Document N2KKZydvv4ZGVrGya4aaeXdVw

C* ^ ' COM-72-10419 ^ Polychlorinated Biphenyls and the Environment Interdepartmental Task Force on PGBs Washington D.C. ' May 1972 010011 LEXOLDMON000384 WATER PCB-00035851 1 ' ---- ....... . inm-tt SH 010012 Distributed by the National Technical Information Service, U.S. Department of Commerce, Springfield, Virginia 22151. Price $6.00 LEXOLDMON000385 WATER PCB-00035852 M BtBLIOSRAPHIC DATA 1. No. SHEET ____________ JTF-PCB-72-1 4. iriilf tiui nrT PCBS AND THE ENVIRONMENT 7. AviMt) |9< P<r(Mmi<t| Ot(nti*d`an Nem tiul A^esi Interdepartmental Task Force On PCBs 3. Recipient's Accession Mo. CCM-72-lOlq? i. Keant Dm 20 Mar. 72 I. Pnlstmiflf Otj.niittion R*,<. No. ` -- 10. Projeci/Tult/Yoflc Unii No. 1). Contraci/Gtant No. 12. Sponioting Organizitjon Nmr ami Addteaa Departments of Agriculture, Commerce, Health, Education, and Welfare, and Interior; and Environmental Protection Agency; plus other participating agencies. 13. Typo of Rcpon t Ptiiod Ceoeted Final 14. IS, SopploiMnioty Noi* It. Abiiticta ~ Jills report is the product of a six month review of the chemicals known as PCBs-- polychlorinated biphenyls--by five Federal agencies, with participation by other agencies. The Interdepartmental Task Force on PCBs had as its goal the coordination of the scientific efforts of the Ooverment aimed at understanding PCBs and the strengthening of the Ooverment'a ability to protect the public from actual or potential hazards associated with them. The task force Riade nine findings, con clusions, and recommendations, primarily pointing out that PCBs should be restricted to essential or nonreplaceable uses which would minimize the likelihood of human exposure or leakage to the environment. Supplementing the 20-page report are eight appendices detailing current knowledge about various aspects of PCBs, including their use and replaceability) occurrence, transfer, and cycling in the environment! occurrence and sources in food; and PCBs effects on man and animals. 17. Key Tlt end Document Antlyzi*. 17 DtieriptArt (Pollution, Chlorine aromatic compounds, Biphenyl/chloro, Envirormental surveys, Insulating oil, Economic factors. Government policies, Toxicology, Public Health. 17b. ldcMiliett/Opfi-Eii4d Tn 17c. COSAT1 FicW/G<ouj> J^B, 6T tie AviiUbifity StitendH ro*M wyi* mtv. * 17. Secythy Cl (Tbit Rtpott) UNCLASSIFIED io. Sec.tity Chit* (thii Unclassified 21. No. of P** 192 22. Pie PC $6.00 osw 010013 LEXOLDMON000386 WATER PCB-00035853 Table of Contents Page PREFACE.................................................................. ................................ 1 FINDINGS, CONCLUSIONS, AND RECOMMENDATIONS........... ....................... 2 I. PRODUCTION, DISTRIBUTION, AND USE OF PCBs........................ $ II. CHEMICAL AND PHYSICAL PROPERTIES AND ` IMPURITIES................................................................................ 10 III. BENEFITS, UTILITY, AND ESSENTIALITY..................................... 11 IV. OCCURRENCE, TRANSFER, AND CYCLING IN THE ENVIRONMENT............ lti V. A. BIQLOOICAL EFFECTS ON MAN (METABOLISM, TOXICOLOGY, AND RESULTS OF HUMAN EXPOSURES)...................... ................... 1? V. B. BIOLOGICAL EFFECTS ON ANIMALS OTHER THANMAN.................... 18 i DSU 010014 LEXOLDMON000387 WATER PCB-00035854 Table of Contentst Appendices ESS , Contents and Authors....,................ 21 A. Chemical and Physical Properties of PCBs................... 22 B. Use and Replaceability of PCBs.................. hi C. The Need for Continued Use of PCBs as Electrical Insulating Liquids........... ............... 75 D. Occurrence. Transfer, and Cycling of PCBs in the Environment,...................... 83 E. Occurrence and Sources of PCBs in Food........... ................... .. 107 F. Human Directed Aspects of PCBs...,................................. . 122 G. Biological Data on PCBs in Animals Other Than Man............................................................................... 158 H. Regulatory Action on PCBs........................ .................................... 173 ii OSH 010015 LEXOLDMON000388 WATER_PCB-00035855 I Table of Contents (Continued) Figures Page Chapter I 1, U. S. Domestic Sales of PCBs by Grade............. ......... 8 2. U. S. Domestic Sales of PCBs by Category........... 9 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........... ...................... 31-36 1U0 lljl Tables Chapter I 1. PCB Manufacturing and Sales Data From Monsanto Industrial Chemicals Co. 19?7 trough 1971............*.......................................... Chapter III 1. Underwriters* Laboratories Flammability Ratings................... ...................... . iii DSW 010016 LEXOLDMONOOQ389 WATER PCB-00035856 Tables (continued) Page APPENDIX A 1, General Physical Properties of the Aroclor Clorinated Compounds........................ 26 2. Relative Retentions, Hass Spectrmetric Data on PCB Fractionated Sample................................... 30 APPENDIX B 1, typical Properties of Liquids Ii5-b6 2. Physical and Other Properties of Lubricating Oils, Engine Oils, and Hydraulic Fluids........ 3. High-Tenperature Lubricant %>eoiideations... ii. Some Properties of Punping Fluids........... . 17-50 56 57 5. Decomposition Temperature Ranges of Several Chemical Classes.......................................... 60 6. Approximate Maximum Compatibility, pbr, of " Plasticizers With Various Resins................... 7. General Properties of Some Aroclors (PCB)...... 61 63 appendix C 1, Composition of Different Liquid Chlorinated Biphenyls..................... .......................................... 77 2, Underwriters* Laboratories Flammability Ratings 3, Alternate Insulating Fluids.......................... 76 80 iv OSW 0100i7 LEXOLDMON000390 WATER PCB-00035857 Tables (continued) Page APPENDIX D 1. PCB Manufacturing and Sales Data from Monsanto Industrial Chemicals Co. 1957 Through 1971............ 8^-86 2. Concentration of PCBs in Municipal Sewage Treatment Plant Outfalls.......................... 88 3. PCB Concentrations in Industrial Effluents............ 89 b. Total Estimated Contribution of PCBs to the Aquatic Environment......... ............................................. 90 . Concentration of PCBs in Sewage SLudges........... 91 6. A Sailing of Measured Occurrences of PCBs in the Environment.................................. 93-98 7. Accumulation of PCBs by Various Aquatic Organisms.................. TOO APPENDIX ~ 1. Positive Analyses of Random Food Samples.......... 2. Positive Follow-Up Investigational Samples............. 3. Summary of PCB Findings in FDA Total Diet Samples. ............... ............... ................. ............... . h. Objective Samples - CT 1971 Fbr PCBs........................ m 112 H7 120 LEXOLDMON000391 WATER PCB-00035858 * Tables (continued) ' Page APPENDIX F 1. Subjective Symptoms Complained by Tusho Patients.................................. ....................................... 126 2. Oral Toxicity of Chlorinated Biphenyls........... . 127 3. Dermal Toxicity of Chlorinated Biphenyls........................ 126 b. Vapor Exposure Toxicity of Chlorinated Biphenyls................................................................................ 129 5. Toxicity of Arodors................................................ . 131 6. Pathologic Changes Induced by PCBs.................... ...132-133 7. Residues in Tissues of Rats Orally Dosed With * Aroclor 125b ($00 mg/kg).............................. ....................... 13b 8. Storage of Ar odors (In PPM) 2b-Hours After Oral Ingestion by Stomach Thbe..................... ......................... 138 9. Distribution of PCB-Derived Material Following 98-Day Exposure to a Dietary Level of 1000 PPM Arodor 139 ' 10. Distribution of PCB Levels in Adipose of General Population as Shown in Analysis of Hunan Monitoring Survey Samples Since April 15, 1971........... . lb5 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. Grim, R. W. Jennings and R. E. Linder.................... 150 12. Some Biological and Toxicological Effects in the PCBs...................................... 153 13. Possible Future Studies Involving PCBs, Their IndividualIsomers and Contaminants.. ........... 15b vi .. OSH 010019 LEXOLDMON000392 WATER_PCB-00035859  Tables (continued) . Page APPENDIX H 1. FDA Proposed Temporary Tolerances for PCB Residues......................................................................... 178 vii OSU 010020 LEXOLDMON000393 WATER_PCB-00035860 PREFACE On September 1, 1971* representatives of several agencies of the Federal Goveriment established an interdepartmental task foroe to co ordinate the scientific efforts of the Government aimed at understanding the family of chemical compounds known as polychlorinated biphenyls (PCBs), and to strengthen the Goverrment's ability to protect the public from actual or potential hazards from PCBs. On September 5 it was announced that the task foroe 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 units of five Executive Branch depart ments: Department of Agriculture; Department of Commerce (Assistant Secretary for Science and Technology and National Oceanic and Atmospheric Administration); Environmental Protection Agency; Department of Health, Education, and Welfare (Food and Drug Administration and National Institute of Environmental Health Sciences of the National Institutes of Health); and Department of the Interior (Bureau of Sport Fisheries and Wildlife). The report which follows represents the results of the task force's re view and reflects the position of the operating agencies of the Federal . Government 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 example, 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 Quail Roost Conference Center,. Rougemont, North Carolina, One hundred persons--from Government, universities, industry, and the press-- attended. The proceedings of this conference soon will be published by the Institute. The task force also met from time to time with a group of scienti fic advisors from outside the Federal Government, which was already at work prior to September 1971 examining a nurtoer of hazardous trace substances, one of which was PCBs. The individuals who served on the task force included: Dr. John E. Spaulding and Dr. Harry W. Hays (Department of Agriculture), Dr. Robert W. Cairns' and Dr. William Aron (Department of Commerce), Er. John Buckley ('Environmental Protection Agency), Dr. Lawrence Fishbein, John R. Vfessel, and Dr. Albert Kolbye (Department of Health. Education, and Welfare), Dr. Lucille Stickel (Department of the Interior), Dr. Edward J. Burger, Jr. (Office of Science and Technology), and Dr. Terry Davies (Council on Environ mental Quality). Mary others participated in some 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. 010021 LEXOLDMON000394 WATER PCB-00035861 FINDINOS, CONCLUSIONS, AND RECCMMENDATIQNS Polychlorinated biphenyls (PCBs) have been used in the United States and elsewhere over the past hO years, for many industrial and consumer applications* taring the past three years evidence has accumulated to indioate that PCBs are widely dispersed throughout the environment and that they can have adverse ecological and toxicological effects. The prinoipal uses for^PCB fluids are in the electrical industry. PCBs have superior cooling, insulating, and dielectric properties and hence are widely used in various electrical devices. Transformers and capacitors filled with PCBs can be used in inside 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 from the fire and explosion hazards associated with oil-Insulated and oil-cooled electric devices. Stability at high temperatures is another major factor in the attractiveness of these compounds. The principal advantage of PCBs over substitutes is the relative freedom from flammability in some applications that previously had been plagued by serious fires. PCBs also give electrical equipment the critical advantages of reliability*. long life, and compactness. PCB impregnated capacitors, for example, are markedly more reliable and longlived, and 1/6 the size, 1/5 the weight, and 1/U the cost of comparable oil impregnated capacitors. Small capacitors with PCBs have a use-life expectancy of 10 to 15 years, and large capacitors 20 to 25 years. PCBs in transformers are replaced only every 25 to 30 years. PCBs have been discovered to have a widespread distribution in the environment, and seme environmental occurrences have been associated with adverse effects on certain forms of animal life. Beginning in 1971, the Monsanto Company, the sole U. S, producer, has reported taking volun tary actions to reduce the volume 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 Administration and the food Industry have increased their surveillance to assure that PCBs are not used in food plants, products, or packaging. Ihe task force has reviewed all of the available scientific informa tion on various aspects of the PCB problem. It has found muoh data that it regards as inadequate and many questions that remain unanswered. But on the basis of available information, the task force concurs on the following findings, conclusions, and recommendations; . Sti 010022 2 LEXOLDMON000395 WATER PCB-00035862 1. PCBs-should be restricted to essential or non-replaceable uses which involve minimal direct human exposure since they can have adverse effects on human health. There currently are no toxicological or ecologi cal data available to indicate that the levels of PCBs currently known to be in the environment constitute a threat to human health, but additional experiments are underway to evaluate the impact of low level, long-term exposure to PCBs. 2. PCBs have been used so widely over such a long period that they are ubiquitous. Even a total cessation of manufacturing and use of PCBs would not result in the rapid disappearance of the material, and ultimate disappearance from the environment will take wary years. The elimination of non-essential uses and prohibition of discharges fbora 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 involves accidental contamination of food from leakage or spillage of PCBs into feed or directly into food. The dietary intake of PCBs is of lew order and does not present an imminent health hazard. fo date, all of the high levels of PCBs encountered in human or animal foods have been associated with accidents, 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 o? J'CBs into the food supplir and to reduce the current levels of PCBs as food and environmental contaraina utfl. The Food and Drug Administration (FDA) has acted, under the authority of the Fbod, Ibug, and Cosmetia 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 deleterious substances that may migrate into the food if the contamination by such substances is deliberate or avoidable. It has proposed temporary tolerances for unavoidable PCB residues in food packaging materials and in certain foods. The Department of Agriculture has acted under the Wholesome 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 use or distribution of the chemical, to control imports, and to collect certain types of information. The task force believes that such authority is needed. This authority would be provided by the Toxic Substances Control Act proposed by the Administration and now pending before Congress. 3 010023 LEXOLDMON000396 WATER PCB-00035863 f>, Housekeeping Is particularly important in the manufacture, use, and disposal- of PCBs. Under a program of limitation on the sale or PCBs, the electrical industry will continue to be the principal user of PCBs* 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 as possible, and in any case below FDA's interim action level of $ parte per million, concentrations in rivers or lakes from all sources should " not exceed 0.01 parts per billion. 6. The use of PCBs 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 PCBs in transformers and capaci tors presents a minimal risk of environmental contamination. The Monsanto Company, the sole domestic producer, has reported voluntarily eliminating its distribution of PCBs to all except manufacturers of electrical trans formers and capacitors. . Pending passage of the Toxic Substances Control Act, the Federal Government 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 Goverment does not have the authority to control PCBs at their source. 7. Most capacitors presumably have been disposed of in landfills. PCB containing material buried in soil is 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 disposal such as high-temperature (at least 970C) incineration must be used instead. 8. PCBs are manufactured in countries other than the United States, importation of PCBs as a chemical or as a component in psoduots remains legally possible because the Toxic Substances Control Act has not yet become law. Electrical products imported 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 PCBa 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 Organization lor Economic Cooperation and Development (OECD) through its Environment 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 states plus Japan and Australia, has been giving priority attention to the problem of PCBs over the past year. 9* More scientific Information about PCBs is needed, and several Ooverrment agencies are seeking it through research. The task force recognizes that ihe scientific basis of much of our knowledge must be v ^ DSW 010024 LEXOLDMON000397 WATER PCB-00035864 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 bodymust 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 PCB3 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 environment. Continuing vigilance on the part of Government agencies, industry, universities, and many other agencies both within and outside the Government 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 Governoent laboratories as well as a number of non-Government scientists recently have embarked on additional research on PCBs, and the results will be communieated to the scientific public completely and promptly through normal channels such as meetings and journals. I. PRODUCTION, DISTRIBUTION, AND USE OF PCBS 1 Polychlorinated biphenyls (PCBs) were first manufactured commercially in 192?. Ejy virtue of their unusual chemical and physical properties, they achieved widespread use in a variety of applications. PCBs are now manu factured in Oreat Britain, FVance, Germaiy, 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 Company, and marketed under the tradename "Aroclor". Table 1 gives a breakdown, by category of use and by type of PCBJ of the total U. S. production, domestic sales, and U. S. export sales from 1957 to the 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 $00jCOO tons* (l) Corresponding data on production and use of PCBs outside the 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. vaa marketed domestically. Between 1963 and 1971, the pro portion of the production which was exported averaged 13 percent. In 1971, the Monsanto Company reportedly undertook a variety of voluntary restrictions on the distribution of PCBs to various categories of industries. Both St* 0l005 LEXOLDMON000398 WATER_PCB-00035865 FCB. MANUFACTURING AND SALES DATA FROM MONSANTO INDUSTRIAL CHEMICALS CO *CM, ucsn r*N o CCO'N CD UN \D, UN cf<o\ $On XA C^* ca t- \A rH CM ^3 V\ i--< CO OCQ CM BHCKnO CN f\ Ov nrl C^\ACO I O -3 rW UNCO H HO PNCN l4i--Ni VH>C1M A0\OO\ I O-iJ-ac^UNUNCMQ r3- CCMM UUNNnO-----C--M---O---n---O---N-- H-- -3 r*NUN-3CM i*NNO'NO gm 4ril^ rN-3 O WOO On -3 CNI CM On -3 >g UN CM CO O CM UN nS H HOn-3 NO no CO r*N UN , CN nO CN| o o 0Q} o 50 o\ -H4 51 CA VcmA cnos h r--3 CM UN CM NO 3 UNUNOn On CM I CM t-4 C--nO NO JCM fC'N rNUNvoO-COONOON OUNONCMCOrOCMCO H r-l r-l CO O N C'N i-< Cr-Ol CM NO C- CM UN f*N UNO\4fO\*N OO \Q CD Ov f- ONNO UN On-3 UN Pm |PCM H VNvq-If n s fO H NO f~t ... HCM JOUn UNN HOnOOnnO^n UNSUp-\O_^ O(An I nO(*N-30\HCM.3CM H JJ-3 UN On OO CO t" LJ 3 UNNO On H ~ O. CM n) UN H NO CM ,k *Ov Ov CM CM CA CM_5JT\0O r-l P VNCM NO C^ On O l-t CM r HH ICN CNNO CM ON r- O- H CM On CNI r-- vO CO CN H OCM HC-J-3CUN- On On CM CM C'N rMCNJCNICO-SOCNICO CM fN-3 J UNnOnOnO ssssasss ho oht ohho ho ho ho jaj OOOOOOOOOOOOOOOO azzaMnaz 7-pl pt-< 8 r-t CM LEXOLDMON000399 WATER PCB-00035866 66 t OsB\* vOpIa\ucOaI\ MM -a n 4HH irwj vr O OnO u\m in CO(SH c*-a-a CO On CM mri 'Q ^Is->nr*Ho ^vo H V>rin CO H CM OllAH COO rH d\| Sm-Sa *3. Hi V><MCO p-- o 0\00 CM 4j-\r> CO O co oC u\3\\o O in o a ooft-n3 saa /~N s Ce/>3 66 OO n *n iit I VN\A CM CM I cOoCanCf'O-CcOvXoAfoM , c\Cro\Nco-naeco^vcccoom cco^o \t<a*n- nr* Oj i O On OnU\CM O On lArng-q ocncoo oH ChJ Voc\mM3-^---3--- ONlAmiAO-3 UCM\NNp CNO VCO\VW>OJ MlAHrj NiO jo t-- N JHrt Os <*\ I HWH nQp0lA0f0-r\tOoOJOrOt r^o h onO nrt4U\4 On SSSigfcS CM H OCMn-Na ONnONn 4p*Ncn 4HNO|0On rA vO, On UN <n I iv yv. R^P" -3 I vO If ^psOOHooOrf-^OHJOa-Pf>s"ir"0) ^Nss^sr r M Oo / o o m-a o o Os UN On h cm On X/N Cm QO COCO OO CM t*** CM 44COU\ -camCuMn vVnN-OaOnoNrH~-aoCcO- 4 O t^-NQ 4 00^ <n a v vq n o0^Nt*-mVHmVVUUNoNNtm^hI-S*cHVOnC\uOO\IONAONH n pnH o UN NO o JK HS COCO n4 On UN cnuNNO co <vl *aagaii cCoM CO UN UN r- H CM CM CO-Cj O CM OO IM n44VN%D NO vO ssssspisa oooooooo HHHHHHHH OUOPOOOO OOOOOOOO 4S<33<3<<< LEXOLDMON000400 WATER PCB-00035867 CO > c; o co Ll) _I < CO o CO u.t s o Q CO FIGURE |.US DOMESTIC SALES OF PCBs BY GRADE The uppermost curve represents the total sate Freni Ktsbetj X#C*T*j end Saroflnif A*F# (I) OSM 010028 LEXOLDMON000401 WATER PCB-00035868 DOMESTIC SALES ( 1 0 ' lb s ) FIGURE 2. US DOMESTIC SALES OF PC3s by CstOpOPy (The uppermost curve represents the total sales.) From Hfsbet, I.C.T., and Seroflm, A.F. (1) 9 OSH 010029 LEXOLDMON000402 WATER PCB-00035869 production and sales figures for 1971 were roughly half of those for 1970, when these volumes were at their peak (Table 1 and Figures 1 and 2). Pro jections for 1972 indicate an even lower volume. Prior to 1971 about tiO percent of the PCB material in the United States was used in applications where containment was difficult and losses into the environment were probable. These uses included plasticizers, hy draulic fluids and lubricants, surface coatings, inks, adhesives, pesticide extenders, and microencapsulation of dyes for carbonless duplicating paper. The remaining 60 percent of domestic sales was used mainly in electrical applications (transformers and capacitors). In 1971* this fraction is ex pected to have reached 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 up..the majority of the products produced. Frcnt the flares in Table 1 it can be seen that Aroclor 12li2 and grades with lower percentages of chlorination characteristically composed one half or more of the total production between 1963 and 1970. The largest categories of use of PCBs have been in capacitors and transformers and in certain "plasticizer" applications including carbonless duplicating paper. A large percentage of the production of Aroclor 12b2 went into these three categories of products. (2) The major uses for PCBs prior to 1970 (in the order of importance as a reflection of the volume of material used) were: Capacitors Plasticizer applications Transformer fluids hydraulic fluids and lubricants 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 products. The degree of chlorination determines the chemical and physical properties of the Arodors; the first two digits of the numbered Aroclor represent the molecular type, the last two digits the average weight percent of chlorine. Their physical state thus varies from colorless, oily liquids to more viscous and increasingly darker liquids to, in the hitter series, yellow and then black resins. The PCBs are not readily biodegradable. They resist breakdown by water, adds, and alkalis and have boiling points ranging from 278 to h75C. Analytical Techniques Whereas in the past it waB difficult to identify PCBs in the presence of other organochlorine compounds such as DDT and DDE, they can now be separated from interfering ccmpounds and identified and measured by means of thin layer aw! gas liquid chromatography at levels less than 1 part DSW 010030 LEXOLDMON000403 WATER PCB-00035870 per million in food and at 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 microcoulometric detectors. Contaminants and Impurities ._ The starting materials used in eynthesis of PCBs determine to a large degree the type of inpurity on contaminant in the commercial product. The contaminant variation, of course, renders some divergence in the LD 50 values or other toxicologic response of the PCBs. Fractionated sanples of seme PCBs of foreign manufacture have shown them to contain as contaminants the tetra- and pentachlorodibenzofur ans, the hexa- and heptachloronaphthalenes. Further work is needed to ascertain whether additional impurities or contaminants are present in the various U. S. 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 . III. BENEFITS, UTILITY, AND ESSENTIALITY The task force reviewed the several categories of uses oo which PCBs 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 four major types of applications examined were: 1. Dielectric fluids for capacitors and transformers. 2. Industrial fluids fbr hydraulic, gas turbine, and vacuum pump uses. 3. Heat transfer fluids. h. Plasticizers and miscellaneous uses. ' This review of utility was undertaken by the National Bureau of Standards. The review was materially aided by information from the National Industrial Pollution Control Council and from 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 they can be used as fluids at temperatures up to 700F without the danger of explosions and fire. The major disadvantage of the PCBs is their toxicity and environmental contami nation. . The other ccnparable class of non-flammable fluids is the fluoro carbons, which typically have a lower vapor pressure and lower boiling point than the chlorinated compounds. 11 DSM 010031 LEXOLDMON000404 WATER_PCB-00035871 Electrical Uses PCBs are used in fluids (known as askarels) for electrically insulating and cooling transformers when the transformers are used in or near buildings. Being virtually free of fire and explosion hazards, PCBs can be used where failures of oil-insulated 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. 0 Table 1 Underwriters* Laboratories Flammability Ratings Fluid Flammability Rating Ether Gasoline Ethyl Alcohol. . Kerosene (100 F.P.) Mineral Oil Aroclor 12li2 and MCS 1016 100 90-100 60-70 30-1(0 10-20 2-3 PCBs are used in transformers wherever fire protection is particularly important--for about 5 percent 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 the equipment. The amount of Aroclor used in various types of transformers ranges from hO to 500 gallons (5l6 to 6,1(50 pounds) with an average of about 235 gallons (3,032 pounds). During 1968, the last complete "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 (8.1) thousand tons). The 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). Mineral oils are the preferred fluids when fire does not create a hazard. Dry 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 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 compati ble with equipment and installation requirements. 12 DSU 010032 LEXOLDMON000405 WATER PCB-00035872 Almost 80 million PCB-impregnated capacitors are manufactured annually, most of them for first-time vise. The principal types are high voltage power capacitors used primarily for power factor correction in the distribution of electric powerj 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, etc. Capacitors used in lighting and air conditioning applications contain 0.0005 to 0.0? gallons of PCB per unit. The largest power capacitors contain about 6.7 gallons of askarel. The National Electrical Code requires that any installation of capacitors in which ary single unit contains more than 3 gallons of combustible liquid shall be in a vault like that required for ' transformers. During 1968, the last complete "normal" year for the electri I cal industry, the amount of PCBs used in capacitors was approximately lit.b thousand tons. Possible alternatives to PCB-impregnated 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 I 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, but substitute fluids are available. Oas turbines require lubrication at high tenperatures. PCBs can be used but 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 punps, bul non-flaramability is not especially important for diffusion pump liquids, and alternative liquids are available. Heat Transfer Materials - Flammable heat transfer fluids present a fire hazard if they leak into a fUrnace or onto hot surfaces. The use of PCBs prevents this danger. In sac cases water is a suitable substitute at moderately high temperatures, and other satisfactory heat transfer fluids are commercially available and in use. Plasticizers The PCBs are good plasticizers for use with adhesives, textiles, surface coatings, sealants, and copy paper. In seme oases the PCBs act as fire re tardants. There are no unique properties of PCBs for plastlcieer uses, and equally effective alternatives are generally available (e.g., phosphate esters are often used as fire retardants). 13 010033 V ' < LEXOLDMON000406 WATER PCB-00035873 IV, . OCCURRENCE, TRANSFER, AND CYCLING IN THE ENVIRONMENT Given the diversity of uses, of PCBs and their chemical characteristics (greater 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 certain that PCBs do reach the environment 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 being released to the atmosphere unchanged. ~ Vaporisation from paints, coatings, plastics, etc. (Nisbet and Sarofim, 1) estimate that as much as 20 percent may be vaporized. -- Municipal and some industrial sewers (PCBs present in treated as well as untreated wastes). -- Accidental spills 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). -- Dunping of sewage sludge, municipal and industrial solid waste, and dredge spoil at sea. -- Sewage sludges disposed of on land. -- Migration from surface coatings (paints, ato.) and packaging materials into foods and feeds. Probably the largest amounts of PCBs circulating in jhe environment reach it through industrial and municipal discharges to inland and coastal waters. The recommendation by the task force that "more scientific information about PCBs is needed" is illustrated by the sparsity of knowledge about PCBs in the environment. Only general statements can be made about how PCBs reach the environment, how they reach target organisms, and how much is present. Miebet and Sarofim (l) estimate that the total loss of PCBs into the U, S. environment over the last LO 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 dunps. DSW 010034 LEXOLDMON000407 WATER PCB-00035874 Thousands of envirormental and biological samples have been analyzed for the presence of PCBs. One or more of the FOB conpounds have been de tected in all environmental media, and in many organisms. Water Ihe 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 envirorments suggest accumulations at the downstream ends of the drainageways. 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 the lipids of animals. Also like the chlorinated hydrocarbon insecticides, they resist metabolic changes, and tend to be concentrated at exceedingly higher levels in animals hitter in the food chain. The higher chlorine PCBs are the most stable. Occurrence and Sources of PCBs in Food The identification of PCBs as a potential food contaminant was first reported in 1966. Subsequent investigations, including the development of analytical procedures for PCB3 in foods and their incorporation in Federal programs for monitoring the nation'e food and feed supply for pesticide residues and other chemical contaminants, established several sources from which foods may become contaminated with PCBs. Environmental Contamination of Food 7"L" -- ~ *9 PCB residues in fresh water fish appear to be widespread geographically as a result of the environmental contamination of lakes and streams. Depending upon the location of saspling and the species of fish, PCB levels generally range from 1 to 10 parts per million. Foods of animal origin, such as meat, poultry, eggs, and milk contain, in some instances, low background levels of PCBs that may be attributable to envlromental contamination. Industrial Accidents The widespread industrial uses of PCBs have resulted in a number of identified isolated accidents involving the direct contamination of animal feeds, which, in turn, caused human food to become contaminated. t -- Poultry and eggs became contaminated as a result of the leakage of PCB heat transfer fluid during the pasteurization of fish meal (poultry feed component). 1? DSW 010035 LEXOLDMON000408 WATER PCB-00035875 -- 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 febd 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 migration 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 containing PCB carbonless ncarbon" papea. is the prime source of PCB in paperboard pro duct. Virgin paper products, however, have also been shown to oontain 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 IDA'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 consunption approximately twice as high as the normal diet, was less than 0.0001 in FY 1971 and 0.0001 in the first-half of FY 3*972. As a point of reference, from 1965 to 1970 dietary intake of DDT was 0.0007 mg/kg body, weight/day. Other investigations further disclose that except for unavoid able background levels in certain foods, 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 mierograms 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 per 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 DSM 010036 16 LEXOLDMON000409 WATER PCB-00035876 one trillionth of the distance to the moons and a part per million is about 5 steps on a walk from Washington to San Francisco. 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 have 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 75,000 times that present in the water, and to be accumulated from concentrations as low as O.Co parts per billion (the lowest concentration for whit* experimental data are available). Thus, to keep levels in fish as low as possible, and in any case 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 Dart ner billion, or to allow some safety factor, 0.01 ppb. Ibis level in water should be sufficiently low that fish and shellfish are not themselves adversely affected. Existing 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. These 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 cam9 from used carbonless carbon paper, which is no longer used in making food packaging material. V.A. BIOLOGICAL EFFECTS OH MAN (METABOLISM, TOXICOLOGY, AND RESULTS OF HUMAN EXPOSURES) Human beings occasionally have been exposed to high levels of PCBs. Some exposure has been the result of occupational experience 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 fish 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 burden of PCB in their fat tissue. In contrast to the ubiquity and levels of DDT and its metabolite, DEE, in humans in this country, the current levels of PCBs do not appear to be as uniform in distri bution. At the levels in which they are found, PCBs do not appear to present an imminent hazard. 17 OSM 010037 ^ LEXOLDMON000410 WATER PCB-00035877  The acute toxicity of commercial PCBa in experimental animals appears to be low. In the case of the human exposure with the Yusho episode, the . average dose to that exposed population was calculated as 2 gm. From this incident, it was estimated that the minimum dose necessary to produce posi tive clinical effects was O.J> gm. With a sufficiently high dose it is possible to distinguish a number of toxic actions of PCBs and their contaminants in mammals. 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 bydrpericardium (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 embryotoxicity and mutagenicity, however, are poorly studied and, hence, are ill-defined. Because of the possibility of human exposure 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, metabollsn, and excretion of the technical PCBs as well as a num ber of key isomers and the chlorinated dibenzofurans. - 3. Elaboration of the subcellular and intraoellular actions of the technical PCBs as well as a number of representative isomers and chlorinated dibenzofuran s. b. More definitive epidemiological studies of the PCBs with both more representative population sampling and standardization on the basis of lipid content of the' tissues. V.B. BIOLOGICAL EFFECTS ON ANIMALS OTHER THAN MAN 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 be lethally toxic to some fish and aquatic invertebrates when concentrations in the water are parts per billion or less. They are metabo lized and excreted very slowly by these organisms. 18 DSM 010036 LEXOLDMON000411 WATER PCB-00035878 They are only moderately toxic to birds and raawmalsj lethal levels are similar t those of DDE. PCBs may have contributed to direct mortality of some adult birds in the field, but not to an extent to affect populations. In sublethal exposure, PCBs are physiologically active and induce enzyme activity. Direct effects on reproduction have been shown for chickens, but not for ducks, quail, or doves. Some studies tentatively suggest the possibility of subtle behavioral effects and of interactions with disease organisms or other environmental chemicals. - Rill evaluation of actual or potential effects in the environment is hampered by the complex nature of the mixtures that compose PCBs, and by the inclusion of contaminants in these mixtures* As experimental studies have been conducted with the unaltered products, as sold, the results may not properly reflect the effects of the components as they exist in the environment. Although fully conclusive data are not available, the evidence for toxic and physiological effects indicates that the PCBs must be viewed as potential problems at present environmental levels. 19 OSM 010039 LEXOLDMON000412 WATER PCB-00035879  FOOTNOTES 1. Niabet, I.C.T., and A.F. Sarofim, "Rates and Routes of Transport of PCBs in the Environment". Paper delivered at International Scientific Meeting 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 Monsanto Company. $W 01004Q LEXOLDMON000413 WATER PCB-00035880 APPENDICES / Contents and Authors Page Chemical and Physical Properties of PCBs H. F. Kraybill Food & Drug Administration Department of Health,'Education, and Welfare 22 Use and Replaceability of PCBs Martin 0. Broadhurst National Bureau of Standards Department of Commerce 1)1 The Need for Continued Use of PCBs as Electrical Insulating Liquids Electrical and Nuclear Sub-Counoil National Industrial Pollution Control Council Department of Commerce 75 Occurrence, Transfer, and Cycling of PCBs in the Environment John L. Buckley Environmental Protection Agency (with assistance of Edward Greening, EPA) 03 Occurrence and Sources of PCBs in Food John E. Spaulding Department of Agriculture John R. Weasel Food & Drug Administration Department of Health, Education, and Welfare 107 Human Directed Aspects of PCBs "* 122 Lawrence Fishbein National Institute of Environmental Health Sciences Department of Health, Education, and Welfare Biological Data on PCBs in Animals Other Than Man Lucille F. Stickel Bureau of Sport Fisheries and Wildlife Department of the Interior 158 1 Regulatory Action on PCBs Terry' Davies Council on Environmental Quality Executive Office of the President 373 21 OSM 010041 LEXOLDMON000414 WATER PCB-00035881 f*\ ICVJ 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 III. Contaminants, Inpurities, or Other Chemical Moieties in PCBs Tables 1 - Oeneral Physical Properties of the Aroclor Chlorinated Compounds 2 - Relative Retentions, Mass Spectrometric Data on PCB Fractionated Sample Figures 1-6. Chromatograms of various representative PCBs, according to Armour Page 27 27 29 37 26 37 31-36 22 OSW 010042 LEXOLDMON000415 WATER PCB-00035882 APPENDIX A Chemical and Physical Properties of PCBs I. Chemical and Physical Characteristics Hie PCBs (trade name Aroclors 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, plasticisers, hoat 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 concern about extensive environmental contamination by the Aroclors, have recommended discontinuance and curtailed uses in equipment or products which inadvertently lead to con tamination of the environment (food products, potable water supplies, and as an air pollutant). Presumably the history of the polychlorinated biphenyls 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 awareness of the environmental contamination came about with the realization that after 1<0 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 fact that PCS has been found in fish and birds in their surveillance in 1966, and soon this alerted investigators in other countries to the problera. Surveillance of total diets by FDA failed to report any PCB in fruits and vegetables. a Perhaps the accumulation of PCBa in environmental substrates or living organisms can be associated with the particular chemical and physical proper ties of these series of synthetic ohlorinated aromatic compounds. For example, the nonenrironmental degradability or biodegradability accounts for it as a 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 concentrations. 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. (Widnark, 1), -vdio made Ms calculation in developing XX XX criteria for these limitations, noted that the criteria were bassd on com pounds containing five to eight chlorine atoms per molecule and the number of chlorine atoms per ring differing by not more than one. The Aroclors may consist of chlorinated biphenyls, chlorinated terphenyls, or a mixture of these compounds. Invariably, although a specific numbered Aroclor may represent a molecular type and degree of chlorination or weight percent of chlorine, the product is a mixture of compounds in a series such as 1200, 2^00, MOO, and J&00. The first two digits represent the molecular typo. 23 OSH 0100*3 LEXOLDMON000416 WATER PCB-00035883 and the last two digits give the weight percent of chlorine. For examples 1200 - chlorinated bipheynls 2500 - blend of chlorinated biphenyls and chlorinated triphenyls (75*25) hbOO - blend of chlorinated biphenyls and chlorinated triphenyls (60:h0) 5b00, - chlorinated triphenyls . Thus Aroclor 12b2 would be a chlorinated biphenyl containing b2 percent chlorine. These biphenyls produced by Monsanto range from 21 to 68 percent chlorine. To refer back to the existence of many possible isomers, it is of interest that Aroolor 1260 would show the presence of 11 isomersj five containing six chlorine atoms, five containing seven chlorine atons, and one containing eight chlorine atoms (2). Bagley, et al, (3) studying Aroclor 125h, observed 18 distinct conpounds. However, as previously stated,the num ber of conpounds present or identified by mass 3psctrographic studies is much less than theoretically deduced. The polychlorinated biphenyls which are chemically inert were described in the literature back in 1881 by Schmidt and Shultz (If) but achieved by Swann Oompany in 1930 and fblly developed for industrial use in that year. During the IfO-year era, 1930-1970, it was discovered that Aroclors could be used to extend the effectiveness or lethality of organochlorine insecticides such as chlordane, aldrin, and dieldrin in pestlddal formulations, thus enhancing the possibilities for proliferation into the environment (). Additionally, there were indications that PCB had a synergistic effect on lindane (6). The Aroclors, as previously stated, are chemically inert, making them ideally suited for certain industrial uses. They are not hydrolysed by water and resist alkalis, acid, and corrosive0chenlcals. Since they are not volatile, their boiling points rang9 from 278 C for Aroclor 1221 to li5lC for Aroclor 1268. They are stable to long heating and c^n be distilled at ordinary pressure without any carbonization or decceiposition. As might be expected, since they are insoluble in aqueous media, they are quite soluble in hydrocarbon solvents. It is believed that PCBs are more stable than DO? and metabolites and, accordingly, resistant to biodegradability or biological decomposition. The proximity of the aromatic rings probably accounts for the lack of degradation of transformation as with DDT, which has an ethane linkage intervening the aromatic Traciie. PCBe and formulations thereof have a wide range in viscosity and physi cal state, from colorless mobile-like oily characteristics to yellow-green clear mobile oil, to light yellow viscous oil, to light yellow soft sticky resin, to white powder, to light yellow clear brittle re3in, 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 make them versatile for industrial uses. Many of these OSW 010044 2h LEXOLDMON000417 WATER PCB-00035884 PCB preparations 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 problems of contamination of certain food products. A rather complete compilation of these properties is listed in the attached table from a report by Monsanto Company. 25 OSH 010045 LEXOLDMON000418 WATER PCB-00035885 yTbi* or ctui, musical yitoocimra or ft* mncuii CH.OH1HH7F3) cwpomos ftroctw 1??1 xsMlt oil JO Hir. (Am) Aridity. Ha*lNn (tpw* WH per Oft,)..,.,., 0.011 Average CftffficlfTt or xnar.alor.*..cc/ee/'C 0*00071 OSp-W*C) Typical IVjJty DlatlllaUa- 3W [>-?0 (M-jd.) Crrr. "C.................................. ................................ l.m-i.iw (75/t5.5C) 9.05 * FTf-iFO0 Fvafrtratlo' fx*A - f - A5W P-^Mod. If/C..............................................................S hfi. 1K>"C........... ....................t hr. 0 Waxh pci*.t * Cleveland Op*r Cup,....... 1.0 u 1.5 rtt- jo? li t f.*it - Clmlt'iJ (We Cup..*.,. C f sw Pir feint . *!W D.*7.................................... *C f Scrif ll* Polf 1 - 5TK t-7t.......................... *G F Refreciivr Index- tMi*r ....... CtyaUla it 16C Crriltli it 1Lh 1.617.1.610 Vlarn.lljr - S*ytw>l 1 ll'twaraal !H*T ($6.9**C> JO-Jl Srr. (S - ) i&r eri.i,c) 35-57 1P0*F (3?.SC) fc-il Araeloe 1237 Poetically iteMlt ell 50 Max* Cama) O.PIIi 0.00073 (7*-lC0*C) 1.170-1.760 (jt'vis.y'o lO.PS 3W.)7S 3.9 to 1.5 X* `310 738* WO -35.S" -37" - 1.170-1.677 31-37 39-Ll bb-n Ataclor 17t2 Practically nettle on <>*) 0.010 0.00069 (T55- 65*0 1.301-1*397 <75/15.5C> 3.0 to 3.6 0.0 to o.i 17f*.l#o' 316-356 K0M _ -i * 1 .iZUlM 3b-35 b-S6 97.97 MCtit Indicates-"Ko Hr# paint p to **151** tnffriUff Orl IKo-rtt* (wrox.) - nf/tef J9fi0 UiTO* W50. SHi KM> rabbit? >('*( AtlMnrrH 7000a 3ieo* >!?> <70000 ?! <1760* HltJlhM *-=Wlr:letrrrd M 5Of wl 4r. corr oll#33l/)ff in wr. oil 701 ooln* in corn oil. Areeler 17V0 Colorless to lifht yellow. mM1 oil 50 Max. (im) 0.010 0*00070 (75-65C) i.bos-i.bis (fS"'15.5*C) 12,OC 3W-)7S* 3.0 to t.O 0.0 to 0.3 i}0-mo 379-3&b" Rone -7 19.1^ Arcelor 1751 L1|M yellow tilCOUl oil Arocl :ttn LlfM 1* Mf ort sticky $Haa. (ATM) (tfIM) 0.010 A.000& ~ (75-65C) o.ou o.Qitf * (70*.ior?) lV9$-1.505 (65/15.rc) 17.67 l.55S-).5tt 3<5B-3H>0 ` yis^uo0 1.) to 1.3 0.0 to 0.7 0,5 t> O.P 0.0 to 0.1 tone Hose Ifer* 10* so* Vne 31* M* - 1.630-1.(31 36-3 73-60 ies-?M> - l.tjw.ai Mr-W 760* 3W J0OO-XOO - 1.H7-1.6L9 77-76 3700.1510 - ll.OOOt ** 79li* 11,900* '1760* 2000* fti 10* eolit. in ro'n oil. 10,000* **176*>* H OSH 0100*6 LEXOLDMON000419 WATER PCB-00035886 Arc)*r 67 Llfhl I'D* UeVy eJ#*r twin 50 Hu. UWU) O.Oll 0.00l t?S-65C> 1.5M-1.5BJ CW/1S.5C> 13.73 its'-ms* 0.5 to 0.6 0.0 to 0.1 Mont irwlff thiu u 1.5 Xu. m (MlUn) 0.0$ 6.Ntt)----------------(TO*-100*0) l.MLM.hl---------(!5*/15*C) 15 .Of l3S-t50* 0.1 U 0.2 0.0 U 0.06 Mom ' Mom w - 150'to 1KT l!2lf.nU. (iMio pi.) (6-100 600-850 (|607 or 71C) - Aroclor Mt6$ U|HUpnotr elr. brlttl* ruin Aroclor 5bU THw Mm* prt itlekr ruli AtMlov Sb60 OMr, Tvllew. U.tmbvr, Wittl* t*9tn r*lw 7565 Kick, oplqut brlltl* mil 7 Hu. XfA (uelUn) 0.0$ (75^/lSc) 19.91 ? Hu. *A (uolUn) 0.05 e) 1.M0 SSP'w ins. IH (aolton) 0.05 0,0017? ^ {$-12lC> * {15^/25*0 u.n 1.1 0.00046 (2?-65t) 2J0*-J2OP . 11 L m. Hr. 0.2 to OO 0.0 to 0.02 Mom Mom __ ___ Ji5-300 t 1 ...______ Mo-3 tUgiA 0.2 O.OJ 0.01 1.S to 1.7 . (it HO-* Ora.) 317 177* Mom T& Mem 0.2 t* OO Mom Km $$to*l51 1.661-1.667 l$r 130*0) u<* sva- 300.100 9flto lOS.f 6*to 227* 1.660-1.665 - * to 77 . U7*to 167* - - U,J00** rl?6DM ))60m 10,900** 16,000m 2000m <Ol60 10,600h rl!(OK OOOOm u.ioof *7170. 6,31067 .new <3160 26* OSW 01004? LEXOLDMON000420 WATER PCB-00035887 II. Problems in Analytical Chemistry - Comparison of Methods II. 1 Separation One of the primary and early problems in the identification of the polychlorinated biphenyls (PCBs) was that of possible interference in the OLC determination of organochlorine pesticides, where the PCB occurred along with the pesticide residue. During 1969 and 1970, various investigators worked on methods for separating PCB from pesticides (7-lii). An excellent treatment of the subject of PCB as a contaminant in the environment, as ' related to its detection in t)je presence of other compounds, is covered by Jensen (15). Jensen (l5), in his review, has shown that some of the earlier studies of DDT and DDE in human fat by OLC must have been inordinately high. He first identified some OLC peaks in wildlife in 196U-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 ascribed to PCB. The possibility that these peaks could be attributed to naturally occurring constituents in fish eaten by man was dis carded when it was suggested that these sane peaks could cane from environ mental pollutants. To farther establish the then uncertain composition of the chemicals causing the false DDT peaks, Jensen (15) separated out one of the chemicals by OLC and subjected this fraction to mass spectrometry. The mass epeotrometry data showed compounds with molecular weights of 32li, 356, 392, and 1)26. The molecular weight differences or differences of 3b mass units suggested one less 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 8 chlorine atoms in the molecule. He verified his conclusion by introducing a synthetic or known PCB into the mass spectrometer. He also found that PCB standard chromatogram matched those with the same retention times as observed in various samples he analysed, i. e., eagles, fish, or other wildlife. It is interesting to point out that failure to recognize*such inter ferences 'led to spurious results and data and obviously led to the over estimation of DDT in our environment, in man, in wildlife, and aquatic organisms. Jensen (15) referred to PCB as a new pollutant, but, as stated earlier, PCB was with us in the environment since 1930 and thus it would be an old pollutant only recently correctly identified by appropriate analytical chemistry. In earlier work in the identification of acme organochlorine pesticides such as p,p'DDTj o,p-TDE (DDD), lindane, dleldrin, aldrin, heptachlor, and lindane, seme unidentified spots and peaks in TLC and OLC interfered with the detection of these pestioidal chemicals. Jensen (15) in his work extracted the compounds from biological sanples and, by appropriate cleanup of some con taminants, identified the pesticides and PCBs by thin layer and gas liquid chromatography followed by mass spectrometry. In 1961i, Jensen used TLC to separate the fat soluble chlorinated hydrocarbons from the rest of the sample. 27 DSW 010048 LEXOLDMON000421 WATER_PCB-00035888 . For pesticide analysis, the common detector is the electron capture detector. For sensitivity, one can determine levels at the picogram 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 oxygen containing impurity is some what higher. This system has certain inherent disadvantages in that two different compounds can 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 the Instrument and thus secure a good separation. To further demonstrate whether a compound which is responsible for a certain peak contains chlorine, one can concentrate the sample and analyze by a less sensitive chlorine specific detector such as the raieroeoloumetric detector. This, therefore, enhances the specificity in this residue analysis. ' When Jensen (l) analyzed human fat for DDT 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 peaks 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 H2SOI, which would chemically alter DDT but not the more stable or inert polychlorinated biphenyl. 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 ehowed 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 19l<3 (prior 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, Tish and pheasants 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 (l6). Identification by means of a combination of high resolution gas chromatography and mass spectro metry has been carried out by three independent laboratories in Sweden (17), Holland (2) and the United States (3) in addition to those named above. f , There is a need to measure PCBs 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 been extensively used with occasional identification and structure con firmation by gaa chromatography mass spectrometry. This involves such steps I as (a) sample preparation, (b) extraction of PCBs, (c) removal of interferences, (d) concentration, and (e) final gas chromatography and measurement. 28 OSH 010049 L EXO L D M O N000422 WATER_PCB-00035889 Some biological samples require more extensive pretreatnent thaiTfor water or effluents from industrial plants. The measurement of POB concen tration of effluents is a simple procedure involving chromatogram of sample and then chromatograms of standard samples developed from known PCBs. For more accurate analysis, calibration graphs can be developed from known speci fic peaks in the standard sarnies (l). 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 made relevant to separation and quantita tion of PCBs. First of all, inr separation, the methods used prior to quanti tation of residues in samples containing PCBs and chlorinated hydrocarbons fall essentially into two categoriess (a) those which necessitate destruction or alteration of one or more of the compounds and (b) those which do not. Peakall and Linear (19) have described in detail the procedures used for separation. p Briefly, the first group requires nitration (UNO j HgSty.) treatment at 0 C for minutes, which destroys or alters many of the organochlorine pesti cides} thus FOB is left unaffected along with Jlndane and BHC. Soma workers such as Armour and ftirke (l) reported that complex chromatograms resulted after nitration, which could not be related to the unreaoted 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 dehydrochlorinate some pesticides such as Perthane, Tbxaphene, DDD and DDT to their respective olefinic compounds (20). Perhaps the more desirable technique allows for special separation of many chlorinated hydrocarbon pesticides from PCB. nils 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 1 the peaks in a phenachlor DP6 mixture as standard. Risebrough (22) quanti tated relative levels of PCBs by assuming that each PCB compound produced the same peak height with the electron capture detector as the same amount of weight by p,p'-DDE. After adding the heights of the individual peaks, the total was multiplied by a factor derived from measurements of standard solutions with EC and MC detectors. Jensen and co-workers (23) reported concentrations of PCB as the sum of all PCB components and based the esti mation on several detection systems such as mass spectrometry and EC and MC detectors. In spite of all these techniques, these Investigators consider the method approximate 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 29 DSU 010050 LEXOLDMON000423 WATER PCB-00035890 - GAS CHROMATOGRAPHIC CONDITIONS Figures 1-6 Columns : (l) 1056 DC-200 on Chromosorb W HP (2) 15% QF-1/10* DC-200 on Chromosorb W HP 6 ft x limm id. 200C 120 ml Ng/min. . Detectort electron capture (tritium) 200C one nanogram heptachlor epoxide causes one half scale recorder deflection -- - 30 OSH 010051 LEXOLDMON000424 WATER PCB-00035891 p p DDT' A ld rin / I Up c 3L 31 OSH 010052 LEXOLDMON000425 WATER PCB-00035892 / I I I LEXOLDMON000426 WATER PCB-00035893 Figure 3. A ro c lo r 1254 10% DC-200 33 OSW 0100S4 LEXOLDMON000427 WATER PCB-00035894 Figure 4. A roclor 1221 157. QF-1/107. DC-200 3b OSH 010055 LEXOLDMON000428 WATER PCB-00035895 A ld rin p p 'D D T LEXOLDMON000429 WATER PCB-00035896  I i 36 OSW 010057 LEXOLDMON000430 WATER PCB-00035897 only approximate' At such time, whan one is able to synthesise the individual PCB components commonly found in the enrviroment and identify them In .terms of individual peaks, then the estimation remains, ss stated, a relative concentration. However, tor most biological assessment work, the correct order of magnitude and accurate relative amounts of PCS provide the requisite in formation for tnis purpose. III. Contaminants. Impurities, or Other Chemical Moieties in PCBb In the analysis of the polychlorinated biphenyls, one encounters a problem similar to that of the polychlorophenols ana 2,li,5-T in that certain contaminants or Impurities prevail, these impurities arise from the basic starting materials, or coapounds used in the synthesis and also frcm the pro cessing conditions used in the chlorination procedures. In this respect, the series of compounds Identified through otc and mass spectrometry are somewhat similar in nature to the spectrum of dioxins found in working with chlorinated phenols, hexachlorophene, 2,It,5~T and related synthetic organic chemicals. It has been noted in the bioassay of various Aroolors for toxicity, usually testily on chickens, that there was a variance in toxLclty of cer tain PCB preparations. Since the occurrence of lesions resembled those of chick edema in birds fed PCB, this prompted a comparative study between three compounds, Phenoclor CP6, Clophen A60, and Aroclor 1260 by Vos et al in 1970 (2li). In this study, the specific PCBs were fractionated, analysed, and bioassayed using the chick embryo assay. these studies revealed the presence of certain polar compounds which are present as impurities in the various PCBs and thus explain the variance in toxicity of certain commercial PCB preparations. In Table 2 some of the retentions and mass spectranstric data of some of the peaks identifying the presence of some dibensofurans, chlorinated naptholenes, end associated chlorinated biphenyls are indicated, proving the presence of inpurities. Table 2 Relative Retentions. Mass Spectrometrlc Data on PCB Fractionated Sarnie Peak Ho. 1 Relative Retention 1.1*0 Mass Nos. and No* of CEL atans per mol 30ii a Cl) Identity of Compound 1 -W Tetracblorodibensofuran 2 1.58 332 (6 Cl) Hexachloronapthalene 3 1.7U 358 (6 Cl) 372 (7 01) Hexachlorobiphenyl Heptachlorofciphenyl h 2.li2 338 (5 d) 392 (7 Cl) Pentachlorodibenzofuran Meptachlor obipheiyl 5 3.1# 366 (7 a) Hsptaehloronapthalene 37 DSW 010058 LEXOLDMON000431 WATER PCB-00035898  / Thus far, the dibenzofuram, the chlorinated napthalones and chlori nated dipehnyls appear to be the major contaminants or impurities detected in various PCB sanples. It is not unlikely that other chemical moieties will be characterized a3 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 usod. Through this HaOH treatment at elevated temperatures, sequentially polychlorohydroxy- biphenyla sure produced and then, through loss of hydrochloric acid, the dibenzofuran derivatives result (25). - The chlorinated napthaienes are far less toxic than the chlorinated dlbenaofurans (26). Thus, one might expect, with the varying ratios of impurities with variant tojdcities in different PCB samples assayed for biological effects and toxicity, that the end result will depend on such factors in examining various commercial PCB preparations. 38 OSH 010059 LEXOLDMON000432 WATER PCB-00035899 TOOINDIES 1. Widmark, 0. 1968 - OECD Report - Sweden. 2. Xoeman, J. J,, Ten Noeverde Brauv, M. C. and de Vos, R, H. (1969) Nature 221 1126-28. . 3. Bagley, G. E., Reichel, W. I. and Cromartie E. (1970) J. Assoc. Office, Analytical Chemistry 251-262. I. Schmidt, H. and Schultz, G. (l68l). Ann Chem. 207 338-3W*. 5. Sullivan, W. N. and Hornstein, I. (1953) J. Econ. Entonol lj6, 158-159. 6. Tsao Ching Hsi, Sullivan, V. N. and Hornstein, I (1953) J. Econ. Entomol b6, 882-88I4. 7. Laboratory Information Bulletin, PDA 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. 9l8B, Sept. 30, 1969, Davenport, J. E. 10. Laboratory Information Bulletin, FDA FSCS/ACFC No. 9l8C, Oct. 13, 1969, Armour, J. and Burke, J. II. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918D, Jan. Ifc, 1970, Armour, J. and Burke, J. 12. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918E, Mar.il, 1970, Amour, J. and Burke, J. 13. Laboratory Information Bulletin, FDA FSCS/ACFC U57, June 17, 1970, Westfall, J. E. and Fehringer, N. V. liv. Armour, J. and Burke, J. JAQAC 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), IAOAC, July Edition. 17. Widmark, 0. (1967), JAOAC JJO, 1069. 18. Armour, J. (1970) EDA Laboratory Information Bulletin No. 918P FSCS/ACFC, pp. 1-17. 39 .DSW 010060 LEXOLDMON000433 WATER PCB-00035900 1?, Peakall, D. B. and Lincer, J. L. (1970) Bio Science 20, No. 17, pp. 958-96b. 20. Archer, T. E. and Crosby, D. (1966), Bull Environ Contam Toxicol 1, 70-75- " 21. Simmons, J. H. and Tatton, J. (1967) J. Chromatogr. 27, 253-255* 22. Risebrough, R. W.' (1969), Chemical Fallout, G. C. Berg and M. W. Ittller (Ed.). 23* Jensen, S., Johnels, Q. A., Olason, J. and Otterlind, 0. (1969), Nature 22b, 250. ' 2b. Vos, J. G., Koeman, J. J., Van der Hals, H. L., Ten Noeverde Brauw, H. C., aid DeVos, R. H. (1970), Fd. Cosmet. Toxicol 8, 625-633- bO DSW 010061 LEXOLDMON000434 WATER PCB-00035901 t+J APPENDIX B Use and Replaceability of PCBs Table of Contents I. Dieleotrio Fluids A. Capacitors 1. Advantages and Disadvantages of PCB in Capacitors. 2. Replaceability of PCB in Capacitors* 3* Extent of Capacitor Use. B. Trano formero 1. Advantages and Disadvantages of PCS in Transformers. 2. Replaceability or PCB Transformers. 3* Extent of Transformer Use. . Page li3 x II. Industrial Fluids For HjrdraulU, Cas Itobino, and Vacuum Pump Uses. 53 A. Hydraulic B. Qas Turbines C. Vacuum Pug> Applications III. . Heat Transfer Applications 58 A. Advantages and Disadvantages of PCBs as Rgat Transfer Fluids. B. Replaceability of PCBs as Heat Transfer Fluids. IV. Plasticiser am Miscellaneous Uses. 59 A. Adhesives ' B. Textile Coatings C. Surface Coatings D. Sealants E. Printing F. Fire Retardant am Flame-Proofing Compositions. 0. Miscellaneous Applications. OSH 010062 LEXOLDMON000435 WATER_PCB-00035902 APPENDIX B Use and Replaceable, ty of PCBs Table of Contents (Continued) V Summary Tables 1. Typical Properties of Liquids...................... W-b6 2. Physical and Other Properties of Lubrio&tlng Oils, Engine Oils, and Hydraulic Fluids............... 2t?-f>0 3. High-Temperature Lubricant Specifications...................... 56 ii. Some Properties of Pumping Fluids..................................... 57 5. Decomposition Temperature Ranges of Several Chemical Classes............................................. .................... 60 6. Approximate Maximum Compatibility, phr, of Plasticizers With Various Resins...................... 61 7. General Properties of Some Aroclors (PCB).................. 63 DSW 010063 1*2 LEXOLDMON000436 WATER PCB-00035903 APPENDIX B Uao and Baplaceabllity of PCBa / I. DIELECTRIC FLUIDS Dielectric (electrically Insulating) liquids are important to the electrical industry for filling agents or inpregnatvts in transformers; capacitors, and other devices. Besides their electrical functions, the liquids nay also be used for cooling and 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 area 1. Non-flammability (important for preventing fires, particularly in Indoor use). 2. Dielectric constant matching that of paper. A good match reduces electric field ihhcmogeneities, increases dielectric strength and lifetime, and allows decrease in capacitor size. 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 size). . High chemical stability (increases capacitor lifetime and stabili zes its performance). 6. Low vapor pressure (increases physical stability). 7. Inert decomposition products in an electric arc (prevents explosion or oorrosion following breakdown). 8. Low toadcity of the material and its decomposition products. 9. Low cost. 1. Advantages and Disadvantages of PCB in Capacitors "" Die PCS capacitor liquids, commonly called askarels, are mixtures of chlorinated biphenyls and chlorinated benzenes. Several standard mixtures are specified by ASM (5). The askarel capacitor liquids and their de composition products are non-flammable. Thus their use In capacitors greatly reduces fire and explosion hazards. This characteristic permits economies where safety codes require fireproof enclosures for capacitors containing flammable liquids. Tha 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 capacitor electrodes, and a significant saving in the cost of construction and installation. The dieleotric constant of askarels closely matches that of the capacitor paper. U3 DSM 010064 LEXOLDMON000437 WATER PCB-00035904 - 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. Ihls dictates the use of special corrosion resistant materials inside the capacitors. The major disadvantage of the askarels is their suspected toxicity. In ordinary capacitor usage the askarels are used in closed systems to pre vent contamination from moisture. This practice also prevents the askarels from reaching the environment. 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 dielectrics* Dry capacitors have inferior electrical strength to liquid-filled capacitors and, for comparable performance, mus't be made larger. The major disadvantage of alternative capacitor liquids is their flammability. When comparing flesh 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 is not indicative of a fire hazard (5)* The require ment of non-flammability for most capacitor uses is critical, and capacitors with flaranable liquids are forbidden in many cases by the National Electrical Code (6). In other cases replacement of askarel capacitors with flammable capacitors requires use of fireproof installations (6). 1 The fluorocarbons are one' group of non-flammable liquids which are used for some dielectric applications (l). The ones listed in Table 2 have low dielectric constants and could not directly replace askarels without increas ing capacitor size. The fluorocarbons have low toxloity but the decomposi tion products may be toxic (l). They are generally more 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 flaranability, possible PCB replacement liquids generally lack either a sufficiently high dielectric constant to keep capaci tor size down or a sufficiently high dielectric strength. For example (see Table 1} the silicones have the disadvantage of a low dielectric constant whereas the org&nio esters often have poor dielectric strength. Some sili cones deteriorate rapidly under electric arcing (7). The acceptance of a PCB substitute is a complex process involving not only users but also various regulatory groups. In most of the electrical industry, regulation is non-goverrmental, and the primary regulatory influ ence comes from Underwriters Laboratories, who test products and decide on their suitability (8). In addition, control over electrical materials is hU OSW 010065 LEXOLDMON000438 WATER PCB-00035905 I %' V- * | rI ?! <W rv*l'Ifcti> i i ' Sr.1 fclo tk ( PS7 oI > n "h 3 t S~i i ** I SSI ot*f nv !rf ;* op 4> M* ,U 5 K: Stf-axs 3 if "15 ils 2 o - fcl- 6 on * "9 3i Klq *|R D.N 8 6 |*I 5 b jfi IS " s 4 . J** .assiii *OS| sg"ii ili if ly s t !i*b** A : !o iS A 1 281* Iffs 3 .. 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AN.. r* .. _A__N______A___A___A___A___A__O___O__ . 4 '' *f 4 TT 44TT44NNNN C * ,, wyv w Wv wwwwwww y K * AO a * M i 5 leannnoo o 8SR * *8 'SlSSSRft * j ! C*i g* oiinapi SR*'RSS' i*M p n l into OOM RSf'SRasS !l friifniasSo! . 5n ii ti imaou iS >i <i bono Ckl i BnnN n A a * * * 25 v Sv Sri^a|tSfSl RS<&St#SHanSNS^KoSfSnS? %u ic^ If! SSi 82. , , ,, , Pc II I2 * $ I F FI I 1 0.8 3 `rr' :ii trt fi Vvo! VvvV vV O i AA9i t pi A 0 0 0 0 p*p0*0 t I .* flftfiittftffl I I l M I M > I I M * iMmlllif!l 4 t|o *4 yw vW H1v4W * ** inis blit ij o<`8e Se S 31 |1 .s ssksScS t MsI^I 4iTi4lSI 81 Al 1 aas AAS |L . I. _____ 4 <OP # &. *4** i>M4 * W 2J o4 M S 4 .O3 #<* 0. 0. Z# 5M* * J| - - -rf 5 4*44*44*4<*4 -z*044 WX8K 4 4 4^ ."js"jsHsl Hia issasa ?0 OSH 01007J. T*t2 (Coat) LEXOLDMON000444 WATER PCB-00035911  exercised through companies which insure against fire, utilities which Bupply electrical power, and building codes. 3, Extent of Capacitor Uae Almost all industrial capacitors contain PCBs. In 1968 95 percent of the V. S* production of capacitor liquids (2.b6 million gallons) were PCBs (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 lamp ballast capacitors produced that year numbered 21.7 million units with a value of $15.5 million (10). In 1970 there were 50.9 million ballast units produced with a value of $163 million (11). These ballast units are in extensive use inside buildings where non flammability is important. Phase correction capacitors are necessary on power circuits to correct for the inductive loading of much electrical power equipment. Xhe amount of phase correction capacitance is ordinarily specified in kilovolt aoperes of reactive current or kvars. Most power capacitors are rated at from 1/2 to 25 kvars so that the number of capacitors is very roughly the kvar value divided by 10 (12). As examples of the extent of power capacitor use, TVA has 2-l/h million kvars (13) and a power coupany serving suburban New Jer sey has 3.6 million kvars on their power lines with 1/2 million kvars on order (lU). The value of these capacitors is roughly $5 per kvar (lit). More than 20 million kvars of power capacitors were produced in 1970 (16). Ibe procurement lag for these capacitors is 1-1/2 to 3 years, and esti mates for redesignirg new systems range from 3 to 10 years, according to power company representatives to AS1M Committee D-27 (lb,15). Extensive re-designing is anticipated if distribution capacitors 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: 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). h. High chemical stability (allows higher temperature operation and deduces degradation of the transformer). 51 OSH 010072 LEXOLDMON000445 WATER PCB-00035912 5. Compatibility with other materials .. 6. Inert decomposition products (reduces fire danger and damage to other materials following breakdown). 7. Low toxicity of the liquid and its decomposition products. 8. Low cost. 1. Advantages and Disadvantages of PCB in Transformers The PCB transformer liquids, commonly called askarels, are mixtures of chlorinated biphenyls and chlorinated benzenes. Several standard mixtures for transformers (differing from the capacitor askarels) are specified by ASTK (17). These liquids are used to overcome the fire and explosion hazards present with transformer oils. For most power transformer applications where occasional 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, askarel and dry-type transformers are re quired by electrical codes (6). Other advantages of the askarels include *1. their superior chemical stability, which eliminates the sludge formation com mon in mineral oils, 2. a high dielectric strength, which reduces electrical failures, and 3. suitable viscosity. . The disadvantage of the transformer askarels include* 1. a poorer resist ance to impulse voltages and production of highly corrosive HC1 during arcing, 2. a tendency to damage common insulating solids inside the transformer, 3. probable toxicity, and b. higher cost (about $1.60 per gallon compared to $.25 per gallon for mineral oil (15, 18). 2. Replaoeability of PCB In Transformers - Askarel 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 percent of transformer liquids in uBe in 1968 were mineral oil (9). However, fire underwriters will not accept the use of oils, silicones, and other flammable liquids for indoor transformers. Dry-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. Dry-type transformers could possibly replace askarel trans formers in many oases. Ho currently available liquid which will replace askarels in existing transformers is known. Possibly, non-flammable fluorocarbons could be de veloped as a suitable fluid, similar in important properties to the askarels. Fluorocarbons are currently in use as convective and evaporative dielectric coolants. One main disadvantage of the fluorocarbons is their high volatility, and high cost (about ho tines the cost of oil and 6 times the cost of askarels (18) ). . 3. Extent of Transformer Use . In 1967, 1.7 million liquid-immersed 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 - h city build ings. These transformers can fall and cause fire damage if'filled with a 52 OSH 010073 LEXOLDMON000446 WATER PCB-00035913  flammable liquid. An annual report on such failures is 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)* 1. High lubricity (lowers heating and increases lifetime of moving components). 2. Stability (increases lifetime of use). 3. Appropriate visoosity and high viscosity index (2b). . b. 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 from the implication of a more con stant volume over a wide temperature range, a low thermal expansion inpliea a high viscosity index and the constancy of certain other properties with respect to tenperature. ' 11. Good demulsibility. 12. Inhibitor (necessary to prevent oxidation of metals or rusting). 13. Good fire resistance (very important in high temperature environments). lb. Low density (desirable in transportation, particularly airborne, I applications). 1. Good dielectric properties (reduces arcing or short circuiting should the fluids come In direct contact with electrical conponents). 16. Non-toxicity (reduces the danger to human beings from 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 composition. The results from inquiries with respect to FOB content have been somewhat contradictory; No definite knowledge is available 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 pouf point of oil8 may be lowered by extensive dewaxing, the use of additives is much cheaper. There are other inexpensive additives which are often used for theee applications and which aopear to be adequate. For 53 DSW 010074 LEXOLDMON000447 WATER_PCB-00035914 example, TCP (tricresyl phosphate) is chemically stable as an additive in lubricants, and, although quite toxic, it is more biodegradable than the PCBs. An Important requirement for many applications of hydraulic fluids 1b 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. PCBo have excellent fire resistance characteristics. The flash and fire points given in the literature for the pentachlorobiphenylB are attributed to the burning of residual contaminants (29). At very high tenperatures, however, PCBs with higher chlorine content may emit phosgene (a very toxic gas) in the presence of oxygen. (No evidence Is available that high chlorine content PCBs are being used here). Aircraft hydraulic fluids are an exanple of an application where excellent heat and fire resistance are necessary in view of moderately high operating tewperatures and frequent accidents involving ruptured hydraulic conponents in the proximity of hot metallic surfaces. Also the liberglas acoustic blankets in the jet engines become soaked with leaking hydraulic fluid within as 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 "snuffer s" 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 correction with fire resistant hydraulic fluids for military aircraft. Seme of the hydraulic fluids being tested do not contain PCB additives^but do contain TCP. It is possible that under appropriate processing, PCBs 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. The boiling points of these fluids are too low to permit their use in aircraft. It la possible that PCBs are also used in phosphate ester and other halogenated hydraulic fluids for industrial applications at high temperatures. The requirements here are similar to, but not as stringent as, those for air craft hydraulic systems. B. GAS TURBINES The characteristics of a good gas turbine lubricant are similar to those of hydr&uHo fluids except fbr the additional requirement of lubricity at high rates of shear (35). Particular emphasis is placed on heat resistance, high $h DSU 010075 LEXOLDMON000448 WATER PCB-00035915 viscosity index, low pour point, and 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 above requirements. In the case of the turboprops, 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 ia no evidence that PCBs are currently used for this purpose. Research along these lines has been done, and there is seme 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 turbines. This corrosion is accelerated by decomposition of the PCBs and the forma* tion of hydrochloric acid at high temperatures. The corrosiveness of PCBs is a major deterrent against their use in these lubricants. TCP also has the desirable property of-reacting with metallic surfaces at high tempera tures to form a protective coating. Jet engines are run for .approximately 18,000 hours (37) between over hauls. The lubricants are not usually changed 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 respeot 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 acidify and viscosity during use, recycling of gas turbine fluids would demand expensive redistillation and reblending. C. VACUUM PUMP APPLICATIONS (22, 23) Both mechanical and diffusion pump applications require fluids of one highly fractionated conponent. Accordingly, additives generally are not U3ed. However, PCBs are used in pure form as a diffusion pump oil in commercial applications. - The characteristics (38) of a good diffusion pump fluid aret 1. Relatively high vapor pressure at operating temperatures. 2. Low vapor pressure at room and lower temperatures. (The vapor pres sure imposes a lower llmiit on the ultimate vacuum). w 3. Heat resistance (prevents cracking or molecular degradation at operating temperatures). li. Narrow vapor pressure range 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 resistance (important because air may enter a diffusion pump during operation either accidentally or through slow leakage). 6. Nonhydroscopie (absorbed water increases pump maintenance and may contaminate the vacuum system). ' 7. Compatibility (must be compatible with pump and vacuum system components). * 8. Stability in the presence of the vapor being pumped. w Seme of the pertinent properties of many diffusion pump fluids are given in Table U (3?). 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 & OSM 010076 LEXOLDMON000449 WATER PCB-00035916 Table 3 High-Temperature Lubricant Specifications Viscosity, oa at r.,'oF 4U0F 210F I00F -30F -40F . Viscosity stability teal temp Vis change In 3 hr ' Vis after 3 hr, ca Vis after 72 hr, oa ' Via at~40F after 12 hr Hhear stnbllity at 212F Pout point, F Flash point, F Spontaneous ignition temp, F Vapor pressure at 500F, mm Hg Evaporation loss test tamp % Loss 6-1/2 hr at 29.9" ]|g V. Loss G-1/2 hr at 5.5" U8 Specific heat, UTU/lb/F at I00#F Spool Tic heat, UTU/lb/F at 600F Rubber swell, 72 hr Rubber swell, 16S hr Foaming sequence 1*24, max vol Foaming collapse time, max, min dear scuff at I6SF X reference dear scuff at teat temp, % reference dear fatigue, hr to failure -- 1,0 min -- Report ' -- - -- 65F $7! max 21,000 max 24,000 max -- -- -78 max 425 min 750 min -- a fee 0oo 16 max -- -- -- 12-25% at 400F -- 100-25-100 ml 5-4-5 56 min (8 sides) Report (400 F) Report (400 #F) MiL-L-artoa 1,0 min - Report Report 13,000 max - -30F tH max 13,000 max 17,000 max - .-- --40 max 600 min Report 5,0 max 500F . 10 max ' Report 0.35 min 0.45 min 12-25% at 500F - 100-25-100 ml 6-3-5 100 min (8 sides) Report (500 F) Report (500 F). ~ pekh aoi 2*0 min 8.5 mar 13,000 max -65P -- Report 3% KV/210F -- 500 min 752 min -- 392 F Report -- -- -- _. 15-25% at 158 F 100-25-100 ml 5-3-5 - 100 rain (392F) (Ref. oil nt 230F) $6 DSM 010077: LEXOLDMON000450 WATER PCB-00035917 T a b le 4 * III? s????frrss : Us222* 2* sg-g x 1 5 p PP * 28 * OMfMl>I XX * " *OH Wi SgsasSSSSaS mi<ifc 11 ISI r1 S1 PMKS1 tis 8 8 ggap a a2<QNrht r1 f a O f ape Ps S- IGs t 7 < o g *x* X* M r SUSS s s" till 30t nrW>fl 7-ft 2H 1 ssssPsPs 8^8- e P O O CaX/> ft *r04 IH-i*st S3 38 SSS 1rw*8* 88 8 1 2SSS 8 1 c isf0 ? if ii iiili a $ ??8? MlHHH * 4HH1*9S4H 9n *1*8* u i.T> 35?553885SS 5 S3B 8 8S58 5 I ft rf $i 5ii B51 ut ft* I (?otJ i l*[ lip c Itl *411 fpsg ISise J3 f 11 * 11111 I............./ *|Sjj 5 s _S 9: set ? 2>8&fsJ II mmmi iiill <=SUoE2R|1I iggggsa^ftf mm 11 -if s 11| f- J fill* V g 2g ys 5 > SS&fc oouo 0s tided Jill sSvsi 1 y0 Sjj .5? LEXOLDMON000451 WATER PCB-00035918 PCBs is limited by their relatively high vapor pressure at lw temperatures, their use at high boiler pressures makes possible operation with poor force vacuums. Hence thny are useful as booster puitp fluids. In this respect the vapor pressure-temperaturs properties are closely matched by amyl phthalate. Except for certain applications where alternative liquids may be incom patible with the vapors being punqped, the advantage of using PCBs diffusion pump oils appears to be mostly an economic one. Other fluids may often be preferable through considerable more costly. TCP is used as a commercial diffusion pump fluid and is also inexpensive. Its vapor pressure (h9) 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 use by incineration. This service is available mainly for dispoaal 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 (til, h2). The properties required of heat transfer fluids are (til) 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 change). 1. Hig?i heat conductivity (Increases heat transfer). h. Low viscosity (necessary for fluid flow through system). 5. Physical stability (will not have unpredictable phase or property changes). 6. Chemical stability (will not degrade, oxidize, etc.). ' 7. Radlolytlc stability (will not suffer damage from radiation if present). 6. Low cost. 9. Low surface tension (redices fluid flow and heat transfer between fluid an) surroundings). 10. Low corrosion (reduces damage to metal parts of the system). 11. Low flammability (reduces fire and explosion danger). 12. Low toxicity. Electrioal properties, refractive index, appearance aqd odor may be considered for BCme applications. . A. ADVANTAGES AND DISADVANTAGES OF PCBs AS HEAT TRANSFER FLUIDS The main advantage of the PCBs as heat, transfer llulds is their fire 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 up 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 DSW 010079 LEXOLDMON000452 WATER PCB-00035919 / toxicity, a tendency to decompose to fora highly corrosive HOI, a lower decomposition temperature than some alternate liquids (1*3) and relatively poor radiation resistance (bit)* B. REPLACEABILTTY OF PCBs AS HEAT TRANSFER FLUIDS Increased risk from fire and explosion is a major disadvantage with most PCB replacement fluidb. Other non-flammable fluids arei 1. fluoro carbons, which have low toxicity, high thermal stability, and In spite ofhigh cost are used as convective or evaporative coolants (1), 2. water, which is quite corrosive, has a high temperature limit of 37UC and requires extremely expensive high pressure eyetens for its use above the atmospheric boiling temperatures and 3, molten salts 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 a variety of chemical classes. Few of these liquids are non-flanmable, however, as can be seen from Table 2, The phosphate esters, silanes, and aromatic ethers' have high fire points (around 600^F), but they are flammable and it is not dear how high the fire point must be for a fluid to be safe in a high tem perature system, especially in the event of leakage into a furnace. The details of specific heat transfer applications are necessary to evaluate the suitability of PCB replacement fluids. IV. PLASTICIZES AND MISCELLANEOUS USES + A plasticiser is a material incorporated in a plastic to increase its workability and flexibility (t?,l|6). The addition of a plasticiser may lower the melt viscosity and flow temperature (increasing the ease with which the plastio can be made to flow),or lower the elastic modulus (making the plastic softer) (h6). Plasticizers are generally non-volatile liquids or low-melting solids. A major requirement of a plasticizer is that it have high compatibility*' (mixes will to form a homogenous composition with useful properties) (i|2) with the material being plasticized. Figures are given in Table 6 for the compatibility of some common plasticizers with some common synthetic thermosetting or thermoplastic resins (ti5)> 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 cost (li7) Of course, the properties of the final plasticized material are of prime importance. Certain plasticizers provide formulations with speoifio properties such as: 1. phthalate esters - general purpose. . 2. adipates and ozalates - low temperature flexibility. 3, highly aromatic esters - fast processing, strain and extraction resistance. h. epoxies - heat stabilization during processing. $. phosphate* esters and PCBs - fire retardant materials. The information in this section about specific uses was obtained from Chemical Abstracts (l?28-l?69) 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 ita use earlier in this appendix. In the earlier case, compatibility meant that two materials could coexist without either being affected by the other. The present meaning is quite the opposite. 5? . 0SM OIOOBO LEXOLDMON000453 WATER PCB-00035920 Docowposition Point Range (*F) Over 800 700-800 600-700 500-600 Table 5 (12) Chemical Class Unsubstituted Polyaromatic compounds Unsubstituted Polyphenyl ethers '- Unsubstituted Aromatic amines Unsubstltutad Aryl silicates Unsubstituted Aryl silanes Unsubstituted Arvl borates Lover alkylaromatic ethers Aromatic phosphates Aromatic sulfones Aromatic ketones - . Silicones Halo-Bubstitutpd aromatic ethers , Halo-substituted polyphenyls ..(including PCB'a) Alkyl borates Alkyl silicates Higher alkylaromatic others Highly refined mineral oils Fluorinsted esters Heopentylpolyol esters . Sebacate esters - Methyl aryl esters Aliphatic tertiary amides i DSM 010081 LEXOLDMON000454 WATER PCB-00035921 m id n amide* Mucinminou^ PoIvcM<-ni jtvcuW * PhuqilMifc* Ia |s- a Of-fill s-8ss~Rga"-3 a a-as (/o^d!<i p*i*H|jora sss8S8-`Rgs--aaasas"as pittrcuoiint -sgSKsasaassaa^asssss pmnu<i||n< wmijoHCtf-lXilia-A' ?8s8s88ss8ssassasa888 JJ-Q x|dwd 8 " 88*'-8 K-i> xapbuej 88 t?-0 j 8 - S8-88 V ------------- -8--8 B JK-U *"U iS = -8"- no>Mp)iia<gj 88 8 8R8"SScS"" 2-88-28 S0 ^Miajiong 8K2"'28",8S2",",",",*'28"Sa eH-TcX)* ;/iii4 8888j|S5S8SS8g88aSfi-3S iW<p)nins.n(|)iil ii/.tfpqanj*: 8888888888828-"`832-88 |Xp a*ohijjjl 83SSS2a8S2-88883-88 8" 1156 s i*,0m3*vMa--sJSRSa88"iasS3f?'*as (XaMMJJ, 821258828888-8 88888-88 88888888882-822288-88 iXMp>wita 8-28S-888---8--88-SB i/ici)iXtn-zia g-2g38-388"-S8-~gs~S8 " pfmwq (Xvni |8J28|8288S"t2a85SS"88 |XxM|n]9XM<I 8888S8-888--828288-2S I^WIO "888-88--lS82-aiS-3 3 jXxnX4W-j4a 8-8888-S88--888-88-88 I-fVWKtl 88888888888-888888-81 lunula 88S88888888,08-"*-88-88 OM8 MP. 3umfv 4 Adipate*, P h fb g la tf*- LEXOLDMON000455 WATER_PCB-00035922 PCBs are attractive as plasticisers because of their high conipatability factor. They have been made with a wide range of properties, as shown in Table 7 (b8). The PCBs are permanently thermoplastic, chemically stable, non oxidizing. non-corrosive, have excellent solvating powers, and are fire re sistant (u8, b9). They are not normally attacked by acids, alkallne3, 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 ($1, 52). The major types of plasticized 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 ahd while the bond is being formed, but solidify at lower temperatures to overcome the problem of excessive softness (53). Among those solid plasticizers used are: o,p-toluenesulfonamide, N-cyclohexyl-p-tolunesulfonamide, triphenyl phosphate, and diphenyl 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 toluenesulfonamides, are employed because they improve the flow properties by reducing the viscosity of the phenolic resins (5b). They help the resin wet the fillers and abrasives. Chlorinated polyphenyls and aryl phosphates (hon-reaotive 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 acoustical glasses. The laminates have improved strength and resistance to delanlnatlon over a broad temperature range, and improved sound-absorption and energy dissipation properties. Polyarylene sulfides, treated with chlorinated biphenyls, are employed to laminate ceramics and metals (58, 5?)* An ethylene-propylene copolymer blended with PCB has been used in a hot melt adhesive having improved 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) Vfeshable 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 (6I1), 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-lustering agent for rayons (67, 68). Poly-alphaolefins, (i. e., polypropylene) films, when coated with a mixture of PCBs, UV 62 . . DSW 010003 LEXOLDMON000456 WATER PCB-00035923 Table 7. General Properties of Some A roclors (PCB) iiu *V H9 !Iv?l Ii I 1 ! -I ;l! W .G ge * o *o o o a a ads 1 63 LEXOLDMON000457 WATER PCB-00035924 light absorbers, and antioxidants show increased stabilization to oxidative degradation on exposure 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 (ij8). C. SURFACE COATINGS ` Tn paints and varnishes, the hard resinous PCBs impart increased hard ness to films, and the softer resins give flexibility (18). The role of these materials is similar to the oil, except that they do not oxidize and lose flexibility on aging. In nitrocellulose lacquers, PCBs either alone or in combination with other plasticizers and resins impart increased weatherability, luster, adhesion, and decreased burning rates (1)8, 72). Some comparison studies have been made recently on the effects 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 adhssion than did film plasticized with dibutyl phthalate or PCB (73). For varnishes prepared from polyvinyl chloride formulations, and plasticized with either di-butyl phthalate or PCB, the films plasticized with PCB had better overall properties with or without pigments (TiOg) (7l))* PCB and other plasticizers can be used in combination with poly (organo- siloxanes) to prepare film casting solutions. These polymeric films could be enployed in electrical coatings, insulating tapes, and protective lacquers (7?-77). ' __ ~ Plastic vessels, i. e. bottles, manufactured from polyethylene, polyvinyl chloride, polyvinylidene chloride or similar resins coated with an epoxy lacquer (which contains PCB) make the vessels pliant, impervious, and resistant to aromas, acids, and alkalis (78). Paints at atomic 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 thi9 purpos9, the vinyl polymers are preferred over epoxy lacquers. The best plasticizers for use in this area are claimed to be the PCBs (79) The extent, if any, of their 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, fyoxy resins in combination with PCB can be used as protective coatings for metals, l.e, encapsulating electrical capacitors (8l), for ferrite magnet cores (82) (used in computers), for corrosion resistant resistors (83), for pigmented metal coatings (81), 85) for winter camouflage coatings (86), and for pipes and blocks (87). ' . OSH 010085 61) LEXOLDMON000458 WATER PCB-00035925 D. SEALANTS Sealing and caulking compositions include a vide range of compourets which can be used -to seal joints or voids against water and water vapor, air and other gases, dust, sound, vermin, heat and cold (88). Specialized applications require resistance to certain chemicals or atmospheric environ ments. PCBs can be used as;.plasticizers in the formulation of putties from copolymers or ethylene-vinyl acetate or styrene (8?). The products are non hardening, and resistant to moisture and frost and show good weatherability A non-sticky, non-hardening putty was also prepared from polysulfide mix tures which employs PCB as the plasticizer. This putty gave good bonding to building materials and had good extrudability and shape retention (90). Elastic pavement or concrete sealing compositions, used for traffic markings, were prepared from coal-tar-polysulfide mixtures which are plasticized with PCB (91). A sealant, effective for concrete and 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 part of the formulations used to prepare pressure-sensitive record (93, 9b) and colored copying papers (95, 96, 102, 103), They have been used to coat papers used in thermographic duplicating processes (97-101) as well as in xerographic transfer processes (lOli* 105). Solvent-free printing on polyolefin plastics can be accomplished by heating a mixture of low molecular weight material, chlorinated biphenyl or terpene resin, and suitable pigments and cfyes. Durable prints can be made on the surface of the polyolefin at the time of their thermoplastic shaping (106). Printing plates, hard enough for high quality letterpress printing, and suf ficiently flexible for use as flexographic plates, can be prepared from com positions containing a liquid resin such as epoxy, polyester, urethan, acrylic or vinyl with an excess of curing agent and PCB as the plasticizer (107). The extent, if any, of current ubss of PCBs in printing application Is unknown, F. FIRE RETARDANT AND FLAME-PROOFING COMPOSITIONS When PCBs are used as plasticizers, they lnpart a certain degree of non flammability to the objects as described previously. However, for Increased effectiveness in flame retardant applications, the PCBs can be admixed with various metal oxides. Seme flame retardant compositions based upon these mixtures aret polyolefin yarns (l08)j organopolysiloxane sealants (I09)j thermoplastic poly (hydroxylethere) (llO)| fireproof panels made from starch which can be used for doors, floors, ceilings, and partitions (ill)3 poly amides (ll2)| and in fireproof fiberboards (ll3). Rigid polyurethane foams (llb-116) and hardboard conpositions (117), when treated only with PCBs do not show any significant increase in flame retardance. a. MISCEU.ANE0US APPLICATIONS * The wide range of chemical and physical properties exhibited by the PCBs (see Tables 6 and 7) make them desirable for an assortment of miscellaneous uses. Some of the more interesting and non-conventional uses are as followst 6? OSW 010086 LEXOLDMON000459 WATER PCB-00035926 1. Catalyst carrier for polymerization of olefins(116). 2. Connererion of water-permeable soil to a non-permeable state. Soil'is made non-permeable by applying to the soil a composition con sisting of an ethoxylene-based resin, polyamide, canphor, and PCB as plasticizer* The cosposition has' a density greater than water, and it hardens wider water. It oan be applied to river banks, where it flows down the bank, and after hardening, prevents penetration of water (soil erosion-retardant) (119). 3. Combined insecticide and bactericide formulations* The com position contains aldrin or dieldrln, naphthalene hydrocarbons, nalathlon, methoxychlor, lindane, chlordano, tsrpineol, and chlorinated biphenyl as active agents (120). . 1. Inhibitors of microbial growth in enamel day formulations (121), 5. Plastic sound insyflhting materials for railway cars (122). 6. Plastic (PVC) decorative articles which give the impression of internal scintillation (123). 7. Increasing the density of carbon plates by impregnation with PCB (I2l). 8. Graphite electrodes with low thermal expansion coefficients and high bending strengths (12). 9. Increasing the coke yield from coal pitch, The coke is very hard, dark, and brilliant (126). 10. As a metal quencher or tempering agent for steel, alloys, and glass (127, 128). 11. As an aid to fusion cutting of staoked metallio plates without ad herence, The cutting is done with an electric arc or oxy-g&s torch (129). We find no evidence that PCBs are indispensable to a particular plasti cizer or miscellaneous application. In most of the formulations and composi tions cited, there were usually alternative plasticizers Included In the citation (see Table 6) which did not appear to be detrimental to the applica tion, V. SUMMARY The major value of the PCB liquids is that those with four or more sub stituted chlorines per molecule are non-flammable as arej>heir decczBosition products. Thus they can be used as fluids at temperatures up to 7<XrF without the danger of explosions and Are. The major disadvantage of the PCBs is their possible toxicity danger. The other comparable class of non-flammable fluids are the fluorocarbonsvhieh typically have a lower vapor pressure and lower boiling point than the chlorinated compounds. ' PCBs are used in fluids (known as askarels) for electrically insulating and cooling transformers when the transformers are used in or near buildingB. Mineral oils are the preferred fluids when fire doee not oreate a hazard. Dry transformers oan also be used but are larger and more expensive, Fluoro carbon liquids require a special transformer design, fluorescent light bal last capacitors and phase correction capacitors utilize the Mg) dielectric constant of the PCBs to effect significant reduction in capacitor size and cost. Few suitable fluids hkve a corparably high dielectric constant. Flammable fluids are not allowed by insurance companies and building codes in capacitors used In buildings. Replacement of PCBs in capacitors and 66 GSM 010087 LEXOLDMON000460 WATER PCB-00035927  transformers would require considerable time and money for reengineering, manufacture, and application of substitute equipment* PCBs are useful in hydraulic systems where leakage onto hot metal sur faces could cause a dangerous fire* Hydraudio fluids can also be made with phosphate esters which are toxic and which will burn at high temperatures* Replacement of PCBs in some hydraulic systems could increase loss of life due to fire. Gas turbines require lubrication at high temperatures. PCBs can be used but tend to be corrosive* Phosphate ester lubricants seenr better in this respect. Chemical stability is more important for high tenderature lubricants than is non-flammability, PCB fluids are useful in diffusion booster pimps to produce -moderately high vacuums with relatively poor fore vacuums. Non-flammability is not especially important for diffus ion punp liquids, and with a few possible exceptions alternative liquids are available Flammable heat transfer fluids present a fire hazard if they leak into a furnace or onto hot surfaces. The use of PCBs can prevent this danger. In some cases water is a suitable substitute at moderately high temperatures. Other heat transfer fluids are commercially available and in use Replace ment of PCBs is satisfactory in some, but may be dangerous in other beat transfer u/ses. The PCBs are good plastioizers for use with adhesives, textiles, surface coatings, sealants, and oopy paper* In some cases the PCBs act as fire retar dants* There are no particularly unique properties of PCBs for plasticizer uses, and equally effective alternatives are generally available (e.g, phos phate esters are often used as fire retardants). The extent of current use, if any, in such applications has not been determined;' 67 OSH 010088 LEXOLDMONOOQ461 WATER PCB-00035928 FOOTNOTES 1* Directory/Encyclopedia Issue, Insulation/Circults, Vol. 17, No. 7, June/July(l?7l), p 17. 2. Encyclopedia of Chemical Technology, 2nd Edition (l?6b). 3. Dielectric Materials and Applications, A. R, von Hippel, ed. Technology Press of MIT and John Wiley and Sons, Inc. N. Y. (195b), pp 156, 189, 211, 221. ' If, Insulating Materials for Design and Engineering Practice, F. M. Clark, John Wiley and Sons (1962). 5. Aetm D2233-70 Standard Specification for Chlorinated Aromatic Hydro carbons (Askarels) for Capacitors, American Society for Testing and Materials, Phil. Pa. 6. National Electrical Code Handbook 10th Ed., 1957 McOraw-Hill. 7. Insulating Materials for Design and Engineering Practice, F, M. Clark, John Wiley and Sons, p 2l6, (1962). 8. Chemical and Engineering Neva, October 18, 1971, p 16. 9. National Industrial Pollution Control Council Report on the Use and Disposal of Electrical Insulating liquids, U. S, Government Printing Office, Washington, D. C., June, 1971. 10; 1967 Census of Manufactureres, Commerce Publication MC67 (2)-36A, ELectrical Measurement and Distribution Equipment. 11. Fluorescent Lamp Ballasts, Summary for 1970 Commerce Publication Series MQ-36C(70)-5, September (1971). 12. Dielectric Materials and Applications, A. R, von Hippel, ed. Technology Press of MIT and John Wiley and Sons, Inc., N. Y. (195b) 4> 197* 13. Private communication. L. E. Smith, Special Engineer Transmission Maintenance and Test Branch, Tennessee Valley Authority, Chattanooga, Tern. lb. Private communication. Herbert C. Erdman, Public Service Electric end Qas 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 Tlssoc., 155 E. bbth St,, N, Y. N, I. 10017. 17. ASM D2283-71 Standard Specification for Chlorinated Aromatic Hydro carbons (Askarels) for Transformers, American Society for Testing and Materials, Philadelphia, Pa. 68 D$W 010089 LEXOLDMON000462 WATER PCB-00035929 18. Private communication. B. 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. (1962). 22. ' W. Espe, Materials of High Vacuum Technology, Vol. 3, Pergaraon 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-temperature coefficient. 2$. The pour point Is related to the lowest temperature 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, Fhila., 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" ASM Special Technical Publication No. ,b06 (1966). ~ 28. "Review of Ignition and flammability Properties of Lubricants", J. M. Kuchta and R. J. Kato, Bureau of Mines technical Report AFAPL-TR-67-126 (1968). 29. ASTM D901-70 Standard Methods of Testing Askarels. Secs, 18, 19. 30. National Bureau of Standards Report of Tests No. TO 10210-21581 FR 3695. 31, See for example* . Raf. 21, p 133 32, Reference 21, Chapter li. 33, Phosphate eater type hydraulic fluids are being recycled byi Eppi Pre cision Products, 227 Burlington Ave., Clarendon Hill, 111. 3b, Sea for example! A, M. Oobry, E. A. Glass, and A. ZLets, "Improved Non-flammable Hydraulic fluid". Bureau of Slips Report M67-Ib (1967). +. 35. Ref. 21, Chapter *>. 36. Ref. 21, P 235. 37. Private communication, R, K, Crother a Maintenance Division, Federal Aviation Administration. 69 OSW 010090 LEXOLDMON000463 WATER PCB-00035930 38. Ref. 22, Chapter 18 39* Ref. 23, P 66. 1*0. Ref. 22, pp 352-353 1*1 W, J. Danziger, "Heat Transfer Media Other than Water", Encyclopedia of Chemical Technology, 2nd Ed., Vol. 10, pp 81*6-861 (1965). 1*2. Paul L. Geiringer, Heat Transfer Media, Rheinhold Publishing Co.j-N, T (1962). 1*3. Ralph L. LeMar, "Thermal Stability of High Temperature Fluids and Fluid Intermixtures" U. S, Army Weapons Command Technical Report DA#lC02ll*01A10B (1967). 1*1*. L. Mandeloorn and R. L. Miller, "Radiation Resistance of Capacitors Dry and Inpregnated" paper # E-9, Conference on Electrical Insulation and Dielectric Phenomena NAS-NRC- (1971). 1*?. J. R. Darby and J. K, Sears, "Plasticisers", Encyclo. Poly. Sd. and Tech., 10, 275 (1969). 1*6. ASM D 883-69a standard Nomenclature Relating to PlastiCB, Amer. Soc. For Testing and Materials, Phila., Pa. 1*7. Qene Wilde and David Press, "Plasticizers", Modern Plastics Encyclo.. 1, 1*28 (1968). 1*8. H. J. Hibbard, "Chlorinated Biphenyls and DerlvativesN, Encyclo. of Cham. Tech,, , 291 (196!*), 1*9* R. H. Mosher, "The Technology of Coated and Processed Papers", Remsden Press Division, N, Y. p 368 (1952). ' 50. - Ref. 1*9, p 2l0. 51. ASM D 907-70 Standard Definitions of Terns Relating'to Adhesives, Amer. Soc* for Testing and Materials, Phila. Pa. 52. Irving Skelst "Adhesive Compositions" Encyclo. Poly. Soi. and Tech., Vol. 1, Inter8cience Publishers, N. Y. p 1*82 (I961i). 53. Ref. 1*9, p 286. 51*. ibid, p 292 55. V. E, Hamilton and J. M. Roseland, S, African. 67 Ot*,865 (McDonald Douglas Corp.) (1968). 56. ibid, ft-. 1,519,535, (1968). 57. Brit. Patent 1,11*8,01*7 (Douglas Aircraft Co.) (1969). 70 DSW 010091 LEXOLDMON000464 WATER PCB-00035931 58, Harry Smith, TJ. S, Patent 3,395*132, (Dow Chemical Co,) (1968), 59. David A, Frey, U, S. Patent 3*380,951 (Dow Chemical Co.) (1968), 60. T. P. Flanagan, U, S, Patent 3,220,966 (National Starch and Chemical Co.) (1965). 61, R. P. Ccoc, J, L. Wawr, and R, J, Sere, If. S, Patent 3,117,000 (E, I, Dupont de Nemours) (1969). -- 62. P. Ruokstuhl, Ger. (East) Patent 1*0,927 (1965). 63, P. Prumier and J. Duthu, Fr. Patent 1,1*82,172 (1967). 61w P. Ruekstuhl, Ger. (East) Patent 37*967 (1965). 65. II, J. Eiehel, U. S. Patent 2,988,1*61 (National Cash Register Co.) (1961). 66. H. 0. J. Velthoven and H. J. WLenjes, Neth. Patent 109,025 (1961*). 67. Bull Kline, U. S. Patent 2,077*699 (E. I. DuPont de Nemours) (1937). 68. ibid, U. S, Patent 2,077,700. 69. 0. Liatner, U, S, Patent 3,1*58,1*71 (Jenson and Johnson Co.) (1969). 70. ibid, D. S. Patent 3,277,01*6 (1966). . 71. Brit. Patent 1,133,050 (E. I. DuPont de Nemours) (1968). 72. R. J. Jenkins and R. N. Foster, Ind, Big. Chen. 2J* 1362-1365 (1931). 73. N. V. Maiorova, M. I. Karyakina, V. A. Kargin* Z. Ta. Bersstneva, L. P. Malysheva, Lakokrasoch. Mater. IKh Priraen, 3* 17-19 (l969). (Of, C.A, 71, 623253 1969). 7l*. S. V. Takubouich, N. Ta. Olcbkova, 7. A. Zubchuk, an8 P.,V. Kozlov Lakokrasooh. Mater. IKh Prinran Ij, 1*6 (1966). (C.A. 6, 188201, 1966). 75. D. P. Spalding, Fr. Patent 1,353,506 (Corapagnie Francaise ThomsonHouston) (1961*). 76. Brit. Patent 1,020,053 (General Electric Co.) (l966). . 77. D. p. Spalding, U, S. Patent 3,288,71*3 (General ELectric Co.) (1966). 78. E* Kemp and Karl Jahn, U, S. Patent 3,393,087 (Monsanto Co.) (1968). 79. H. Wells (Atomic Energy Rbs. Establishment, Harwell, England) J. Oil 'Color Chemists Assoc. Ij8, (l) 26 (1965). 80. Ref. 1*9, p 293. 81. Francis J, Whilby, Brit. Patent 1,138,976 (Standard Telephone and Cables, Ltd) January 1966. 71 D$W 010092 LEXOLDMONOOQ465 WATER PCB-00035932 82. Robert S. Haines and Thomas J. Walsh, V, S. Patent 3,279,9l5 "(IBM Corp) October 1966, 83. Theo A, Helens and Jan Kunnsn, U. S. Patent 3,109,75k (North American Phillips Co.) November 1963, 8Li, Fritz F. freitay, Herman H. Halter, and Lothar Kluth, U, S, S, R. Patent 1^7,031* September 19&3, 85. Margarets K, Helmholtz and Waltraud H, E. Helmholtz* Oer, Patent 1,156,922, November 1963, 86. Fr. Patent 1,358,681i (Konrmanditbolaget Svenake Farglndustri Lundin and Co.) April 196I1. 87. Irvin J. Steltz, Oer. Patent 1,279,262, October 1968 88. Charles T. Rairdon, "Sealants" Enoyclo. Poly, Sci. and Ifech., Vol, 12, p I4I8 (1970) Interscience Publleihers, N. T. 89. Soeiete Civille Fiorillo, Fr. Patent 1,1|02,991, June 1965. 90. Ihiokol Chem, Corp. Neth. Patent Appl. 6,606,3li9, November 1966, 91. J. M. Pachuta, IP, Patent 1,566,1413 (Thiokol Chem, Corp.) May 1969. 92. Edward 0. Millen, Fr. Patent 1,521,788 (ihiokol Cham. Corp.) May 1969. 93- Barret K. Green and Rcfcert V. Sandburg, V, 5. Patent 2,5ll8,36li-5 (National Cash Register Co.) (1951). ... 9h, ibid, V. S, Patent 2,51|8,366 (1951). 95. S. Kiraura, T. Kobayashi, S Ishige, Fr. Patent, l,5U5,5b5 (Hodogaya Chem. Co., Ltd.) November 1968. 96. A. Corredor Garcia, Span. Patent 315,298,November 1968. 97. Brit Patent I,0h7,5l2 (Minnesota Mining and Mfg. Co.) November 1966. 98. Richard Owen, V. S. Patent 3,315,598 (3M Co.) April 1967. 99. Buck StrioKLin, U. S. Patent 3,360,367 (3M Co.) December 1967. 100, Martin Hepher, Brit. Patent 986,053 (Kodak, Ltd.) March 1965. Id. A. O. Gulko, U. S. Patent 3,kOU,99h, October 1968 102, S, Anoar, Brit. Patent 1,025,757, April 1966. - 103. R. Oda, H. Fuju, H. Horiga, and S. Dotani, D. S. Patent 3,389,007, June I960. lDlj. Brit. Patent 1,1149,265 (Xerox Corjv) April 1969. 72 DSW 010093 I LEXOLDMON000466 WATER PCB-00035933 4/ 10J>, B, B, Jaoknow, J, H, Moriconi, and F, M, Paleri&ti, S. African Patent 6,803,560 (Rank Xerox, Ltd.) January 1969. 106. Hans J. Lena# Ger, Patent 1*199*290 (Hoechst Fabweke) August 1965. 107. Daniel L. Ooffredo, U. S, Patent 3*269,308, August 1966, 108. Brit. Patent 1*126,1(78 (Johnson and Johnson Co.) September 1966. 109. Charles A. Berridge, U, S, Patent 3,l5ij,515 (General Electric Co.) October 196!i. 110. . R H, Snedeker, 0, S. Patent 3,1(05*199 (Union Carbide Co.) October 1968. 111. D. Lurie, Fr, Patent 1,529*506, June 1968. 112. W, F. Busse, U. S. Patent 3*ltl8,267 (E. I. DuPont de Nemours) December 1968. 113. R. 0. Quinn, U. S, Patent 2,030,653 (International Paper Co.) February 1936. llh. H. Picchota, Kunstoff-Rundschau* 12 (b), 191 (1965). 115. Paul E. Burgess, Jr., Carlos J. Hilado, and William R. Procps, Space Mil. Appl. Cell. Blast. Syst. Annu. Conf. Cell. Plast. Div., 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. li (2), 67 (1968). 117. T. Kirata, H. Abe, and T. FUkul. Ringyo Shikenjo Kenkyu Hokoku, 1967* No. 200 155. Cf C. A. 22 12779a (1969). 118. H. W. Coorer* Jr., and N. H. Shearer, Belg. Patent 652,653 (Eastman Kodak Co.) December 1961|. 119. Hans Schumann, Oer. Patent 1,298,1(58 (Deutsche Solvay-Wsrke) June 1969. 120. Rene Mikael, Fr, Patent 1,532,115, July 1968. 121. H. T, Kenp. Jr.. T, L. Statler, and E. E. Muellar, Mitt. Ver. Dsut. Emailfachleute (5), h5 (1966). 122. Rolf Bremer, Eberhard Rheinhold, and Hermann Fiebig, Oer. (East) Patent 66,712, May 1969. 123* Belg. Patent 696,820 (Establishment Marechal) October 1967. 12li* 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 OSW 010094 LEXOLDMON000467 WATER PCB-00035934 126. Fr. Patent 1,299,6314, July 1962. 127. Netiv Patent Appl. 6,1*11,169 (Monaanto Co.) Karoh 196$. 126. ibid, 6,l01,l*7l* (Monsanto Co.) August I96I4. 129. K. Sato, U. S. Patant 3,1*68,726, Septenfcer 1969. 71* DSU 010095 LEXOLDMON000468 WATER PCB-00035935 */ ( i' .... APPENDIX C The Need For Continued flee of PCBs As Electrical Insulating Liquids Table of Contents , Page I. How are PCBs Used by the Electrical Industry? 76 II. Die Need for PCBs in Transformers 76 A. Mineral oil-insulated transformers B. Dry-type transformers ni. The Need for PCBs in Capacitors A. Mineral Oil 79 1. Size 2. Reliability and life 3. Safety - B. Other Liquids '. 1. Castor Oil 2. Dibutyl sebacate 3. Silicone Fluids '- . iv* Enrironraental Protection 81 Tables ... 1. Composition of Different Liquid Chlorinated Biphenyls 76- 2. Underwriters' Laboratories Flammability Ratings 77 3. Alternate Insulating Fluids 80 OSH 010096 LEXOLDMON000469 WATER PCB-00035936 APPENDIX C The Need For Continued Use of PCBs As Electrical Insulating Liquids I. HOW ARE PCBa USED BY THE ELECTRICAL INDUSTRY? (l) 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 eurrent level to another, and the conducting parts of those 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 Arodors (the trade name of Monsanto), their vapors, and their arc-formed gaseous products, trans formers filled with PCBs are relatively free of fire and explosion hazards 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, Aroclors also have the advantages of reliability, long life, and small size. Table 1 Underwriters1 Laboratories Flammability Ratings Fluid Flammability Rating Ether 100 Gasoline 90-100 Ethyl Alcohol 60-70 Kerosene (100 F.P.) 30-iiO Mineral Oil 10-20 Aroclor 12li2 and MCS 1016 2-3 II. THE NEED FOR PCBs IN TRANSFORMERS PCBs are used in transformers wherever fire protection is particularly important -- for about 5 percent 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 sucfi buildings, and require no special enclosures other than nec essary to prevent accidental hazardous mechanical or electrical contact of persons with the equipment. See Table 2 for some liquid chlorinated biphenyls. 76 DSM 010097. LEXOLDMON000470 WATER PCB-00035937 V ty soo tIenil -3 UN Hi -CaO o vOO iinn CO O' o o4 o *CO a r I 8 0<n\ va A I CM o\ $ IB TABLE 2 C0 5HL0 CVJ o Ct*M- vO m in * -C3M -3 CM M3 in CM i CM m 1 CmM CM CM -r3- m a n V. ml 9H SI Em nTt mm Voi co in ov CM -3 8 0c -a rl jion vO CM- Si s 1 W.I H > 8) 77 a w s I LEXOLDMON000471 WATER PCB-00035938 The amount of Aroclor used in various types of transformers ranges from 1*0 to $00 gallons ($16 to 6,1*50 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 PCBs used in trans formers was approximately 1.3 million gallons (8.1* thousand tons). The 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 PCB 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 transformers (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 substitution: : 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 units 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 tenporary malfunction of related equipment. 3. Some dry-type transformers are larger by 10 to 30 percent thaa comparably rated liquid-insulated units, and most are expensive. , 1*. Dry-type transformers are noisier by $-10 db than are liquidinsulated transformers. $. Open dry-type transformers, which are cheaper than sealed drytype transformers, cannot be used in certain corrosive or hazardous / atmospheres, e.g., on furnaces or on electrostatic precipitators near hot stacks. Clearly there is no substitute for PCB-filled transformers where fire protection is required. 78 d$H LEXOLDMON000472 WATER PCB-00035939 in, THE NEED FDR PCBs IN CAPACITORS ~\ PCBs sire 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* Ihe 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 capaoitors 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 euch equipment as air conditioning units, pumps, fans, etc. Almost 80 million such capacitors are manufactured annually, most of them for. first-time use. Capacitors used in lighting and air conditioning applications contain 0.00? to 0.09 gallons of PCB per unit. The largest power 5 capacitors contain about 6.7 gallons of askarel. The most popular size 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 complete "normal" year for the electrical industry, the total amount of PCBs used in capacitors was approximately Ut.U thousand tons. Possible alternatives to PCB-irapregnated capacitors are capacitors impregnated with mineral oil, or certain other liquids. ' A. MINERAL OIL 1. Size Ihe single most important property of a 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 (Aroolor 121*2) is $.8$ while thtrt of mineral oil is 2.2$. (See Table 3) Reverting to an oil-paper dielectric' system would increase the average capacitor .voluan(size) by approximately 600 percent the weight by 00 parcent,and the cost by approximately 1)00 percent. At the present levels of demand for capacitor AVAR, 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 consumer. . 2. Reliability and Life ' , PCBs. are thermally and oxidatively more stable than mineral oils, and discharges, which can occur in capacitors, are less likely to generate gases from askarels than from mineral oils. The chemical stability,of PCBs in the presence of capacitor tissue and plastic films and . the favorable etress distributions between solid and liquid have made it * possible to design low-cost capacitors with a life expectancy of more than 10 years life in lighting applications and more than 20 years in electric utility applications. In each application the first-year failure rates are less than 0.2 percent. Ibis level of life and reliability had not been achieved prior to Ihe introduction of PCBs. _ OSW 010100 LEXOLDMON000473 WATER PCB-00035940 p sh; 00. s Op 3 $ * s On <as p* PI H 0 fu 0) Vi On cn H & C"\ *> CVJ H * o .- olo-l M a i-l H r-l -mHa H9 & I Table 3 In 8" u\| CM \A \A \A Ok *H -P CO 00 r CM u 4s - U\ VA VN CM i V Vi H *" !3 \OH0 rO? -CaM S| a 1 I rooVo-t. *o4 8 3Vi iS $ 80 LEXOLDMON000474 WATER PCB-00035941 3. Safety The relative non-flammability of PCBs significantly reduces the fire hazard that might otherwise accompany those failures that result in nature of the case* B. OTHER LIQUIDS 1. Castor Oil* The dielectric constant of castor oil is lw> and this material is useful as an impregnant in D.C* energy storage capacitors. However, A.C. capacitors filled with this liquid have relatively short lives and are not very stable under A*C* discharges and in the presence of water derivable from the cellulosic paper. 2. Dibutyl sebacate. This ester is especially useful in high frequency parallel plate capacitors because of its low, flat loss charac teristics over a broad frequency range. In this type of construction the liquid is the sole, dielectric material. When used to conjunction with paper,this ester is aiso unstable. 3. Silicone Fluids. These materials have a dielectric constant of 2.7 and would generally be subject to the same disadvantages as mineral oil.. In the interest of achieving a higher degree of environmental compatibility the capacitor industry switched during 1971 from Aroclor 12li2 to Aroclor MCS 10l6, from which the higher-chlorinated persistent fractions have been substantially removed. IV. ENVIRONMENTAL PROTECTION Hie 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 also 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 recommendations made by a previous NIPCC Sub Council report (The Use and Disposal of Electrical Insulating Liquids. June 1971) and are judged to be well on their way toward implementation t witness the introduction of the new capacitor dielectrio, the provision of facilities for the incineration of liquid and solid wastes,,and the instructions to operating personnel and users regarding the need for care in waste disposal, an activity now being further formalised and strengthened by ANSI's committee C107. The annual residual leakage to the environment from the oontinued use in transformers and capacitors has been estimated between one part in a thousand and one in ten thousand of the existing environmental FCB burden. i. The above paper was prepared by the Electric and Nuclear Sub-Council, National Industrial Pollution Control Councilt Chairman, D. C. Burnham,1 Westinghouee Electric Corporation} Vice Chairman, Fred J.Borch, Chairman and Chief Executive Officer, General Electric Company] Members: A. P. Fontaine, President and Chairman, The Bendix Corporation} Raymond H. Qiesecke, 81 D$W 010102 LEXOLDMON000475 WATER PCB-00035942  / President and Chief Executive Officer, McGraw-Edison Company} c.. Lester Hogan, President and Chief Executive Officer, Fairchild Camera and Instru ment Corporation; Robert w. Sarnoff, Chairman of the Board and President RCA Corporation. * 82 DSW 010103 LEXOLDMON000476 WATER_PCB-00035943 APPENDIX D my Occurrence. Transfer, and Cycling of l*CBs in the Envirorment Table of Contents I. Occurrence in the Environment II. Behavior in the Envirorment A. Air B. Water and Sediment III. Exposure and Biological Accumulation 17, Discussion V. Research Needs and Opportunities Page '92 99 9? 102 103 Tables 1. PCB Manufacturing and Sales Data From Monsanto Industrial Chemicals Co. * 2. Concentration of PCBs in Mirdcipal Sewage Treatment Plant Outfalls 3- PCB Concentrations in Industrial Effluents 1*. Total Estimated Contribution of PCBs to the Aquatic Environment 5. Concentration of PCBs in Sewage Sludges -. 6. A Sampling of Measured Occurrences of PCBs in the Envirorment 7. Accumulation of PCBs by Various Aquatic Organisms 8j>-86 88 89 90 91 93-98 100 83 0$w 010104 LEXOLDMON000477 WATER PCB-00035944 APPENDIX D Occurrence, Transfer, and Cycling of PCBa In the Environment PGBs have been in use for more than four decades, not only in the United States but throughout the developed world. They were not recognized as environmental contaminants until (Jensen , l)in Sweden identified a series of unknown peaks on gas chromatograms 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 civilization 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 3^,000 tons In 1970, Table 1. Sales doubled I960-1970} 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 are few. It is estimated that Japan manufactured 13,000 tons per year (2). PCBs are also produced in West Qermany, the United Kingdom, Spain, France, Italy, Russia, and possibly new producers in Brazil, Argentina, India, and East Ger many. 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. Monsanto's 1971 sales dropped to half the 1970 level, and 1972 sales are expected to be 12 - 15,000 tons. Prior to. 1971, when Monsanto (the sole U.S. manufacturer) curtailed sales to non-closed system uses, about 1*0 percent was used in plasticizers, hydraulic fluids and lubricants, 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 sane percentages held worldwide, ij0,000 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 0,000 tons or more. (Niobet and Sarofim, 3)provided rough estimates of the losses of PCBs to the North American environment in 1970? 1500 to 2000 tons to the atmosphere (mostly Aroclor 125it to 1260 from plastics and 121*2 from burning dumps)} 1*000 to 5000 tons to freA and coastal waters (Aroclor 121*2-1260)} 22,000 tons into dumps and landfills (mostly Aroclor 12l*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 be 1 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* DSW 010105 LEXOLDMON000478 WATER PCB-00035945 D m . FROM MONSANTO INDUSTRIAL CHEMICALS CO (VI, co CO $ %co CO eo cO CO t^\AH -3 CM-4 VX H CO CO OO CM r-C On MO On CO \ OrIN UNCO rf I 0-3-3 rOUWACM O -a CM VANO CM On CO H h cvOiocao NoOtnnOacvi CM CO -oa GO CO ft CO \UDX rx CO ft c*\ o -a h moo rlHcs 09> I JHNHvCOJUCVvOOv SCOO CUCOX- dj H f-co.3 O H CO CN-3 N W On-3nQ UN CM CO O WUVOrl Oj-3nO vO CO CO Ur>No - nO o-M *O4 o (XOA COOn r-l C--3 cm vmm no -a UMAOxOvCM I CM r-t f-'O.'O I (OUNnO C-CD O no On O UX ON CM CO CO CM CD HHHOOOOH CO CM NO C" i--C -3 H CM UN CO o 3 a5 8 H CO WUN'OOsW-3OOnvCNO WlO NO UN On-3UN IcO I rtCM H UXnQ -3 I ||vHi .3 O CO .3-3 On Ox CM UCNM-C3VOlUn CXOtOUrN-xHQUCNOQi-* CO CO NO NO ft CO +o> p On UN On On On I H u\-^ro i 2O?x CM CcMo CM -31ACO H O UN CM I NdO S- On CHM O IHS UJ CO -3 C_ A H N J CM UN On CO CO C" H aUNvQ On r-i O CM u5 UN r H M> O no CXI 'SICO CM CM c.o. Or>r^ni3v3Hn1cScA--o- fdo i CM CM CO rIc) uCOx H8tffst O *> ft O lj C P. 4) (0 9O so ^a On O H5 3& sM CO s if & 1* M PO O 4-C 2n o *> o 8 OQ ' HCMCMCO-aO CM CQ CM CO-3 -a VXNp NO NO 33888888 r-- CM o ooqoqoqo 3Hoo Hoo oHo ooHoorlor6tyrolod a 1h * h 5 ^ ^ 43 P5 LEXOLDMONOOQ479 WATER_PCB-00035946 OSW 010107 / ea rj a, MN JI <**> | o$Gt a Bs n*i sis col SlS ft si ssa *1 H sset 4> ,, non O Hl StR || Set 5g| S& #1* 3$ 00 OO rv<N ''M'' n cm O f^CO oo \A CM nn r| ^ tiffonrcljNOS\H'tOM-CnMON>NtJo0p'-H'N0nfv\ I 'a CM H 0C\M1A^cOnCk\OAktOA ^ I cm <CMOiJ\*No rNt Osort 8S3g3, 2fgIS rt-3 rt COCO rj I a3SS8S$ . CM1ACO OMJ rt **8a, H 888 88 t*\ f^O O -9 I M> CI sj3 rt rt U\H I CM ssspagaa a'-gsgash N-nHO CM Os OUNNN\4Qgv\\AbAC0(OMX " \OOn4H woo f^O\U\0\pvWN{MB r-i CQQQCO CM K CM 44oo \rv CM VMA^fig Is- O N* 9 Cm V\0 0\ H-ijeo 3 5iw ,ut^o\rt*I0rAT\i wIOrAt>riPNrn>VCw'--O\ovro-d.2Ca>M ^OvNnV\N hco >o A cava On 40 ap!8SR CM * SH tes^3" cm nSStitSSS saasaaaa 35,535^55 88 8...8.... ssss. <8U 66 LEXOLDMON000480 WATER PCB-00035947 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 dumps probably have undergone less degradation. Given the diversity of uses of PCBs and their chemical stability (greater stability in the higher chlorine species), it is not surprising that residues are now widespread. While satis lying 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 sources* - -- Open burning or incomplete incineration (at usual temperatures) 0 of solid wastes, municipal and industrial. Incineration at 2000 F or above for two seconds will destroy PCBs, but poorly operated . Incinerators or open burning nay result in PCBs being released to the atmosphere unchanged. -- Vaporisation from paints, coatings, plastics, etc. (Nisbet and Sarofim, 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 envirorment as ingredients of pesticides or as carriers for pesticides (such uses 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* environment . reach it through Industrial and municipal discharges to inland and coastal' waters. Tables 2, 3, and li present data on such discharges. Based on Table 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 $ presents results of analyses from several such sludges. Sewage sludge ie disposed of by incineration, landfill, spreading on the land, and dumping at sea. Fbur million tons per year reach the Atlantic Ocean and Qulf of Mexico, which would include only 10 or so tons of PCBs (lj). 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 thantons per year. 87 DSU 010108 LEXOLDMON000481 WATER PCB-00035948 TABLE Z - CONCENTRATION OF PC3S IN MUNICIPAL SEWAGE TREATMENT PLANT OUTFALLS Collection Site Collection Date Aroclor Compound Detected (ppb) Flow per Day Mgd 1/ Est, PCB -- Discharged per day (lbs.) Source of Data Ohio . Mlani River Dayton 1-19-71 0800 to 1-20-71 0800 1254 17 48 6.2 EPA Unpb. Data Heal1ton 1-19-71 0000 to 1-19-71 2400 1248 10 8 0.6 If Middleton 1-19-71 0800 to 1-20-71 0800 ND* 91 ' Wisconsin Milwaukee River. West Bend Fredonia Seukville 3-26-70 If 19 1254 1254 1260 0.25 0.12 0.13 1.4 0.1 0.1 0.002 0.002 0.002 Velth & Lea If H ' Grafton 9 1254 0.04 0.8 0.002 II California . East Bay (San Francisco} 12-70 San Francisco Terminal Island tfl tf 1254 3.1-3.8 1254 1254 3.8-5.8 5.8-12.8 155 31.5 9.3 4.2 *0 * 1.2 0.7 Schmidt, et al, *71 If II Orange County Hyperion ff ft 1254 1254 0.21-0.64 0.16-0.37 130 340 0.4 0.7 ft ft White Point If 1254 76 350 213 ft Richmond San Diegp ND* ND* -- - Oxnard AND - Not Detected ND* 1/ mgd = million gallons per day = (8,000,000 lbs,/day) " 88 OSW 010109 < - LEXOLDMON000482 WATER PCB-00035949 *4 f* i-4 eft s U* O f-* H *J 0 0 i 0 0 (3 6 Q *4 < O H g Sfr =44 *o 0 o, s z 0 4J 0 0 < t4 o XI *0 M *J 0 * 0 g3 0 o f4 t/> > Id 3 Q ou 2a ga U ft JO m tSJ <MH Id ' 5 3 o 3 u! r- O O8h o5 o M SM5 M WO ou0R1) O pq s 44 3 PQ > * H 'O US 3 0uo!|l oc 0> s B0 i8i 0(ft * I O * Q LEXOLDMON000483 WATER PCB-00035950 TABLE 4 TOTAL ESTIMATED CONTRIBUTION OF FOBS TO THE AQUATIC ENVIRONMENT Municipal Outfalls Assume! ; *" 150,000,000 sewered population x . 130 gallons sewage per person per day x 8 pounds per gallon of sewage Approximately 160 billion lbs./day. With concentration of 0.1 ppb in sewage, 16 lbs./day; With concentration of 10 ppb in sewage, 1600 lbs./day. [Note that only the White Point outfall and Dayton (largely serving industrial communities) exceed the 10 ppb concentration] ' Annual contribution would not exceed 300 tons from this source, even if the average concentration in municipal sources was 10 ppb. Industrial and Other Sources Basis for Estimate: Concentrations in the Creat Miami River of 5.8 ppb and flow rate of 728 cfs yield estimated dally ' carriage to the Ohio River of '**93 lbs. per day. Contribution from the sewage treatment plants at Dayton (6.2 lbs./day) and Hamilton (0.64 lbs./day) account for 6*8 lbs. (~-7% of the amount present in the river). In the Milwaukee River, the estimated discharge of PCBs to Lake Michigan, based on a concentration in the water of 0.15 ppb (Veitb and Lee, 1970) and flow rate of 500 cubic feet per second, Is'vO.S lb. per day. Contributions from the sewage treatment plants at West Bend, Fredonla, Saukville, and Grafton, total 0.002 lbs./day, (about 0.4% of the amount present). Extrapolation The Great Miami River drains a heavily industrialized area and represents something near the upper limit of PCBs to be expected in municipal discharges. The Milwaukee River is less industrialized. If one assumes ' . that municipal sources contribute on the average not more than 51 of the total, the annual contribution from other sources would be on the order of 300 * 20 6,000 tons per year. 0S 010111 LEXOLDMON000484 WATER PCB-00035951 TA B LE 5 . CONCENTRATION OF FOBS I N SEWAGE SLUDGES fua u * g Muif*f Owco PH, <4 Ai 5 43 W -D S S' !3 1U0 Si O o MI *o*o fS4 MCO O <* o *-4 w oc aJ 5v ga o CN O' I irv <9 f** n o CO o sfr *ol Vo 43 Iff a3 : a 5 Is o O ~* CM Ov N M O r* o oo -* CM CO 88888 OftOA hA 'OA NA O m ^A M N N iff N O o a o<0 x* CM O HN O CO * CO *o M OM 3 8 *m *v> 4iffi^ff4in4iff4iff u" > <8 o* 3,CM N CM CM CM CM CM CM CM m *0 -a a oa U8 O Iff Is UM rvflt - 6C 14!<*_ M +u4 >4Mc eC Uri om |ti VUvJCM* 4 CJ U SvBC w PM C sllss M CU S6 *oUA-f^/ UH--4 4OC8*3 Hb6>}sJ3 a J)c Jb o 8* I g W H * a5 91 m * C-- Iff MIff 5 AJ o Mo H <AJ X LEXOLDMON000485 WATER PCB-00035952 By far the largest quantities of PCBs must end up In dumps and landfills. As noted above, open burning will doubtless release some 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 will be sequestered or only slowly released to the environment. Analyses of:stagnant water close to a Swedish landfill were below the level of detection of l parts per billion, suggesting little leaching from such sources (5). PCBs are known to have reached the environment or man's food supply in a variety of other ways, no one of which is important as a source of environmental contamination, but each of which may have serious consequences locally. Spent transformer oil containing PCBs, used as an herbicide 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 h&tchability of eggs in some chicken flocks, and residues in excess of the FDA 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. from 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 ofc2.*>i residues are in the top 3 inches; the weight of 3 inches of sediment is 62.It (wt. of a cubic foot of water) x 1)3,560 sq. feet/acre*l,600,000 lbs./ acre,, owl billion lbs. per square mile (1.6 million x 61i0). At 10 parts per billion, the PCB burden would be 8,000 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 less than 1/10 the amount Nisbet and Sarofim (3) estimate may be present in freshwater and coastal sediments^ I. OCCURRENCE IN THE EN7IR0IMBNT Thousands of samples from various parts of the environment 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 immediate sources of waste 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 eedimpnts contain a few parts per billion, up to several hundred parts per million (ppm) near some industrial outfalls; from tenths of a parts per million to tens of parts per million in fish and up to hundreds of parts per 92 DSW 010113 LEXOLDMON000486 WATER PCB-00035953 6. A SAMPLING OF MEASURED OCCURRENCES OF FOBS IN THE Sm ith CFSLP DSW 0 1 0 1 1 4 4 uft U ,0 S.a ocV c 344 H 4*3*444 -"OCa4 S3 &Z eO IS ft -4 lPi c ft Q 1ft4 Af1t t- H iM X i& to 8 p c *3 S 8. .Oft* i .2 44 C 05 * *3 6 g s n* S8 5S gna II s 0Su4 C *fot 3 g.8 Ot si 78 R& )C 9 > o m r\ &.i*f+mt *9dp30m j m ft U4 -I g-.r fftt Qufti4ff>tt U6Or4 H<fDt i ITI Sn S '* CM . JV & *so A JC ij o 3 u r> *>S*-4' Hf4 ono O Q V f|H 4HO O1 O O1 CD CM O 0 4 IK *K sa C1M OI HI CM o o *1* p 9u HOu oft.gull B _ ft <UP 5o5 5! (2A ax as US as (A 2 o 00 o & R H CM CM O ||3 8 CP 4frJtt a 3 1 >& a <*4 O i U o514 ?*4 f 3 3 c j? *O8 1 SI a) 5*1 ?3 XNe. t cm : <N o N CM -or*s.#r^--r Mft Own4n-1 M h4 i t i O or- U *>4 Ou w0 k 8 3 fftt 9* & J} 3 < M V &f4B S. CO Uft 1. 35 2S LEXOLDMON000487 WATER PCB-00035954 TABLE 6 (Continued) c Mi 44 *9j 2H<Ow *MP8MD> K *** t* CM ft e > v l. i,, S'S1 ^V umi48o O . ft 44 4-1 mJ Wi <044 I a M *04 8M SB *J vfOiSO * boo> Irt r4 M O O o> a O ft Of-4 o CoM . 01 y uo 5 oy ft ft o H V ^|*S <Bo oooeo .oo]]' *ft CM o & ft frI*t u0. ASO It Si 8 CM ft ft CM 91 O M oo-4 V h- 8r> v* V a as M (M CM fftt fot >fot ft CO o oUaC*goco* -w34oop0o9rOJ1J'f. 5H I3 s 8 Wh <tH 1 0 I vl c .H II M 5ofi . 3fe 3 (A 43 If 9O Mvtr m tf Mrf ^IeS 4>s>m3 3f 5' 6 a ?Il 0 H 0 V) *D gu a* fl ?0"4 OP *Mi '0rt I<8 j*uojbMs JJ 6 3W at! Sti -3 sa l| a*. K ft ft ft ft LEXOLDMON000488 WATER PCB-00035955 OSH 0 1 0 1 1 6 u o H CM ^N SS ft N =2 AJ H8 A 5|IUi SB fc w X4 O H 4i <H 18 *- V) 8 > o9 UaS ia *C41l*B4 <U 8 ft 2 <3 U 2 *u ia MnfOtp'U*MS* NM SO2 OM' c 5 u* us, {. uoe0 0 U33H OC3 u *Cd ! Ho o3 4o1; sfj 3(0 < o o 8 IX wOrt* (3 W *2 * o H, # qUH <5-U O8S f8wal5 .*MU4s o 3S o is *4 I 8 Ov O i 8 R e 4T> s s0 43 U3 *f9t * U> H UU ss S 3* M a 8 ON 8o *8 S ICM H O 32) I2rt *0 CM s- ia 4 * CM 2 -* & CM tcO* .A s s o s ss ft V3S uMMMs ots *o4 a & m& 33 Js8 2. si CA ^ O O O' O' s H s H s f4 S S 4 tl n -* 8 8 nH n b rt A1*f4t 4 S Cd *O-u* r *5 +tpo44 *fMf4ttO a8 u os O cirtr* O' O' 8 O' O' 8 Ho * A& *%k04 u Ao*4 1 * 5ft- OS f8id,I2t* cron 031 c 8 3A o I 5su* * 3 8* 11 Uf !i 1 m S o V 3 U O u 2 US 3 l 95 LEXOLDMON000489 WATER PCB-00035956 TABLE 6 (C ontinued) oO' u0 N acs*ilj5e* 4J 5 ETE 1g* X4 6 i* t uft i *N4 ft 3fMt *-t *0 g 'wM O* ft 5* 33 s sf004 Uft . s.a OottfoI> o o g in rm> 8 Mo HoI hwo r-n 1 . to Oo u >o HhoOOQt5oiV0w: <pG aoap s, M 9B >Po O' _4 *A 8 8 HCM n a O' 8 fl> sf r* V3) _w 3J5 s*8 S3 0 I! Ha si W< . (H g ^ *M 31 m*9 n CM CM Or>. Ok O 8 t 2 tu g 3 I! w ft 6ft 5 441 1Mf4t 5 PQ| #* OS & o 96 40 w H & SoM '*f*t sS.U 8c eK 3-S ** 6 S* 8* O M ft II5g-- ii k e -u SB! 5c <EM g S vaf i& -*Hs sft a> ON -uS u *> foCt rbfl ^ Ho | 6 j? 3 8 aH *f,t aH? 93 MM>HOaOwCq b f0 . 0 &S4 !b0B?Uff4t: ft I "50 1 C44 *fSt Ow o5 "** c0t * W M .wft '-gUgUS> 9 ft *r4 C D IM .VCBB N/-s rf fi .g hr fc ucBP<n <tWT O aV..O.-'i 8 N<t O jj *S ! *J& 0.0 So >* f6 90 Slarf-s |.iiu iM.j f--Ol 5iO^n-HP -gmf-aaSs3*s3w Mab**> r *ss&*ismri 8 3 l$? K OC9OHHJ2 A OS < J o fB Q X / Q LEXOLDMON000490 WATER PCB-00035957 QuC0! o VM O9 to gH 4asJJ..o' su 3 o tVoao * *u20>*. VI p o 9 7M^ *A 8 *S 5 5rt Inr* r2p-* 0 foO A C1M oo o IT) o o o ooI o *4o1 U S 3AUo * oi o 8O om*s oo oo o 00on*0o4it9o0^ oo oo ow o 8 8 m is* *? CO t-- TABLE 6 (C o n tin u e d ) iI I LEXOLDMON000491 WATER PCB-00035958 M.*! C ure5 o Ol d o uhn -ja s$ co u S* Ott*o' o* S-* 30,000 30,000 5 ,7 0 0 \A -3 eg SeOmg#' * vcA5 ~ .* H *JCM Q>v 3(4 J4 rO C r4 Du O O* 4 UV ft so =s M O' V e *4 o MO u i-4 CO a ji 0 o CO fC CO o 9c PH o u V ff s OS < t9-a WO *1 IU o ** o s s o r4 IX IX IX eCM eg & j*QOto O O o as 8- ^ 8i 8 8 /CVM O o*4 o 3C6* Q OMOP0 O**0J1| *<s5 asP| o p0 CO vs Ss as 00 o tCoO **%. o o o CM H 1 n CM ctoo O' ooal CMM <1N*T1| NOOl Hf0lO0 o<0 <o| <c4 38 to u 5 a I $ -VH -O3 uotaa *uoV9 I U o 40> (O Q B B LEXOLDMON000492 WATER PCB-00035959 million in some fish and birds near the top of the food chain (l/8 of an inch ie about one trillionth of the distance to the moon; and a part per , million is about 5 steps on a valk 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 TOE ENVIRONMENT A. Air - The relative importance of the atmosphere as a transport mechanism is not known. While 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 arotlo lakes or in more or less wilderness areas of the North where woodcock summer* Nisbet and Sarofijn (3) suggest airborne PCBs will have been adsorbed on particles and have & relatively short residence time-- thus most will have bean redeposited on the U. S. continent, but some will have reached 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 tho receiving waters, and the down stream reaches of the waterways demonstrate transport through the aquatic sys- tern* Measured residues in fishes from various environments suggest accumulations at the downstream ends of the drainagevays. * 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 Nimmo and his colleagues at Qulf Breeze (8) has shown that at least pink shrimp and fiddler crabs are able to take up PCB residues from this source* Fiddler crabs and pink' shrimp exposed to clean flowing sea water in aquaria containing sandy silt with initial residues of 61 parts per million (dry weigSt basis) of Aroclor 12$h accumulated an average of 80 * 2$ parts per million in the whole crab and 2li0 parts per million (one pooled sample) in the hepatqpancre&s of the shrimp. Accumulation was much less, 17 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 hepatopanisreaa) from silt initially containing 2.$ parts per mil lion. The same investigators have shown transfer of residues iVom sediments to overlying water. Effluent water from the aquarium with 6l parts 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 O.J> parts per billion. III. EXPOSURE AND BIOLOGICAL 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 OSH 010120 I LEXOLDMON000493 WATER_PCB-00035960 TABLE 7. ACCUMULATION OF PCBS BY VARIOUS AQUATIC ORGANISMS Species A roc lor Compound Exp. Time Environmental Concentration Residue (opb) ... (ppb) Coneentration Factor Source Catfish Bluegi11 Fiddler Crab 1248 1254 1248 1254 1254 Pink Shrimp 1254 60 da. 60 60 60 30 30 13.3 4.1 4.9 6.8 3.5 0.5 3.5 0.5 953,000 312,000 312,000 87,000 80,000 17,000 240,000 6,100 72,000 76,000 63.700 12,800 22,900 34,000 69,000 12,000 Stalling and Mayer, '72(7) r * . ft ft t < ft 100 010121 LEXOLDMON000494 WATER PCB-00035961  hepatopanereas of pink shrinp. The data reported in the preceding section demonstrate that pink shrimp are able to accumulate PCB residues from "environ mental levels as low as 0.5 parts per billionj and Table 7 shows accumulation by fish from levels as low as 1 part per billion. Evidence from environmental 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 soluble, 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) at 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 environment by various trophic levels; e.g., soil to earthworms; water to phytoplankton, zooplankton, larger invertebrates, and fish. The fish and plankton data from the North Atlantic reported by Nisbet and S&rofim (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 (9) 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 environmental uptake is probably the most important for aquatic invertebrates and fish. That humans are exposed to PCBs is evident from th8 data in Table 6. There are a number of possible routest air, water, food. Fish and 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 FDA and the various States where fish are known to have substantial PCB contamination. Other foods have been found to contain PCB residues, but these residues are for the most part traceable to aecidents; 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 traceable to silage stored in silos painted with PCB-oontaining 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 1*79 of 15,000 food samples by FDA during November 1969-June 1971 (200 of the li79 were followups on saaples found to contain PCBs). In the FDA 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 B. S. food supply contains detect able levels of PCBs. 010 Uz 101 LEXOLDMON000495 WATER PCB-00035962 *J Other routes by which nan nay be exposed, or nay 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 PCBs (10). Carbonless ,"carbon" paper was reported to contain 2-6 percent of PCB Kanechlor 300 (11); experiments with this paper demonstrated that FCBs rubbed off when handled, and that even after washing the hands, approximately two-thirds of the PCBa 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 where it is thought to be more or less sequestered from the rest of the environment. It Is clear from environmental samples that smaller but significant amounts are present in the terrestrial and aquatic environments. Much smaller total amounts are present in the biota, but levels in some organisms in some 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 PCBs is required to contaminate a large part of the biota (for example, 10 tons would be sufficient to contaminate the en tire 0. S. population to a level of 1 part per 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 7,000 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 $ 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 Bafety 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 erviroiment--both through restricting sales'for such uses and by providing a disposal service for its customers. (During the first year after this service was announced, more than 500,000 pounds accumulated awaiting disposal in the 10,000,000 pounde-per-year incinerator being constructed (3). Despite those steps, substantial amounts of PCBs are still reaching the environ ment. They are present in detectable levels in virtually all municipal sewage effluents. Effluents from many industrial plants such as paper mills, appliance manufacturers, electrical equipment manufacturers, and chemical 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. * _ Mien the restrictions become fully effective, the principal source to the aquatic environment can be expected to be that part of the electric equipment manufacturing industry and the electric utility industry that require these valuable materials because of their fire resistance and dielectric properties. 102 DSW 010123 LEXOLDMON000496 WATER PCB-00035963 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. 7. RESEARCH NEEDS AND OPPORTUNITIES 1. Data provided by Kuratsune and Masuda (11) suggest that PCB-containing carbonless copy paper may have been an important source of PCB 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 PGBs in house dust by Price (lb) 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 present. A set of samples 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* b.. Data on pesticides in air are unsatisfactory. A few samples, in eluding both vapor and particulates, should be collected from industrial areas and analysed. If the methodology proves satisfactory, a small-scale survey should be undertaken to determine the importance of the atmosphere as a trans port mechanism. $. 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. Shallscale sampling should be undertaken to determine the concentrations brought to dumps, the fate of PCBs 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. 8. 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 OSW 010124 LEXOLDMON000497 WATER PCB-00035964 PCB content of plankton from equal volumes of water in inshore aria mid* ocean waters, as well as sampling of the surface film.in both areas, would be informative, 9- Carbon filter samples going back to the roid-l?60's are available from some fresh water locations. If a satisfactory analytical method can be worked out, samples from 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. Fish samples should be considered for the same purpose. - 10lj OSH 010125 LEXOLDMON000498 WATER PCB-00035965  mS FOOTNOTES 1. Jensen, Soren. 1966. Report of a new chemical hazard. New Scientist, 326l2. 2. Isono, N. 1970. Jishu Koza, 1 (l)*60, 1 (li)t$8 (in Japanese). 3. Nisbet, Ian and Adel Saroflm. 1972. Rates and routes of transport of PCBa in the Environment. Environmental Health in Perspective. 1, (in press). h. C.E.Q. (Council on Environmental Quality). 1970. Ocean dumpings A national policy. Ashington, D. C. 5. Lidgett, R. A. and H. A. Vodden. 1970. PCB -- the environmental problem pp 88-96 in PCS Conference, Wenner-Oren Center, September 29, 1970. Stockholm: National Swedish Environment Protection Board. 6. Acker, L. and E. Schulte. 1971. Vorkcnmen von ohlorieten biphenylen und hexachlorobenzol neben chlorierten lnsektiziden in human milch and menschlichen fettgewebe. Naturwiss, 57 * Ii97. 7. Rieebrough, Robert W., and Brock de Lappe. 1972. Accumulation of poly chlorinated biphenyls in ecosystems. Environmental Health in Perspective. 1, (in press). 8. Nlmmo, D. R., P. 0, 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, David and Foster L. Mayer, Jr. 1972. Toxieities of PCBs to fish and environmental residues in fish. Environmental Health in Perspective. 1, (in press). 10. Price, Harold A. 1972. Occurrence of polychlorinated biphenyls in humans. Environmental Health in Perspective. 1, (in press). ^ 11. Kuratsune, Masanori and Toshito Hasuda. 1972* Polychlorinated biphenyls in non-carbon copying papers. Environmental Health in Perspective. 1, (in press). 12. Veith, 0. D. and 0. F. Lee. 1970. A review of chlorinated biphenyl con tamination in natural waters. Water Research, Ij*265-269. 13. Schmidt, T. T., R. W. Risebrough, and F. Oress. 1971. Irpit of poly chlorinated biphenyls into California coastal waters from urban sewage outfalls. Bull. Envir. Contain. & Toxicol,, 6(3)*235-2li3. llj. Duke, T. W., J. I. Lowe, and A. J, Wilson, Jr. 1970. A polychlorinated biphenyl (Aroclor 125L) in the water, sediment, and biota of Escambia Bay, Florida. Bull. Environ. Contamin. Toxicol., 5*171-180. 15, Tarrant, K. R. and J. 0*0. Tatton. 1968. Organochlorine pesticides in rainwater in the British Isles. Nature, 219*725-727. 105 OSW 010126 LEXOLDMON000499 WATER_PCB-00035966 16. Smithsonian Institution, Center for Short-Lived Phenomena. 1970. S. W. Sweden snow pollution. Event 19-70, Item 876. 17. Veith, 0. D. 1972. Chlorobipheryls (PCBs) in Wisconsin natural waters. Enviromental Health in Perspective. 1, (in press). 18. Holdgate, M. W. (ed.). 1970. Ihe seabird wreck of 1969 in the Irish Sea. Unpublished report (with supplement). Natural Environment Research Council. Referred to in Nisbet and Sarofim, 1972. 19. Jensen, S., A. Q. Johnels, S. Olsson, and 0. Otterlind. 1969. DDT and PCB in marine animals from Swedish waters. Nature, 22h*2li7-2;>0, 20. Zitko, V., 0. Hutzinger, and P. N. K. Choi. 1972. Contamination of the Bay of fUndy - Gulf of Maine area with polychlorinated biphenyls, poly chlorinated terphenyls, chlorinated dibenzodioxins. and dibensofUrans. Environmental Health in Perspective. 1, (in press). 21. Henderson, C., A. Inglis, 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, Wennsr-Gren Center, Stockholm. Sept. 23. Finklea, John F., Lamar E. Priester, John P. Creason, Thomas Hauser, and Tom Hinners, 1971. Polychlorinated biphenyl residues in human plasma expose a major urban pollution problem. Read before the American Public Health Association, Minneapolis, Minnesota. Oct. nit 2li Wes too, 0. and K. Noren. 1970. Levels of organochlorine pesticides and polychlorinated biphenyls in fish caught in Swedish water areas or kept for sale in Sweden, 1967-1970. Var Foda, Z2*93-1U>. 2>. Risebrough, R. and V. Brodine. 1969. More letters in the wind. Environment, 12*16-27. * 26. Acker, L. and E. Schulte. 1971. Vorkoramen von ehlorieten bipherylen und hexachlorobenzol neben chlorlerten insektiziden In human milch und menschlichen fettgewebe. Naturwiss,' 57*li97 27. Yobs, Anne R. 1972. Levels of polychlorinated biphenyls in adipose tissue of the general population of the nation. Environmental Health in Perspective. 1, (in press). DSW 010127 106 LEXOLDMON000500 WATER PCB-00035967 I. n. . m. IV. V. VI. VII. VIII. n. 1. 2. 3. U. APPENDIX E Occurrence And Sources Of PCBb In Food Table of Contents FDA Pesticide Surveillance Program EDA 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 . Positive Analyses of Random Food Samples Positive Follow-Up Investigational Samples Sunnary of PCB Findings in FDA Total Diet Samples Objective Samples - Cl 1971 for PCBs 108 109 109 * 109 no no 113 116 ns in 112 117 120 OSW 010126 LEXOLDMON000501 WATER PCB-00035968 APPENDIX E Occurrence and Sourcea of PCBs In Food Residues of polychlorinated bipheryla (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 organochlorine pesticide residues, particularly DDT and its analogs. (Widmarck, Z). In 1967 the Food and Drug Administration initiated a methods development project to determine the analytical behavior of PCBs and to devise a means of separating PCBs from chlorinated pesticides in the regula tory analysis of food. Experiments demonstrated that PCBs are recovered and detected by the FDA methodology routinely employed for multiple residues of organochlorine pesticides at a sensitivity of detection approximately onetenth that for p,p*DDT. For exaiqple: using PDA's standardized procedures the limit of detectability for p,p'DDT in butterfat is about 0.15 parts per million, while for PCBs It is about 1.5 parts per million* Further investi gation led to a procedure,(Amour and Burke, 3) that separates PCBs from organochlorine pesticides after initial sample 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 step, has application to a wide variety of food and animal feed commodities and many types of environmental substrates. In July 1969, FDA field laboratories were provided with the analytical instructions for separating and determining PCB residues in foods. Since all objective food samples 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 samples for PCBs and reporting of results in November 1969* The United States Department of Agriculture in corporated similar procedures in its sampling programs for meat and poultry in January 1971* The objective sampling programs represent the basic Federal activity for monitoring the Nation's food and feed supply for pesticide residues (Duggan and Cook, li). The main components of these programs are as follows: I.FDA PESTICIDE SURVEILLANCE PROGRAM This program is designed to gather information on the extent of pestloide (including PCBs) contamination of foods and feeds on a geographical basis through the use of a statistical sampling plan. Samples are collected at shipping points to facilitate compliance action when Illegal residues or potential residue problems are encountered. FDA field offices select canmodities grown or processed within their areas. Sampling is based on possible residue problems, volume of production, and other related factors. Commodities may include fresh fruits and vegetables, dairy produots, shell eggs, grains, fish, animal feeds, and processed foods. The limits of detect ability as applied to objective samples is about 0.3 - 0.5 parts per million PCBs in non-fatty foods and about 1.5 parts per million PCBs in the fat for fatty foods. 108 OSH 010129 LEXOLDMON000502 WATER PCB-00035969 II. FDA TOTAL DIET STUDIES The total diet program is designed to determine the levels of pesticides. PCBs, and trace heavy metals in the dietary intake on & geographical and seasonal basis. Market basket samples, representing the two-week diet of a 1JJ-20 year old male -- which is approximately twice that of the norrial 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 PCBs. The limit of detectability as applied to total diet composites is approximately 0,0$ parts per million PCBs. >0100 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 is contributing the ex* cessive residues and to determine whether compliance action is warranted. III. USDA SAMPLING 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 other chemical or biological con taminants. The USDA program involves all federally inspected slaughtering plants (about 1,200) and egg breaking establishments (about lbO). The instructions for sampling request that the agricultural producer of tiie animal, bird, or eggs, be named so that the State of origin will . be known. This facilitates follow-up if a violative sample is found and identifies those samples which originate from the same farm. Inspectors are instructed to collect objective samples from different agricultural producers. The time of sampling and the plant location are determined on a random basis, by computer, for this program. 17. .OTHER REGULATOR! PROGRAMS .. . In addition to these routine sampling activities, FDA and USDA learn 6f PCB contamination of fooda in other ways. As part of their enforcement responsibilities, they conduct in-plant establishment inspections; con duct special investigations end 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 OSM 010130 LEXOLDMON000503 WATER_PCB-00035970 the extent of the problem* and the degree of regulatory control required to safeguard the wholesomeness of the food sxqjply and to correct the problem. The selective program has been used to' control specific PCB incidents. V. SOURCES OF CONTAMINATION Because of their widespread industrial applications* their chemical Bt&bility and persistence* and their ubiquitous presence in the ecosystem* it is not unexpected that PCB residues have been detected in a variety-of food commodities. Several sources of contamination have been Identified. These can be generally divided into three categories: 1. Environmental contamination - background levels of PCBs 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 to 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 as to the source of the residue. , Since examination for PCB residues was incorporated into the routine sampling programs of IDA and USDA* thousands of objective samples have been analyzed. Additionally* numerous investigative surveys and selective samplings have been conducted to respond to specific "accidents'1 and other problems associated with PCBs in food. VI. RESULTS OF SURVEILLANCE SAMPLING PROGRAMS Since November 196?* FDA has analyzed for PCB residues all raw agri cultural commodities and other food classes sampled under its pesticide surveillance program. More than 15*000 sanple examinations had been completed as of June 1971* A .total of 279 of the objective samples was reported to contain PCBs (Table 1). An additional 200 food samples* collected as follow-up samples 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 (U79). The levels in fish reported ip 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 residues in fresh water fish is widespread geographically. Residue levels are delated 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 fish containing excessive residues of PCBs* FDA (February 1970) established 110 OSH 010131 LEXOLDMON000504 WATER PCB-00035971 Is i |1 ZZ X f Siic*\a*.*j4 n N t 5 a siv444 X i II wi g iw* 3 w* 8 2 O 8 I a& * a p * IS w*o> 3 ft 4 <CM* or-4 o (aA I 8 5 a i xM wh.t s r i r* s ote * * oS . ai 8S 8 a: ? a* e? t 8 * a (s I i If 1 I 52 J I I I I d 3a a a5 a a.. a trf I 5M t ft I 6 3 8 5M m LEXOLDMON000505 WATER PCB-00035972 s *4 n <mn o o (/ o ^ # N jx T*.: 8 83 *! ^ ^ft ^M .. R S ft s iI Jl j C N 22 ?* ' te /mN t ft S* gt 41 *ft4/ &0 &9* ft ft t l i! I i I! f 119aa *g J& I 3 a & i i ! 3 a g 3 0t 1 A * a 2 a e " i* <"& *- 112 LEXOLDMON000506 WATER PCB-00035973 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 class 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 FCBs 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. These analyses showed 5h composite samples to contain PCB residues ranging from a trace to 0.36 parts per million (Table 3). Twenty-air of the positive samples were present in the meat, fish, and poultry composite, and nineteen in the grain and cereal composite. Findings in other food class composites were at less than 0,0$ parts per million, with no consistent pattern of PCB occurrence. These studies indicate the dletarv intake of PCBs is of a low order. Expressed as me/kg body weight/day, the PCB level for FT 70 was less than 0.0001 and 0.0001 in IT 71 and FT 72. The objective phase of the USDA sampling program for meat and poultry during 1971 detected PCBs in l6li of the U,175 samples analysed. There were 25 samples positive in the 2,l*0l* samples collected from cattle, swine, calves, and sheep with a range in the positive results from .1 parts per million to 3*0 parts per million. The poultry samples reflected the contaminated feed supply In the Southeastern United States and in the 1,80!* samples analysed, there were lltO positive with an analytical range of 1 parts per million to over 1$ parts per million. The three poultry classes, young chickens, fowl, and turkeys, all had between 7-9 percent sauples positive for PCBs with a range of 1 parts per million. Only two samples were over guidelines established by IDA. YU, 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. POULTRY 1, New Tork State Incident. The Campbell Soup Company, Camden, New Jersey, noted in December 1970 surveillance data excessive PCB residues in chickens n*own in New York State. State .of New York 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 26.8 parts per million. IDA advised the State of New Tork and USDA on February 1, 1971, that FDA would not object to the 113 OSH 01013* LEXOLDMON000507 WATER PCB-00035974 distribution of poultry containing less than 5 parts per million. This level was applicable to the edible tissue on a whole tissue basis or to the separate fat removed during 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 samples 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 PCBs: 1,566 dozen eggs, 196 feed, and 5,790 chicken samples. Host of the analytical work was done in the New York State chemical laboratory. On the results of these samples, Ib0,b50 chickens were killed on the farm and buried, 75,7hO chickens were passed for restricted slaughter, and b0?,000 chickens were released for normal slaughter. The alleged source of the PCBs 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 PCS levels were ground with the bakery goods* : 2. East Coaet Terminal Incident (FDA. Actions). The Monsanto Chemical Company informed FDA in July 1971 that large amoupts of fieh meal night have been contaminated with Aroclor 12b2 leaking from a heating system during pasteurization of fish meal at East Coast Terminal, Wilmington, North Carolina. Aroclor 12t2 was used as the heat exohange fluid. FDA 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 fiBb 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 were distributed. Over 2,000 tons were recalled. Individual fish meal sauries examined contained from lb to 30 parts per million PCB. FDA 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, 22b samples of eggs had been analyzed with 71 containing residues in excess of 0.5 parts per million. FDA seized 3 lots of eggs. The samples representing these lots contained from 0.7 to 1;9 parts per million PCB. FDA seized 5 shipments of fish feeds that were manufactured from contaminated fieh meal. These seizures were in the States of Louisiana, Georgia, and Mississippi, and ware on feeds that contained from 0.6 to b.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 levels in excess of 350 parts per million FOB; Catfish sampled from commercial fish farms contained less than 3.0 parts per million PCB. ' . nb DSW 010135 LEXOLDMON000508 WATER PCB-00035975 ) East Coast. Terminal Incident (USDA Actions). The Meat and Poultry Inspection Program, USDA, was notified by Holly Farms, Wilkeaboro, North Carolina (July 1971) that poor hatchabillty had alerted them to a problem in their poultry operation. The cause was PCBs in the poultry ration. The 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 EDA, showed the contaminated 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. 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,l72j 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 1b being made by.USEft. 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 as having violative levels of PCBs by this final testing program will remain under surveillance until disposed of by slaughter. It. Minnesota Incident. 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 foun& in the turkeys were caused by the feed* In addition, it appeared that the fab'used as an ingredient of the turkey feed wae 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 fat being manufactured at that time contained negligible levels of PCB. The aource of the PCB levels found In the turkeys waB not established. '**" USDA surveyed turkey flocks for PCBs in the immediate geographic area, which included parts of Minnesota, North Dakota, and South Dakota. There were 3J4O flocks tested, and no residues of PCBs were found above 2 parts per million (fat basis) except In the original growerfs flocks, where PCBs were present at levels up to 20 parts per million (fat basia). . . 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 .qSW 010136 LEXOLDMON000509 WATER PCB-00035976 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, USM 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. FDA 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.ltl 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, the source of the PCBs could not be determined. B. MEAT BI-PRODUCTS . ' National By-Products, Inc., Mason City, Illinois Incident - On July 28, 1971, FDA inspection of this fim revealed that PCBs were used in heat treatment equipment. Sampling showed the pasteurised meat meal to contain PCBs. The fizm 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 ' Kartinsburg, 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 milkv EDA identified the residues as PCBs and advised the State of a guideline of 0,2 parts per million (whole milk). The State of Ohio and FDA investigated the problem and determined that the dairy farms were using a PCB-containlng sealant in silos that migrated to the silage. The State of Ohio banned milk from some producers and destroyed an undetermined amount of milk. 3. FIorida-Qeoreia 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. . Till.PAPER POOD 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 116 OSW 01013? LEXOLDMON000510 WATER PCB-00035977 ia t < * - CO mr-4 o o va> A> OF PCB FINDINGS IN FDA TOTAL DIET a B fe g H g fi H 117 LEXOLDMON000511 WATER PCB-00035978 4/ packaging material was identified as the source of PCB in the food. The manufacturer of the packaging material used about 95 percent recycled paper to manufacture paperboard containers. FDA analysis of different types of the firm* a paperboard showed PCB levels ranging from about 2 to li33 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, EDA initiated a nationwide survey in September 1971* to determine the extait 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 338 parts per million; 19 percent of the food portions of the samples contained PCB 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 materials, 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 PC& 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 some 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 oarbonless carbon paper. Although it is not know if this practice has been instituted industry wide, data provided ty the Grocery 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 samples contained less 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 samples 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. 118 DSU 010139 LEXOLDMON000512 WATER PCB-00035979 The survey covers feeds for cattle, sheep, swine, chickens, turkeys, and other miscellaneous animals. The survey results available to date show that less than 5 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 PCS. Another investigation survey was recently initiated by FDA to survey the milk supply on a State by State basis to determine the extent of PCB contamination of milk Intended for bottling and manufacturing use. Results from this survey are not available at this time. *'" The results of tissue sample studies of several domestic animals and poultry are shown in Table li. n? DSM ; 010140 LEXOLDMON000513 WATER PCB-00035980 TABLE 2j - OBJECTIVE SAMPLES - CY 1971 for PCB*s SUMMARY PPM - fat Basis ANIMAL AND POULTRY TISSUE CY 1971 Class N.D. Animals 2379 .01-.1 1 .11-.50 9 .51-1.5 11 1.51-3.0 3.01-5.0 5.01-7.01 4 7.01-15 Over 15 Poultry 166A 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 Samples Exceed ing Guidelines Cattle 722 9 1.2 0 - 0.0 Calves 66 4 6.1 0 0.0 Swine 1436 7 0.5 0 0.0 Sheep . 160 5 2.8 0 0.0 Young Chickens 1637 127 7.8 2 . 0.1 Mature Chickens 69 5 7.2 0 Turkeys 8B 8 9.0 0 Ducks 10 0 0.0 0 0.0 0.0 0.0 4208 165 3.9 2 0.04 120 D$W 010141 LEXOLDMON000514 WATER PCB-00035981 FOOTNOTES 1. Jensen, S. (1966). New Scientist 2, 612. 2. Widraark, 0. (1967). J. AOAC 0, 1069. 3. Armour, J. A. and Burke, J. A. (1970). J. AOAC ), 762-768. ii> Duggan, R. E. and Cook, H. R. (1971). Pesticide Monitoring Journal , 37-li3 J. Trout, P. E. (1971). Grocery Manufacturers of America "PCB Workshop", November 17, 1971. 121 OSH 010142 LEXOLDMON000515 WATER PCB-00035982 APPENDIX F Hunan Directed Aspects of PCBo Table of Contents Page I, Introduction -12li II, Toxicological Aspects 12li A. Human Episodes B. Animal Toxicity C. Contaminants in Polychlorinated Biphenyls III, Epidemiological Aspects lbb IV, Studies in Progress lb6 V, ' Summary and Conclusions 152 Tables 1. Subjective Symptoms Complained by Tusho Patients 126 2. . Oral Toxicity of Chlorinated Biphenyls 127 3. Dermal Toxicity of Chlorinated Biphenyls 126 1). Vapor Exposure Toxicity of Chlorinated Biphenyls 129 5. Toxicity of Aroolors 131 6. . Pathologic Changes Induced by PCBs m .. 132-133 7* Residues in Tissues of Rats Orally Dosed with Aroclor 125I| 13b 8. Storage of Aroclors (in PPM) 2b-Houra After Oral Injection by Stomach Tube . 138 9. Distribution of PCB-Derived Material Following 98-Day Exposure to a Dietary Level of 1000 PPM Aroclor 125b 139 10. Distribution of PCB Levels in Adipose of Oeneral population as Shown in Analysis of Human Monitoring . Survey Samples Since April 15> 1971 lb5 .S 122 .. OSW 010143 LEXOLDMON000516 WATER_PCB-00035983 Tables 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. Orijn. 12. Some Biological and Toxicological Effects in the PCBs 13. Possible Future Studies Involving PCBs, Their Individual Isomers and Contaminants List of Figures Page 150 153 151/ 1. Storage of PCB-Derived Material in Tissues and Plasma lho 2. Excretion of PCB and PCB-Derived Material in Ffeees and Urine ! llil 12? OSH .0101^4 LEXOLDMON000517 WATER_PCB-00035984 APPENDIX P Human Directed Aspects of PCBs I. INTRODUCTION The salient aspects dealing with the chemistry and toxicology of the polychlorinated biphenyls have been summarized previously in a number of Status Reports of the FDA (Kolbye, lj Burke and Fitzhugh, 2; Cook, 3) Additional literature reviews have stressed the chemical and biological aspects of the PCBs (Peakall and Lincer, It; National Swedish Envirorment Protection Board, 5} Reynolds, 6; Zitko and Choi, 7; and Fishbein, 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. TOXICOLOGICAL ASPECTS A. HUMAN EPISODES Compared to the chlorinated hydrocarbon pesticides, definitive aspects of acute, sub-aoute and chronic toxicity still remain rather poorly known. Chioracnegen 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 (Flinn and Jarvik, lli; Qreenburg, et al., l; and Drinker, et al, 16). In all cases histological examination revealed liver fatty degeneration, necroses and olrrhosis. It is important to note that chlorinated naphthalene (as well as chlorinated diberrtfofUrans) have been recently identified in two commercial polychlorinated biphenyl samples (Phenoclor DP 6 and GLophen A60),(Vos, et al., 17). ' Human intoxication with the heat exchanger Kanachlor ItOO, a Japanese manu factured PCB with 1)8 percent chlorine and containing as its main components, 2,1), 3', 2,5,3', l)*- 2,3,l),l)'- and 3,l),3',I)'-tefcrachlorobiphenyl, and 2,3,li,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 liOO. 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). 122) DSW 010145 LEXOLDMON000518 WATER PCB-00035985  A/ 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 PCS via placental passage. (The dark skin discoloration re gressed after a period of 2-5 months). Gingival hyperplasia with pigmentation was seen in several cases. Decreased birth weights were also noted but no evidence could be obtained in regard to the possible retardation in physical and mental activities of the babies (Yamaguchl, et al., 19). Ihe skin 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 (Kojima et al., 20 j Inagami et al., 21), The components of Kaneolor hOO with longer retention times have been detected in sputa and fatty tissues of patients (Kojima, 22), Serum triglyceride levels were higher than 300 mg/ml in 60 out of 396 subjects Investigated before the end of 1969 (Ozawa et al., 23, 2li). Among the incidence of hyperglyceridemia (triglyceride>300 mg/ml) of the six decade groups (age 0-9 10-19, 20-29, 30-39, I4O-I49, 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., Zb)* 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., 2hf Nagai et al., 25). Nearly I4O percent of the examined patients exhibited an elevated excretion of steroids with the 17-ketesterolds (androsterone, etiocholanolone and dehydroepiandrosterone) found to increase in males and to decrease in females (Nagai et al., 25). ' Examination of autopsy tissues of two Tusho fatalities revealed the presence of chlorobiphenyls in all of examined organs, especially mesenterial fatty tissues, skin and bone marrow (Kikuchi, et al., 2o). Kojima, et al.,(20) found PCBs with longer retention times (probably pentaohloro- 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 2-1 describe the oral, dermal and vapor exposure 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 LDo (rats) and skin MLD (rabbits) is summarized in Table 5. a. Sublethal and acute effects: Analogously with the chlorinated hydro carbon pesticides, thermost important effects are long-range sublethal effects. Ihe pathologic changes in various organs are summarized in Table 6 illustrating some interesting differences between mammals and birds. For example, the most 125 DSM 010146 LEXOLDMON000519 WATER PCB-00035986 TABLE 1. SUBJECTIVE SYMPTOMS COMPLAINED BY YUSHO PATIENTS*b. Symptom Dark brown pigmentation of nails Distinction of hair follicles Increased sweating at palms Acnelike skin eruptions Red plaques on limbs Itching 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 Vomiting 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 % 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 aE1ghty-n1ne 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 Chioroblphenyls", Kuratsune, M., Yoshimura, T., Matsuzaka, J. and Yamaguchl, A, Fukuoka Acta Med., 60[6] (1969) 513. OSH 010147 126 LEXOLDMON000520 WATER PCB-00035987 y-N -3 \A cf <V w ejo>^ r- rr> \T\ **v^ U 00 CO (7) r-- 13 4) * l_ ^ C fO O'! 01*- r *0* CM * u im > S +> L +1 a> i-- oai V* r- 0) 0M r-- iO r* > H- E p* * Ui c to * t- "O u E "O r- fl) V> O r- 4> nj </i i/> +J ft) tf 43 0) r~ C > 0) 0<r v> > 8S8.g -o w g c 4J > c} *r- sc O -- U 6 S 2-3 m > E 4/ oui o on tAfO V) *0 w VI r" fil 1-- +> 40 VI <s * EO Ea i- tJ r CL c ai C <0 >, N) I/I vr- s ^ QJ DIM V *5 EO > LT> ID -- i-- CM r- 13 19 C Ep c ai <0 C/I o> to 0) 13 o r Q. E <v *f* C c r* <9 CO 10 DC +> 10 v c + -t- SL o CO u H CM 3" CM ** tr> o OSW - 010148 127 ORAL TOXICITY OF CHLORINATED BIPHENYLS LEXOLDMON000521 WATER PCB-00035988 DERMAL TOXICITY OF CHLORINATED BIPHENYLS. rn Ol ^ 001 *or V) ">1Q/0> r-- O - 6r- f CM^fl5J <e0 J*crZ- 0L1. tt0--1 rpC-* >- --r (o<0u UN eo TJt u*OoM^O-* ty L. 4-> Cft *f>>" f0>-) <U0*>--r 9 (OO M L -- r* OC *Cf" **r* < as u>w 4-> rUd C*\ 01 c: in c4> 0J V> 0$- *rE JK* vo01>i x+:j "O 2"oO:^o00>0 *o 1c0 EV ns o a c eg as c *r- ad* o.a> 10 TSCtJ-* )--rIfl*.j _l EQ. 5 r-- i/> 0/>> ns m d -o oo U>(1,1 e r- in* u 0) ^> fO o -s, TnJs Tn3s coin E ess u> s- >as to o cn *-- CL 0 c O9r 4-> o<c0 +> 40 o*r O*' r-4 oMo tao as e +- co co CO >*- ns Oi. ----- M CVS C**M 128 LEXOLDMON000522 WATER PCB-00035989 VAPOR EXPOSURE TOXICITY OF CHLORINATED BIPHENYLS. ISO j IA --> - trv 01* J U 0015 ^ B C <9 *r U) WO SO (04- C 9>f<0 U\ 'w'* IA 10 --0 m 9k b r- t- C* 10 c r> v\ u\ # t0 9UU vvr>s IA Vocio>j-0cMtai^onst C Cp ^IA co'*' ro Ot k* ro U C* o T> 01 a -r- o> ol l/ f- c C 01 c> M E Co4J>jr Ooi ot h- r *t-- V3 -- *J in LC A OO mi O U * *- IA *-- Ot O > 0> -> * i- 4- ^-0 Cf- f* *r-- L Cn 0 0O w U 01 Of >r-- I-- C 4-> 0 0c > AO L. 4- 4J Ol >> 4- O to If- f 4- A O IA **j c u d> jc p Ow * 0> O r 4* oc 4o)>ac 0 01i ux>a Uo ton O oi E oS +J +> * O 19 C > fc. tn 4-> > e a> 1 "0O 0 0*r O IA - C fl> f-- s- c 10 1000 SB 1- Ol O. SS 10 Jw 3C *f- U 01 J3OW l/l *f- >, o u 10 Ui CM CM *-- CM CM CO 0 CO CO 9 1C-* r-- " CM 1 N CM CO TT V. L JL 9 0> </> 8.1 KC UI is*. c-- c$ 3 - e 40 IA > -- 1r01E- O 4> N . sa S- 1- c Q> OfO C O< O E91 rO0o0 to CO rs*. N totoo O r49 ro 00 sC to tn vd co tn r-- fS4 fO LO lo as r-- oo 01 o c u JuZ ro CM CO u*> tf> ro CM 49 Lf> ro u43>- 129 N in to otA-4 O>o4 Q LEXOLDMON000523 WATER PCB-00035990 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 rats with dosage levels of 25, 75* 150, 300 and 500 parts per million of Aroolors 125h and 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 foundin liver aniline hydroxylase and nitroreductase activity at all levels with the magnitude of the increases approximately the same at all time levels for both Aroclors. Aroclors 1251i and 1260, in contrast to many chlorinated hydrocarbon pesticides, did not stimulate liver aliesterase activity. (Nishizuml, 27) studied the effects on mouse and monkay liver of chlorinated biphenyls (1|8 percent chlorine, equivalent to three to four atoms of chlorine per molecule, vith 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 FCB in olive oil by stomach tube each day for l to 26 weeks resulting in marked liver en largement. (Light microscopy revealed only slight liver changes, but electron microscopy disclosed marked alterations in the liver cells.) A similar study with eight monkeys (5 cyncmolgus and 3 squirrel) given chlorinated biphenyls in dosage levels of l.b 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 Increase in the smooth endo plasmic reticulum in the liver cells. - The metabolism and distribution of Aroclor 125b in normal and carbon tetrachloride-treated Wistar strain rats have been studied by (Orant, et al., 28). Residues of Aroclor 125b (following oral administration of a 500 mg per ml corn oil solution of Aroclor at 500 mg/kg) were found in all tissues analysed with fat and blood having the greatest and least concentra tion, respectively (Table 7). Aroclor 125b was found to potentiate the toxicity ofcarbon tetra chloride in a manner similar to that reported for DDT (McLean and McLean, 1966) Cawthorne, et al., 1970). The studies (Orant, et al., 26) suggest, that the liver is the main Bite of Aroclor 125b metabolism since rats with carbon tetrachloride .damaged livers were unable to metabolise this mixture of chlorinated biphenyls as rapidly as rats with normal livers. Aroclor 125b significantly increased the else of the liver and also the percent lipid in the liver. The same study revealed that the components of Aro clor 125b with the shorter QLC retention times, presumably with the lowest chlorine content (Bagley, et al,, 29), were metabolised to a greater de gree than those with the longer retention tines. This effect is in agree ment with the studies of Phenochlor EP6 fed to Japanese quail (Koem&n, et al., )0) Yoshimura and co-workers,(31) studied the effects of a single 2.0 mg/ mouse dose of polychlorinated biphenyls of the KC-bOO type. The concentra tion of PCB in the skin one day after ingestion was twice as high as that in the liver. Although tetrachloroblphenyls were almost completely elimi nated from the tissues in 3-b weeks, small amounts of penta- and hexachloro- biphenyls were still detectable after 9-10 weeks. . 130 ' OSH 010151 LEXOLDMON000524 WATER PCB-00035991 UN> r" O o <a/> I I *8c- ES 8 r* i t" S IS 01 I U4 U OV) H S 2 o o ou CO 131 * R I to *ec I LEXOLDMON000525 WATER PCB-00035992 $ eu0OPtc-f u *l*\ S?-' 1c0 uJE UV 9V-- c0>*o ccn 2%2 0W.0 u S3 S31! 0P> SS S&g fi-o ieP *fP*e- rSu L. pcdo> (ccAr <X soc u 0<oY0t> t; gcb 4*->'| SL 44PC33 a--% 4 ^5 esa -|| iv5 -I Si 43( Is (4/3) rQ--\ vVO\ OXSpcU=3*CtfL--4o-h0-.1 {a f t- Ti- P tO. Tt3CPoC mu{f-.T(mu-.T1mu*.*+0lr.5-x0_> &&&&? r*- ->O'0>,*>0t>c>.=uc </> X XX if>t r* O o (aO s? 1IT3 r tPwCOiu/> r 13 09 01 P PO * ID * C VO V> i~ >* r- rL2$ VI0Lft). 1 *Cr- p 3* Oo lm-Pc XPcn r0*1L>006f| T 0 0 1- S?g,M 4o4 Qe tok i S0- *inr ouS H V 40 O CM & 4 C M*S i~ . N e i aO) 4Jr-4* o40 P|0A> *O--3f "V03 JC 0 0P1I*B0*- o-o *+s *TE--JX03o'-+Cs>7hi+0l--iamC- mpV* Ml^P^wgWgVcr r0* 0 r> 9 13 C10 0i- 9** %O S1.14W33 >/>1 gs X s .*!* drU0?<e-10i "ts0UUc*J1 --oCitfatCJ?*-D1Prt3- B*gsia f PlU w- vmS n id con 00S- 00 L'OriN-I r-* P Ur- C0H _r--C CCNO P r* f-- J43*0 S 0 0XJ - <4- P> P 40-0f- 0C DS oOc0 zruo QTou*n vI0CD1*P. i*M-5 5 S3 10 O U> cc ec QV)) PO 8 Vc ~ O S> P p OY DH0 ^ V- 'V o & U E'P e *0Dtwo 43 XID omc 1_ tft >> c si o OtOr- wS o aS> 132 U) 3w Hm G ftr* Q ut3 0.0(0 f"*P 1 0+N C _ 0w O 0 2 I" v> CM r* P C C pPp p0 p0p0pP^-* r- #- *** CM c c c c ''""'T"'" *- aaaau 8S8I r*NO CO*--" PATHOLOGIC CHANGES INDUCED BY PC8s. LEXOLDMON000526 WATER PCB-00035993 4 V> 0u0 as T3 M *O sc u 1u-4 g I v> 8c 8 V (X M S> C O u0> rQ--J t 0 V V) e i 01 i U tt- ti. 01 a0) fi. 4-|tn <naKo -- U *eo - \8s 5Z |w vi o<o* ocu SSp . r U oUiSw- id vci U^eo CflMJr u-o 9 0o0-<rV=--I a.**- f- m . P Q-u g8 C o5lp c"n <-s 10M ^ Os r va e a. sr O c4> -- 0C1 i.a (A Or* O 01 g id sill So r- <A V ft. <_ c? 8 O |- *=,2 S <P fa? uc *T^" t--10*D,.>4r4- C *5 ^ C iSd1. .4te3!4c>| WIO *Lr 44 UC 8&"8 au MC fC- Ovi Ot S~ *->**- *o m _C V Olid 3 *g S**" d *- o 4JBVITJOf .818. . t- u 6 o r- C C V)*r Vlf- OH* VI D,l,COl >5 TJ 0 9^0 S a f->- XT'r 0 aEoCvo 9i t*fc o V _ to Wf- g CO eo 4* CL Of- > avi CT> 3 C r-- H- DO 0 VI O o 3 VI *" c o. C &4J a digm C4J vo IQ QN _ VI Ol 9 a. Ur-*0 c tx p 5S*0 88 8 tM <A L 0.* i- U r-------- g*^ * idSSI > <d 44 if 4o4 Vco* vo**i^e sfcu r* C U S- o. Q ^ 1. ai*c 8 cl a oi *r ^ .H T3 8 rsj di o o co *- vtga VI So. E *id c f 44 id XV 9> E44. pU pt eO* C pe Od* DIO Ul C o V-P tff2> "iP> 1 *D 8Oc 44A u dV- 0 c X<Or*-- ?? iT3 9 L 01 in co R &V) *D O ne o rO-- * <SI *o D C ti $ VI V Ol c IQ 4= 9 c 01 4ft a 5s &CO CL U * $ 5f 4>v^ L. Vo 0 *f* " V) > Ol a -aoi oOl 44 tc Li0O 0 id o > 9>^& c s Of C 0*0 O S3*w'J O r C IO S.CI 44 * O VI fN Ol Id r-- f * * r* * L r- o WP^^NWO 01 He^-gig^ts o ga^-sEoBS' L4 C*- X f- 44-------- s r X Id 9 DIC C *f 01U. CO VI v0*1 _ 40 P-- f30 O O r-- t VO U fcSE 133 e o JC u 4d4) *X3 VI C >4 r- I04N Igs-"" u8 I 1o0 o V *9 C VI Vc 0Xa0-- 4T0Vf--1t UX r ir> H O o cn a LEXOLDMON000527 WATER PCB-00035994 ** TABLE 7. . RESIDUES IN TISSUES OF RATS ORALLY DOSED WITH AROCLOR 1254 (500 mg/kg)\ Group Blood Testes Heart Spleen Kidney Brain Liver Liver*1 Fat Residue found (ppm, wet tissue) 1 23 4 1.96a 0.23b 19.22 * 0.59 24.16 * 2.84 29.17 i 3.44 31.14 2.09 39.98 5.91 115.66 10.55 . 1868.14 1 166.63 996.16 98.58 0.42 0.07 4.30 0.44 5.83 1 0.53 5.82 1.17 11.20 i 1.76 4.01 0.31 18.85 1.65 -- . 672.66 + 155.12 3.85 0.46 ; 0.25c 33.18 1.35 5.62 62.40 4.37 6.17 36.60 4.39 -- 57.38 3,91 11.08 41.91 i 3,30 5.96 796.47 64.96 18.79 6137.64 556.06 -- 900.46 106.16 1149.05 *Mean of five values. "Standard error of the mean. ^Single value. Ppm on a fat basts. *Grant, D. L.. Phillips, W. E. 0. and Vllleneuve, D. C., Bull. Env, Contain. Toxicol., 6 (1971) 102. (3lj) 13b DSW 010155 LEXOLDMON000528 WATER PCB-00035995  M/ [Street and opTworkera (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 rate for 15 days. Iheir effect on sleep ing time induced by hexobarbital* in vitro rates of aniline hydroxylation and demethylation of p-nitroanisole, and the rate of excretion were all found to be increased with increasing chlorine content. Arcelor 1221 (50 parts per million) reduced hexobarbital sleeping time by 11 percent* whereas for Aroclor 12b8 and 1268 the figures were 35 percent and b8 percent, respectively. Liver weights were aleo found to increase with increasing chlorine content of the Aroclors. The storage of dieldrin was decreased in relationship to the chlorine content. For example* with Aroclora 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 hydroxylating enzymes has been demonstrated in the American kestrel (Peakall and Llncer* b), and pigeons (Risebrough* 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. Ihe most potent inducer was 2,3', b,b'* 5-pentachlorobiphenyl and the effect induced with a single dose of 3> 31 *b * b'-tetr achlorobiphepyl was found to persist for 6 weeks. Villeneure* et al. (3b) studied the effects of PCB administration on micro somal enzyme activity in pregnant rabbits. The no-effect level of Aroclor 125b 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 stored per liver, protein levels* aniline hydroxylase enzyme activity, serum . cholesterol* no effect in reproductive processes. The drug-metabolizing enzymes aniline hydroxylase and aminopyrine-n-demethylase were both induced by 10 mg/kg Aroclor 125b. Irto 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. (Ihe concentration of serum tri glycerides was abnormally increased). ' Kimbrough (36) described some aspects of the toxicity of Aroclor 125b and 1260 in Sherman strain rats. Ihe acute oral LD$0 for Aroclors 125b and 1260 in adult rats was greater than b and .10 grans/kg* respectively. The salient features of the subacute feeding and reproduction study in both male and female rats can be euimnarlzed as follows * 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 less weight gain as well as lowered hematocrit. 2. Some male rats fed Aroclor 125b at a dietary level of 100 parta per million (approximately 5 mg/kg per day) developed porphyria. Porphyria was also found in female rats fed Aroclor 125b at the 20 parts per million level and in both male and female rats fed 100 parts per million Aroclor 1260. 135 DSH 010156 LEXOLDMON000529 WATER_PCB-00035996  1 3. Liver changes found with both Aroclor 125b and 1260 include accumulation of fat, inclusions within the liver cells and so-called marginatlon (also found with chlorinated hydrocarbons). b. Male 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 any of the dietary levels that were tested. 5. Adenofibrosis was found ins (a) 1/10 males and 6/10 females at the dosage level of 100 parts per million Aroclor 125b in the diet for about 6 months; (b) in 1/10 female rats at 100 parts per million Aroclor 1260 in the diet for about 8 months; and (o) in several 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 some to represent proliferated bile ducts. 6. Two bladder cancers in rats fed 100 parts per million of Aroclor 1260 were also 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 Fga 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 number of young. Curley and co-workers (37, 36) studied the distribution and storage of PCBs in body fluids and tissues of Sherman rats following! (a) a single oral dose; (b) repeated dietary intake! and (c) after discontinuance.. The salient findings of this study could be summarised as follows! (l) Following acute or chronic administration of Aroclor 125b or 1260, residue amounts can be detected in all body tissues, flulds*&nd excrement. . (2) Pronounced changes in the gas chromatograms or mass spectroscopic total ion current traces between the Aroclor standards and components observed in the fat and urine suggest possible metabolism or differential absorption. (3) Rats 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 hour8 (although Individual variation was high). (b) At the same dosage level rats store more PCBs than DDT. (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. DSW 010157 ' LEXOLDMON000530 WATER PCB-00035997 (6) Toxicity of the Aroclors apparently increases with decrease in chlorine content suggesting the enhanced reactivity and/or less stability of some isomeric chlorobiphenyl in the mixture. (7) Rats fed Aroclor 125b at 100 parts per million for 58 days and untreated food for 71 days showed gradually increasing residues during dosage while the ex cretion trend was quite erratic. (8) Aroclor 125b administered at a dietary dosage of 1000 parts per. million for 98 days resulted in deaths of 9 of 10 male rats and 8 of 10 females with deaths commencing on the 3?th day. Although the survivors appeared normal) there was no weight gain after 77-8b 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 ? depicts the distribution of PCB-derived material following 98-day exposure to a dietary level of 1000 parts per million of Aroclor 125b. Figure 1 shows the storage (mean cone. vs. time) of PCB-derived material in tissues and plasma. Figure 2 shows the excretion of PCB and PCB (mean cone. vs. 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 OLC patterns of PCB varied ffora tissue-to-tissue (Sekita et al., 39). , The intestinal absorption in the rat of a number of isomeric chlorobipbenyls has been studied by'Albro and Fishbein - (bO). PCBs having from one to six chlorine atoms per molecule were very well absorbed and/or metabolised when the confounds were fed in a single dose between 5 and 100 mg/Kg body weight. No significant difference in excretion rates (e.g., retentions) were observed over the molecular weight range 116.5 to 289, suggesting that diffusion may not be rate-limiting for the uptake of these compounds, (Wien similar tests 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 li-day period) indicating a high -degree of absorption and/or metabolism of these compounds. b. Long-term studies8 The chronic PCB studies of Honsanto with Aroclors 12b2, 125b, and 1260, e.g., two-year albino rat and beagle dog, three-year rat reproduction as well as the twenty-five week chicken, have been completed and a copy of the results sent to the FDA. As of this writing, the full report has not been evaluated. However, Ik. Elmer Wheeler of Honsanto has verbally touched on the highlights of these studies supplementing information previously reported in the FDA Status Reports of the PCBs of June, 1970, and December, 1970j as well as reported by Keplinger and co-workers (bl) and discussed with the Interdepartmental PCB-Task Force-at a meeting in Washington on September 15, 1971. These results can be briefly summarised as followst 137 OSH 010158 t . - LEXOLDMON000531 WATER PCB-00035998 * TABLE 8. STORAGE OF AROCLORS (IN PPM) 24-HOURS AFTER ORAL INGESTION BY STOMACH TUBE. o* in *4 O o (4 Q t. 41 41 41 41 41 41 41 sCM i*-- Ot I o I tOo 0O0 S? ouo SS 85- * rc--o Ct,,aO 88 (SI CCOOtlOo *rf--RU> 138 Mean SE Brain Mean SE Fat Mean SE Liver Mean SE Kidney Mean SE Lung Mean SE 41 41 +1 44 +1 41 41 M VinO oCM* 8 15.79 0.99 145.17 23.50 930.0 426.6 236.1 116.3 328.5 114.9 105.17 21.13 37.00 22.37 fgO--vf<vp U>J LEXOLDMON000532 WATER PCB-00035999 OSW 0 1 0 1 6 0 TABLE 9. DISTRIBUTION OF PCB-DERIVED MATERIAL FOLLOWING 98-DAY EXPOSURE TO A DIETARY LEVEL OF 1000 PPM AROCLOR 1254. 8 C 8 8 o CM 8 o in No 5? OA O A 9 o A O A O. Q. C. co to r- Ol fO IS* 3 CO r-- in cpxm. CM O in cm MO* C--M in 'CP cm r-- rm" CM 8 fs to. NCCMO CM UIs> 41 41 rtt--oo rrf---s 41 ICsO CoM 41 ipr-----* r-- 41 min 41 trt*oo* 8 +1 10 go C<0 UCOi *-> C<0 UtoI r<4o--A1 C40 linli *c oc> <U/>f #cr0- (cO 2 CO SE SE V>^ t cu<0 * 0U>1 C10 * utoi 139 iii LEXOLDMON000533 WATER PCB-00036000 II4O LEXOLDMON000534 WATER PCB-00036001 iFigure . Storage o f PCB-Derived M aterial in Tissues and Plasma* OSH 0 X 0 1 6 1 Figure 2. Excretion o f PCB and PCB-Derlved Material in Feces and Urine. OSH 0 1 0 1 6 2 LEXOLDMON000535 WATER PCB-00036002 (1) Aroclor 12li2 is the least toxic of the Aroclors 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 and 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 12$Ii, and decreased mating indices with 12li2 at 100 parts per million were also observed. No adverse effects were found at any of the three levels of 1260 or at 1 or 10 parts per million levels of Aroclors 12ii2 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 hatchability of eggs from chickens fed 10 or 100 parts per million of 12li2 or 100 parts per million of 12?b. 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 and 8 parts per million level and decreased hatchability was observed at 6 parts per million. A rat teratology study of Monsanto following FDA protocol- in which 35-6? 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 12b2, 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 comparison to recite the reproduction studies of the Atlanta Laboratories of the FDA (FDA Status Report, December, 1970). Wean ling male and female rats were fed diets containing Arocler X2$h at dosage levels of 0, 100 or ?00 parts per million for 67 days and then pair-mated. The rats fed 100 parts per million were comparable with the controls in numbers of litters and pups per litter. ' However, 76.fi 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 gm and that of the controls was 39*2 gm. Only two of ten females fed 500 parts per million of Aroclor 125b had litters (l 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 Koeraan, b2) 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 mass spectra lb2 DSW 010163 LEXOLDMON000536 WATER PCB-00036003 (Koeraan et al., 30). One hundred precent mortality, centrolobular liver, necrosis and abdominal edema were found only in chicks fed the samples of Clophen A60 and Pbenoclor BPS. 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 tetra- and pentachlorodibenzofuran as well as hexachloronaphthalene in Phenoclor DP6 and Clophen A60, but not in the Aroclor 1260 sample. Since hydroperi cardium occurred occasionally in chicks fed Aroclor (Flick, et al.}b3). yoa and co-workers (17) felt that this could possibly be indicative of email 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 EP6, Clophen A60 and Aroclor 1260) as well as fractions containing tetra- and pentachlorodibenzofuran have been recently described by Vos and Beems (bb). FCB-induced skin lesions were hyper plasia and hyperkeratosis of the epidermal and follicular epithelium following application of 118 mg of the three PCBs ($ times per week for 33 days) in the back skin of adult female New Zealand rabbits. Histopathology of the liver in cluded centrolobular degeneration, centrolobular liver cell atrophy, focal necor8is and cytoplasmic hyalin degeneration. PCB-Induced kidney lesions were hydropic degeneration of the convoluted tubules and tubular dilatation with the presence of casts. 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 2J> percent diethyl ether in hexane) while the fraction from Aroclor caused a minimal hyperplasia and hyper keratosis of the follicular epithelium.' Other effects 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 akin and the liver of the rabbit to the three PCB mixtures, and from the response of the ear to the 2? 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 Beens, kh)< and the prior studies (Vos et al., 17) . .The extent 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 impurities. Vos and Beems (lib) also raised the possibility that sinoe PCB is a porphyrogenie chemical, it is possible that the skin lesions in man due to PCB may be due to a combination of chloracne and acquired porphyria cutanea tarda. It is important to additionally stress the toxic nature of the polychlorodibenzofUrans. Fbr example, tri- and tetrachlorodibenzofhran in a single.oral dose of 0. - 1.0 mg/Kg caused severe and often lethal liver necrosis in rabbits (Bauer et al* b5) The related compound 2,3,7,8-tetrachlorodibenzo-p-dioxin Ibj DSW 010164 LEXOLDMONOOQ537 WATER_PCB-00036004 (which has been identified as a contaminant in 2,L,5-trichlorophenol and 2,l*,5-T) caused a lethal liver necrosis in the rabbit after a single oral dose of 0.0$ 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 dibenzofVtran,' resulted in chloracne. Vos and co-workers (l*li) 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-dioxin.) (Higginbotham et al., 60). Ihe relationship between the toxic nature of PCB and the chick edema factor 1,2,3, 7,8,5-hexaehlorodibenzo-p-dioxin has been described by Flick and co-workers (58). III. EPIDEMIOLOGICAL ASPECTS Finklea d co-workers (2*6) 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 dieldrin residues were found in 82* and 63 percent of the people, respectively, and p,p'-DDT and DDE residues were almost universal. PCB residues were intermediate in concentration (e.g., less 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 reeidues. 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 an-arithmetic mean of 0.3 parts per billion, urban blacks, 1.5 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. fobs in a preliminary report in the Hunan Monitoring Survey (originally established by th^-Pestioides Program of the DREW, now Division of Pesticide Community Studies, EPA). Table 10 depicts the preliminary summary of distribution of PCB levels in adipose tissue of general population (as analyzed ty three laboratories) in the analysis of Human Monitoring Survey samples since April 15, 1571. A total of 668 samples were analyzed of which 23$ (3li.2 percent) ware negative for PCBs and h53 (65.8 percent) were positive for measurable amount of PCBs by TLC; of these 225 (333 percent) contained trace to<1.0 parts per million and 188 (27.3 percent) contained*2.0 parts per million PCBs. Die Aroclor formulation most frequently encountered is 12$U with Aroclor 1260 also well represented in human tissues (Enos, 2i7). (Aliquots of all samples in which measurable amounts of PCBs were found will be analyzed by mass spectroscopy at the Perrlne Primate Laboratory for future confirmation). The correlation of PCB information in this study with age, sex, geographic distribution or diagnoses has not yet been completed. These samples were collected in late 1568 and 1565 end the sties of the positive samples were located in the following states* Michigan, New fork,. Minnesota, California, Massachusetts, Georgia, Kentucky, Illinois, North Carolina, South Dakota, Ohio, Louisiana, Delaware and Arkansas. . lllii DSW 010165 LEXOLDMON000538 WATER PCB-00036005 TABLE 10. DISTRIBUTION OF PCB LEVELS IN ADIPOSE OF GENERAL POPULATION AS SHOWN IN ANALYSIS OF HUMAN MONITORING SURVEY SAMPLES SINCE APRIL 15, 1971. (parts per million, wet tissue basis) Michigan No. % Florida No. X Colorado No. % Samples Analyzed 144 100 274 100 - 270 100 Total No. % 688 100 PCB Levels Negative Trace--<1.0 ppm 1.0 - 2.0 ppm >2.0 ppm 12 8.3 181 66.0* 42 ` 15.6 235 34.2 64 44.4 44 16.0* 121 44.8 229 33.3 55 38.2 40 14.6 93 34.4 188 27.3 13 9.0 9 3.3 14 5^2 36 5.2 ^Actual decimal reading .05. OSH 010166 LEXOLDMON000539 WATER PCB-00036006 Dr. 0. J. Love (6l) of EPA has reported that 72 sets of specimens (blood, urine, and hair) collected from 36 workers occupationally exposed to burning automobiles or refuse dumps and from an equal number of controls are to be collected and analyzed for PCB levels. It is of interest to note the analysis of PCB in human adipose tissue. Biros and co-workers (1$) examined two human adipose tissue samples by combined QLC-mass spectrometry and found substantial quantities of PCBs ranging from pentachlorobiphenyl to decachlorobiphenyl and including at least l!j isomers and chlorine homo logs. The samples were estimated to contain 200 parts per million and 600-parts per million total PCB, respectively, as determined by electron-capture gas chroma tography. IV. STUDIES IN PROGRESS Curley and co-workers (37) have described results in a study with Aroclor 1Z$U 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 the 7th through the 15th day of gestation at 10 mg/Kg, respectively, by stomach tube. Table 11 lists the experimental protocol for the above studies. This is summarized as follows* Fetus Analysis8 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 1.1)2 . 2.1)2 Mother 2 0 1.2b 2.90 Mother 3 0 1.1b 2.93 10 mg/Kg Mother 1 Mother 2 Mother 3 Wt. at onset (gms) 25h 265 258 Age (days) 90 - 90 90 Mother 1 Mother 2 Mother 3 ,, . 2b2 2bb 261 Iti6 90 ' 90 . 90 OSW 010167 LEXOLDMON000540 WATER PCB-00036007 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 SO mq/Kq Males Females Males Females Males Females Liver <0.05 <0.05 Mean X S.5. * 4.06 3.28 2.70 3.35 0.39 2.85 8.28 4.11 5.08 1.64 17.36 25.56 11.80 18.24 4.00 21.63 12.02 15.99 16.55 2.79 Controls Males Females IQ mg/Kg_ Males Females - so ng/Kn Males Females Brain <0.08 <0.08 Mean X S.E. i 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. 1 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/Kq 50 mq/Kq Range Mean S.E. 0 0 16.48 - 24.90 20.60 1.59 45.80 - 100.29 66.35 18.36 Ar 7-70-G4- * 3il7 OSH 010168 LEXOLDMON000541 WATER_PCB-00036008 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 for analysis. 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) S.E. Ar-7-70-B12 Fat Liver Kidney Muscle Brain Plasma 778 9.9 5.1 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. 11*8 DSW 010169 LEXOLDMON000542 WATER PCB-00036009 Experiment No. Ar-7-70-B12 Tissue Fat Liver K1dney Muscle Brain Plasma Mean pnm (3 animals) 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 data are compared with 8 mo. study test for significant difference shows p <0.05 for liver only. Experiment No. Ar-7-70-B12 Tissue Fat . Liver Kidney 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 - S.E. 48 .10 .06 .05 .50 .06 OSW 010170 LEXOLDMON000543 WATER PCB-00036010 r 0 oc fe sc CQ -* 01 cs M Hi o 2E 3 >- Ul z %/i Ui DC SZ ZD CL. fiO ~4 S =* SE * 2 S3 S f o3 o <c o. 00 of u ex Ui Ul OO -fe as M <A s Ui 3 o t/1 r> M H O 5 to z cco of s -J U. ill o CO o asr 5 if 13 -4 gDC Ul g 0) 4-> 3 O V. 0> C7 <0 (A < 4-> :* I 40JX01 0) aX. 0?U> : o1c/1 K V /> IA + & Ho sos 5 > O W jg ts ie EfsS aN g* rOO=- <1O*>- re"o * * CM CM o n js c id 2 > o /i #o c^ r *0 Oi ill o*"* f-- 4- CO * O ro 0) cd o fO 41 V. *r > O tD <11 >.0 c <o -- *r- "D Dl X EcBo-IciOoo SEai o t-1-- oo r= H- eo * <dCM CM to CO ao> M >0 Kc) IS CO 5,, CT3 D T* ^ U KO Co\J <o*- *-- * 5 CM t~ V Oi 55 VI Q 1 5 O 3O Cr+> O V) c cO >Ql O *cr-n TJ 2<d *r 41 d r- C E =3 ci p o cu O 03 r 4> 4-> 2u S w" *-tsnl- 8 ttl CM 4- r- A . C O 9* r 4* U -2 CH OUI O o vj in O. i/> 01 t- c0) C OIW r C W gi- o orc-aC xC->xIj<U*o Lcon s Nl 25? >>X id 0 0)3 C id 2 m 2a "+J +j < (A >- i/i -a cs a 01 r. xwz * /) J 2 01 co: r U 2 2 Co 0 V) <p <r* N VI -- 01 u5 s* UC IS "feto tJT <2 % 01 c>0> J5-& o 3E tM M *P R X V IS aL:. CM CM o 5 CO CO ti II I RO N 9 N R li. r-. CO R i r-* ti LJL t~ t c< < <c : 150 *4 o o 3B 00 o 4* i TABLE 11 LEXOLDMON000544 WATER PCB-00036011 Mink reproductive studies are being carried out by Ringer, Johnson and Hoopingarner (L9) of Michigan State University involving the initial feeding salmon containing 15 parts per million PCB or 10 parts per million each of Aroclor 12t2, 125b and 1260 was fatal to mink which appear to be extremely sensitive to PCB. Reproductive failure in ranch mirk fed Coho salmon and other Great Lakes list) (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 (CD-I strain) given a variety of Aroclors at a level of 200 mgAg. Mixtures of PCBs and DDT have been found negative as well in the above strain of rats. Studies involving Individual isomeric chlorobiphenyls as well as commercial 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 (Na++K+) ATPase with the polychlorinated biphenyls. Enzyme activity was inhibited by,50 per cent in the presence of Aroclor 1221 or Aroclor 1251 at PCB concentrations in the range of 8-12 parts per million at 57. Under similar conditions 2.5x10-5n ( 9 parts per million) DDT also Inhibits the beef brain enzyme by about 50 percent. The PCB- and the DDT-sensitivity of the (Na++K+) ATPase are similar whether the enzyme is obtained from beef brain or from fid) (blue gill) brain. On a parts per million basis a commercial preparation of 3-cblorobiphenyl is about as inhibitory as Aroclor 1221> whereas biphenyl, b-chlorobiphenyl and 2, b-dieblorobiphenyl were less inhibitory. The technique for exposure of the (Na++K+)ATPase to the Aroclor preparations was found to influence the degree of the enzyme inhibitory response. Beef brain (Na'l'+K+)ATPase responsiveness to commercial PCBs has been demonstrated to simulate several aspects of enzyme responsiveness to DDT. Toung (50) of the Virginia Folytechic 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, narking tags, turkey fat, heavy fowls, eggs and poultry feeds are also being assessed and have been found in all but two samples with concentrations ranging from O.O63 parts per million to b*56 parts per million. **' ,.v. The possibility of the PCBs exhibiting immunosuppressive effects is being further studied by.Vos. (5l)* The leucopenia, the reduced number of germinal centers in the spleens and lymph nodes, the atrophy of the cortex of the thymus (Vos and Beems, bit), and the atrophy of the white pulp and lymphoid foci found in the spleens of chicks fed PCB (Vos and Koeman, b2) are believed by Vos to be strong indications for an immunosuppressive effect. It was further suggested that the extent to which these observation are due to stress (release of gluco corticoids) would have to be elaborated. Elamra and dive NIEHS. (52) are studying the mutagencity of a spectrum of Aroclors 'as well as individual isomers of polychlorinated biphenyls in L5178-Y mouse lymphoma cells heterozygous at the thymidine kinase locus (TKV")3. 151 DSM 010172 LEXOLDMON000545 WATER PCB-00036012 / Spalding NIEHS,(6L) is elaborating the effect of Aroclors 1221, 12li2, 1251, 1260 and 1268 as well as a number of isomeric polychlorinated biphenyls on nouse lymphoma and DOT-resistant mouse lynphoma cells. V. SUMMARY AND CONCLUSIONS Despite the nearly four decades of PDB use in a broad spectrum of applications, the increasing awareness of its enviroimental aspects as well as an increasing number of recent mammalian toxicological investiga tions, aspects of definitive acute, aub-acute and chronic toxicity sti-ll 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 as the non- or ill-defined nature of the material actually used or reported in many studies, have all certainly contributed in making the evaluation of toxicity and biological data difficult. Table 12 suimnarizes some biological and toxicological effects of the PCBs. The above review of the current status of the toxicologic 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 fbture studies are outlined in Table 13. 152 DSW 010173 LEXOLDMON000546 WATER PCB-00036013 TABLE 12. SOME BIOLOGICAL AND TOXICOLOGICAL EFFECTS IN THE PCB'S. M 1. Acute oral LDcq in mammals varies from approximately 2-10 gm/kg. (Apparent increase In mammalian toxicity with decrease In chlorine content). 2. Generally, enzyme Induction increases with Increase in chlorination" of PCB's. 3. Induction of hepatic hvdroxylating 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 hydropericardial 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. Possible 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. Hyperqlyceridemlc 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 dlbenzofuran contaminants In several species, . la. Chloracnegenlc effects of chlorinated naphthalene contaminants In man. 1$3 DSW 0101?* LEXOLDMON000547 WATER PCB-00036014 TABLE 13. POSSIBLE FUTURE STUDIES INVOLVING PCB'S, THEIR INDIVIDUAL ISOMERS AND CONTAMINANTS. 1. Definitive studies on the mamqallan distribution of the Aroclors, a number of key common 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 Isomers of PCB. 3. Elaboration of the effects of Aroclors and Isomeric PCB's In mammalian reproduction studies are required because of the apparent anomalous relationship found in the pattern of chronic studies. 4. Elaboration of the teratogenicity of Aroclors and Isomeric PCB'sin several mammalian 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 microsomal enzymes, study the Influence of dllantfn 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 mammalian' 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? Does It affect the pancreas, etc.? 12. Study of Induced porphyria anddlnical consequences. osw 010175 LEXOLDMON000548 WATER PCB-00036015 FOOTNOTES 1. Xolbye, A.C., Jr., Current Status of Toxicological Effects of PCBs (FDA.), Sept. 1 (1971)} 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. b. Pe&kall, D. B. and Lincer, J. L., BioScience 20 (1970) 958. 5. National Swedish Environment Protection Board, PCB Conference, Stockholm, Dec. (1970). 6. Reynolds, L. M., Residue Revs. 2k (171) 27. 7. Zitko, V. and P.M.K. Choi, Fisheries Research Board of Canada, Tech. Rept., No. 272 (1971). , 8. Fishbein, L., Chromatog. Revs., in press. 9. Schwartz, L., Am. J. Publ. Hlth. 26 (1936) 58. 10. Schwartz, L., J. Am. Med. Soc. 122 (l9b3) 11. Schwartz, L. and F. A. Barlow, U. S. Public Hlth, Repts, 7 (I9li2) 17l7. 12. Jones, J. V. and H. S. Alden, Arch, Dermatol. Sjyphilol. y} (1936) 1022, 13. Meigs, J. K., J. J. Albom and B. L, Kartin, J.Am, Med. Assoc. 15b (195b) lbl?. lb. Flinn, F. B. and D. E. Jarvik, Proc. Soc. Exp. Biol. Med. (1936) 118. 15. Oreenburg, L., M. R. Mayers and A, R. Smith, J, Ind. Hyg. Toxicol. 21 (1939) 29. 16. Drinker, C. X,, W. F. Warren and 0. A. Bennett, J. Ind. Hyg. Toxiool. 19 (1937) 283. . ** . 17. 7os, J. 0., J> H. Koeman, H. L. Vandermaas, K. C. Tennoever deBrauw and H. DeVos, Food Cosmet. Tbxicol. 8 (1970) 625. 18. Saeki, S., A. Tsutsul, X. Oguri, H. Toshimura and N. Hamana, FUkuoka Acta Med. 62 (1971) 20; C.A. 71* (1971) lb629b. 19. Tamaguchi, A., T. Toshimura and M. Kuratsune, Rikuoka Acta Med. 62 (1971) 117. 20. Xojima, T., H. Fukumoto and J. Makisumi, Jap. J. Legal Med. 2% (1969) bl5- 21. Inagami, X., T. Xoga and T. Toraita, Shokuhin Eiseigakuzasshi 10 (1969) 312; C.A. 2i (1970) 120116. 22. Kojina, T., Fukuoka Acta Med. 62 (1971) 25. ' 155 OSH 010176 LEXOLDMON000549 WATER PCB-00036016 J 23" Uzawa, H., I. Ito, A. Notomi and S. Katsumi, Fukuoka Acta Med. 60 (1969) 1iIj9. "" 2lj. Uzawa; H., 7. Ito, A. Notomi, S. Hori, 7. Ikeura and S, Katsuki, F\ikuoka Acta Med. 62 (1971) 66} C.A. 7U. (1971) 138797. 2$. Nagai, J., M. Furukawa, 7. 7ae and 7. Ideda, Fukuoka Acta Med. 60 (1969) 1*75} C.A. 72 (1970) 11077. "" 26. Kikuchi, M., 7. Mikagi, M. Hashimoto and T. Kojima, Fukuoka Acta Med. 62 (1971) 89. ~ 27* Nishizuroi, M., Arch. Env. Hlth. 21 (1970) 620. 28. Grant, D. L., W. E, J. Phillips and D. C. Villeneuve, Bull. Env. Contam. Toxicol. 6 (1971) 102. 29. Bagley, Q. E., W. L. Beichel and E. Cromartie, J. Assoc. Off. Anal. Cham. 22 (1970) 251. 30. Koeman, J. H., M. L. Tennoever deBrauw and R. H. DeVos, Nature 221 (1969) 1126. 31* Yoshimura, H. and M. Oshima, Fbkuoka Acta Med. 62 (1971)} C.A. 7 (1971) 3563 32. Street, J. C., P. M. Urry, D. J. Wagstaff and A. D. Blau, 158th American Chemical Society Meeting, New York, Sept. 8-12 (1969). . 33* Risebrough, R. W., P. Reiche, D. B. Peakall, S. G. Herman and M. N. Kirven, Nature 220 (1968) 1098. 3ii* Villeneuve, D. C., D. C. Grant, W. E. J. Phillips, M. L. Clark and D. 0. Clegg, Bull. Env. Contam. Toxicol. 6 (1971) 120. 35* Ito, 7., H, Uzawa and A. Notomi, Fukuoka Acta Med. 62 (1971) i8} C.A. 7h (1971) 138798. ^ 36. Kimbrough, R. D., Interagency Meeting on PCBs, Dept. H. E. W., Washington, D. C., August 5 (1971) 37. Curley, A., V. W. Burse, M. E. Grim, R. V. Jennings and R. E. Linder, Presented at l60th American Chem. Soc. Meeting, Washington, D* C. (1971). 38* Curley, A., V. W. Burse, M. E. Grim, R. W. Jennings and R. E. Linder, Interagency Meeting on PCBs, Dept. H. E. W., Washington, D. C., August 5 (1971). 39* Sekita-, H. M. Osawa, Y. Ito and H. Tanabe, Shokuhin Eiseigaku Zasshi 11 (1970) 361} C.A. Xk (1971) 13681*8. \ I|0. Albro, P. W. and L. Fishbein, NIEHS (1971), Dnreported results. 156 OSW 010177 LEXOLDMON000550 WATER PCB-00036017 1/1. Keplinger, M. L., 0. E. Fancher and J. C. Calandra, Abst. of 10th Annual Meeting of Society of Toxicology, Washington, D. C., March 7-11 (1971), 1/2. Vos, J. G. and J. H. Koeman, Toxicol. Appl. Pharmacol. 17 (1970) 656. 1/3. Flick, D. F., R. 0. O'Dell and V. A. Childs, Poultry Sci. 1^(1965) 11/60. 1/1/. Vos. J. G. and R. B. Beems, Toxicol. Appl. Pharmacol. 19 (1971) 617, 1/^. Bauer, H., K. H. Schulz and U. Spiegelberg, Arch. Gewerbepath. Gewerbehve. 18 (1961) 538. 1/6. FLnkea, J. F., L. B. Priester, J. P. Creason, T. Hauser and T. Hinners, Presented at Amer. Publ. Health Assoc. Meeting, Minneapolis, Minn., Oct. (1971). 2/7. Enos, H., Personal Communication, Oct. 12 (1971). 1/8. Biros. F. J., J. C. Walker and A, Madbery, Bull. Env. Contam. Toxicol. 5, (1970) 317. 1/9. Ringer, R., J. Johnson and R. Hoopingarner, Interagency Meeting on PCBs. Efept. H. E. W., Washington, D. C., Aug. 5 (1971). 50. Young, R., Status of PCBs, ARS Rept., Oct. (1971). 51. Vos, J. 0., Personal Communication, Oct. 25 (1971). ' 52. Flamm, V. 0. and D. Clive, KEEPS (1971). Wbrk in progress. 53. Miller, J. W., U. S. Public Health Repts. 9 (191/1/) 1085. 51/. Bennett, G. A., C. K. Drinker and M. F. 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. i. Wagstaff and A. D. Blau, 158th American Chemical Society Meeting, Hew Tork, Sept. 8-12 (1969). 57. McCune, L., J. E. Savage and B. L. O'Dell, Poultry Sci, l/l (1962 ) 295. 58. Flick, D. F., R. 0. O'Dell and V. A. Childs, Poultry Sci. Uh (1965) ll/6o. 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, Mature 220 (1968) 702. ** 61. Love, 0. J., Personal Communication, Oct. 8 (1971), 1*7 DSW 010170 LEXOLDMON000551 WATER PCB-00036018 62. Aulerich, R. J., R. K. Ringer, H. 1>. Seagran and W. 0. louatt. Can. J. Zoology h9 (1971) 611. 63. Wilson, W. E. and C. Sharp, NIEHS (1971)} Studies in progress. 6li, Spalding, J. W., NIEHS (1971), Studies in progress. 6. Courtney, D. C. and Chernoff, N., Personal Communication, Nov. 1? (1971). 66. Fujita, S., H. Tsuji, K. Kato, S. Saekl and H. Isukaraoto, Fukuoka"Acta Medica 62 (1971) 30} C. A. ? (1971) 3797. 157-A DSW 010179 LEXOLDMON000552 WATER_PCB-00036019  MJ APPENDIX 0 Biological Data. On PCBs In Anlmal8 Other Ilian Man Table of Contents I. Toxicity A. Birds B. Insects C. Fish and Aquatic Invertebrates II. Physiology A. Metabolism and Kinetics B. Reproduction 159 162 III. IV. Summary Conclusions 156 167 OSH 010180 158 LEXOLDMON000553 WATER PCB-00036020 4* S APPENDIX 0 Biological Data On PCBs In Anlinala 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 exposure, as shown by frequency and levels of occurrence of PCBs in the environment, is essential to complete the understanding. These are summarized elsewhere in this report. I. TOXICITT . 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 toxicities of different PCBs to pheasants (Phasianu3 colchicus), mallards (Anas platyrhynchos), bobwhite quail (Colirns virginlanus), and coturnix quail Vcoturnix coturnix) were compared with the toxicities of DDT, dieldrin, and other insecticides (Heath, et al., i). 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, toxicities 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-h times as sensitive as coturnix. Special tests with coturnix quail showed that the toxic effects f DDE and Aroclor - were additive but not synergistic. ' In other studies, Aroclor 12li was approximately as toxic as DDE to four species of blackbirds* grackles (Qulscalus quiscula), cowbirds (Molothrus ater), starlings (Sturnua vulgaris), and redwings (Agelaius phoeniceus) (Dustman, et al. ,~2). Redwings were somewhat more susceptible to DDE than to PCBs. Signs of poisoning were sluggishness with slight tre mors of moderate amplitude, 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 I25k 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 those observed among blackbirds) the finches had enlarged kidneys and I some had hydroperieardiua. 1$9 DSW 010181 LEXOLDMON000554 WATER PCB-00036021 Chicks kept in batteries recently painted with an epoxy-resin paint, (McCune et al., b). died aa a result of Aroclor 12b2 in the paint. Others fed this compound developed hydropericardium and enlarged livers and kidneys. Egg injection studies showed that Aroolor 12l)2 had a relatively high toxicity (McLaughlin, et al,, 5). Aroclor 12b8 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-b of 10 chicks survived each of the three higher dosages. Growth rates were reduced at 20, 30, and I4O parts per million in a second experiment; mortality was 16 of 30 birds at 50 parts per million dosage, b of 20 at I4O parts per million, and 1 of 30 at 30 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 bO 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 cookerels fad a dietary dosage of 500 parts per million of Aroclor 125b from the day of hatching;' the birds died between the third and tenth week of feeding (Platonov and PUnnell, 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 small, and testes were small. The effect on combs 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 PCBs were Phenoclor DP6, manufactured in franco; Clophen A60, manufactured in Germany; and Aroclor 1260, manufactured in the United States. Twenty-four birds fed 1)00 parts per million of Phenoclor EP6 all died within 60 days; all had liver necrosis and-18 had hydropericardium. Twenty-two of 2b birds fed Clophen at the same 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. Biese different effects or the three brandnamed products were later largely explained by the identification of chlorinated dibensofiiran and chlorinated naphthalene as contaminants in Phenoclor and Clophen (Vos et al. ?). In a further study with coturnix 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 PCBs (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. 160 OSW 010182 LEXOLDMON000555 WATER PCB-00036022 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 I4O to 700 parts per million. Residues in livers were 120 to 2,900 parts per million. Cofcurnix quail poisoned by PCBs (Fhenoclor DP6) contained residues of 3h2-1710 (av. 1158) 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 parts per million in the livers; those sacrificed at the end of the experiment contained 3 to 63I1 parts per million (Prestt,et al., g). Residues in brains were 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 DDE in the brain were 385 parts per million, which is with in the lethal range for DDE (Stickel 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 O.Lt 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 1251; to a grasshopper (Clorthlppus brumous) produced delayed mortality that occurred at the time of molt (Moriartyj ib), C. PISH AND AQUATIC INVERTEBRATES Shrimp (Panaeus duorarum) are sensitive to low concentrations of PCBs (Duke,et al,,l5y. All individuals died as a result of a fa6-hour exposure to flowing seawater containing 100 parts per billion of Aroclor 125b; 80 percent died in 2li hours. These Bhrinp 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 5 parts per billion of Aroclor 125b and the tissues accumulated 16 parts per million. Crabs (Callinactes sapidus) were less sensitive, but accumulated an average of 23 parts per million in a b-week exposure at 5 parts per billion are! 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.(Qanwarus oceanlcus) had a lethal threshold in 30-day tests between 0.001 and 0.01 parts per billion in colloidal solution and between 161 DSN 010183 LEXOLDMON000556 WATER PCB-00036023 0.01 and 0.1 parts per billion in emulsions of Aroclor 125b solubilized in Corexit 766b (a commercial nonionic surfactant preparation) in seawater (Wildish, 16). Oammarus that died had severely necrosed branchiae, and some animals exposed to as little as 0.001 parts per billion developed a leas extensive sublethal necrosis. Moulting or freshly 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 1|0 percent in _ exposure to 10 parts per billion and the oysters accumulated 33 parts per million of PCBs in their tissues (Duke, et al., 1J>). Plnfish (Lagodon rhomboides) survived exposure to 10 or 100 parts per billion of Aroclor 125b for LB hours, but those exposed to 100 parts per billion accumulated 17 parts per million (Duke, et al., 15). In further studies at the same laboratory, pinflsh and spot (Leiostomus xanthurua) died when exposed for lli-ii5 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 dayB (Hansen, et al,, if), Onset of death in both species exposed to 5 parts per billion was delayed. Pinfish developed fungus-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 (3almo galrdneri) are very sensitive to the terpheryls (Outhrie and Acres, 18)7 ' Fifty percent of the fish exposed to Santowax CM# 30 percent high boilers at concentrations of 10 parts per billion or greater died in 18 hours or less under normal oxygen conditions. With reduced oxygen, 50 percent died in less than 2 hours even at a concentration of 2 parts per billion (the lowest tested). The fish became hyperactive in less than 1/2 hour in water containing 25 parts 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. II. 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. let 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 KINETICS 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 excreted * Monsanto (hendcal Coryary trade name. Santowax is a mixture of ortho-, meta-, and para-terpheiyls. HB-bO is a mixture of hydroterphenyls and terpheryls. High boilers are tar-like decomposition products produced as a result of the exposure of terpheryls to a high radiation field. .. 162 D$W 010184 LEXOLDMON000557 WATER PCB-00036024 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 (Haliaeetus alblcilla) and fish and mussels (Mytilus edulis) to seals (Phoca vitulina and Pusa hispida), concentrations increased hundreds to thousands of tines from prey to predator (Jensen, et al.f 19). Fish contained hundredths to tenths of parts per million; fresh mussels contained hundredths of parts per million; seal blubber contaimd 5- 21 parts per million; and the muscle of the white-tailed eagle contained 1502I4O parts per million. In Qreat 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 peregrinus) contained greater amounts, one as high as 98 parts per million in muscle (Risebrough, et al., 20), while fish in the same area 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 U86 parts per million. Clysters (Crassostrea virginica) contained 2-3 parts per million, shrimp (Penaeus duorarumj 1.5-27f> parts'per million, blue crabs (Calllnectea aapidus) 1-7 parts per million, and pinfish 6- 12 parts per million (Hike, et al., 15). Subsequent samplings from three stations In. the Bay showed little change in concentrations of PCBs in sediments even after 9 months (Nimrao, et al,, 21). Experiments were then undertaken that showed that shrimps (Penaeus duorarum) and fiddler crabs (Uca minax) could accumulate Aroclor 125b from the sediments. Relationships between concentration of PCBs in sediment and concentration in crabs and-shrimps were variable. The maximum accumulation was from sandy silt containing 6l parts per million (dry weight) of Aroclor 125b; fiddler crabs accumulated 80 parts per million (wet weight) in their bodies; shrimp accumula ted 2bO parts per million (wet weight) in the hepatop&ncreas Some PCBs were present in the water and a portion of the accumulation could have been from that source. The ratio of individual POB isomers maintained integrity in the sediments and tissues of test animals throughout the investigation, indica ting no pronounced metabolic changes of the PCBs. . Spot (Leiostcmus 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), Maximum concentration in whole spot was 37,000 times that in the test water. These results were very similar to those for DOT reported earlier from the same laboratory. "5he PCBs were lost slowly from the tissues of spot after they were placed in clean flowing water. After 8b days of flushing, the concentration had dropped 73 percent and the absolute amount had dropped 6l percent. Isomers of Aroclor 125b, with the exception of one peak, maintained their integrity in spot. 163 ,DSW 010185 LEXOLDMON000558 WATER PCB-00036025 Marine diatoms (Qylindrotheca closterium) exposed to Aroclor 12b2 at 0.01 and 0.1 part per million In culture flasks absorbed the chemical to a concentration of U.7 and 109.2 parts per million, hjO and 1,100 times the concentrations in the surrounding medium (Kell, et al, j ^22), Iho 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 effects were produced by the 0.01 part per million concentration. Some early eluting PCB materials not com mon to the known mixture of Aroclor 12b2 were isolated from the diatoms,,suggest ing possible metabolism of the Aroclor. A species of salt-water diatom (Thalassloslra pseudonana) grew at a signi ficantly reduced rate when exposed to Aroclor 125b at concentrations of 25, 50, and 100 parts per billion in the culture medium (Mosser, et al., 23). 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 more'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,(Garonarus Oceanians).appeared to absorb Aroclor 1251i across the general integument (Wildish and Zitko,, 2li). Uptake was not altered by removal of branchiae epi-flora and by removal of epi-fauna, or by the stage of intermoult. Rate of uptake was greater at higher concentrations and declined after a few hours. Dead dammarus absorbed significantly smaller amounts of PCBs from the seawater than did the living animals. PCBs Inhibited AlPases in bluegills (Leporols maorochirus). Aroclor 125b was the most effective inhibitor, followed by Aroclor 1221 (Yap, et al,, 25). Aroolor 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 the Netherlands, the PCBs of lower chlorination were more common in fish (Leuciacus rutilus) than in sea birds, and it was concluded that compounds with fewer .chlorines probably were 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 present in the egg of a mallard duck and the pattern of the Aroclor 125b that the duck had eaten (Heath, l). PCBs increased the breakdown of estradiol in domestic pigeons (Risebrough, et al#, 20) and kestrels (Falco sparverious) (Lincer and PeakalD i, 27). demon strating their capability to induce microsomal enzyme activity. The PCBs were given by injection (pigeons) or ingestion (kestrels) of relatively high dosages; the birds were sacrificed and in vitro laboratory studies were made of the homog enized livers. ` 16b 010186 LEXOLDMON000559 WATER PCB-00036026 Mallard ducklings demonstrated the possibility of interacting effects between PCBs and disease organisms (friend and Trainer, 28). Thirty-fire 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 lb percent of the birds exposed only to the virus. Swedish robins (Erithacus rubecula) given 5 micrograms of Clophen A50, for 11-13 days showed & greater migratory restlessness than controls (Ulfstrand and Sfidergren, 29). " Pheasant hens absorbed 9b percent of the Aroclor 125b given as a single capsule dose, a very efficient entry of this chemical into the system (Dahlgren, et al.f 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 uncontaminated feed was restored (fries, et al, 3l). The rate of loss of EDE residues was identical. PCBs in milk fat decreased from 12.6 parts per million to 58 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 dose released an average of 3*9 parts per million into the whole milk during the next li days' milking. A dosage of 100 mg/kg produced 36 parts permillion in the milk of another cow (Platonov, et al^, 32). The gas chromatographic pattern of the Arodors in the milk was very similar to that of the fed compound. B. REPRODUCTION ' ___ Pheasants given a capsule dose of 50 mg of Aroclor 125b weekly for 17 weeks produced fewer eggs than controls, and a higher percentage of chicks pipped the shell but did 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, more of the chicks from the dosed parents made the undesirable choice of jumping to the deep side, or made no choice, in the 5-minute test ppriod. None of these effects occurred among the groups whose female parents were dosed with 12.5 mg. Mallards fed a dietary dosage of 25 parts 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 Aroolor 125b in the diet for about 5 weeks laid eggs with normally thick shells. Bobwhite quail fed diets containing $0 parts per million of PCBs, or 30 parts per million of DDE, or a ccmbination of 25 parts per million of PCBs plus 15 parts per million of IDE for about 11 weeks before their first breeding seaspn reproduced as well as controls. . * Ring doves (Streptopelia risorla) 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 intraperitoneally with 160 mg/kg 1-b days before egg laying confirmed the lack of effect of PCBs on shell weight. 165 ' ` DSW 010187 LEXOLDMON000560 WATER PCB-00036027 t/ Chickens fed Aroclor 1212 at 10 parts per million or 100 parts per million and Aroclor 12^li at 100 parts 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-feet Laboratories. Those fed Aroclor 12l>2 at 1 part per million, Aroclor 12l at 1 part per million or 10 parts per million, or Aroclor 1260 at 1 part per million, 10 parts 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 DDE residues correlate much better with shell thinning than do residues of dieldrin or PCBs (Blus, et al,, 3!>l Anderson, et al.,'36) reported similar results from studies of shell thinning and residue content of the eggs of cormorants and white pelicans. Reproductive failure occurred among ranch mink that were fed fish from the Qreat Lakes and the Miraraichi (Gilbert, 37 ; Aulerich, et al., 38).. 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 Polyohlorinated biphenyls have become ubiquitous in the world ecosystem in quantities similar to those of DDE, Experimental studies have shown that PCBs have a toxicity to mallards, pheasants, bobvhite quail, coturnix qiiail, 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 Wthoae caused by compounds of the DDT group. Toxic effects of DDE and Aroclor 12J>ii to coturnix chicks were additive, but not synergistic. PCBs containing higher percentages of chlorine are more toxic to birds than those contain! lower 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. . Ibxiclty to insects of PCBs of different degrees of chlorination is the reverse of the pattern in birds the lower chlorinationa are more toxic to insects. PCBs enhanced the toxicity of dieldrin and DDT to insects. 166 OSH 010188 LEXOLDMON000561 WATER PCB-00036028 Shrimp are very sensitive to PCBs and most will die as a result of 20-day exposure to a concentration of 5 parts per billion. PCBs also inhibit shell growth of oysters. Crabs are less sensitive; all accumulate residues to many times the concentrations in the water, and a test with crabs ehowBd that they lost the residues very slowly. Growth of certain species of marine diatoms was experimentally inhibited by PCBs, but algae were not affected. Hie small marine crustacean, Gawmarus. is sensitive to PCBs in concentra tions of thousandths to tenths of a part per billion. Exposure to 5 parts per billion of Aroclor 12li caused mortality of two species of fish in lh-h$ 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 oxygen 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 testa. Egg production and hatching after pipping also were affected. Migratory restlessness was increased in English robins ex posed to PCB3. Long-term studies of the reproductive effects of ArSclor 1251 on mallards and bobwhite quail and of Aroclor 125b plus DDE on quail showed no significant differences from controls. In studies of chickens, however, egg production and hatchability were impaired by high doses of Aroclor 125b and by low doses of Aroclor 12^2. 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 dieldrin or PCBs, confirming observa tions with cormorants and white pelicans. IV. CONCLUSIONS * PCBs are man-made biologically active substances that are dispersed throughout the environment and stored in the tissues of animals. Ihey are lethally toxic to fish and aquatic invertebrates in concentrations measured K7> DSVt 010169 LEXOLDMON000562 WATER PCB-00036029 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 Bimilar to those of 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. Pull evaluation of their actual or potential effects in the environment is hampered by the complex nature of the mixtures that compose them, and by the inclusion of contaminants in these mixtures. Experimental studies have been conducted with the unaltered products, as sold, and the results may 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 a3 potential problems. The difficulties of attaining a proper evaluation in any reasonable length of time suggest that the least costly course would be to take all measures possible to prevent their escape into the environment. 168 DSW 010190 LEXOLDMON000563 WATER PCB-00036030 FOOTNOTES 1. Heathy R. G., 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, E. H., L. F. Stickel, L. J. Blue, V, L. Reiohel, 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: 118-131. 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. li. McCune, E. L., J. E. Savage, and B. L. O'Dell. . 1962. Hydropericardium and ascites in chicks fed a chlorinated hydrocarbon. Poultry Science hi*295-299. 5. McLaughlin, Joseph, Jr., Jean-Pierre Marliac, H. Jacqueline Verrett, Mary K. Mutchler, and 0. Garth RLtzhugh. 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. Rehfeld, Betty M., R. L. Bradley, Jr., and M. L. Sunde. . 1971. Toxicity studies on polychlorinated biphenyls in the chick. Poultry Science 50(It) *1090-1096. 7. Platonow, N. S., and H. S. Funnell. 1971. Anti-androgenlc-like effect of polychlorinated biphenyls in cockerels. Veterinary Record 88(U)*109-110. 8. Vos, J. O., and J. H. Koeman. 1970. Comparative toxicologic study with polychlorinated , biphenyls in chickens with special reference to porphyria, edema formation, liver necrosis, and tissue residues. Toxicology and Applied Pharmacology 17:656-668. . 9. Vos, J. 0., J. H. Koenart, H. L. van der Maas, M. C. ten Noever de Brauw, and R. H. de Vos. 1970. .Identification and taxicological evaluation of chlorinated dibenzofuran and chlorinated naphthalene in two commercial ,, polychlorinated biphenyls. Food and Cosmetic Toxicology 8:625-633. 16? DSM 010191 LEXOLDMON000564 WATER PCB-00036031  -J 10. Vos, J. 0., J. J. T. W. A. Strik, C&therinaW. M. van Holsteyn, and J. B. Pennings. 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)232-2b0. 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. Stickel, William H., Lucille F. Stickel, and Francis B. Coon. 1970. DDE and DDD residues correlated with mortality of experi mental birds, pp. 287-29b in "Pesticides Symposia," edited by W. B. Deichmann, Halos & Associates, Miami. 13. Lichtenstein, E. P., K. R. Schulz, T. W. Fuhremann, and T. T. Liang. 1969. Biological interaction between plasticizers and insecticides. Journal of economic Entomology 62x761-765. . Hi. Moriarty, F. 1969. The effects of polychlorobiphenyls on Chorthippus brunneus (SaltatoriasAcrididae). Entomologia Ejtp. and Appl. 12:206-210. 15. Duke, T. W., J. I. Lowe, and A. J. Wilson, Jr. . ' 1970. A ploychlorinated biphenyl (Aroclor 125b) in the water, sediment, and biota of Escambia 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 Oazmarus oceanicus. Bulletin of Environmental Contamina tion and toxicology J?(3)*202-20b. 17. Hansen, D. J., P. R. Parrish, J. I. Lowe, A. J. WLlsoa, ,<?r., and P. D. Wilson. . 1971. Chronic toxicity, uptake, and retention of Aroclor 125b in two estuarine fishes. Bulletin of Environmental Contamination and Toxicology 6(2)1113-119. 18. Guthrie, J. E., and 0. E. Acres. 1970. Toxicity to fish of two organic reactor coolants. Bulletin of Environmental Contamination and Toxicology 5(2) ilb5-l!>l* 19. Jensen, S., A. G. Johnels, M. Olsson, and Q. Otterlind. ' 1969. EOT and PCB in marine animals from 9wedish waters. Nature ' 22bx2b7-250. 20. Risebrough, R, W'., P. Reiche, D. B. Peakall, S. Q. Herman, and M. N. Xirven. 1968. Polychlorinated biphenyls in the global ecosystem. Nature 220x1098-1102. 170 DSH 010192 LEXOLDMON000565 WATER PCB-00036032 / 21. Ninino, 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. Keil, Julian E., Lamar E. Priester, and Samuel H. Sandifer. 1971. Polychlorinated biphenyl (Aroclor 121:2): 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. 2h. Wildish, D. J., and V. Zitko. 1971* Uptake of polychlorinated biphenyls from sea water by Qamroarus oceanicus. Marine Biology 9(3):213-2l8. * 25. Yap, H. H., D. Desaiah, L. K. Cutkomp, and R. B. Koch. 1971. The sensitivity or 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 ooastal area. Nature 221: 1126-1128. 27. Lincer, Jeffrey L., and David B. Peakall. 1970. Metabolic effects of polychlorinated biphenyls in the American kestrel. Nature 228:783-781). 28. Friend, Milton, and Daniel 0. Trainer. . 1970. Polychlorinated biphenyl: interaction with duck hepatitis virus. Science 170:131I)-13l6. 29. Ulfstrand, S., and A. Sodergren. ~ . 1971. Effect of PCB on nocturnal activity in caged robins, Erithacus rubecula L. Nature 231:1)67-1)68. 30. Dahlgren, Robert B., Ivonne A. Oreichus, and Raymond L. Under. 1971. Storage and excretion of polychlorinated biphenyls in the pheasant. Journal of Wildlife Management 35(li):823-828. 31. Fries, G. F., G. S. Harrow, Jr., and C. H. Gordon. 1971. Similarity in behavior of DDE and polychlorinated biphenyl (Aroclor 1251)) residues in an environmentally contaminated herd of dairy cowa. U. S. Department of Agriculture, " Agricultural Researoh Service Paper 130,Presented at the Annual Meeting of the American Dairy Science Association, East Lansing, Michigan, June 1971. 171 DSW 010193 LEXOLDMON000566 WATER PCB-00036033 / 32. Platonov, N. S., H. S. Funnell, D. H. Bullock, D. R. Arnott, P. W. . Saschenbrecker, and D. 0. Grieve. 1971 Fate of polychlorinated biphenyls in dairy products processed from the milk of exposed cows. Journal of Dairy Science 5b(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)*315-31?* " 3b- 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)JlOO-101. 35. Blus, Lawrence J., Robert G. Heath, Charles D. Gish, Andre A. Belisle, and Richard M. Rrouty. - 1971. Eggshell thinning in the brown pelican* implication of DDE. BioScience 2l(2l) *1213-1215. 36. Anderson, Daniel W., Joseph J. Hickey, Robert W. Risebrough, Donald F. Hughes, and Robert E. Christensen. 1969* Significance of chlorinated hydrocarbon residues to breeding pelicans and cormorants. Canadian FieldNaturalist 83*91-112. 37., Gilbert, Frederick F. ' 1969. Toxicity, to fidi of two organic reactor coolants. Bulletin of Environmental Contamination and Toxicology S(2)*lb5-l5l. 38. Aulerioh, R. J., R. K. Riger, H. L. Seagran, and W. 0. Youatt. 1971. Effects of feeding coho salmon and other Great Lakes fish on mink reproduction. Canadian Journal of Zoology . b9(5)*611-616. 9 DSW 010194 LEXOLDMON000567 WATER PCB-00036034 H/ APPENDIX H I. II. HI. IV. Regulatory Action on PCBs Table of Contents '~ Page Existing Regulatory Authority 17[, A. Federal Insecticide, Fungicide, and Rodenticide Act B. Federal Water Pollution Control Act C. The Refuse Act of 1899 (33 U.S.C. 2t07) D. The Clean Air Act (h2 U,S,C. 1857 et seq) E. The Egg, Heat, and Poultry Acts F. The Occupational, etc..* 0. Act to Regulate Transportation of Explosives and Other Dangerous Articles (18 U.S.C. 831-835) . Standards, Tolerances, or Guidelines Established 177 Application of Regulatory Authorities 179 Future Actions and Needs . 180 Tables 1. FDA Proposed Temporary Tolerances for PCB Residues 178 DSW 010195 173 LEXOLDMON000568 WATER PCB-00036035 APPENDIX H Regulatory Actions on PCBa. I, EXISTING REGULATORY AUTHORITY At least ten Federal laws are potentially relevant for the regulation of PCBs. However, not all of them have actually been utilized to deal with the PCB problem. Federal Food, Drug, and Cosmetic Act (21 U.5.C. 301 et.seq.) Section ii02 of the Federal Food, Drug, and Cosmetic Act (FDC Act) de fines an "adulterated food" as a food which (among other criteria): < 1. Contains any poisonous or deleterious substance which may render It injurious to health j or . 2. Contains any food additive unless the use of the additive con forms to exemptions or regulations issued by the Food and Drug Administration (FDA). FDA has applied both of these criteria to PCBs, depending upon the: circumstances under which the PCB entered the food. The FDC Aot prohibits the introduction of adulterated food in interstate commerce; prohibits the adulteration of food while moving in Interstate commerce; and prohibits the receipt of an adulterated food in interstate commerce and subsequent delivery of it for sale or otherwise when the initial recipient is aware that the food is adulterated. The Act also authorizes IDA to seize any adulterated food products which have entered interstate commerce or which become adulterated while held for sale after receipt in interstate commerce. 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. These inspections Include the collection and analysis of food samples. Some 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 suoh as mercury, lead, cadmium, harmful bacteria, natural poisons, etc. However, the actual number of routine surveillance samples taken is small, and effective enforcement relies heavily on informa tion on tbs known or suspeoted existence of specific instances of food adulteration. A. FEDERAL INSECTICIDE. RINGTCIDB. AND R0DENTIC1DB ACT (7 U.S.C. 135-135k) - Under the Fbderal Insecticide, Fungicide, and Rodenticide Aot (FIFRA) all pesticides (referred to in the act as "eoonomio poisons") l?li OSH 010196 LEXOLDMON000569 WATER PCB-00036036 M 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 ERA) issued a notice (PR Notice 70-25) 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 compiled with, there should be no pesticides which currently contain PCBs. B. FEDERAL WATER POLLUTION CONTROL ACT (& U.S.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 part of the FWPC Act is not a useful tool for dealing with the PCB problem. . Section 12 of the FWPC Act applies primarily to accidential discharges of hazardous polluting substances. It requires the lnsnediate 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 EPA is authorized to remove or arrange for the removal of the hazardous substance 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 seotion could be used if an accidental spill of PCBs into water should occur. C. THE REFUSE ACT OF 1899 (33 U.S.C. 107) " Another legal authority for controlling water pollution is section 13 of the 1899 Refuse Aot which forbids discharge of any wastes (other than municipal wastes) into navigable waters without a permit, issued by the Army Corps of Engineers, which can limit the discharge of substances into water. EPA and the Justice Department are prepared to use the Refuse Act to prevent PCB discharges. D. THE CLEAN AIR ACT (12 U.S.C. 1857 et. seq.) . The general authorities contained in the Clean Air Act are not, for the most part,'applicable to PCBs because PCBs are. not generally .emitted into the air in the normal operations of a municipal or industrial facility. PCBs may become air contaminants through the burning of refuse, but such emissions usually could be controlled only by preventing the substance from initially getting into the refuse. 175 DSW 010197 LEXOLDMON000570 WATER PCB-00036037 *4 J 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 PCBa for the same reasons that the other Clean Air Act authorities are generally not applicable. E. THE EOQ. MEAT. AMD POULTRY 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. ?0-h92)} 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 acts 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. USDA can seize adulterated products or prevent them from being distributed. F. THE OCCUPATIONAL SAFETY & HEALTH ACT (29 tf.S.C. 6*1-678) ' 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 been set for occupational exposure to PCBs* However, the Department of Labor has set exposure limits for comparable substances, and it could enforce limits on PCBs by applying limits Bet for canpounds such as chlorodiphenyl. The standard for chlUTodiphenyl is lmg per cubic rooter - 8 hour average exposure. 0. ACT TO REGULATE TRANSPORTATION OF EIPIflSITES AND OTHER DANGEROUS ARTICLES-(18 U.S.C. 831-835) The Department of Transportation (DOT) regulates the-transport of hazardous substances 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 ha8 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 complied with rests initially with the manufacturer or shipper. sw 010198 176 f I LEXOLDMONOOQ571 WATER PCB-00036038 II, standards, tolerances, or quipelinss established J Hi most important limits which have been established for PCBs have been those established by FDA to deal with particular instances 6f food or feed contamination Standards or, more accurately, tolerances for products such as for PCBs may be established under Section Ij06 or Section h09 of the Food, Drug, and Cosmetic Act, which require a finding that the substance is 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 ttie 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, Drug, 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 from the market shell eggs containing more than 0.0$ parts per million PCBs and feeds containing more than 0.$ parts per million PCB where the PCBs present appears to be from accidental contamination of feed. Hie U,S. Department of Agriculture has also t.dcen action to remove poultry from the market containing 5.0 parts per million PCBs where such contamination was the result of accidental contamination of feed fed to poultry. The action level of 5 parts per million (whole tissue basis) was established in 1?71 by FDA. Thi3 level van reduced to 5 parts per million on a fat basis in 1972. - 1 The Food and Drag Administration has taken no action against any ether products for PC8 contamination but has inforaad the States and others that it would consider action on milk :if PCBs exceed U.2 parts per million (whole basis) and on fish if PCBs exceeds 5 parts per million. Some States have taken action to remove milk from the market that contained more than 0.2 parts per million PCBs. The temporary tolerances recently proposed by FDA artr 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, and children are not considered to have as efficient detoxication mechanism for handling PCBs 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 change. 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 177 DSW 010199 LEXOLDMON000572 WATER PCB-00036039 Table 1 FDR Proposed Temporary Tolerances for PCB Residues Food Tolerance * Milk 2.5 ppm (fat basis) Dairy Products t Poultry 2.5 ppm (fat basis) 5 ppm (fat basis) Eggs 0.5 ppm Complete animal feeds 0.5 ppm Aninuil feed components (including fish meal) 5 ppm Fish 5 ppm (edible portion) Infant and junior food 0,1 ppm '. Food-packaging materials 5 ppm 4 178 OSH 010200 LEXOLDMONOOQ573 WATER_PCB-00036040 materials be established permitting unavoidable PCB residues in-such materials for a period of one year. This will provide an opportunity for the orderly elimination of PCB-contAining 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, and would limit PCB levels in the water to .01 parts per billion. These regulations probably would be enforced through use of the Refuse Act. III. APPLICATION OF REGULATORY AUTHORITIES " Within the past two years there have been several incidents involving PCB contamination. These include the following: In September 1969 FDA detected PCBs in West Virginia milk. The source of PCBs was suspected to be the use of spent transformer fluid as a solvent for herbicide spray. Or&de A milk shippers involved were taken off production by the State. In April 1970 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 silos where dairy feed was stored. Similar occurrences of PCB contamination of dairy herds have been reported in several Southeastern States. " Since June 1971, the Heat and Poultry Inspection Program (MPIP) and the Poultry Division, Consumer and Marketing Service, USDA, have been survey ing specifically for PCBs. Prior to that time, the MPIP's ongoing survey of chlorinated hydrocarbons should have detected any PCBs present in animal or poultry fat at a level of 1 parts per million or above. None was detected in the fat of poultry, swine, cattle, or sheep prior to December 1970. Since that time, there have been five separate incidents of contamination of poultry with PCBs. Each appears to be a single-source, one-time occurrence. The Poultry Division's egg sampling program in the Southeastern U.S. and in Minnesota has not detected levels of PCBs which are significant--most values falling below the sensitivity of the method. -* Contamination of hens slaughtered on December 2, 1970, led to placing all laying hens in Orange, Sullivan, and Ulster Counties, New York, under quarantine through August 30, 1971, requiring pretesting for PCBs prior to slaughter. Levels up to 26.8 parts per million PCBs were found in the fat. Approximately 137,100 hens were condemned and buried on the farms. Flocks containing less than 5 parts per million PCBs were sold in commercial channels, frequently at drastically reduced prices. Eggs from contaminated flocks were destroyed. The source of contamination was feed containing returned bakery product wrappings. Frozen turkeys produced on farms from Modesto, Fresno, Stockton, and Santa RoBa, California, were found to contain up to 28 parts per million of of PCBs in the fat. The source of contamination is unknown. All turkeys DSW 010201 17? LEXOLDMON000574 WATER PCB-00036041 from those sources (approximately 100,000 lbs.) wore detained until " testing was completed (Feb.-May 1971). Muscle meat was salvaged and used in turkey rolls. Fat and skin containing over $ parts per million PCB3 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 1971 in Wilmington, N.C. One immediate and noticeable result was poor habchability of eggs from the poultry fed the PCB contaminated diet. Accordingly, USDA . required that all poultry coming to market from, these' States be tested - r before marketing. During the first 2 weeks of testing, Zltl samples were analyzed, representing over 2.5 million birds. Of these, 2.h percent were retained until disposition could be made. The 88,000 chickens which 4 had been fed the fish meal were destroyed by the owner of the chickens. FDA seized 75,000 eggs, $ shipments of commercial fidh feed, and 1 ship ment of fish meal which had been contaminated, and USDA barred from market more than 30,000 pounds of processed frozen eggs. In addition, the processing firm recalled over 16,000 tons of the PCB-contandnated fish meal. In September 1971, turkeys from one grower on eight farms in Detroit Lakes, Minnesota, were found to contain up to. 20 parts per million PCBs (fat basis). One hundred forty flockB in the immediate area, including parts of Minnesota, North Dakota, and South Dakota, were tested , but no levels above 2 parts 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 beat exchanger is suspected. Also in Septeriber, the State of Michigan stopped its annual program of distribution of Cohoe Slamon from Lake Michigan, because the fish contained high residues of PCB and DDT. In February 1972 chickens in Maine were discovered to contain PCB contamination of up to 172 parts per million in their fat. These con taminated chickens had been given feed from a plant in Thorndike, Maine, but officials have been unable to locate the exact source of the PCBs. More than a million chickens have been destroyed. Mapy of these incidents have evoked criticism of the' Federal Government for failure to detect the problem sooner or for failure to act more stringently. t 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 small fraction of the foods being shipped. Factory inspection I can detect some problems, but even this approach is severely limited by available resources. The prime reliance must be on controlling the use of the offending substance. .. IV. FUTURE ACTIONS AND NEEDS* i * Enough data are available to indicate that PCBb are pervasive in'.the environment. The basic regulatory challenge is thus twofold: to minimize human exposure to PCBs already present in the environment and to prevent more PCBs from entering the environment. DSW 010202 LEXOLDMON000575 WATER PCB-00036042 </ 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 has 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. However, there will still be problems, as evidenced by the Coho Salmon contamination, the mysterious Minnesota turkeys, and the discovery of high levels 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 authorities. Even with better understanding we can probably expect future isolated incidents of PCB contamination. Existing regulatory authority is generally inadequate to prevent more PCBs from entering the environment. The Monsanto Company has reported volun tarily limiting the distribution of PCBs to ''closed systems'1 but this limit has no force of law behind it. The government has no power to restrict imports of PCBs by foreign manufacturers, and if it disagreed with Monsanto's judgment on allowable uses it could not impose more stringent limitations 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, sent to the Congress in Pebruary 1?71, would authorize the Administrator of EPA to restrict or prohibit the use or distribution of a chemical substance if such restriction were necessary to protect health and the environment, and 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 and uses of new substances. Thus, in addition to providing tbe regulatory authority needed to deal with the PCB problem, it would also establish a system for preventing new chemicals from becoming similar problems. Action by the Congress to approve tbe Toxic Substances Control Act is the most important step which can be taken to deal with PCBs and similar problems. .. '* 181 DSW 010203 U. t. OOVOHMEHT rftJMrtNO OtriCt * l*--(7$*) LEXOLDMON000576 WATER PCB-00036043