atrophy of the white pulp aid lystphoid foci foind in the spleens of cfaicks fed PCB (Vos and Koeman, 1*2) are believed by Vos to be strong indications for an lasnunosuppressive effect. It was further suggested that the extent to which these observations are due to stress (release of gluco corticoids) would have to be elaborated. Plasm and Clive NIEHS (52) are studying the nutagenclty of a spectrum _ of Aroclors as well as Individual isomers of polychlorinated biphenyls in L5176-1 mouse lymphoma cells heterozygous at the thymidine kinase locus {HEV*)3. 151 MOMS 202001 Spalding NXEHS,{6ii) is elaborating the effect of Areclors 1221, 12h2, 1251i, 1260 and 1268 as well as e number of isomeric polychlorinated biphenyls on mouse lymphon* and DDT-resistent mouse lymphoma cells. V. SUMMARY AND CONCLUSIONS Despite the nearly four decades of PCB use in a broad spectrum of applications, the increasing awareness of its enviromental aspects as well as an increasing number of recent mammalian tortcologlcal investiga tions, aspects of definitive acute, sub-acute and chronic toxicity still remain poorly known as regards man. The chemical and physical properties, e.g., the stability, complexity and heterogeneity of the material per se, the difficulty of separation and analysis as well aa the non- or ill-defined nature of the material actually used or reported in mary studies, have all certainly contributed in making the evaluation of toxicity and biological data difficult. Table 12 suimarizes some biological and toxicological effects of the PCBs. The above review of the current status of the tosdcologic and biologic aspects of the PCBs suggests a number of future studies that hopefully should yield additional Information to enable a more definitive evaluation of the risks involved in exposure to chlorinated biphenyls. A number of possible future studies are outlined in Table 13. HONS 202002 152 TABLE 12. SOME BrOLOfirCAL AND TOXTCOLORI CAL EFFECTS IN THE PCB'S. 1. Acute oral LOg* In mammals varies From aporcxlmately 2-10 gm/kg. (Apparent increase In mamnallan toxicity with decrease In chlorine content). 2. Generally, enzyme Induction Increases with Increase In chlorination of PCB's. 3. Induction of hepatic hydroxylatlng microsomal enzymes and Increased estrogenic activity In the rat. 4. Enlargement of the liver and vacuolar or fatty degeneration of liver cells In rats, guinea pigs and monkeys. 5. Production of hydroperlcardlal edema In chickens and Japanese quail. 6. Teratogenic effect In chick embryo. 7. Adverse reproductive effects In rats at levels of ca. 100 ppm In diet. 8. Posslhle adverse reproductive effects In mink. 9. Possible Implications In aberrations In calcium metabolIsm and reproduction In ring doves. 10. Effects on hatchablllty In chickens, Japanese quail. 11. Skin, liver and kidney lesions In rabbits following dermal exposure. 12. Possible Immunosuppressive effects In rabbits. 13. Chemical porphyrogenlc effects In many species. 14. Chloracnegenlc and hepatotoxlc effects In man. 15. Hyperqlycerldemlc effects In man. 16. Human miscarriages, still births and transplacental transmission In abnormal pigmentation from "rice-oil disease" ("Yusho"). 17. pcb residues In human adipose tissue, serum and milk. 18. Hepatoxlc, chloracnegenlc and porphyrogenlc effects of chlorinated dibenzofuran contaminants In several species. 19. Chloracnegenlc effects of chlorinated naphthalene contaminants In man. MOMS 202003 153 TABLE 13, POSSIBLE FUTURE STUDIES INVOLVING PCB'S, THEIR INDIVIDUAL ISOMERS AND CONTAMINANTS. 1. Definitive studies on the mamnallan distribution of the Aroclors, a . number of key conmon individual Isomers and their metabolites and/or degradation products In different tissues, the metabolic rate, retention times or turnover and excretion rates. 2. Elaboration of the relative toxicity of a number of the various purified liomers of PC8- 3. Elaboration of the effects of Aroclors and Isomeric PCB's In mamnallan reproduction studies are required because of the apparent anomalous relationship found In the pattern of chronic studies. 4. Elaboration of the teratogenicity of ArocJors and Isomeric PCB's In several manmallan species at a range of dose levels. 5. Mutagenic studies Involving the Aroclors and Isomeric PCB's In test systems other than the Dominant Lethal (e.g., host mediated assay). 6. Elaboration of short-term toxicity effects on liver mlcrosomel enzymes, study the Influence of dllantln and hexobarbltal and possible synergism and/or potentiation. 7. Study of the Interaction of PCB's with other chemicals and drugs. 8. Study of the toxicity of the Aroclors and their Individual Isomers for different cell systems. 9. Elaboration of mameallan tissue distribution, metabolic rate and retention times of chlorinated dlbenzofUrans. 10. Liver function studies as well as cytogenlc studies on workers In a) PCB production, b) application, e.g., packing of transformers, capacitors, c) waste disposal, and d) fishmeal processing plants. 11. Elaboration of aspects of hyperlipemia. Does It occur with low exposures and could It aggravate arteriosclerosis? Ooas It affect the pancreas, etc.7 12. Study of Induced porphyria anddIni cal consequences. 15b MOMS 202004 FOOTNOTES 1. Kolbye, A.C., Jr., Current Statue of Toxicological Effects of PCBs (FDA), Sept. 1 (1971)i Sept. 29 (1971). 2. Burke, J. and Fltzhugh, 0. 0., Suppl. No. 1 Status Rept. on the Chemistry and Toxicology of PCBs (FDA), Dec., 1970. 3. Cook, J. w., Status Rept. on the Chemistry and Toxicology of PCBs (FDA), June, 1970. I, . Peakall, D. B. and Lincer, J. L., BioScience 20 (1970 ) 958. 5. National Swedish Environment Protection Board, PCB Conference, Stockholm, Dec. (1970). .6 Reynolds, L. H., Residue Revs. (171) 27. ' 7. Zitko, V. and F.M.K. Choi, Fisheries Research Board of Canada, Tech. Rept., No. 272 (1971). 6. Fishbeln, L., Chromatog. Revs., in press. ' 9. Schwartz, L., Am. J. Publ. Hlth. 26 (1936) 58. 10. Schwarts, L., J. Am. Med. Soc. 122_ (I9b3) 158. II. Schwartz, L, and F. A. Barlow, U. S. Public Hlth, Repts. (I9b2) 17L7. 12. Jones, J. W. and H, S. Alden, Arch. Dermatol. Byphllol. ^ (1936) 1022. 13. Meigs, J. X., J. J. Albom and B. L. Kartln, J. Am. Med. Assoc. ll (195b) lbl7. lli. Flinn, F. B. and D. 3. Jarvik, Proc. Soc. fixp. Biol. Med. (1936) 118. 15. Oreenbnrg, L., M. R. Mirers and A. R. Smith, J. Ind. ^jrg. Toxicol. 21 (1939) 29. 16. Drinker, C. X., W. F. Warren end 0, A. Bennett, J. Ind, Hyg, Toxicol. 19 (1937) 283. 17. Vos, J. 0., J. H. Koeman, H. L. Vandermaas, M. C. Tennoever deBrauw and H. DeVos, Food Cosmet. Toxicol. 8 (1970) 625. 18. Saeki, S., A. Tsutsui, S. Oguri, H. Toshimura and M. Hamana, Pbkuoka Acta Med. 62 (1971) 20i C.A, TJt (1971) lix629b. 19. Tamaguchi, A., T. Toshimura and M. Kuratsune, PUkuoka Acta Med. 62 (1971) 117. 20. Kojlma, T., H. Fukumoto and J. Makisumi, Jap. J. Legal Med. 2^ (1969) bl5. 21. Inagami, K., T, Koga and T. Tcraita, Shokuhin Eiseigakuzasshi 10 (1969) 312; C.A. 72 (1970) 120116. 22. Kojlma, T., Fukuoka Acta Med. 62 (1971) 25* 155 MOMS 202005 23. Uzawa, H., T. Ito, A. Notomi *nd S. K&tsumi, Fukuoka Acta Mad. 60 (1969) ttL9. 2h. Uz&wa, H., Y, Ito, A, Notomi, S. Hori, T. Ikeura and S. Katsukl, Fukuoka Acta Mad. 62 (1971) 66; C,A. 2k (1971) 138797. 2?. Nagai. J., M. Furukawa, Y. Yae and Y. Idada, Fukuoka Acta Mad. 60 (1969) UlSi C.A. 72 (1970) 11077. " 26. Kikuchi, M., Y. Mikagi, M. Hashimoto and T. Kojima, Fukuoka Acta Mod. 62 (1971) 89. ~ 27. Nishizumi, M., Arch. Erv. Hlth. 21 (1970) 620. 28. Or ant, D. L., W. E. J. ftiillipa and D. C. Villaneuve, Bull. Env. Contain, Toxicol. 6 (1971) 102. 29. Bagley, 0. E., W. L. Reichel and E. Cromartle, J. Assoc. Off. Anal. Cham. 2 (1970) 251. 30. Koaman, J. H., M. L. Tennoever dafirauv and R. H. DeToo, Nature 221 (1969) 1126. 31. Yoshimura, H. and M. Oshima, FUkuoka Acta Med. 62 (1971); C.A. 75 (1971) 3563. " 32. Street, J. C,, F. M. Urry, D. J. Wagstaff and A. D. Blau, 158th American Chemical Society Meeting, New York, Sept. 8-12 (1969). 33- Rieebrough, R. W., P. Reiche, D. B. Peakall, S. 0. Herman and M. N. Kirven, Nature 220 (1968) 1098. 3b* Villaneuve, D. C., D. C. Orant, V, E. J. Phillips, M. L. Clark and D. 0. Clegg, Bull. Env. Contain. Toxicol. 6 (1971) 120. 35. Ito, Y., H. Uzawa and A. Notomi, Fukuoka Acta Med. 62 (1971) b8; C.A. 2k (1971) 138798. 36. Kimbrough, R. D., Interagency Meeting on PCBe, Dept. H. 8. W., Washington, D. C., August 5 (1971). 37. Curley, A., V. W. Burse, M. E. Qrlm, R. V. Jennings and R. E. Linder, Presented at 160th American Cham. Soc. Meeting, Washington, D. C. (1971). t 38. Curley, A., V. W. Burse, M. E. Orim, R. W. Jennings and R. E. Linder, Interagency Meeting on PCBs, Dept. H. E. W., Washington, D. C., August $ (1971). 39. Seklta, H. M. Osawa, Y. Ito and H. Tfcnabe, Shokuhin Elselgaku Zasshl 11 (1970) 361j C.A. 7b (1971) 1388L8. bO. Albro, P, W. and L. Fishbein, NIEHS (1971), Unreported results. 156 MONS 202006 1*1. Keplinger, M. L., 0. E. Fancher and J. C. Calandra, Abst. of 10th Annual Moating of Society of Toxicology, Washington, D. C., March 7-11 (1971). 1*2. Vos, J. 0. and J. H. Koeman, Toxicol. Appl. Pharmacol. 17 (1970) 6$6. 1*3. Flick, D. F., R. 0. O'Dell and V. A* Childs, Poultry Sci. (j(j (196?) 11*60. LI*. Vos. J. G. and R. B. Beans, Toxicol. Appl. Pharmacol. 19 (1971) 617. 1*5. Bauer, H., K. H. Schulz and U. Splegelberg, Arch. Gsverbepath. Gewerbehyg. 18 (1961) 538. 1*6. Ftnkea, J. F., L. E. Priestar, J. P. Creason, T. Hauser and T. Hinners, Presented at Amer. Publ. Health Assoc. Meeting, Minneapolis, Minn., Oct. (1971). 1*7. Enos, H., Personal Communication, Oct. 12 (1971). Ij8, Biros. F. J., J. C. Walker and A. Msdbery, Bull. Env. Contain. Toxicol, 5, (1970) 317. 1*9. Ringer, R., J. Johnson and R. Hoopingerner, Interagency Meeting on PCBe. Dept. H. E. W., Washington, D. C., Aug. 5 (1971). 50. Young, R., Status of PCBs, ARS Rapt., Oct. (1971). 51. Vos, J. G., Personal Communication, Oct. 25 (1971). 52. Flamm, W. G. and D. Clive, NXEHS (1971). Wbrk in progress. 53- Miller, J. W., U. S. Public Health Repta. 2 (l9l*li) 1085. 51*. Bennett, 0. A., C. It. Etinker and M. P. Warren, J. Ind. Hyg. Toxicol. 20 (1938) 97. 55. Treon, J. F., Am. Ind. Hyg. Assoc. Quart. 17 (1956 ) 201*. 56. Street, J. C., F. M. Urry, D. J. Wagetaff and A. D. Blau, 158th American Chemical Society Meeting, New York, Sept. 8-12 (1969). 57. McCune, E. L., J. E. Savage and B. L. O'Dell, Poultry Sci. 1*1 (1962 ) 295. 58. Flick, D. F., R. 0. O'Dell and V. A. Childs, Poultry Sci. M* (1965) 11*60. 59. Preset, I., D. J. Jeffries and N. W. Moore, Environ, Pollution 1^ (1970) 3. 60. Higginbotham, 0. R., A. Huang, D. Firestone, J. Verrett, J. Ress and A. D. Campbell, Nature 220 (1968) 702. 61. Love, G. J., Personal Comunication, Oct. 8 (1971). HONS 20*007 157 62. Aulerlch, R. J., R. K. Ringer, H. L. Seagran and W. G. Touatt, Can. J. Zoology b9 (1971) 611. 63. Wilson, W. E. and C. Sharp, NIEHS (1971)? Studies in progress. 6b. Spalding, J. W., NIEHS (1971), Studies in progress. 65. Courtney, D. C. and Chernoff, N., Personal Comnunication, Nov. 15 (1971). 66. Fujita, S., H. 'Rsuji, K. Kato, S. Saeki and H. Tsukamoto, Fukuoka Acta Medica 62 (1971) 30j C. A. 7 (1971) 3797. 157-A HONS 202006 APPENDIX Q Biological Data On PCBb In Animals Othar Than Han Table of Contents I. Toxicity A. Birds B, Insects C. Fish and Aquatic Invertebrates II. Physiology A. Metabolism and Kinetics B. Reproduction III. IV. Summary Conclusions Page 159 162 166 167 WINS 202009 158 APPENDIX G Biological Data On PCBs In Animale Other Than Man Polychlorinated biphenyls have become ubiquitous in the world ecosystem in quantities similar to those of DDE. Their presence has caused concern and stimulated research to evaluate their role in the biosphere* The significance of PCBs to wild animals depends upon both their lethal toxicity and their sublethal physiological effects. These are the subjects of the present paper. Coordinate knowledge of level of closure, as shown by frequency and levels of occurrence of PCBs in the enviroment, is essential to complete the understanding. These are summarised elsewhere in this report. I. TOXICITY Outright mortality of wild animals can affect populations, particularly those of long'lived species. Measurements of direct toxicity are therefore important first steps in evaluation of a chemical. Other laboratory studies also are needed for proper interpretation of field observations. These in clude studies to diagnose cause of death by behavior of poisoned animals, tissue changes, and concentrations of chemical in critical tissues. A. BIRDS ' The toxlcities of different PCBs to pheasants fPhasianus colchicus). mallards (Anas platyrhvnchos). bobwhite quail (Collnua virginianua). and coturnix quail (Coturnlx coturnlx) were compared with the toxlcities of DDT, dieldrin, and other insecticides (Heath,et al., l). Tests of six PCB mix tures, containing 32 to 62 percent chlorine, showed that the toxicity in creased with the percentage of chlorine. In general, toxlcities were similar to those of DDE. There were some differences in sensitivity of the species. Bobwhite were most sensitive, followed in turn by pheasants, mallards, and coturnix quail. Bobwhite were 3-b times as sensitive as coturnlx. Special tests with coturnix quail showed that the toxic effects of DDE and Aroclor 125b were additive but not synergistic. In other studies, Aroclor 125b was approximately as toxic as DDE to four species of blackbirds! grackles (Qulscalua qulscula), cowbirds (Molothrus ater). starlings (Sturms vulgaris). and redwings (Agelaius phoenlceua) (thistman, et al.,2). Redwings were somewhat more susceptible to DDE than to PCBs. Signs ol poisoning were sluggishness with slight tre mors of moderate aaqslitude, much as with chemicals of the DDT group. Inter nally, livers frequently had hemorrhagic streaks or spots, and the gastro intestinal tract commonly contained blackish fluid, but these signs were not sufficiently consistent for distinctive diagnosis, Aroclor l2Jb was approximately 1/13 as toxic as DDT to Bengalese finches (Lonchura striata) (Prestt, et al., 3). Tremoring and other signs were simi lar to~thoae observed among blackbirdsj the finches had enlarged kidneys and some had hydropericardium. MOMS 202010 159 Chicks kept in batteries recently painted with an epo^-resin paint, (McCune et al., L) died as a result of Aroclor 12L2 in the paint. Others fed this compound developed hydropericardium and enlarged livers and kidneys. Egg injection studies showed that Aroclor 12L2 had a relatively high toxicity (McLaughlin, et al., 5). Aroclor I2j0 fed to 10-day-old chicks depressed growth rates at dietary levels of 50, 100, and 150 parts per million (Rehfeld et al., 6). Only 2-L of 10 chicks survived each of the three higher dosages. Growth rates were reduced at 20, 30, and LO parts per million in a second experiment; mortality was 16 of 30 birds at 50 parts per million dosage, L of 20 at LO parts per million, and 1 of 30 at 3 parts per million to 5 weeks of age. Birds fed diets containing more than 20 parts per million developed general edema;those fed diets containing liO and 50 parts per million developed noticeably smaller combs and wattles than normal. Liver weight increased as a percentage of body weight, primarily as a reflection of lower body weights. Mortality was high among White Leghorn cockerels fed a dietary dosage of 500 parts per million of Aroclor 12$lt from the day of hatching) the birds died between the third and tenth week of feeding (Platonov and Minnell, 7). At 250 parts per million birds did not die until the thirteenth week. At this dosage, weight gain was poor, livers increased in weight relative to body weight, combs and wattles were abnormally snail, and testes were small. The effect on conbs appeared before the effect on the testes. Polychlorinated biphenyls supplied by three different manufacturers gave strikingly different results in toxicity tests with domestic chickens, although all formulations contained 60 percent chlorine (Vos and Koeman, 8). The PCSs were Phenoclor DP6, manufactured in France; Clophen A60, manufactured in Germany; and Aroclor 1260, manufactured in the United States. Twenty-four birds fed LOO parts per million of Phenoclor DP6 all died within 60 days; all had liver necrosis and 16 had hydropericardium. Twenty-two of 2h birds fad Clophen at the sane dosage also died with liver necrosis and 20 with hydropericardium. However, none of the birds fed Aroclor died; none had liver necrosis, and only three had hydro pericardium. Chickens fed all formulations developed atrophy of the spleen and excess quantities of porphyrins. These' different effects of the three brandnamed products were later largely explained by the identification of chlorinated dibenzofuran and chlorinated naphthalene as contaminants in Phenoclor and Clophen (Vos et al., ?). In a further study with coturrrLx quail, porphyria again resulted from dosage with Aroclor 1260 that was carefully tested to insure the absence of measurable amounts of contaminants (Vos et al., 10). Males given a daily_<dose of 50 mg/kg of PCSs (the lowest dosage, tested) developed porphyria, as did'females given 100 mg/kg, although those given 10 mg/kg or less did not. The porphyria was closely associated with an increase of mitochondrial ALA synthetase. HONS 2020LI 160 1. Residues in Birds Killed by PCBs. Chickens killed by PCB dosage in the studies of(Vos and Koeman, 8) generally contained from 120 to b20 parts per million in the brains, but the overall range was from 1*0 to 700 parts per million. Residues in livers were 120 to 2,900 parts per million. Coturnix quail poisoned by PCBs (FTienoclor DP6) contained residues of 3L2-1710 (av. 11?8) parts per million in the brain and 1079-8350 (av. 3280) parts per million in the liver (Koeman, 11).. Bangales finches killed by PCBs had residues of 70 to 697 parte per million in the livers} those sacrificed at the end of the experiment contained 3 to 63b parts per million (Prestt,et al., g)4 Residues in brains ware somewhat lower; the proportional amount in the brain in comparison with the amount in the liver averaged higher in the birds that died than in those that were sacrificed. A bald eagle found sick in the field contained high residues of both DDE and PCBs in its brain, suggesting that PCBs may have contributed to its death. Residues of ODE in the brain were 385 carts per million, which is with in the lethal range for ODE (Stlckel et al., 12). However, the brain also con tained 230 parts per million of PCBs, 6 parts per million of DDD, 2.2 parts per million of dieldrin, and 0.1* parts per million of heptachlor epoxide. B. INSECTS The toxicity of PCBs to insects also is related to the chlorine content, but in the reverse order to the result with birds. PCBs with lower amounts of chlorine were more toxic to flies than PCBs with higher chlorine content, and the toxicity of mixtures with more than 1*8 percent chlorine was very low (Lichtenstein et al;, ll). Toxicity of dieldrin and DDT was enhanced beyond an additive effect by the addition of the lower chlorinated PCBs. Topical applications of Aroclor 125L to a grasshopper (Clorthippus brunneus) produced delayed mortality that occurred at the time of molt (Moriarty, lb). C. FISH AND AQUATIC INVERTEBRATES Shrimp (panaeus duorarum) are sensitive to low concentrations of PCBs (Duke,et al,, ljj). All individuals died as a result of a L8-hour exposure to flowing seawater containing 100 parts per billion of Aroclor 1251} 80 percent died in 2b hours. These ahrlsp accumulated 3.9 parts per million in their tis sues. Shrimp exposed to 10 parts per billion did not die, but accumulated 1.3 parts per million of PCBs in their tissues. Seventy-two percent of the Juvenile shrimp died from a 20-day exposure to $ parts per billion of Aroclor 125b and the tissues accumulated 16 parts per million. Crabs (Calllnectes sapldua) were less sensitive, but accumulated an average of 23 parts per million in a b-week exposure at 5 parte per billion and still contained 22 parts per million after a week in clean water and 11 parts per million after b weeks in clean water. The small crustacean,(Qammarus oceanicua) had a lethal threshold in 30-day tests between 0.001 and 0.01 parts per billion in colloidal solution and between HONS 202012 161 0.01 and 0.1 parts per billion in emulsions of Aroclor 125b solubilized in Corexlt 766b (a comercial nonionic surfactant preparation) in seawater (Wildish, 16). Qammarus that died had severely necrosed branchiae, and some animals exposed to as little as 0.001 parts per billion developed a less extensive sublethal necrosis. Moulting or fleshly moulted animals were particularly vulnerable. Shell growth of oysters stopped completely in a 96-hour exposure to 100 parts per billion of PCBs. Shell growth was reduced by bO percent in erqjosure to 10 parte per billion and the oysters accumulated 33 parta per million of PCBs in their tissues (Duke, et al., 15)* Pinfish (Lagodon rhomboldes) survived exposure to 10 or 100 parta per billion of Aroclor"IfSlTTormiours, but those exposed to 100 parts per billion accumulated 17 parts per million (Duke, et al., 15). In further studies at the same laboratory, pinfish and spot (Lejostomus xanthurus) died when exposed for lb-b5 days to 5 parts per billion of Aroclor 125b, "but spot appeared unaffected by exposure to 1 part per billion for periods up to 56 days (Hansen, et al., 17), Onset of death in both species exposed to 5 parts per billion was delayed. Pinfish developed ftingus-like lesions on the body, with some hemorrhaging. Spot usually ceased feeding, became emaciated, and developed ragged fins and lesions. Some fish that survived exposure to 5 parts per billion Aroclor 125b became diseased and died even though they were placed in flowing water free from PCBs. Rainbow trout (Salmo galrdneri) are very sensitive to the terpheryls (Outhrie and Acres, lt})i Fifty percent of the fish exposed to Santowax (M# + 30 percent high boilers at concentrations of 10 parts per billion or greater died in bS hours or less under normal oxygen conditions. With reduced orgrgen, 50 percent died in less than 2 hours even at a concentration of 2 parte per billion (the lowest tested). The fish bectme hyperactive in less than 1/2 hour in water containing 25 parta per billion or more. Within 1 to 5 hours, gills reddened, swimming slowed, and balance and avoidance reactions were altered. Less than 5 percent of the fish recovered after showing these signs. HB-bO* was less toxic, and less than 25 percent of the fish died within b8 hours. XI. PHYSIOLOGY The effects of PCBs on reproduction and other physiological processes of wild animals are apt ultimately to have the most serious Impact on the popula tions. Yet these effects are the most difficult to evaluate. Pertinent data are summarized here, with the exception of data for laboratory mammals, which are included in other sections of this report. A. METABOLISM AND KIHBTIC5 In Swedish waters, lower organisms such as mussels and fish contained a greater preponderance of PCBs with lower chlorination than did birds, which suggested that the compounds with fewer chlorines were metabolized or exeretad * Monsanto chemical Company trade name. Santowax is a mixture of ortho-, meta-, and par a- terpheryls. HB-bO is a mixture of hydroterpheryls and terpheryls. High boilers are tar-like decomposition products produced as a result of the exposure of terpheryls to a high radiation field. 162 MOMS 202013 faster than those with more chlorines, so that the latter were subject to greater Increase in the food chain (Jensen, et al,, 19). In two simple food chains, fish to eagles (Hallaeetus albicilla) and fish and mussels (Mytilus edulia) to eeals (Phoca vltulina and Pusa hispida). concentrations increased hundreds to thousands-of times from prey to predator (Jensen, et al., 19). Fish contained hundredths to tenths of parts per million! fresh mussels contained hundredths of parts per million! seal blubber contained 5- 21 parts per million; and the muscle of the white-tailed eagle contained 1502L0 parts per million. In Great Britain, birds that feed on birds or mammals contained the highest concentrations of PCBs, those that have a mixed diet contained the next highest, and those that feed on insects had the lowest (Prestt, et al., 3), The fish eating herons from the southeast of England contained higher residues of PCBs than birds of ary other area. Many species of California birds contained hundredths to tenths of parts per million of PCBs; peregrines (Falco peregrinue) contained greater amounts, one as high as 98 parts per million in muscle^Risebrough, et al,, 20), while fish in the same ares contained only thousandths of parts per million. Residues of PCBs in the industrially polluted Escambia Bay increased in the expected order. Water contained a maximum of 275 parts per billion, and sediment a maximum of b86 parts per million, tyatars (Crassostrea virginica) contained 2-3 parts per million, shrimp (Penaeua duorarum) 1.5-2.? parts per million, blue crabs (Callinectes sapidus) 1-7 partaker Million. and pinflsh 6- 12 parts per million (IXike, et al,, 15). Subsequent samplings from three stations in the Bay showed little change in concentrations of PCBs in sediments even after 9 months (Nlmmo, et al,, 21), Experiments were then undertaken that showed that shrimps (Penaeus duorarum) and fiddler crabs (Uca mlnax) could accumulate Aroclor 125b from the sediments. Relationships between concentration of PCBs in sediment and concentration in crabs and shrinks were variable. The maximum accumulation was from sandy silt containing 61 parts per million (dry weight) of Aroclor 125b; fiddler crabs accumulated 80 parts per million (wet weight) in their bodies; shrimp accumula ted 2b0 parts per million (wet weight) in the hepatopancreas* Some PCBa were present in the water and a portion of the accunulation could have been from that source. The ratio of individual PCB isomers maintained integrity in the sediment* and tissues of test animals throughout the investigation, indica ting no pronounced metabolic changes of the PCBs. Spot (Laiostomus xanthurus)exposed to 1 part per billion of Aroclor 125b for 56 days attained maximum concentrations in lb-28 days, although absolute amounts continued to increase as the fish grew (Hansen, et al,, 17). Mud.mum concentration in whole spot was 37,000 times that in the test water. These results were very similar to those for DDT reported earlier from the same laboratory. The PCBs were lost slowly from the tissues of spot after they were placed in clean flowing water. After 6b days of flushing, the concentration had dropped 73 percent and the absolute amount had dropped 61 percent* Isomers of Aroclor 125b, with the exception of one peak, maintained their integrity in spot. 163 MOHS 202014 Marine diatoms (Cylindrotheca closterium) exposed to Aroclor I2ii2 at 0.01 and 0.1 part per million inTulture flasks absorbed the chemical to a concentration of b.7 and 109.2 parts per million, b70 and 1,100 times the concentrations In the surrounding medium (Keil, et al.,'22). The higher concentration (0.1 part per million) sharply inhibited growth as indicated by harvest weights and cell counts and reduced RNA synthesis and the chlorophyll index but had no effect on DNA levels. No such sffecta were produced by the 0.01 part per million concentration. Some early eluting PCB materials not com mon to the known mixture of Aroclor l2b2 were Isolated from the diatoms, suggest ing possible metabolism of the Aroclor. A species of salt-water diatom (Thalassiosira pseudonana) grew at a signi ficantly reduced rate when exposed to Aroclor 125b at concenteations of 25, 50, and 100 parts per billion in the culture medium (Moaser, et al., 2J), Survival was reduced by exposure to 50 and 100 parts per billion. A second species (Skeletonema costaturn) was more sensitive and grew somewhat more poorly when exposed to 10 parts per billion. Both species were mors sensitive to PCBs than to an equivalent amount of DDT. By contrast, a marine green alga and two species of freshwater algae were not inhibited by these or higher concentrations of PCBs. The small crustacean.(Omamarus ocean^cus 1 .appeared to ebsorb Aroclor 125b across the general integument (Wildish and Zitko.t 2b) Uptake was not altered by removal of branchiae epl-flora and by removal of epi-fauna, or by the stage of intermoult. Hate of uptake was greater at higher concentrations and declined after a few hours. Deed Oamwarus absorbed significantly smaller amounts of PCBs from the seawater than did the living anlmele, PCBs inhibited Aliases in bluegille (Lepomls macrochlrus). Aroclor 125b was the most effective inhibitor, followed by Aroclor 1221 (Tep, et el., 25). Aroclor 1268 and 5b60 showed less pronounced effects. Tissues (brain, kidney, liver, and muscle) also differed; muscle ATPase showed the greatest sensitivity, with a response similar to that observed for DDT. In ths Netherlands, the PCBs of lower chlorination were more common in fish (Leuciscus rutilus) than in see birds, and it was concluded that compounds with fewer chlorines probably wars metabolized or excreted relatively rapidly (Koeman, et al,, 26). This hypothesis was confirmed in an experiment with Japanese quail; the gas chromatographic pattern of PCBs In the quail tissues was considerably altered from that of the fed material, and many of the peaks representing lower chlorinated compounds disappeared. There was a similar difference In pattern of the PCB compounds preeent in the egg of a mallard duck and the pattern of the Aroclor 125b that the duck had eaten (Heath, 1). PCBs increased ths breakdown of estradiol in domestic pigeons (Risebrough, st al., 20) and kestrels (Falco sparvarious) (Linear and Peakall., 27). demon strating their capability to induce microsomal etuyme activity. The PCBs wars given by injection (pigeons) or ingestion (kestrels) of relatively high dosages; the birds ware sacrificed and in vitro laboratory studies were made of the homog enized livers. 16b MONS 202015 Mallard ducklings demonstrated the possibility of Interacting effects between PCBs and disease organisms (PYiend and TVainer, 28). Thirty-five to bb percent of the 10-day-old ducklings exposed for 10 days to a dietary dosage of 25 50, or 100 parts per million of Aroclor 125b died upon sub sequent exposure to duck hepatitis virus in contrast to only lit percent of the birds exposed only to the virus. Swedish robins (Erlthacus rubecula) given 5 micrograms of Clophen AJO, for 11-13 days showed a greater migratory restlessness than controls (Ulfstrand and SBdergren, 29). Pheasant hens absorbed 9b percent of the Aroclor 125b given as a single capsule dose, a 'ery efficient entry of this chemical into the system (Dahlgren, et al,, 30). Residues in muscle declined 82 percent in 28 days after dosage. Residue were excreted in both eggs and feces. Residues in the milk of cattle inadvertently exposed to PCBs declined at the rate of 1.3 percent per day when uncontaninated feed was restored (Pries, et al., 31), The rate of lose of IDE residues was identical. PCBs in milk fat decreased from 12.6 parts per million to 5*8 parts per Million in about 3 weeks and to 2.1 parts per million in about b months. A cow given 10 mg/kg of Aroclor 125b in a single does released an average of 3*9 parts per million into the whole milk during the next b days' milking. A dosage of 100 ng/kg produced 36 parts per. million in the milk of another cow (Platonow, et al., 32). The gas chromatographic pattern of the Aroclors in the milk was very similar to that of the fed confound. B. REPRODUCTION Pheasants given a capsule dose of $0 mg of Aroclor 125b weekly for 17 weeks produced fewer eggs than controls, and a higher percentage of chicks pipped the shell but Cld not hatch (Dahlgren and Linder, 33). Chicks that hatched weighed less and survived more poorly than controls. Eggshell thick ness was not affected. In behavioral tests of the offspring on a visual cliff, mor& of the chicks from the dosed parents made the undesirable choice of justing to the deep side, or made no choice, in-the 5-minute test period. None of these effects occurred among the groups whose female parents were dosed with 12.5 mg. Mallards fed a dietary dosage of 25 parte per million of PCBs from about 11 weeks before their first breeding season and through their second year laid eggs with shells of normal thickness (Heath, et al,, 1). The number of eggs laid, hatchability, and survival of young did not differ significantly from the untreated controls. In another test, mallard ducks fed 10 or 500 parts per million of Aroclor 125b in ,the diet for about 5 weeks laid eggs with normally thick shells. Bobwhite quail fed diets containing 50 parts per million of PCBs, or 30 parts per million of IDE, or a ccobination of 25 parts per million of PCBs plus 15 parts per million of IDE for about 11 weeks before their first breeding season reproduced as well as controls. Ring doves (Streptopelia rieoria) fed 10 parts per million of Aroclor 125b for 6 months laid eggs no lighter than those laid by control birds. (Peakall, 3b). Fourteen birds fed 10 parts per million of PCBs before and after dosage and nine birds injected intreperitoneally with 160 mg/kg 1-b days before egg laying confirmed the lack of effect of PCBs on shell weight. 165 MOMS 202016 Chickens fed Aroclor 12L2 at 10 parts per million or 100 parte per million and Aroclor 12514 at 100 parte per million laid fewer eggs, hatched fewer chicks, and laid eggs with thinner shells than controls in tests made for the Monsanto Chemical Company by the Industrial Bio-Test Laboratories. Those fed Aroclor 12L2 at 1 part per million, Aroclor 125b at 1 part per million or 10 parts per million, or Aroclor 1260 at 1 part per million, 10 parte per million, or 100 parts per million did not differ significantly from controls. The studies with chickens and with ducks differed in dosage levels and in the type of PCBs employed, so that the differences cannot necessarily be ascribed to the difference in species. Further tests with ducks and with other species are needed in order to understand the potential for PCBs to affect reproduction of wild birds. In recent studies at the Patuxent Wildlife Research Center, a statistical evaluation of the role that different chemicals may play in thinning the shells of brown pelicans In the field has shown that DOE residues correlate much better with shell thinning than do residues of dieldrin or PCBs (Blus, et al,, 3$| Anderson, et al, , 36) reported similar results from studies of shell thinning and residue content of tile eggs of cormorants and white pelicans, Rsproductlve failure occurred among ranch mink that were fed fish from the Qreat Lakes and the Mlramichi (Qilbsrt, 37 ; Aulerich, et al., 30), Such effects could not be produced experimentally by dosages of DDT or its metabolites In levels far in excess of those present in the fish (Aulerich, et al* 38). This led to the belief that other contaminants must be responsible, and tests have been initiated with PCBs as a possible candidate. III. SUMMARY Polychlorinated biphenyls have become ubiquitous in the world ecosystem In quantities similar to those of DDE* Exper1mental studies have shown that PCBs have a toxicity to mallards, pheasants, bobwhite quail, coturnix quail, red-winged blackbirds, starlings, cowbirds, and grackles that is of the same order as the toxicity of DDE to these species. Overt signs of poisoning also are similar to those caused by compounds of the DDT group. Toxic effects of DDE and Aroclor 1251t to coturnix chicks were additive, but not synergistic. PCBs containing higher percentages of chlorine are more toxic to birds than those containing lover percentages. PCBs of foreign manufacture contained contaminants to an extent that greatly increased their toxicity. Residues of PCBs in the brains of birds killed by these compounds measure in the hundreds of parts per million. PCBs may have contributed to mortality of some birds in the field. Tbxlcity to insects of PCBs of different degrees of chlorination is the reverse of the pattern in birds: the lower chlorlnatlons are more toxic to insects. PCBs enhanced the toxicity of dieldrin and DDT to insects. 166 HONS 202017 Shrimp are very sensitive to PCBs and most will die ae a result of 20-day exposure to a concentration of 5 parts per billion. PCBs also inhibit shell growth of oysters. Crabs are leas sensitive! all accumulate residues to mary times the concentrations in the water, and a test with crabs showed that they lost the residues very slowly. Qrowth of certain species of marine diatoms was experimentally inhibited by PCBs, but algae were not affected. The small marine crustacean, Oammarus, is sensitive to PCBs in concentra tions of thousandths to tenths of a part per billion. Exposure to 5 parts per billion of Aroclor 12J>lj caused mortality of two species of fish in lli-15 days. Onset of death was delayed and was accompanied by fungus-like lesions. Rainbow trout were quickly killed by polychlorinated terphenyls at 10 parts per billion under normal oiygen conditions and at 2 parts per billion with reduced oxygen. ' Metabolic changes of PCBs have been suggested by environmental observa tions of different isomeric patterns in animals of different trophic levels. Quantitative differences also are pronounced, with magnifications of hundreds to thousands of times. Laboratory studies have shown no metabolic changes of PCBs by crabs and shrimps, minimal changes by fish, and pronounced changes by birds. PCBs induce microsomal enzyme activity in birds. Exposure to PCBs in creased the susceptibility of mallard ducklings to duck hepatitis virus. Offspring of pheasants whose parents received high dosages of PCBs made poor choices in visual cliff tests. Egg production and hatching after pipping also were affected. Migratory restlessness was increased in &iglish robins ex posed to PCBs. Long-term studies of the reproductive effects of Aroclor 12$U on mallards and bobwhlte quail and of Aroclor 12SU plus ODE on quail showed no significant differences from controls. In studies of chickens, however, egg production and hatchability were impaired by high doses of Aroclor 125k and by low doses of Aroclor 12k2. Statistical evaluations of the role that different chemicals may play in thinning eggshells of brown pelicans showed that DDE residues correlate better with shell thinning than do residues of dieldrln or PCBs, confirming observa tions with cormorants and white pelicans. IV. CONCLUSIONS PCBs are man-made biologically active substances that are dispersed throughout the envlrorment and stored in the tissues of animals. They are lethally toxic to fish and aquatic invertebrates in concentrations measured 147MOMS 20201$ in parts per billion or less. They are metabolized and excreted very slowly by these organisms. They are only moderately toxic to birds and mammals and the lethal levels are similar to those oT DDE. In sublethal exposure, they are physiologically active and induce enzyme activity. Effects on reproduction have been shown for chickens but not for ducks, quail, or doves, and for rabbits only at high dosages. - Full evaluation of their actual or potential effects in the environment Is hampered by the complex nature of the mixtures that conpose then, and by the Inclusion of contaminants in these mixtures. Experimental studies have been conducted with the unaltered products, as sold, and the results nay not properly reflect the effects of the components as they exist in the environ ment. The evidence available, however, indicates that PCBs must be viewed as potential problems. The difficulties of attaining a proper evaluation in ary reasonable length of time suggest that the least costly^course would be to take all measures possible to prevent their escape into the environment. HONS 202019 166 FOOTNOTES 1. Heath, R. 0., J. W. Spann, J. F. Kreitzer, and C. Vance. 1970. Effects of polychlorinated biphenyls on birds. Presented at and to be published in proceedings of 15th International Ornithological Congress. The Hague, 1970. 2. Dustman, . H, L. F Stickel, L* J Blue, W. X,. Reichel, and S. N. Wiemeyer. 1971. The occurrence and significance of polychlorinated biphenyls in the environment. Transactions of the 36th North American Wildlife and Natural Resources Conference: U8-131. 3. Prestt, Ian, D. J. Jefferies, and N. W. Moore. 1970. Polychlorinated biphenyls in wild birds in Britain and their avian toxicity. Environmental'Pollution 1:3-26. L. MeCune, E. L., J. E. Savage, and B. L. O'Dell. 1962. Hydropericardium and ascites in chicks fed a chlorinated hydrocarbon. Poultry Science 1*1:295-299. 5. McLaughlin, Joseph, Jr., Jean-Pierre Marliac, M. Jacqueline Verrett, Mary K. Mutchler, and 0. Qarth Fltshugh. 1963. The injection of chemicals into the yolk sac of fertile eggs prior to incubation as a toxicity test. Toxicology and Applied Pharmacology 5*760-771. 6. Rshfeld, Betty M., R. L. Bradley, Jr., and M. L. Sunde. 1971. Toxicity studies on polychlorinated biphenyls in the chick. Poultry Science 50(1*}: 1090-1096. 7. Platonov, N. S., and K. S. Funnell. 1971. Anti-androgenic-like effect of polychlorinated biphenyls in cockerels. Veterinary Record 88(1*) *109-110. 8. Vos, J. 0., and J. H. Koeman. 1970. Comparative toxicologic study with polychlorinated biphenyls in chickens with special reference to porphyria, edeau formation, liver neorosis, and tissue residues. Toxicology and Applied Pharmacology 17:656-668. 9. Vos, J. 0., J. H. Koeman* H. L. van der Maas, M. C. ten Noever de Braun, and R. H. de Vos. 1970. Identification and taxioological evaluation of chlorinated dibenzofuran and chlorinated naphthalene in two commercial polychlorinated biphenyls. Food and Cometic Toxicology 8:625-633. MONS 202020 169 10. Vos, J. 0,, <J. J. T. W. A. Strik, Catherine W. M. van Holsteyri, arid ' J. H. Pannings. 1971. Polychlorinated biphenyls as inducers of hepatic porphyria in Japanese quail, with special reference to 8 .aminole vulinic acid synthetase activity, fluorescence, and residues in the liver. Toxicology and Applied Pharmacology 20(2)232-2li0, 11. Koeman, Jan Hein. 1971. The occurrence and toxicological implications of some chlorinated hydrocarbons in the Dutch coastal area in the period from 1965 to 1970. Doctoral Dissertation, University of Utrecht. 139 p. 12. Stlckel, William H., Lucille F. Stickel, and Francis B. Coon. 1970. DDE and DDD residues correlated with mortality of expert-, mental birds, pp. 287-291* in "Pesticides Symposia," edited by W. B. Deichmann, Halos fc Associates, Miami. 13. Lichtenstein, E. P., K, R. Schulz, T. W. Fuhrematon, and T. T. Liang. 1969. Biological interaction between plasticizers and insecticides. Journal of economic Entomology 62)761-765. Hi. Moriarty, F. 1969. The effects of polychlorobiphenyls on Chorthlppus brunneus (SaltatoriaiAcrididae). Entomologia txp. and Appl, 12)206-210. 15. Dike, T. W., J, I, Lowe, and A. J. Wilson, Jr. 1970. A ploychlorinated biphenyl (Aroclor 1251*) in the water, sediment, and biota of Escvibia Bay, Florida. Bulletin of Environmental Contamination and Toxicology 5)171-180. 16. Wildish, D. J. 1970. The toxicity of polychlorinated biphenyls (PCB) in sea water to Qammarus oceanious. Bulletin of Environmental Contamlnation and Toxicology ?(3))202-20l*. 17. Hansen, D. J., P. R. Parrish, J. I. Lowe, A. J. Wilson, Jr., and P. D. Wilson. 1971. Chronio toxicity, uptake, and retention of Aroclor 1251* in two estuarine flrfies. Bulletin of Environmental Contamination and Toxicology 6(2)tll3-119> 18. Quthrie, J. E., and 0. E. Acres. 1970. Toxicity to fid) of two organic reactor coolants. Bulletin of Environmental Contxoination and Toxicology 5(2) <11*5-151* 19. Jensen, S., A. 0. Johnels, M. Olsson, and 0. Otterlind. 1969. DDT and PCB in marine animals from Swedish waters. Natqre . 221* <21*7-250. 20. Risebrough, R.W., P. Reiche, D. B. Peakall, 3. 0. Herman, and M. N. Kirven. 1968. Polychlorinated biphenyls in the global ecosystem. Nature 220:1098-1102. 170 MONS 202021 21. Nijimo, D. R. P. D. Wilson, R. R. Blackman, and A. J. Wilson, Jr. 1971. Polychlorinated biphenyl absorbed from sediments by fiddler crabs and pink shrimp. Nature 231*50-52. 22. Kell, Julian ., Lamar E. Prlester, and Samuel H. Sandifer. 1971. Polychlorinated biphenyl (Aroclor 12L2)> effects of uptake on growth, nucleic acids, and chlorophyll of a marine diatom. Bulletin of Environmental Contamination and Toxicology 6(2)*156-159. 23. Mosser, Jerry L., Nicholas S. Fisher, Tzu-Chiu Teng, and Charles F, Wurster. 1972. Polychlorinated biphenyls: toxicity to certain phytoplankters. Science 175 (1*018): 191-192. 2L. Wildish, D. J., and V. Zitko. 1971. Uptake of polychlorinated biphenyls from sea water by Gammerus oceanicus. Marine Biology 9(3)>213-210. 25. lap, H. H., D. Oesaiah, L. K. Cutkomp, and R. B. Koch. 1971. The sensitivity of fish ATPases to polychlorinated biphenyls. Nature (In press). 26. Koeman, J. H., M. C. ten Noever de Brauw, and R. H. de Vos. 1969. Chlorinated biphenyls in fish, mussels and birds from the River Rhine and the Netherlands coastal area. Nature 221t 1126-1128. 27. Lincer, Jeffrey L., and David B. Peakall. 1970. Metabolic effects of polychlorinated biphenyls in the American kestrel. Nature 228:783-78b. 28. Friend, Milton, and Daniel 0. Trainer. 1970. Polychlorinated biphenyl: interaction with duck hepatitis virus. Science 170>131b-1316. 29. Ulfstrand, S., and A. Sodergren. 1971* Effect of PCB on nocturnal activity in caged robins, Erithacue rubecula L. Nature 231 :I>67-1*68. 30* Dahlgren, Robert B., Yvonne A. Greichus, and Rsyraond L. Linder. 1971. Storage and excretion of polychlorinated biphenyls in the pheasant. Journal of Wildlife Management 35(b)>823-028. ,'31. Fries, 0. F., G. 3. Marrow, Jr., and C. H. Gordon. 1971. Similarity in behavior of DDE and polychlorinated biphenyl (Aroclor 125b) residues in an environmentally contaminated herd of dairy cows. U. 3. Department of Agriculture, ' Agricultural Research Service Paper 130.Presented at the Annual Meeting of the American Dairy Science Association, East Lansing, Michigan, June 1971. HONS 202022 171 > 32. Platonow, N. 3., H. S. Funnell, D. H. Bullock, D. R. Arnott, P, W, . Saschenbrecker, and D. 0. Grieve. 1971. Fate of polychlorinated biphenyla in dairy products processed from the milk of exposed cows- Journal of Dairy Science 5UC 9):1305-1308. 33. Dahlgren, Robert B., and Raymond L. Linder. 1971. Effects polychlorinated biphenyls on pheasant repro duction, behavior, and survival. Journal of Wildlife' Management 35(2):315-319. 3Li. Peakall, David B. 1971. Effect of polychlorinated biphenyls (PCBs) on the egg shells of ring doves. Bulletin of Environmental Con tamination and Toxicology 6(2):100-101. 35. Blus, Lawrence J., Robert G. Heath, Charles D. Gish, Andre A. Belisle, and Richard M. PTouty. 1971. Eggshell thinning in the brown pelicant implication of DDE. BioScience 21(21*)0213-1215. ' 36. Anderson, Daniel W., Joseph J. Hickey, Robert W. Risebrough, Donald F. Hughes, and Robert E. Christensen. 1969. Significance of chlorinated hydrocarbon residues to brdeding pelicans and cormorants. Canadian FieldNaturalist 83>91-112. 37. Oilbert, Frederick F. 1969. Tracicity to fish of two organic reactor coolants. Bulletin of Environmental Contamination and Toxicology 5(2):lL5-l5l. 38. Aulerich, R. J., R. It. Riger, H. L. Seagrao, and W. 0. Touatt. 1971. Effects of feeding coho salmon and other Great Lakes fish on mink reproduction. Canadian Journal of Zoology 1*9(5) >611-616. HONS 202023 172 APPENDIX H I. II. III. IT. Regulatory Action on PCBa Table of Contents Existing Regulatory Authority Page A. Federal Insecticide, Fungicide, and Rodsnticide Act B. Federal Water Pollution Control Act C. The Refuse Act of 109? (33 U.S.C. I|07) D. The Clean Air Act (ti2 U.S.C. 1057 et seq) E. The Egg, Meat, and Poultry Acts F. The Occupational, etc*.. G. Act to Regulate Transportation of Explosives and Other Dangerous Articles (l8 U.S.C. 831-835) Standards, Tolerances, or Guidelines Established 177 Application of Regulatory Authorities 179 Future Actions and Needs ]_go Tables 1. FDA Proposed Tmporary Tolerances for PCBResidues 178 HONS 202024 173 appendix h Regulatory Actions on PCBs I. EXISTING REGULATORY AOTHORITT At least ten Federal laws are potentially relevant for the regulation of PCBs. However, not all of then have aotually been utilised to deal with the PCB problem. Federal Food, Drug, and Cometic Act (21 P.S.C. 301 st.aeq.) Section ti02 of the Federal Food, Drug, and Cosmetic Act (FDC Act) de fines an "adulterated food" as a food which (among other criteria)t 1. Contains any poisonous or deleterious substance which may render it injurious to health; or 2. Contains any food additive unless the use of the additive con forms to exemptions or regulations issued by the Food and Drug Ackainistration (FDA). FDA has applied both of these oriteria to PCBs, depending upon the circumstances under which the PCB entered the food. The FDC Act prohibits the introduction of adulterated food in interstate cosnerce; prohibits the adulteration of food while moving in interstate commerce; and prohibits the receipt of an adulterated food in interstate coranerce and sifcsrequent delivery of it for sale or otherwise when the initial recipient is aware that the food is adulterated. The Act also authorises FDA to seise any adulterated food products which have entered interstate commerce or which became adulterated while held for sale after reciipt in interstate casmerce. The FDA enforces the FDC Act by various means Including inspections of food establishments (other than meat, poultry, and egg breaking plants) to determine whether the provisions of the Act are being violated. Tbese Inspections include the collection and analysis of food samples. Seme of the samples are of a routine surveillance nature to determine the presence of adulterants such as pesticides which exceed tolerance levels and other contaminants such as mercury, lead, cadmium, harmful bacteria, natural poisons, etc. However, the actual number of routine surveillance samples taksn is small, and effective enforcement relies heavily on informa tion on the known or suspeotod existence of specific instances of food adulteration. A. FEDERAL INSECTICIDE. FUNGICIDE, AND RODENTICIDE ACT (7 D.3.G. 135-135k) Under the Fbderal Insecticide, Fungicide, and Rodenticide Act (FIFRA) all pesticides (referred to in the act as "economic poisons1*) HONS 202025 shipped In interstate commerce must be registered with the EPA, EPA can refuse to register a product If it will cause injury to man or the environment if used according to the label. The registration of a pro duct can be suspended or cancelled if it is found to no longer meet the criteria for registration* On October 29, 1970, the Pesticides Regulation Division (then In the Department of Agriculture; now in EPA) issued a notice (PR Notice 70-2?) to all pesticide manufacturers, formulators, and distributors. The notice stated that, "Formulators and manufacturers of economic poisons containing polychlorinated biphenyls and polychlorinated terphenyls should change their formulations to eliminate such chemicals either as active or inactive ingredients. It is believed that a period of six months is a reasonable period of time within which to affect such formula changes." Assuming that the notice has been ocnplied with, there ehould be no pesticides which currently contain FCBs. B. FEDERAL WATER POLLUTION CONTROL ACT (33 D.3.C. U66 et.seq.) The federal Water Pollution Control Act (FWPC Act) authorizes the Administrator of EPA to enforce State water quality standards established by the States and approved by the Federal Government if the State is not adequately enforcing the standards. No States have established water quality standards relating specifically to PCBs. Thus the water quality standards pert of the FWPC Act is not a useful tool for dealing with the PCB problem. Section 12 of the PWPC Act applies primarily to aooidential discharges of hazardous polluting substances. It requires the immediate reporting to EPA or the Coast Guard of any discharge of a hazardous substance from a vessel or an onshore or off-shore facility. The discharger is responsible for making the report and for clean-up, but SPA la authorized to restove or arrange for the removal of the hazardous subetanoe if the discharger is unable or unwilling to do so. PCBs are being designated as hazardous sub stances under section 12, and the authority contained in the section could be used if an accidental spill of PCBs into water should occur. C. THE REFUSE ACT OF 1899 (33 tJ.S.C. 107) Another legal authority for controlling water pollution is section 13 of the 1099 Refuse Act which forbids discharge of any wastme (other than municipal wastes) Into navigable waters without e permit. Issued by the Army Corps of Engineers, which cen limit the discharge of substances into water. EPA. and the Justice Department are prepared to use the Rafuse Act to prevent PCB dischargee D. THE CLEAN AIR ACT (1*2 tT.S.C. 1057 et. eeq.) The general authorities contained in the Clean Air Act ere not, for the most pert, applicable to PCBs because PCBs ere not generally amibted into the air in the normal operations of e municipal or industrial facility. PCBs may become air contaminants through the burning of refuse, but such amissions usually could be controlled only by preventing the substance from initially getting into the refuse. HONS 202026 175 Section 112 of the Clean Air Act authorizes the establishment of national emission standards for hazardous air pollutants. However, It is unlikely that section 112 would be Invoked to deal with PCBs for the same reasons that the other Clean Air Act authorities are generally not applicable* E, 1HE EOQ. MEAT. AND FQULTRT ACTS the Consumer and Marketing Service of the U.S. Department of Agriculture (USDA) administers three acts relevant to the PCB problem The Egg Pro ducts Inspection Act (P*L* 91-597)) the Wholesome Poultry Products Act (P.L. 90-1x92); and the Wholesome Meat Act (P.L. 90-201). These authorities apply to meat, egg, or poultry products from the time they reach the processing plant until they are purchased by the consumer. Once they leave the plant, they also fall under the legal authority of the FDC Act as do all foods. USDA routinely checks meat, poultry, and egg processing plants, but relies primarily on local jurisdictions for inspection at retail outlets. ,, The egg, meat, and poultry acta essentially define a product as adulterated if it contains any substance in an amount which is judged deleterious to health. USDA follows guidelines established by FDA under the FDC Act for determining what amounts of a particular substance are deleterious. U3DA can seise adulterated products or prevent then fron being distributed. P. THE OCCUPATIONAL SAFETY & HEALTH ACT (29 U.S.C. 651-678) Chemical hazards in the workplace are regulated under the Occupational Safety and Health Act. The Secretary of labor, in cooperation with the Secretary of Health, Education, and Welfare, is authorized to set and enforce occupational safety and health standards applicable to businesses affecting interstate commerce. No specific standard has bean eet for occupational exposure to PCBs. However, the Departaient of Labor has set exposure limits for coaiparable substances, and it could enforce limits on PCBs by applying limits set for compounds such as chlorodiphenyl* The standard for chlorodlphenyl ie lmg per cubic meter - 9 hour average exposure. o. ACT TO RS3JUIS oh or. ARTTCIfiS US g.S.C. 831-935 sires Am eggs m The Department of Transportation (DOT) regulates the transport of hazardous substance# under the Act to Regulate Transportation of Explosives and Other Dangerous Articles. The Act authorizes DOT to promulgate regula tions for the safe transportation of such materials. DOT has issued tentative test protocols for classifying substances according to their acute toxicity, but these have not yet gone into effect. Responsibility for Insuring that standards are compiled with reate initially with the manufacturer or shipper. HOMS 202027 176 IX, STANDARDS, TOLERANCES, OR GUIDELINES ESTABLISHED The most important limits which have been established for PCBs have been those eetablished by FDA to deal with particular instancee of food or feed contamination. Standards or, more accurately, tolerances for products such as for PCBs may be established under Section h06 or Section U09 of the Food, Drug, and Cosmetic Act, which require a finding that the substance ie required in the production of the food or cannot be avoided by good manufacturing practices or a showing of safety and a need for use* No permanent tolerances for PCBs have been established, since all the safety data necessary and the need for use to support such tolerances are not available at this time. In the absence of tolerances, the Food and Drug Administration, in order to respond to accidental contamination, has set interim guidelines for levels of PCB in some foods at which it will take action under the Food, ttrug, and Cosmetic Act. It is now proposing to establish temporary tolerances for permitting unavoidable PCBs in several categories of food. ' FDA has taken action to remove frcm the market shell eggs containing mare than 0.05 parts per million PCBs and feeds containing more than 0.5 parts per million PCB where the PCBs present appears to be frcm accidental contamination of feed. Die U.S. Department of Agriculture has also Uken action to remove poultry-from the market containing $.0 parts per million PCfio where such contamination was the result of accidental contamination of feed fed to poultry. The action level of 5 parts per million (whole tissuo basis) was established in 1971 by PDA. This level <nn reduced t> 5 parts per million on a fat basis in 1972. The Food and Drug Administration has taken no action against any other predicts for PCd contamination but has lnforn-jd the States find others that it would consider action on .illk if PCdo exceed 0.2 parts per million (whole basis) find on ftsh if PCBa exceeds 5 parts per million. Sono States have tak.v.i action to remove milk from the market that contained :n?re than 0,2 parts pur million PC8o. The temporary tolerances recently proposed by FDA are listed in Table 1* The guidelines and the temporary tolerances taken into account avail able toxicological data, the estimated amount and type of Intake of PCB from food, and also the sensitivity of the methods used for detecting PCB. Thus more PCB is allowed in poultry than in eggs because children are fed egg yolk, sod children are not considered to have as efficient detoxication mechanics for handling PCBe as adults. It should be noted that these limits were established to deal with particular incidents# and thus may be changed as new knowledge develops or as circumstances ohange. Some food has been discovered to be contaminated because of migration from food packaging materials containing PCBs. Thus FDA also has proposed that a temporary tolerance of 5 parts per million in paper packaging HONS 202026 177 Table 1 PDA Proposed Temporary Tolerances for Pen Residue* Food Tolerance Milk 2.5 ppm (fat basis) Dairy Products 2.5 ppm (fat basis) Poultry 5 ppm (fat basis) Eggs 0.5 ppm Complete animal feed3 0.5'ppm Animal feed components (including fish meal} 5 ppm Fish 5 ppm (edible portion) Infant and junior food 0.1 ppm Food-packaging materials 5 ppm MOMS 202029 178 materials be established permitting unavoidable PCB residues in such materials for a period of one year, nils will provide an opportunity for the orderly elimination of PCB-cont*ining raw materials used in the manufacture of food packaging materials. EPA recently has proposed regulations which would prohibit all intentional discharges of PCB into the water, end would limit PCB levels in the water to .01 parts per billion. These regulations probably would be enforced through use of the Refuse Act. Ill. APPLICATION OP RBOUUTORT AUTHORITIES Within the past two years there have been several incidents involving PCB contamination. These include the followingi In September 196? FDA detected PCBe in Meat Virginia milk. The source of PCBe was suspected to be the use of spent transformer fluid as a solvant for herbicide spray. Qrade A milk shippers involved were taken off production by the State, In April 1?70 FDA identified the presence of PCB residues in milk sampled by the Ohio State Department of Agriculture. The Department removed a large quantity of milk from the market. The chemical was traced to a material used as a sealant in the allot where dairy feed was stored. Similar occurrences of PCB contamination of dairy herds have been reported in several Southeastern States. Since June 1971, the Meat and Poultry Inspection Program (MPIP) and the Poultry Division, Consumer and Marketing Service, USDA, have been survey ing specifically for PCBa. Prior to that time, the MPIP*a ongoing survey of chlorinated hydrocarbons should have detected any PCBe present in animal or poultry fat at a level of 1 parte per million or above. None was detected in the fat of poultry, swine, cattle, or sheep prior to Deoesiber 1970. Since that time, there have been five separate incidents of contamination of poultry with PCBa. Each appears to be a single-source, one-time occurrence. The Poultry Division's egg sampling program in the Southeastern Q.S. end in Minnesota has not detected levels of PCBa which are significant--most values falling below the sensitivity of the method. Contamination of bent slaughtered on Decaaiber 2, 1970, led to placing all laying bans in Orange, Sullivan, and Ulster Counties, New fork, under quarantine through August 30, 1971, requiring pretesting for PCBe prior to elau^iter. Levels up to 26.0 parte per million PCBe were found in the fat. Approximately 137,100 hens were condemned and buried on the farms* Flocks containing leas than 5 parte per million PCBe were sold in conaerclal channels, frequently at drastically reduced prices. Eggs from contaminated flocks were destroyed. The source of contamination wee feed containing returned bakery product wrappings. Frosen turkeys produced on farms from Modesto, Fresno, Stockton, and Santa Rosa, California, wars found to contain up to 28 parts per million of of PCBe in the fat. The source of contamination ia unknown. All turkeys MOMS 202030 179 from those sources (approximately 100,000 lbe.) wore detained until testing was completed (Feb.-May 1?71). Muscle meat was salvaged and used in turkey rolls. Fat and skin containing over 5 parts per million PCBs went to nonfood uses. Contamination of anchovy fish meal with PCBs from a leaky heat ex changer was discovered by the Monsanto Company In July 1571 In Wilmington, N.C. One limedlate and noticeable result was poor hatchablllty of eggs from the poultry fed the FCB contaminated diet. Accordingly, USDA required that all poultry eoming to market from these States be tested before marketing. During the first 2 weeks of testing, 5bl sauries were analysed, representing over 2.5 million birds. Of these, 2.b percent were retained until disposition could be made, The 68,000 chickens which had been fed the fish meal wsra destroyed by the owner of the chickens. FDA seised 75,000 eggs, 5 shipments of commercial fish feed, and 1 ship ment of fish meal which had been contaminated, and USDA barred trcm market more than 30,000 pounds of processed frozen eggs. In addition, the proceseing firm recalled over 16,000 tons of the PCB-contamlnated fish meal. In September 1971, turkeys from one grower on eight farms in Detroit Lakes, Minnesota, were found to contain up to 20 parts er million PCBs (fat basis). One hundred forty, flocks in the Immediate area, including parts of Minnesota, North Dakota, and South Dakota, were tested , but no levels above 2 parte per million were found. Approximately 1 million turkeys were withheld from market by the single grower until residue levels were acceptable. The source of the PCBs has not been determined, but feedgrade fat contaminated with PCBs from a heat exchanger is suspected. Also in September, the State of Michigan stopped its annual program of distribution of Cohoe Slnon from Lake Michigan, because the fish contained high residues of PCB and DDT. In Fabruary 1972 chickens in Maine were discovered to contain PCB contamination of up to 172 parta per million in- their fat. Iheee contaminatad ohickens had been given feed from a plant in Thorndike, Maine, but officials have been unable to locate the exeot source of the PCBs. More than a million chickens have been destroyed. Many of these Incidents have evoked criticima of the Federal Oovernment for failure to detect the problem sooner or for failure to set more stringently. It must be recognized that insofar as detection of problems relies on in spection of food products being shipped to market, it is impossible to Inspect even a aaall fraction of the foods being shipped* Factory inspection can detect soma problems, but even this approach is severely limited by available reeources* The prime reliance must be on controlling the use of the offending substance. IV. FUTURE ACTIONS AND NEEDS Enough data are available to indicate that PCBa are pervasive in the environment. The basic regulatory challenge is thus twofoldt to minimise human exposure to PCBs already present in the environment end to prevent more PCBs from entering the environaent. MOMS 202031 100 Based on available monitoring data and reports, one route of human exposure to PCBs currently in the environment is through food. The PCB contribution made by other routes of exposure hat not been sufficiently measured. The FDA has Issued a proposal which will prohibit the use of PCBs in and around food processing plants and will establish limitations on the use of salvaged paper containing industrial chemicals for food packag ing. These proposed actions should prevent occurrences such as the Wilming ton incident and the problem of PCBs in food packaging materials. Howsver, there will still be problems, as evidenced by the Coho Salmon contamination, the mysterious Minnesota turkeys, and the discovery of high levele of PCBs in cardboard food containers. The solution to these problems seems to lie in a better understanding of the path which PCBs follow through the environment and on full use of existing regulatory authoritiee. Even with better understanding we can probably expect future isoleted incidents of PCB contamination. 1 Existing regulatory authority is generally inadequate to prevent more PCBs from entering the environment. The Monsanto Company has reported volun tarily limiting ths distribution of PCBs to "closed systems" but this limit has no force of law behind it. The government has no power to restrict imports of PCBs by foreign manufacturers, end if it disagreed with Monsanto's Judgment on allowable uses it could not impose more stringent llmitetione on Monsanto or on any other potential manufacturer. This regulatory gap would be filled by the Administration's proposed Toxic Substances Control Act. The proposed Act, aent to tbs Congrats in February 1971, would authorize the Administrator of EPA to restrict or prohibit the use or distribution of e chemical substance if such restriction were necessary to protect health end the environment, end it would also authorize him to issue standards for tests to be performed and for results to be achieved from such tests for various classes end uses of new substances. Thus, in addition to providing the regulatory authority needed to deal with the PCB problem, it would also establish e astern for preventing new chemicals from becoming similar problem*. Action by the Congress to approve the Toxic Substances Control Aot ie the most important step which can be taken to deal with PCBe end similar problems. HONS 202032 161 * i. i oovEfl.vifKkT PMsfme ortrct r VE; tkiiiM*.Irt= l-AKiwIA<_,w>i-UL-it EN TOX1COLOGIE DER RIJ<SUN!VcRSlTEIT TE UTRECHT DiSCTuR: Pro*. M. VAN GENOEREN No Blritht Op BeirtKmdc :4 UTRECHT, June 24, 1970* Bill,trait 17 2 Ul*fooNo.; T5S44 Dr. R.E. Keller, Applied Sciences Section Monsanto Company, 1700 South Second Street, ST. LOUIS. Missouri 63177. USA Dear Dr. Keller, Enolosed you vill find a photooopy of the manueoript conoerning the identification of chlorinated dibenmofursns in PCB. We use fraotionati QC/mass spectrometry techniques} the details are given in the manuscript which is not for general distribution since it is not yet accepted by the Editors of the Journal of Food and Cosmetics Toxicology. During the visit of you and your colleagues at our Institute ve mentioned a.o. severe skin lesions (hyperkeratosis) in cattle, Hie floor of the stable in which the animals were housed was covered with second-hand conveyor belts, covered with a new anti-slip laysr. Gas chro matographic analyses of a sample of the rubber mat and of the liver of a severely affected cow revealed a peak pattern which was very indicative for PCB, as we also mentioned during your visit. Mass apectronetrie ana lyses of the rubber revealed compounds with molecular weights of probably penta- and hexAchloronaphthalene, well known for their hyperkeratotio aotion In cattle. Chlorinated naphthalenes are not for sale and sinoe they are ver important for us as referenct compounds in gas chromatography, we would like to ask you to mediate for the supply of chlorinated naphthalene mixtures and psrhape a pure sample of octa ohloronaphtalor.e (perchloronaphthalene) Dr. Koeroan told me that he will send you a total-body sample of a cormorant containing a high concentration of PCB's, for a comparison of the quantitative aspects of the analytical methods. Sincerely yours, Institute of Veterinary . Pharmacology and Toxicology, University of Utrecht, Biltetraat 172, umasHTt 'The "Netherlands J.G. Vos. MOMS 202033 Identification end 'Zoiacoloyicwl Evaluation of Ciilorinatci Dibcjizorura^i and Chlorinated i/aplithaleno in Two Comorcial lolyc2;lcri:i;.ted Eiphcnyla. J.G. "00. Institute of Veterinary Jathoiojy, .Bilt struct 17-# Utrecht, The yothcrlnudu. J.lj. r.oenan and -<L. van dor i.aaa. Institute of Vo twrin-iiy lli&r:2" colony and Toxicology, iill'itrui.t 17*:, Utrecht, Tho ysthorlundc* ll.C, ten Soever do frnuu, Ji.H. do Vo3. Central Inotituto Tor Iiutritioa and i;ooi.Iiar&->rch, TUG, Zoiot, The I.'othorlrr.do. liunninj xitle: Toxic Impurities iu tocinioul JCU preparationo. MONS 202034 2 Abritrv.ct. In a previous study (Vos & iujocir-i:* 1?70) u eit~Jificint difference in Wticity was found botwot-r. 3 eo.r .crclcl iCh prepare.-. ticns; h.l^h aortulity, liver necrosis ar.d chick ocdoun-liko lesions occurred in 2 iCa's. In the proocni. study it WU3 found by mens of colui.m clirouuto^Tuphy u;:d ci:- cIu'o;.w.Lojiv..-Li/, that in tho 85#' diethyloti'.or fractions of these 2 rCh'o polos ooupouada cro present* A chicken erabryo assay proved the hi<;h toricity of tliio fraction* .Subsequent uauJ cpectruaotrio olid ulcrocoulor trie analyoec rovoalcd tho Identity of those coupoundsf a.o* totra- end pentncijlorodibonsofuran. Tho ai^nificaiico of thcuo inpuritioo cro diccusccd. It la concluded that evaluation of cninaloorporiiacnts with PCJJ*s ia extrencljy difficult Cue to the preoonco of chlori nated dibcn2orurr.no in couo coiuuorfiial fCJ4s. HOMS 202035 IntruA'ieti - it . . i'oljrclilorinatod blphoayia (ECii) ilivo boon identifisd lu tissues or fish and wildlife (je&sca, 1jC5| dolsaa, Jincsn3 St `fat ton, 1967| uoldon & il&rodcn, 1<K>7| Koo:j*n, Ceknup, Yccn, iJrouwcr, liooth, Zvart, von do 2roo- St von Condaren, 1967i lsobrouj;i, Sice'-.a, roahsll, lloi-^an h Zlrvon, I9u3| F'.oati.-ji, tor. .'.'savor do hrauw & do Voo, t?3>; Janson, Joiin'-'la, 01oron St Stt^allnl, and have been recently boon lapllostod in the nortality of eon birda in Britain (liourr.o St .'lead, 1JC9). Co aneroid, FC~ preparations axe oxtrocgly otablo and only slightly soluble in water. They arc ucod as lubrlcaatc, as boat transfer oedia, la protective ooatince for too4 neat no tal and concrete, and la nony othotf cpylioatl'oac. Thoy uro compatible with paints, ayr.thotic rsoina, var-,ii3h*e end vaaec, end laprove nuoh proportion of thoco preducts an their ohcaical resistans:;, water ronictanca, adhoolTonsoo end flexibility (iaonyauo, I^SOj Jiubbaxd, 1>o4)* ilo&'cr, it li&s not yot boon catabliohed which of the aatarij-lo tioatad with ICj has contributed to the present environmental contamination. L'xpcxiccato with ruts and cul"ua jits hevo shown tli&t tho ii.i,aotioa of XCl: nay t;ivo rino to liror injury (liillor, Uh4)* JiyOrovci'lcaruiia.*., occasionally acccaptniod by cwdcuinrl utdoiia, woo found in el.ici.s (ilcCuuo, Cava^c. w O'roll, 12d2| Hie;;, O'fell d Cliiluu, IJdyj Voo d loeoan, 1^70) and Japaucao quail (l.csnau ct al, IJdy) of tor ingestion of Fell of American (Arcelor) rad FrouwU (liionaclor) origin, respectively. 1 cached rooonblcncc between tho jao chrouitocraaa and sac* opsetsa In unco spectroccter onalyceo of j corurorcial FCi proparatiei.e (thenoelor DF6, Clophca AdO, and Aroclor 12C0) was found (Kooman et cl., ^96s) The eccurronce of "Chick oedtaa" li!;o leoiona in birda fed PCIl (Kocaun ot &!*, 19691 JicCuno ct cl., 1962) Fllok ct ol. 1?G5) vao HONS 202036 4 the reason foi* a recent cooperative toxieolocical test with the 5 ncnticr.ci PC3 preparations in chickens (Voo J* KocDca, I97O)* In this study a elsnificant difforcuco ia toxicity botuocn the 3 tested compounds vco found* Cloven /.6o and Fhenoalor 3*6 shoving the hiyhoot, .\rotlcr 12GO shoving tUo lowest nortality Subcutaneous end aLdociual oeucua, end conirolobular liver necrocla van recorded oiily in i'looo oiiicl:c fed with Clopheu and Pheneclor. Hydropc ricr.rdiio wau rcoordod in nearly til chicho fed with Clophen and Fhonoclor and only occasionally in chichii fed with Aroclor. Chomlcal porpli >i'i.'. Win found as a general 1`OJJ effect* In the precont study, tho oo:|uol to that nentioned r.hovoj vo dosoribo tho identification end evaluation of eonpovxda reoponaiblo for tho difforonco in toxicity botveen tho 3 ooMnoroial fCB preparations* HONS 202037 .oo PCd preparations, which co/italn an nvaraj; of 60,' chlorino, wore obt&inod fron rrcdolcc, Franco (Fhcnoolor Drf), Dayor, Germany (ciophea aSO, Lot no. 912434), and llenor-nto, U.3.A. (Aroclor 1260, Lot so. Ak-3). The screening'sethod, used for do taction of chick oedema factor (finu.'ijTsiio, 19<?0n) van sodifiod and uood to isolato from tha FC.'J preparations, conpound(n) responsible for dlfforer.coa In toxicity, Tho elocn-up atop of this proceduro voa out t toil. In tha oolunn chrcnatoT-aplif 0c. activatod florioil (oolunn 0 10am) van uood instead of 15;. activated oluoino, For fraotlonution rodijd. hexans was uoou as elution solvott inotoad of pstrolouu other, Two as PCD vao diasolved in 2 si iioxauo and fractionated on ilia floricil column. This coltran uos clutod with hoxono uutll noarljr ell PCIi'o voro elutod (tortod by cos ohronatocraphy). The 2nd e friction (5r* dlotiiylother In hemwo) vaa oleo totted until no uoro PCD could to dotoetod. 'l'ho final fraction (fraction 3), olutod with 25'A dlothylothor (roas,-ont ;rodc) in hezono, vao evaporatod to 1 ml. An aliquot of tklo concentrate woe injocted into a 204-ID Varlan Aorocraph cat) chrotmto^rph with olootron capturo do tout! on. Tho Fyrox claca column (5 foot x l/li inch), filled with 10/i DC 200 on Caochron s, (60-iOQ aaeh) was operated at 200C with nitio,;on as oartior fat (about 50 nl/nin.). iho coue prooeduro wan uoed to fractionate aliquots cf about 550 kc of the PC- preparations in order tc obtain sufficient quar.titioo for a ohicken embryo assay and for ncoe epootrometer analyreo. Tho FC2 was dissolved in 200 ml herons. The column (0 52 en) was filled with 160 c activated florioil. The sore polar compounds were eluted is tko final (3rd) fraotlou and, after evaporation, tooted by cos clirosatocraphy, A chicken esbryo assay (Vorrett itarllac . iioLamhlin. 1964) woo used to doteruin* tho toxicity of tho 3 FC3 preparations, MOMS 202038 -0- (doooj 3*5 ,`/ec.; discolvod and kopt at 37C In ethanol. Croup t Aroelor, frov.p '! Fhouoclor and group 5 . Clophon) and of the 3rd fraction of Clophcn (doeei 3rd fraction obtained fron 35, 3,5, an* 0,33 and 0.033 ng. Clopkoa in groups 4, 3# u aud 7 respectively). Tho uaaplog, after dioaolving in 0.03 ol ethanol wore injected into the air cell of fresh White Leghorn CCC prior to incubc.ticn. Vho liven of t'-ll hatched chi eh a wore removed for hiotologicol ey.'-ninr.- tio:i, fixel in 10,1 buffered formalin ird procnoncd In c. conventional wanner, Horoovor, cryoatnl eootlona woro ctodlod I11 a fluorcsccuco nicrooeope. Kane apoctrooetry vao uood to identify oonpomtdo prcoont in tho polar 3rd fractions. thio analyolo vae carried out uoieg a g.no ehronatograph-ncso apoctrcuotor combination. Tor thin purpooo a CII4 nnoe apoctrocator (Yarian Jlat. C.n.b.li.) t/ao coupled to a Yarion Aorocxapli ovon, typo 155011, with a ryrox cl*00 colunn (5 foot x 1/3 inch) filled with 10;i DC200 on Coachron f; (c:0*100 crab). Partionler attention vao paid to tho dosich Of tho interface betwoon tho 13 ohror.atocraph and the aaoc apsotroceter in order to obtain tho beet operatise conditions (ten Soever de flrauw & Lrunnde, 19^7). High rooolution nr.00 opectra woro taken on a doublo focus opectro- ootcr typo (Parian Hat. C.n.b.i;.). Ihcact naao noasuremnto wore done with the peak * oatohlnr cethod (tbaourosonts woro doo done fron spectra which were rocorded on photographic piate0 proceosed by Tories Hat. on a Pelts corporator SAMI). To obtain information about ths quantities, clorocoulo- nctric analyses cf the 3rd fraotiona were carriod out* Tho equip- nont ucjd vac t Cohreana clerocoulcnotar, coupled to a .'dictate!: Iff 220 io chromatograph, with a glase column (6 feet x 4 Ieoh). The er.ir.e 10;S SC 2C0 coluan packing vae uoed. Tha column effluents voro cxiilaod in a Dohriiann corsbaotion furnace orl tho HCt, produced by chlv.. inatod conpoundo, vao dotectod and quantitatively ao.-cui'd 1 *7 n. y~ f' - i. -*> 4 * 4* * * * HONS 202039 IhS rocultinr; ezn c'iror;atocron of friction }, obtained ultli the snail coluoi (0 10ns) revealed t.i* proames of polar co-3i.O'mda In Jbetioeler and Clophoa Tho.ic vero n^t found in the Aroelor cztraot* fho sui rooulto voro found with fraction } obtained with the large coluan (0 }2 ram). The 3rd fraction J, of Clophen van cubsc^uontly unod In the ehicknn onbryo ac.-a;,. XMo area}- (table i) confined the diffarencoo in tex'.eity "ostvuen tho 3 teotod ffX proper-ticuo found in the previous study (Voo u u.0Gnr.i;( *27j). :k>rtcllty in croup 1 (Arcclcr) did not differ eiffiiilieantly (X tost) fron nortallty in croup 9 (oontrol). IJortality in croup 4 and J io doco rolufeod; oexly rortallty in tho for'-er* ocattci'ed nortality in tho lettor erour* Corresponding nortollty in croup 3 (?!? nc Clophcu) and croup 5 (3rd fraotiou froa 3*3 E Clophen) lndicatoo strongly tiiai the polar roeiduo in tho letter detoralnoc tho toxicity of tho codiaorcicl fCL. a ^Dincoofelon of all frogh cnbryol and of tlio one-day-old ohioks revailed no ab.norunlitioo except for ono o.nbryo of croup 3 which ohoi/od.a covax*c cuboutonopua oudoLia* Oodona and bool; doforuitioa aro dioorilied after yolk oac iujootion of 23 da and 10 u <troolor 1242, resulting in rcapectivoly 100,i and eabryonio uorvality (llal&ufhlln, Ufirllac, Vomit Mutchlor Pit*hUh( 19^3) *1.L. otclnei livor oeotious ravjolod no aorpiioloda altorationo, lu tho cryostat oootion of tho livor of tiu only hotoho.I weak eaiakcu of croup 5* a rod fluorooaoneo in co.no lobules uoo oe ;n in tho uv. uiuronoo^e* this fluoreaaeneo io indiontivo of tho porphyrin bionyntLasla disturbance found In the prior otudy (Voa L Keexen, 1973)* liasa apectronotrlo cjiulycds revealed identical chlorinated compounds In fraction 3 fron Mienoclor und Cloplion in centrist with Aroclor. The roeulte ore <;ivon in tablo 2* iluoo opeofera of conpoundn with aauo ou.ubor J04 nnd 350, oi-talnod froa ponk 1 and 4 (fio*0 arc clvon in fi(j2 and 3* Frou exaot onao acaaurcnento It vaa found that the formulas of tho colocul o poal:o 304 arid 330 voro Cv,, MOMS 202040 0- CUV35C14 "d 241 and 273 ore can be concludod that the parent don hen o preferential frasaeutation for tho lose of c oin^ls Clt'O unit* liaco npoctra were coujr.red with the epoctrun of a compound, isolated from toxic fat (rjootton i Com chene. 1?64) Subsequent ctuAy, tutins >t-rr.y diffrac tion, hc.o rove tied that the identity of ono of the ter.ic fr.ctorj was 7, 2 3 7, Lt 9"ii---chlorodibeneor-iio*in (Woottsr* i, t'rureUcnet 1964), i'ha ce.oo-spcctruji of t'.iiu coapovcd lisa a aimilax fra^Licntation pattern i.o. loot* of eu.ccoouivo 2 naso uuito Cl ou^jeots n, I033 of 2 CIO) units. ilicrocoulonetric analyses of tho Jrd fraction of Clophen end Ihoneclor xcvuoled oljouato^rana with tho smao poak pettcm as In fic.1. The ,,pcrn of tho toir-aciilorcdibancofurnxi (naas number *,04) io too narked by tho proximity of the hoxacliloionuphth-.'Jono pool', (peak no.2) to r.r.he quantitative calculations poouiblo. fur a ini lor i-oauon peak no *4 lu tho cl>rotuto^TaLi, found to be a fciixtuxe of ho pt &eb 10 robipher.yl rj:d poiitachlorodibcjiEofm-aij, could not le xcacurod direoily. iiouever, when uncurlin'; that the whelo punk Is produced by tho dibenaofuran confound alone, a curtain ouxinun level enu bo iudicaiod. Iliie level wtto found to La 5 ppn penticlilorculhu.co.'.'uiuu lu Clophcu and fio ppn in Hicnoclor. Houover the .sininuu level could bo Indicated with the oubiaated lower liuit of detection of tho unco spectroi.'otrie eqelpnont. Under the cot-ditic no usou this level was \ ppm. MOMS 202041 .a. Elccusiio". ; liaus cpoctxouctrio results have not conclusively proved the identity ot the chlorinated, dibensofurors Zat epathoaie of those coapoundu, aocoascry for conparlooh vith the naaa cpoctra obtained experimentally! was found extrendy doncerousi a single oral dose ot: 0.5-1.0 tri- and tctraciilorodibonsofuran caused oover*.' and often lethal liver necrosis in rubbito (bailor* JciulB i ofic^vltei'ot 1?6l* hofnan 193'3). Application on the oar of a rabbit resulted in chloracno (honor ct d.( lg(Jl)* Hie reiatod conpomd 2, ), 7, C-totreciilorodibonio-p-dio.tin (following the , description of Cheaieul Abctr.acto), ifaich nay eppoar in tl> ayn- thesio of 2, 4* 5-trichlorpheaol by hydrolysis (undor pressure end with the prcao.nco of ootliua tiydroxido >ond Esthonol) of 1 2, 4 5-tatxachlorotcnccno (favor ot al** 1j6l), usually ocuscl a lethal liver necreoio in tho rabbit after a circle oral dese of 0.05-0*1 ecAs* far cpplication, also in a 10 tins* lovor Uooe conperad with chlorinated dibouaofurrr.* reauljrod in chloracao (Taucr ct d* 151| Liiui Jor.ce ti Frisch* igdf). 1 2t37-?-hcr.a- chlorod.<bcnco-j>-dioxlnt which can arieo in tho pyrolycio of 2i5i46*tet'vchlorophcinol (111tcinbo than, Hucjic* lirectono, Venott* eoo i Campbell, IJ'CO), Tmo born lsolctod tnd identified co oro of tlio toxie robotoness of the Chick Codera Factor {'.'ootton 6 Couroncnc* 13<>4; inonyr.ue, 1960b). Tho relationship between tlio toxic nntuxo of PCD and tho Cklok Ccdona Factor has. nlready boon dioounuud (flick et ul. igCp)* dr cell injection in chichca occ'j of 0.05 lioaa- certrJLity chloroaiton:o-p-dioxin resulted in IOC1/; cnbryonic (lUccinbothcn 0' ot al* 1>6h). exporinent using an injection of the 3rd fppmt fmotion obtained'35 s<j Clophen into the air cell result?! In 100,' itov tel .Ivy (tablo 1), It ccui bo calculated that ths :ir.::i^uu HOMS 202042 10 dooo, jc lo 0.2 us pentachlorodiba .ofuraa (using a valuo of qox. 5 ppm). Thin confisas tbo order of toxioity discussed above The combination of toxicological, pathologieal and oboalcal analytical data caltoo It aluoot Oorttin that tho compounds of nass nunhern 304 and 330 oro rospeotively totraand pentaohlorodlbenzofuran. Tho origin of thoao toxlo fc-ctoro In Clophen A60 and Phonoclor DF<5 can pocolbly be orplainod by difforoncco in nonufacturo. Fartioularly in tho diotillation procodura of orude FCiJ, in which codiun liydroxido can bo ucod (Fay U Qichord% 15747)* PCD raaoto with Dodiuahydroxide at elevated tCsporaturos to yiold phonolio eoapounds* o.g. PCD ie eapoaifiod into polyolilorchytirorybiplionylo by ooono of oodiua hydrorido in a polyhydrie alcohol nodlun (Anonyauo, 1957)* A further loots of hydxochlorio aoid oould produco dibonsofuran derivatives* . Chlorinatod naphthalenoo oro for looo toxio than chlorinatod dibonoofurano (llsfnann, 1930). Thoroforo the lattor nay be asouaod to dotoxalno tho toxicity of fraotion 3* Tho occurrence of hydropericardium in chick fod vith Aroclor (Filch et ol.f 19^3)* Day lndicato tlio prooonco of a very email quantity toxic factor* From this otudy It is coneludod tliat ovaluation of PCD rosiduaa In vildllfo nnioalo, based A on effeoto and residues in tost animals, is ostrenoly difficult duo to difforonoon in toxioity botveon cotnorci&a FCfi preparations* V/ork is in progress to dotoot and identify ohlorlnatod dlbonzofuron from vildllfo opooiaono* HONS 202043 11 Acknoulad<TC moots. - Wa acknowledge tho contribution of Ur. E.V.a. Kasipsrdljk and Hr. P.P. lUjlzaop, and the toohnlool ooslstonoo of Ur. J.U. Pcanlr Thlc investigation woo oupported by a grant from tho Central Organization for Applied Solentifio Sonoarob (T.IT.O.) which mode it possible to accomplish the seas speotra onalyooo* HONS 20204* BafcrmcoL. -12 Anonyraia, (1557) Method for producing piouolio substenooo through tho treatacnt of chlorinatod diphenyl a end polyphonyla er.4 substances obtained thereby* Brit. Pot* 775* 221, duly 17 (to 1'rocil)* Anonyaua, (l?Co). Arooior Plastlolsers. Honeanto Coapany Teoh. hull, no* PL-306* Anonynuo, (l96Ga). Chances In Methods, 26* Clio, fata and waxes* J. Asa* Offlo* Anal. Choo. JL*. 403-490. Anonyauo, (ijfiob)* Tho clilch odoca faotor* huts* Bov* 26. 20-30* Bauer, B., Sohuls, K*I1* & Spiocolborg, D. (1961), Berufliok? Torcif- tuscsn be! dsx Earstollun$ tod Cblorphouol-Terblndlnaon, Arch. Covorbopath. Osworbohyc. 10* 530-535* flourao, B* L Hoad, C. (1369)* Stabird slauchtox* B.T.O. Howe, ed. by Kolth Clark for the Bxltlo^^or Omit!iolcy* no* 36* Fay, J.W.J. A Richordo, J.H. (1947)* Ioprecnentfl usad in German pepor capacitors. Offloe Tech. Sorv. PB xopt* 75059* BIOS Final flopt. 695* Flick, B.F., O'Doll, B.O. & Childo, V.A. (1965)* Studios of the chick edooa dlooaee. 3. Siailaxity of eynptoas produced by foedinc chlorinated biphenyl. Poultry Sol. 44. 1460-1465. BlCCinbothaa, G.H., Huanj, A., Flrootono, S, Tsrrot^ J., Bose, J. A Caapboll, A.D. (1960)* Choaical and toxlcolocicel evaluations of isolated uul cynthotio chiorodorIratires of dlbeazo-p-dloxln. Baturo, 220. 702-703* llofaann, n.Th. (1950). nouero ilxfohrun^oa Bit hoohtoxiochen - Chlorkohlenwacccrstoffon. Expexioontslle Fatholoclo Fharnokoloci' 232. 220-230. ' Bolden, A.7. A Harcdon, K (1967), Orpinechlorine pestleidoe In caals and porpoises* Uaturo 216. 1274-1276* NONS 202045 Holmeo, D.C., Sinnona, J.H. & Tatton, J.O'G. (1967). Chlorinated hyd. arbono in Britieh wildlife, xture, 216. 227-229. Hubbard. H.L* (1964). Chlorinated biphenyl and related compounds. Encyclopedia of Chemical Technology, ed. by Eller Kirk. R. A Othmer, D.F., 2nd rev. ed.. ^ 209-297. Jenoen, S. (1966). Report of a new chemical hazard. Hew Sci. 321 612. Jensen. S. Johnels, A.G., 01soon, II. & Otterlind, G. (1969). EOT and PCB in marine animals from Bwodleh waters. Hatuxe, 224. 247-250. Koeman, J.U., Oskoup, A.A.G., Veen, J,, Brouwer, E., Rooth, J., Zwart, P., v.d. Brock, E. 6 van Genderen, 8.,(1967). Insecti- cidoo ao a factor in the mortality of the sandwich torn (sterna sandviconoio. Iladed^RijksfacvLandbouwwetonichappen Cent, 32. 641-054* Koeman, J.H., ten Hoevor do Brauv, II.C. & ds Vos, R.H. (19S9). Chlorinated biphenylo in fish, muoasls and birds from the river Rhine and tho Netherlands coastal area. Kature, 221. U26-1126. ` Linn Jonso, E. 4s Krizok, H. (1962). A tcchnlo for testing acnegenic potency In rabbits, applied to the potont acnogon, 2,3,7,8,- tetrachlorodibenzo-p-dioxln. J. Invoet. Doraatol. 39. 511-517* IloCuno, E.L., Savage, J.E. & O'Dell, B.L. (19G2). Hydropericardium and ascitoa in chicks fed a clilorinatod hydrocarbon. Poultry Soi. iit 295-299. McLaughlin, J., Ilarliac, J., Verratt, H.J., Hutchler, H.K. & Fitzhugh, O.G., (1963)* The injection of chemicals into the yolk sao of Tertllo eggs prior to incubation ae a toxicity tost. Toxicol. Appl. Pharmacol., ^ 760-771. Hiller, J.W. (1944). Pathologio ch* anges in animals exposed to c oommorclal chlorinated diphonyl. Pub. Health Rep., 59. 1005-1093. moms 202046 -14aisbrouht B.W., aiocho, P., Penknll, D.3., Hgraim, O.C. A Klmn, li.H. (19^8). Polychlorinated biphcaylo In the global scooyotan. Nature, 220, 1090-1102. ton L'oovcr do Brauw, n.C. & BrumuSo, C.Z. (1367J fcreobniooo nit einor optinicrtcn ILoppldnj von Goa Chronatocrapb und Uaaceuopolctxuuotor. Icitaolix* f. Anal* Clion. 229. 321-355. Vorrett, I1.J. 1'nrllao, J. A HcLaufllilin, J. (1964). Use oX tho ciiiokon onbryo in tho aoeay of aflatoxin toxicity. J. Aoo. Offio. Act. Chen. 4JA;i003-1006, To Of J.G. 6 Jtooaon, J.U* (I970) Coaporative toxicoloeioel study with polyc3-J.orioc.tod biphenyl0 in obickono with opcaiol roforouco to porphyria, edena foxnatlon, livor nocrocln, mid tieeua rooiduoo. Toxicol. Appl. Fharuaool. In prooo* Wootton, J.C. A Courchono, V.L. (iyG4). A contribution to tho knoolcdco of tho otructuro of two hydroporicc-rdiun-producinj fnetoro froa a toxio fat. Act. Food. Chon* 12.-94-90. MONS 202047 Table 1. Chiakcn Enbryo A3 say of Chlorinatod Diphenyls Aroclor 1260, Plicnoclor DP 6 and Clophen A60 and tho 25 per oent Dicthylctkcr Prc-ctlon of Clophen A6Q. Group Compound Dobo/ogga Kimber Kur.bcr of Per cont Batoh Infertile Eggs of Fertile Egga Romrks 1 Aroclor 1260 2 Phenoclor DP 6 5.5 Dg 3.5 DC 3 Clophen A 60 5*5 mg 4 Clophen A 60 3rd fraction of 35 ff 5 Clophen A 60 6 Clophen A 60 7 Clophen A 60 * ft 3.5 nS 0.35 Bg 0.035nc 8 Ethanol 9 Control 15 15 20 15 15 15 15 20 20 0 0 1 0 0 2 2 2 0 00 0 5 0 7 92 100 94 90 Kant cnbryoo died during Irct half of lnoubatlon period. Moot oobryoo died during flxot half of incubation period. All cnbryoo dlod during first four day3 of Incubation porlod Host eabxyoo died during first half of incubation porlod. . *Th8 samples, dissolved in 0.05 ol othonol, verc injootod Into the airooll of fresh eccs before incubation. HONS 2020*8 Table 2. Retentione and Collected Hass Spectronctrie Rata of the Peaks in fiG*1> Poole no. Relative retention8. I loss nunber(s)^1, and number of chlorim .atona/rolec.ulG Identity of the coapound(e). 1 1.40 2 1.53 5 1.74 4 2.42 5 3.48 - 3C4(4C1) 332(6C1) 350(6Cl) 392(7C1) 358(5C1) 392(7C1) ' 5cG(7Cl) te trac hlcrodibenzofuran hexachloronaphthalene hcxachlorobiphenyl heptaohloro biphenyl pent&chlorodibengofuron e lieptachlorobiphenyl beptachloronaphtholene detention related to dieldrln - 1 ^tlaas number calculations baed on Cl - 55 HONS 202049 /97/ -------- ^"7 >I s HONS 202050