Document B5EBK8z409xd7mzvRgNrpM4Bm

GENERAL ELECTRIC COMPANY R.W. Lewis Vice President and Group Executive July 7, 1570 Hr. A. M. Salazar, Executive Secretary - Power Equipment Division NEKA 155 East 44th St. "* Hew York, H. Y. 10017 Dear Al: At the last meeting of the Board of Directors of the Power Equipment Section, I recommended that NEKA take a leadership role in solving the problem of disposition of askarel contaminated materials because it is an industry-wide p r o b l m . The background of this recommendation is that Monsanto, the sole manufacturer of askarels (technically known as polychlo rinated biphenyls), notified us, and Z presume all other purchsers of askarels, that there was a possibility of environmental con tamination due to non-biodegradable materials used in their composition. Monsanto has offered a disposal service for hand ling scrap liquid askarels but the problem of disposing of askarel soaked materials, such as sawdust, rags, and insulations, has not been solved. It is the latter to which I r e c o a e n d e d a HEMA Task Force address itself. I would appreciate it if you would activate the mechanics for getting such a Task Force appointed as promptly as possible. As Z indicated, E. L. R&ab, Manager-Chemical and Processes section. Materials ***** Technology Laboratory, Pittsfield, Massachusetts, would likely be our candidate to serve on the Task Force. " ~ Very truly youra. RKLewis:nt cc: R. B. Ames : * C. J. Meloun 7 ADM 0 7 A 7 9 EXHIBIT *V Lr c i () ANSI C107.M 974 guidelines for handling and disposal of capacitor- and transformer-grade askarels containing polychlorinated biphenyls C107.1-1974 ANSI C 107.M 974 American National Standard Guidelines for Handling and Disposal of Capacitor- and Transformer-Grade Askarels Containing Polychlorinated Biphenyls Secretariat National Electrical Manufacturers Association Approved January 9, 1974 American National Standards Institute, Inc 1 Foreword (This Foreword is not a part of American National Standard Guidelines for Handling and Disposal of Capaci tor- and Transformer-Grade Askarels Containing Polychlorinated Biphenyls, Cl 07.1-1974.) Recognizing that the polychlorinated biphenyls present in askarels were being identified as envi ronmental pollutants and the urgent need for procedures and guides for their safe use and dis posal, the Board of Directors of th Power Equipment Division of the National Electrical Manu facturers Association (NEMA) in June 1970 appointed a committee to review the general problem and propose recommendations. In September 1970, the NEMA board approved, as recommended by the committee, the sponsorship of an American National Standards Commit tee for the use and disposal of askarels in electrical equipment. American National Standards Committee 0 0 7 was established in April 1971. NEMA was desig nated as the secretarial. An organizational meeting was held on September 14,1971. Mr W. B. Papageorge, Monsanto Company, was appointed chairman. Committee member^ included repre sentatives of capacitor and transformer manufacturers, utilities, governmental departments and agencies, and maintenance and disposal service companies. A steering committee and two sub committees - one to develop guidelines for the capacitor industry, the other for the transfor mer industry - were established. The scope and primary objective of the committee was designated as the development of: Pro cedures and guides for the safe use, maintenance, and disposal of askarel and askarel-soaked materials used in electrical equipment. Additional objectives proposed were as follows: (1) To serve as a source for technical information and advice for federal, state, and local authorities and for the information of all others concerned. (2) To encourage the development of suitable disposal facilities and maintain a list of their capabilities and locations, for the information of all concerned. (3) To serve as the advisory group for U.S. participation in the International Commission on: Rules for the Approval of Electrical Equipment (CEE), the International Electrotechnical Com mission (IEC), the Pan American Standards Commission (COPANT), the International Confer ence on Large High Tension Electric Systems (CIGRE), and other international organizations. The final draft of the guidelines was completed in late November 19?2. NEMA issued the guide lines as an Official Standards Proposal in January 1973. It was submitted to the American National Standards Institute for approval as an American National Standard, and was approved by the Standards Institute on January 9,1974. Suggestions for improvement o f this standard will be welcome. They should be sent to the American National Standards Institute, 1430 Broadway, New York, N.Y. 10018. This standard was processed and approved for submittal to ANSI by American National Stan dards Committee on Use and Disposal of Askarel and Askarel-Soaked Materials in Electrical Equipment, Cl 07. Committee approval of the standard does not necessarily imply that all com mittee members voted for its approval. At the time it approved this standard, the C l07 Com mittee had the following members: W, P. Papageorge, Chairman A.M. Salazar, Secretary Orpontiarior. Represented \ Name o f Rcprcsenurivt Certified Ballast Manufacturers Association................................................................. N. R. Clark A. Pozefiky Otem-Trol Pollution Services I n c .................................................................................. Louis E. Wagner Doble Engineering Company........................................................................................... A. L. Ricklcy Electnea! Utilities Com pany........................................................................................... A. O. Hauser E. M. Moore (Alt) Electric Light and Power G roup..................................................................................... F. R Lengefeld H. A. Onishi J.J . Cawley (Alt) Organization Represented Electronic Industries A ssociation................................ Environmental Protection Agency.............. ................. General Services Administration................................... Gilbert Associates Inc . ! ............................................ Institute of Electrical and Electronics Engineers, Inc , Monsanto Company....................................................... National Bureau of S tandards...................................... National Electrical Manufacturers Association............ Rollins-Purle, I n c ................................... ................................................ Tennessee Valley A uthority .................................................................. V S . Department of Agriculture, Rural Electrification Administration U.S. Department of the A rm y............................................................... Name o f Representative Arnold S. Doty Kenneth J. Hood Charles C. Travis R. J. Schatz E. L. Rabb W. P. Papageorge P. G. Benignus (Alt) Stanley P. Wasik K. C. Chang W. S. Grogan R. D. McClain H. R. Rowe Ken McGee (Ait) H. A. Alsentzer William R. Nicholas John Leutritz, Jr D. M. Crabtree \ Contents .. SECT10N 1. S c o p e ............................................... PAGE 7 2. General Information................................................................................................................... 2.1 G eneral................................................................................................................................ 2.2 Benefits................................................................................................................................ 2 3 Risks.................................................................................................................................... 2.4 A lternatives........................................................................................................................ 2.5 Interdepartmental Task Force on P C B s.......................................................................... 7 7 7 7 8 8 3. Capacitor G uidelines................................................................................................................. 8 3.1 G eneral................................................................................................................................ 8 3.2 Capacitor*Grade A skarel................................................................................................... 9 33 Plant Housekeeping and EmployeeS a fe ty ..................................................................... 9 3.4 Control of Water E fflu e n ts................................................................................................. 11 3.5 Scrap*Disposal Procedures....................................................................................................12 3.6 Labeling...................................................................................................................................13 4. Transformer Guidelines................................................................................................................. 13 4.1 G eneral................................................................................................................................... 13 4.2 Specific Guidelines.................................................................................................................15 5. References......................................................................................................................................17 5.1 References to the T e x t ......................................................................................................... 17 5.2 General R eferences...............................................................................................................17 6. Revision of American National Standards Referred to in This D ocum ent............................. 18 Table 1 Typical Properties of Aroclor 1 0 1 6 ............................................................................... 9 Appendixes Appendix A Disposal Services.................................................................................................... 19 Appendix B Analytical Procedures and Laboratory Serv:.j Organizations....................... 20 B l. G eneral..............................................................................................................................20 B2. Laboratories...................................................................................................................... 20 B3. An Analytical Procedure for the Determination of Airborne PCBs..........................20 B4. Analysis of Water and Sedimentfor PCBs.......................................................................31 Figures Fig. Bl Aroclor 1016 Electron Capture C hrom atogram ................................................. 21 * Fig. B2 Comparison of Electron Capture Chromatograms for Aroclor 1221, 1242, 1248,1254, and 1260...................................................... 22 Fig. B3 Aroclor 1221 Electron Capture Chromatogram....................................................23 Fig. B4 Aroclor 1242 Electron Capture Chromatogram...................... ......................... 24 Fig. B5 Aroclor 1248 Electron Capture Chromatogram....................................................25 Fig. B6 Aroclor 1254 Electron Capture Chromatogram....................................................26 Fig. B7 Aroclor 1260 Electron Capture Chromatogram....................................................27 Fig. B8 Sampling T rain......................................................................................................... 28 Fig. B9 Calculating Column Efficiency............................................................................. 30 Fig. B10 Calculating the Tailing F acto r................................................................................30 \ American National Standard ` Guidelines for Handling and Disposal of Capacitor- and Transformer-Grade Askarels Containing Polychlorinated Biphenyls 1. Scope This standard establishes guidelines for the safe use, maintenance, and disposal o f askarel and askarel-soaked material used in capacitors and transformers. 2. General Information 2.1 General. The term "askarel" generally describes a broad class o f nonflammable synthetic chlorinated . hydrocarbon insulating liquids widely used in capaci tors, transformers, reactors, and accessory equipment operated at power frequencies. . Askarels consisting of or containing polychlorinated biphenyls (PCBs) have been used in many applications for more than 40 years, but only recently was evidence discovered that PCBs are widely dispersed in the envi ronment. Systematic investigations of the biological effects of PCBs have been undertaken within the past few years to establish the effects of specific formula tions upon specific species. Some studies have shown that PCBs may be an environmental contaminant. Simultaneously, significant steps have been taken by U-S. industry to limit further releases of PCBs to the environment. PCBs have been used in three broad types of applica tions for the past 40 yean, as follows: (1) " Open-ended" applications; for example, in paints, specialty inks, paper coatings, plastics, etc (2) "Nominally closed" applications; for example, as the working fluid in hydraulic or heat-transfer sys tems ' (3) "Cosed electrical system" applications, specfC- cally u the insulating fluid in certain kinds of trans formers and capacitors' 'The Monsanto Company is the soleU.S. producer of PCBs. It has discontinued supplying the material for all applications pven m 2.1(1) and 2.1(2). Evaluations of the benefits, risks, and alternatives involved in the continued use of PCBs in closed electri cal systems are summarized in 2J2 through 2.4. 2.2 Benefits. Askarel-fllled transformers do not bum or sustain fire under conditions of internal electrical arcing. Askarel-fllled power and industrial capacitors are significantly smaller, more reliable, more durable, and safer than oO-filled capacitors. As a result, askarels have supplanted mineral oils in more than 90% of the power and industrial capacitors made today. Over the past few decades most of the equipment that incorporates such capacitors has been designed to take particular advan tage o f the size, safety, and reliability benefits of askarel capacitors (for example, many types are today less than 14% of the size of equivalent oO capacitors and have a life expectancy o f 10 to more than 20 years). Various federal, state, and local codes, therefore, re quire their continued use in or adjacent to public, com mercial, and industrial buildings, which locations pre sent the greatest potential danger to life and property. 2 3 Risks. In the United States, medical records over a early 40-year period show that the only adverse health effects experienced by U.S. workers exposed to askarels, either during the manufacture of these liquids or of electrical equipment containing these liquids, have been limited to occasional cases of nonchronic chloracne or other temporary skin lesions or irritations. Askarel-fllled transformen and capacitors are de livered to customers as sealed units from which there is no escape of askarel under normal operation. Although certain types of equipment failures can permit loss of some askarel to the environment, transformer failures are limited to approximately 0.02% of the units in ser vice per year. With respect to capacitors, such losses arc limited to approximately 0.02% of the askarel put into service per year. In addition, limited amounts of PCBs can get into the environment during the manufac ture, delivery, improper use, maintenance, repair, and disposal of transformers and capacitors. 7 AMERICAN NATIONAL STANDARD CI 07.1-1974 Specific control measures have been instituted by individual manufacturers and are supplemented and strengthened by national standards and procedures such as this standard, which provides information to prevent the inadvertent loss of PCBs to the environ ment at all stages from initial askare] manufacture through ultimate disposal. 2.4 Alternatives. For technical and local and national code reasons, it would be impossible to replace most askarel-filled transformers now in sendee with oil-filled units of equivalent ratings without major construction changes that would be required to compensate for the fire resistance of the askarel-filled units. For certain applications and locations, dry-type transformers may replace askarel-filled transformers. For new installations, although many of the fore going limitations would still apply, building and instal lation design provisions could be made to accommo date the use of oil-filled, open dry-type, or sealed drytype transformers, provided that necessary technical, code, physical size, and cost considerations are prop erly evaluated. The principal alternative to askarels for capacitors is mineral oil, but such replacement would return capac itor technology to its pre-1932 level and would necessi tate the redesign and replacement of such widely used equipment as fluorescent light fixtures and racks for power and induction-heating capacitors, which could not now accommodate the increased size of oil capaci tors while maintaining their present ratings. The cost of askarel liquids is about five to ten times more than mineral oil. Thus, long before there were any environmental concerns about PCBs, there was a strong economic incentive to find other, less expensive insulating liquids with the desirable characteristics of askarels. Since the 1930s at least ten major chemical or electrical companies have invested large amounts of time and money in this search, all with no success. Al though potential substitutes that are more costly than askarels (such as fluorinated liquids) have also received some consideration, little is known about eithei their electrical performance or posable ill effects upon the environment. There are today no fluids that can be used as a direct replacement for askarels. 2.5 Interdepartmental Tadt Force on PCBs. An indepth study of PCBs has recently been completed by five Executive Branch Departments of the federal gov ernment. This Interdepartmental Task Force on PCBs isaied their report, entitled Polychlorinated Biphenyls and the Environment, in May 1972.3 The following ' Available from the National Technical Information Sepie e, V S . Department of Commerce. Springfield. Va 22151. conclusion is quoted from page 4 of this report: "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 explosion and the disruption of electrical service which would result from a ban on PCB use. Also, continued use of PCBs in transformers and capacitors 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 transformers and capacitors." Reference should be made to the Interdepartmental Task Force Report for additional information and con clusions. 3. Capacitor Guidelines 3.1 General. The environmental effects of askarels are under in-depth study by governmental and other agen cies. Askarels have been considered relatively harmless to humans based on about 40 years of safe industrial usage. There has been no known instance of human in jury when they were used under the normally accepted precautions and conditions of handling in both manu facturing and user applications. Traces of askarels are being found in the environ ment and in fish and bird life. The long-term genetic and ecological effects are not yet completely under stood. For these reasons, care should be taken to con tain askarels and minimize their entry into the environ ment. There are two general classes of askarels used by the electrical industry. The higher chlorinated grades are the more persistent in nature. Because of their high de gree of nonflammability, they are used in transformers where personnel safety is of paramount importance. Capacitor-grade askarel has a lower degree of chlori nation (composed primarily of the 3-chlorine isomers of biphenyl) and a higher degree of biodegradabiliry. Generally, it has not been found in animal life. It is used in capacitors, where the extreme degree of non flammability required in transformers is of less impor tance. Although capacitor- and transformer-grade askarels both contain members of the PCB family, they do differ in composition, degree of biodegradability, persistence in nature, electrical stability, chemical stability, and degree of nonflammability (both are recognized as non flammable). It is for these reasons that Section 3 of this standard is intended to apply to capacitor-grade askarel. 8 AMERICAN NATIONAL STANDARD C I07.M 974 Table 1 Typical Properties of Aroclor 1016 Property Color Condition Specific Gravity ai 25/15.5C Acidity (mg KOH/g) Moisture Refractive index at 25C Inorganic (free) chlorides Pour point Dielectric constant <1000 Hz at 100C) Resistivity (500 V dc at 100C, 0.1-inch gap) Hydrolysis stability test (as chlorides) Thermal stability test (as chlorides) Distillation range (corrected) 10% distilled by weight 90% distilled by weight Higher-Boiling Homologues Sulfates Dielectric strength at 25cC Flash point. Cleveland open cup Fire point Corrosion test (6 hours it 210C with bright aluminum foil), change in weight of aluminum Viscosity at 100F (SUS)t Specific heat at 25 C Coefficient of expansion Fixed chlorine Power factor at 100C, 60 Hz Bulk Drums Test Method (See Note) APHA* ANSI C59.68-1965 (R1973) [2] ANSI Z l l . 131-1964 (R1974)|3J ANSI Z11.59-1958 (R1971) [4] ASTM D 1817-66 (1972) [5] ANSI C59.55-1963 (R1973) [6] ANSI Z l l . 5-1966 (R1972)[71 ANSI CS9.22-1967 (R1973) [81 ANSI C 59J 1*1965 (R1973) [9] ANSI C59.106-1970 [10] ANSI C59.111-1970 [11| ANSI A37.9*1974 [12] ASTM D 3303-74 [1] ANSI C59.2-1974 [13] ANSI C59.19-1968 (R1973) [14] ANSI Z l l . 6-1973 [151 - ' ANSI Z11.2-1956 (R1971) [ 16] - ANSI C59.57-1963 (R1973) [17] Carius Munch [18] Typical Values 40, max Gear 1.362-1.372 0.010, max 35 ppm, max 1.6215-1.6235 0.05 ppm, max -14C or lower 4.70-4.90 500 x 10* D cm, min 0 J ppm, max 0.4 ppm, max 323C. min 356C, max 0.4%, max None 35 kV, min 338F, min None to boiling point 0.0% 71-81 0.30 0.00068 cm '/cm J/C 4).3 i 0-5% 1%, max 4%. max NOTE: Numben in brackets refer to correspondingly numbered ten methods is 5.1, References to the Text. American Public Health Association. tSiybolt Universal seconds. 3.2 Capacitor-Grade Askarel. In September 1971 a new grade o f capacitor imprgnant, Aroclor 1016, was made available to the industry. This new grade contains a typical concentration of 0.4% by weight of the higher boiling homologues of the chlorinated biphenyls. (See ASTM D 3303-74 [1] ,"f Aroclor 1016 replaces Aroclor 1242, which previously was the major capacitor imprg nant and contained around 7% of the higher-boiling homologues (the more persistent in nature). This 0.4% level of the higher-boiling homologues should be the 'Numbers in brackets refer is corresponding numbers in 5.1, References to the Tex L maximum concentration acceptable in any capacitor imprgnant. Aroclor 1242 and 1254, previously used as imprgnants, do not meet this requirement and should no longer be used in capacitors designed and manufactured for alternating-current applications. Aroclor 1016 has the same Underwriters' Labora tories, Inc, nonflammability rating as Aroclor 1242. Its typical properties are given in Table 1. 3 3 Plant Housekeeping and Employee Safety. The procedures and limits given in 3.3 are intended to be minimum requirements to be met by manufacturers and users of capacitors containing askarel. Handling, control, and disposal procedures are given, together 9 AMERICAN NATIONAL STANDARD C107.l-.19.74 with exposure limits and indicated antidotes and clean contained in Section B3 of Appendix B. This procedure up procedures. o r its equivalent should be used. 33.1 Material. Askarel for use in capacitors should Breathing vapor or fumes from heated askarel should consist of homologues and isomers of chlorinated bi be avoided. Provisions should be made for adequate ven phenyl with the concentration of the higher-boiling tilation and regulation of manufacturing operations to homologues at about 0.4%. (See ASTM D 3303-74 [1 ].) avoid open exposure to askarel (especially at tempera Aroclor 1016 is considered to be the standard imprg tures of 55C or higher). The gases produced when aska nant.meeting these requirements. rel is decomposed by very high temperatures (such as Commonly used solvents include benzene, kerosene, that of an electric arc) in the presence of air or organic acetone, trichloroethane, trichloroethylene, and perchlo- insulating materials contain a high percentage of hydro roethylene. Typical vapor pressure data for Aroclor gen chloride, and small percentages of carbon dioxide, 1016 are: carbon monoxide, and oxygen. Minute concentrations 0C = 0.001 mmHg o f this combination of gases are very unpleasant and ir 25C = 0.006 mmHg ritating, thus giving ample warning of their presence. If 150C= 4.3 mmHg exposure to high concentrations of askarel is necessary 200C = 29.0 mmHg under emergency conditions, an approved gas mask or At 25C and 760 mmHg pressure, saturated air con self-contained breathing apparatus should be worn. tains approximately 0.09 mg/T. Such exposure should be under the surveillance of NOTE: I mg/l * 90.0 ppm (v/v) 1 ppm (v/v) = 0.011 mg/l other personnel capable of effecting rescue in case of an accident. If the odor of askarel is detected by the person wearing protective equipment, he should imme diately go into fresh air. All gas masks, respirators, and 3.3.2 .Bulk Fluid Shipment, Receiving, and Transfer. replacement parts should have U.S. Bureau of Mines Shipment of askarel from point of manufacture to point approval and be maintained on a regular schedule in of receiving should be done in closed containers such as accordance with the manufacturer's recommendation. rail tank cars, truck tanks, marine or barge tanks, or 3 3 3 .2 Liquid. In contrast to the situation in sealed drums. Containers should be labeled as to con which mineral insulating oils are handled, there is vir tents and carry .a label cautioning against loss of fluid tually no fire hazard in handling askarel. A limited sol to the open environment. Containers used to transport vent action (similar to that for paint thinner) on the askarel should not be used for storage or to transport fats and oils of the skin with prolonged contact may other material without being completely cleaned of all lead to drying and chapping of the skin. As with insu traces of askarel. (Geaning procedures must take cogni lating oil, some people are allergic to askarel, and con zance of precautions against excessive exposure and of tinued exposure may result in skin irritation. Both the the need for proper disposal of contaminated cleansing liquid and vapor are moderately irritating to eye tissue. solvents and materials as set forth in 3.5). Transfer Operating procedures should be such as to minimize from shipping containers to processing systems should or eliminate contact with askarels. Use of eye protec be through closed piping or tubing with appropriate tion is recommended. The use of porous gloves that valves, pumps, etc. Provision should be made for trap can absorb and retain askarels is to be avoided. Barrier ping and disposing of fluid lost by leakage or spills creams4 or resistant gloves9 should be used if contact from the transfer system and from the storage containers. is unavoidable. Use of enclosed transfer and handling Drums to be retired from use should be cleaned be fore crushing, delivery to scrap dealers, or other dispo equipment, processing equipment, and mechanical washers reduces direct contact. sal. Contaminated cleaning fluids and materials should Medicinal washes or mild detergents followed by the be disposed of as indicated in 3 3 . 3 3 3 General Safety Precautions. Although it is generally accepted that exposure to capacitor-grade application of cold cream will reduce the irritation re sulting from the contact of an open cut or abrasion with askarel. askarel is not hazardous provided that simple precau tions are taken, exposure should still be avoided. Safety glasses with side shields or a face shield should be worn when handling askarels. If liquid aska- 3 3 3 .1 ' V ipon. The odor of askarel is noticeable well below the maximum air concentrations considered safe. Up to 1.0 milligram per cubic metre of air has . been determined to be the maximum safe level o f expo sure during an 8-hour workday. (See reference [19].) The procedure for performing the necessary analyses is *For example, PLY No. 9 Ge! fMilbum Company . Detroit. Mich), or Keiodex No. 7] (Aycnt Laboratories, Ne York.. S.Y.). or the equivalent. 1For example, Edmoni - Solvit 5-352 (Merrick of Bridgeport, Bridgeport,Conn], or the equivalent. 10 AMERICAN' NATIONAL STANDARD CI O '. M 974 re] contacts the eyes, the eyes should be irrigated imme- other filters diately with large quantities of running water for ] 5 (6) Saturated wastes (paper, rags, etc) - minutes and then examined by a physician. (A drop of (7) Saturated, spent gasket materials castor oil has been found to reduce irritation.) (8) Askarel-contaminated vacuum pump oils Persons developing a skin irritation or respiratory (9) Askarel-contaminated stream jet vacuum system tract irritation while working with askarels should be condensates placed under the supervision of a physician. 3.3.6 Miscellaneous Procedures. Other safety con Ingestion or swallowing of askarels is not generally siderations include the following: regarded as a problem of the industry- Should acciden (1) Spills by leakage from finished capacitors should tal ingestion occur, a physician should be consulted. be cleaned up promptly by means of absorbent media, Hands should be washed with warm water and soap be which should then be moved to containers provided for fore eating, drinking, smoking, or using toilet facilities. that purpose within the containment area, and later dis 3.3.4 Manufacturing Housekeeping. Manufacturing posed of properly. equipment and operating procedures should safeguard (2) Askarel wastes should never be disposed of against loss of askarels to the environment through down effluent drains or sewers. The utmost care must proper containment and disposal procedures. Enclosed systems of sealed piping, properly gasketed joints, valves, containers, and processing chambers should be used for any portion of the operation where be exercised to prevent accidental loss by these avenues to the environment. (3) Capacitors failing tests or otherwise designated for disposal must be controlled and handled in accor askarel temperatures may exceed 55C. Enclosure should preferably extend to all other portions of the system insofar as practicable. dance with the intent of the procedures given in 3.3.6(1) and 3.3.6(2), finally being disposed of by one of the means outlined in 3.5. Containment provisions should be established around all askarel processing areas to ensure against inadvertent 3.4 Control of Water Effluents. The industry' goal is to loss to sewer systems by spillage, leakage, or other un eliminate askarel in plant water effluent streams. How controlled conditions or events. ever, it is recognized that existing drain systems in Spills of askarel should be removed promptly by capacitor manufacturing plants are probably contami means of absorptive material, such as sawdust, or nated as a result of past practices, and askarel traces trapped and removed by pumping or other suitable may continue to show up in effluent streams for some means. time. However, the level should continue to decrease Waste fluids containing askarel not suitable for recon with the proper containment of askarel wastes and no ditioning or reuse should be collected (by means of further discharges into drain systems. Other sections of traps, drip pans, trays, etc) from the various parts of this standard provide that no askarel wastes of any kind the manufacturing and processing area (including be disposed of in any water effluent streams and that washers or other cleaning devices). Disposal should be accidental spills be prevented from getting into such made in accordance with 3.5. streams. Wiper rags, clothing, and other extraneous materials 3.4.1 Concentration Limits. The 1972 Environmen saturated with askarels should be collected within the tal Protection Agency proposals are to keep PCB levels containment area for properly controlled laundering or in rivers and lakes below 0.01 part per billion. This is disposal (see 3.5). currently under review by the EPA and standards are 3.3.5 Disposal of Askarel Wastes. Methods for dis expected to be promulgated in 1974. Plant effluent posal of liquids and saturated solids generated by the streams should be managed and controlled in a manner manufacturing operation should be in accordance with anticipating these government standards. those outlined in 3.5, and should include (but not be 3.4.2 Monitoring Streams. On a regular basis con limited to) the following wastes: sistent with plant situations, all effluent streams should (1) Contaminated liquid askarel that is unsuitable be analyzed. The procedure for performing the neces for reclaiming as a dielectric fluid \ sary analyses is contained in Section B4 of Appendix B. (2) Liquid askarel from solvent operations or water This procedure or its equivalent should be used. and detergent type washers 3.4.3 Methods for Minimizing Effluent Stream Con (3) Saturated earth or other absorbent media from tamination. The ideal approach is to isolate totally all filtering operations effluent streams that could be contaminated with aska (4) Saturated sawdust or other absorptive materials rels during manufacturing processes and prevent them from spills from being discharged from the plant. Carbon adsorp (5) Saturated filters from vapoicontrol devices and tion, limestone beds, and solvent extraction are tech- 11 AMERICAN NATIONAL STANDARD C 107.1-1974 niques that can be applied to reduce the askarel content of effluent streams. These techniques may be most use ful in cleaning up water used in plant processing and to permit recycling. 3.5 Scrap-Disposal Procedures. The manufacture and use o f capacitors involve processes that produce askarelsaturated solids and liquids containing or composed en tirely of askarel, which should be disposed of as wastes. Specific sources of these materials are described through out this standard. They may be placed into three cate gories: (1) Capacitor units impregnated with askarel, pro duction and field rejects (2) Manufacturing process liquid wastes containing askarel (3) Solid waste purposely or accidently saturated with askarel Disposal should be done in a manner that is consis tent with proper concern for the environment and minimizes any release of askarels to the environment. 3.5.1 Disposal of Capacitor Units. Scrap capacitor units can be generated during manufacturing processes or during field service. Production rejects are those capacitors that are re jected after the impregnation process in the course of production by the capacitor manufacturer. They may be rejected for mechanical or electrical reasons, or be cause o f obsolescence. Field rejects are those units that are rejected or, for other reasons, are to be scrapped after shipment from the plant where they were manufactured. 3.5.1.1 Production Rejects. Rejected capacitors in capacitor manufacturing plants represent a concen tration of askarel. It is important that their disposition be made in a manner consistent with proper concern for the environment. Therefore, capacitors should be disposed of only in supervised dry landfill sites that meet all applicable state requirements. Care should be exercised to ensure that no loss of liquid will occur during transportation to the disposal cite. Incineration of scrap capacitors in facilities designed to accept such solids should provide an alternative means o f disposal as such services become available in the future. 3.5.1.2 Field Rejects. Small capacitors (dehned as containing less than 2 pounds o f askarel) are practi cally always used as components in other electrical or electromechanical equipment. Typical examples of large quantity usage of such capacitors are in fluores cent lamp ballasts and residential air conditioning equip ment. Failure of such capacitors may result in scrap ping of the device of which it is a part (as in a fluors- cent ballast) or replacement and scrapping of the indi vidual capacitor (as in a room air conditioner). How ever, the majority of such capacitors do not fail in service, but are scrapped as a result of wearing out or obsolescence of the devices in which the capacitors are used as components. Thus, the matter of disposal is characterized by a low concentration of small quantities of askarel throughout the country and, indeed, through out the world. Fortunately, the nature of the devices and equipment in'which such capacitors are used is such that they are normally disposed of in dry landfills as a matter of convenience. Since it is impractical at present to exercise any meaningful control over the dis position of the bulk of such devices and equipment, it is imperative that askarel used for impregnating small capacitors be limited to the recently introduced type, which contains a typical concentration of 0.4% of the higher-boilinghomologues. (See ASTM D 3303-74 [ I ] .) Large capacitors (those incorporating more than 2 pounds of askarel) should be disposed of according to the procedure for production rejects (see 3.5.1.1). 3.5.2 Disposal of Liquid Wastes. All waste askarel or liquid wastes containing askarel should be disposed of in accordance with one of the procedures given in 3.5.2.1 through 3.5.23. 3.5.2.1 Incineration. Present knowledge indicates that proper incineration must involve a suitable balance between dwell time and temperature in the incinerator plus oxygen availability' and, finally, suitable scrubbers to remove the HQ that will be formed; for example. 2-second dwell time at 2000F and 37c excess oxygen in stack gas, or 1.5-second dwell time at 2700F and 2% excess oxygen in stack gas. These facilities should meet the applicable require ments of the state in which they are located, and should control effluents within the limits set forth In this standard. 3.5.2.2 Toxic and Hazardous Waste Disposal Sites. Certain landfill sites have been classified by state governments and the federal government as suitable for the disposal of toxic and hazardous liquids. Where such approved sites exist, they may be used for the disposal of liquid wastes described in this standard. (See Appen dix A.) 3.5.2.3 Packaging and Shipment 3.5.23.1 Transportation to the disposal facili ty should be in containers that will prevent leakage and accidental loss of askarel to the environment. 3.5.2.3.2 Containers should be labeled as to contents and precautions relative to loss to the environ ment. 3.5.2.33 Containers used for this purpose should not be used for any such materials or retired from service until they are completely cleaned. Any 12 AMERICAN NATIONAL STANDARD C107.I-I974 solvents used in cleaning these containers will be con taminated with askarel and should be disposed of ac cording to the same procedures described in 3.5.2. 3.5.3 Disposal of Solid Wastes. (See 3.5.1 for scrap capacitors.) All solid wastes that have been saturated with askarel should be disposed of by the following procedure: (1) The saturated wastes should be placed into leakproof containers and transported to a supervised dry landfill site meeting state requirements. Alterna tively, they can be disposed of by incineration in state-approved facilities. . (2) Solid absorbents used for spills can be disposed of uncontained in the supervised dry landfill site: trans port to the site should be in closed containers. Alterna tively, incineration can be used in accordance with 3.5.2. (See Appendix A for a listing of facilities.) 3.6 Labeling. Capacitor units vary' greatly in size and in end use or application. Small capacitor units are fre quently applied as a component of another piece of equipment, such as a fluorescent lighting ballast, a road way or area lighting luminaire, a motor, etc. In such applications a label on the capacitor unit referencing approved disposal procedure would not normally be visible when the piece of equipment is disposed of. For the foregoing reasons the methods of providing disposal-instructions for small capacitors and large ca pacitors are treated separately in 3.6.1 and 3.6.2, respectively. 3.6.1' Small Units: Small capacitors are defined as those that contain askarel in quantities up to about 2 pounds each and in which the free liquid does not ex ceed 0.4 pound. They are hermetically sealed in metal lic cases. Such capacitors are applied as a component of a large piece of equipment. Attaching a label to such equipment referencing this standard or describing dis posal procedures would be of limited practical value. 3.6.2 Larg- Units. Large capacitor units are defined as those that contain more than 2 pounds of askarel. The capacitor manufacturer should affix a label in a conspicuous place, referencing this standard or de scribing disposal procedures consistent with it. This label should contain, as a minimum, the following infor mation: CAUTION: This capacitor contains a polychlori nated biphenyl (PCB). To avoid possible environmental contamination, it should be disposed of only in super- v vised dry landfill areas meeting state requirements or in incineration facilities designed for disposal of PCBs. See American National Standard C l07.1-1974 for fur ther.information. Copies are available from American National Standards Institute, 1430 Broadway. New York. N.Y. 10018. 4. Transform er Guidelines 4.1 General 4.1.1 Types of Transformer Askarels.6 Askarels of various compositional types are currently in use (for the genera] properties and types, see ASTM D 2283- 73a [20]). Under arcing conditions, the gases produced, though predominantly consisting of noncombustible hydrogen chloride, can contain varying amounts of combustible gases depending upon the askarel type. 4.1.2 Safety Precautions. Based on about 40 years of safe industrial usage, askarels have been considered as relatively harmless materials to humans. There has been no known instance of human injury when askarels are used under the normally prescribed conditions of precaution and handling. Although it has been generally thought that expo sure to askarels is not hazardous provided that simple precautions are taken, exposure should still be avoided or minimized. 4.1.2.1 Vapors. The odor of askarel is noticeable well below the maximum safe air concentrations. De pending upon the composition of the askarel used, from 0.5 to 1.0 milligram per cubic metre of air has been determined to be the upper safe level of expo sure during an 8-hour workday. (See reference [19].) The procedure for performing the necessary analyses is contained in Section B3 of Appendix B. This proce dure or its equivalent should be used. Breathing vapor or fumes from heated askarels should be avoided. High concentrations of vapors can cause irritation of the eyes, nose, throat, and upper re spiratory tract. Provisions shall be made for adequate ventilation and regulation of manufacturing operations to avoid open exposure of hot askarels (55C or higher). The gases produced when askarel is decomposed by very high temperatures (such as that of an electric arc) in the presence of air or organic insulating materials contain a high percentage of hydrogen chloride, and small percentages of other gases. Minute concentrations of this combination of gases are very unpleasant and irritating, thus giving ample warning of their presence. If exposure to high concentrations of askarels or its arced products is necessary under emergency conditions, an approved gas mask of the organic-canister type, or self-contained breathing apparatus, must be worn. Such exposure should be under the surveillance of other per sonnel capable of effecting rescue in case of accident. If the odor of askarel or its arced products is detected The following trademarks are among those employed by eie;tncal manufacturers to designate the askarels used m their products: Asbestol. CWorewol, lnerteen. No-Flamol, Pyranol. and Saf-T-kuhl. 13 ( AMERICAN NATIONAL STANDARD C 107.1-1974 by the person wearing protective equipment, he should tact occurs, remove by washing with soap and water. immediately go into fresh air. All gas masks, respirators, - Following eye contact, flush with water. In case of and replacement parts should have U.S. Bureau of Mines spillage onto clothing, the clothing should be removed approval and be maintained on a regular schedule in ac as soon as practical, skin washed, and clothing laun cordance with the manufacturer's recommendation. dered. 4.1.2.2 Liquid. In contrast to the situation in 4.1.4 Receiving. Handling, and Storage of .Askarels. which mineral insulating oils are handled, there is no Askarels are shipped in tank cars, tank trucks, steel fire hazard in handling askarels. A limited solvent ac drums, metal cans, and test-sample containers. When tion (similar to that for paint thinner) on the fats and received, all containers should be inspected for leaks. oils of the skin with prolonged contact may lead to dry 4.1.4.1 Storage Tanks. Storage tanks should be ing and chapping o f the skin. As with insulating oil, erected so that inspection can be made for leaks or some people are allergic to askarel, and continued expo spills. Construction should be such that inadvertent sure may result in skin irritation. Both the liquid and leakage or spills are prevented from reaching streams vapor are moderately irritating to eye tissue. and sanitary or storm sewers. Operating procedures should require avoidance of 4.1.4.2 Tank Cars and Tank Trucks. All bulk contact with any askarels. The use of porous gloves shipment equipment should be inspected for leaks im that can absorb and retain askarels is to be avoided. Re mediately upon receipt. Drain pans must be provided sistant gloves and aprons of the neoprene, polyethylene, to prevent spillage from unloading hoses and connec or fluoroelastomer1 type should be used if contact is tions. Askarel liquid collected in drain pans should be unavoidable. In case of spillage on the clothing, the placed in drums labeled "SCRAP ASKAREL" for dis clothing should be removed as soon as practical, the position. skin washed, and the clothing laundered. 4.1.4.3 Steel Drums, Cans, and Test-Sample Con Medicinal washes or mild detergents followed by the tainers. On delivery, all such shipments should be care application of cold cream will reduce the irritation re fully inspected for leaks. The containers should be sulting from the contact of an open cut or abrasion stored indoors in an area especially selected for this with askarel. purpose. A curb should enclose the area to provide a Safety glasses with side shields or a face shield basin for containing the askarel from one or more con should be worn when handling askarels. Eyes that tainers should the containers be damaged. The area have been exposed to liquid askarel should be irrigated must not have a drain that is connected to a sanitary immediately with large quantities of running water for or storm sewer. 15 minutes and then examined by a physician if the If an indoor storage area is not possible, the con irritation persists. (A drop" of castor oil has been found tainers should be stored under a lean-to. to reduce irritation.) 4.1.5 Control of Water Effluents. The industry goal Persons developing a skin irritation or respiratory is to eliminate askarel in plant water effluent streams. tract irritation while working with askarels should be However, it is recognized that existing drain systems placed under the supervision of a physician. from manufacturing plants, repair shops, and installa Ingestion or swallowing of askarels is not generally tion sites may be contaminated as a result of past prac regarded as a problem of the industry. Should acciden tices. Other sections of this standard provide that no tal ingestion occur, a physician should be consulted. askarel wastes of any kind be disposed of in any water Hands should be washed with warm water and soap effluent streams and that accidental spills be prevented before eating, drinking, smoking, or using toilet facili from getting into such streams. ties. 4.1.5.1 Concentration Limits. The 1972 Environ 4.1.3 Transport Container Marking. Any container, mental Protection Agency proposals are to keep PCB such as tank cars, tank trucks, drums, cans, etc, used to levels in rivers and lakes below 0.01 part per billion. transport transformer askarels, new or used, should be This is currently under review by the EPA and stan labeled with the following: dards are expected to be promulgated in 1974. Plant CAUTION: This product contains polychlorirtqted effluent streams should be managed and controlled in biphenyls (PCBs). Care should be taken to prevent .a manner anticipating these government standards. entry into the environment through spills, leakage, use, 4.1.5.2 Monitoring Streams. All plan effluent vaporization, or disposal of liquid or containers. Avoid streams should be monitored on a regular basis, consis prolonged breathing of vapors or mists. Avoid contact tent with plant situations. The procedure for perform with eyes or prolonged contact with skin. If skin con- ing the necessary analyses is contained in Section B4 of Appendix B. This procedure or its equivalent should ' For example, Viton. be used. 14 AMERICAN NATIONAL STANDARD C I0 7 .M 9 7 4 4.1.5.3 Methods for Minimizing Effluent Streamshould be placed in open-head drums with suitable clo Contamination. The ideal approach is to isolate totally sures and with the drum properly labeled for shipment all effluent streams that could be contaminated with to a company offering an acceptable disposal service. askarels during manufacturing processes and prevent 4.1.6.5 Liquid and Solid Waste Disposal Service them from being discharged from the plant. Organizations 4.1.6 Disposal Procedures and Services 4.1.6.5.1 General. Disposal of askarels and 4.1.6.1 Sources of Materials Requiring Special askarel-soaked materials should be accomplished by Handling and Disposal Procedures. Liquids containing means in which there is no significant release of askarel PCBs and solids containing or contaminated with PCBs to the environment. At present, disposal is accomplished may be obtained from any of the following sources: by carefully controlled incineration of liquids and transport containers, transformer manufacturing pro soaked software, and by controlled landfill burial of cesses, in-test failures, liquids contaminated beyond- apparatus and other hardware from which askarel has reclamation, in-service transformer leaks and failures, been previously drained and washed. askarel-filled transformers scrapped for any reason, etc. Present knowledge indicates that proper incineration 4.1.6.2 Gasification for Disposal of Materials must involve a suitable balance between dwell time and Containing PCBs. In general, there are three types of temperature in the incineration plus oxygen availability materials requiring disposal: liquids, burnable solid and, finally, suitable scrubbers to remove the HC1 that materials containing PCBs, and nonbumable solid mate will be formed: for example. 2-second dwell time at rials contaminated with PCBs. 2000F and 3& excess oxygen in stack gas. or 1.5- 4.1.6.2.1 Liquids. Liquids containing PCBs second dwell time ai 2`'00eF and 25J oxygen in stack requiring disposal by high-temperature incineration gas. may consist of ihe following: These facilities should meet the applicable require (1) . PCB* contaminated with mineral oil. ments of the state in which they are located and should (2) Mineral oil contaminated with PCBs. control effluents within the limits set forth in this stan (3) Nonreclaimable contaminated transformer aska- dard. rels, arced askarels, askarels from manufacturing spills, Controlled landfill or deep-well disposal can be used and sump accumulation, etc, rich in PCBs, and askarels where permitted by federal, state, and local regulations. from holding basins, drip and drain pans, washings, sam 4.1.6.5.2 Costs. In addition to the normal ple jars and containers, etc. costs of collecting scrap liquids and solids for disposal, 4.1.6.2.2 Burnable Solid Waste Materials Con additional costs bome by the owner of such scrap in taining PCBs. These materials can be disposed of by high- clude shipping containers, cost of transport to the dis temperaiure incineration and consist of cellulosic mate posal service organization, and a disposal fee usuaUy rials, rags, pressboard, wood, sawdust, fuller's earth in based upon a per-gallor. or per-pound charge. bulk or in cloth bags, blotter papers, nitrile or cork gas 4.1.6.5.3 Disposal Services. Organizations* kets, etc. offering disposal services are listed in Appendix A, 4.1.6.2.3 Nonbumable Solid Waste Materials including their location, facilities available, types of Containing, or Contaminated with. PCBs. These mate material handled, and disposal procedures used. Speci rials may consist of coil structures, steel, copper, alu fic shipping directions, disposal procedures, and costs minum filter units of the steel mesh construction type, should be obtained from the organization. askarel drums, cans, etc. Materials of this nature should be allowed to drain 4.2 Specific Guidelines with the liquid collected in drip pans, etc. Further re 4.2.1 Plant Housekeeping. It is necessary to assume moval of adhering PCBs can be accomplished by wash that in filling equipment with askarel, and during fur ing or solvent extraction with kerosene or other ap ther handling of this equipment, an askarel spill may proved washing liquids such as perchloroethylene or occur. Therefore, it is necessary to provide facilities and tricholoroethylene. Accumulated liquids can be dis a procedure for cleanup to prevent contamination. posed of as indicated in 4.1.6.2.1. Solid materials m^y 4.2.1.1 Askarel Filling Aiea be handled as normal scrap., 4.2.1.1.1 The location of the askarel filling 4.1.6.3 Shipment of Scrap Liquids for Disposal. area should be adjacent to the test area and final ship All liquid scrap material should be placed in appropriate ping area to minimize the danger of damage of units metal transport drums, properly labeled, for shipment during handling. to a company offering ar. acceptable disposal service. 4.2.1.1.2 The main manufacturing area for 4.1.6.4 Shipment of Burnable Solid Waste Mate filling equipment with askarel should be provided with rial Containing PCBs for Disposal. Material of this type impervious surface floors or suitable basins so con 15 AMERICAN NATIONAL STANDARD C I07.M 974 structed that any inadvertent leakage or spills are pre- 4.2.1.4.4 All used materials, including rags, vented from reaching streams, sanitary sewers, or storm sawdust, tape, etc, regardless of quantity, shall be put sewers. All askarel-handling equipment, such as pumps, into the appropriate containers for disposition. hoses, etc, shall be of the askarel-resistam type. 4.2.2 Transformer Labeling 4.2.1.1.3 Drip pans shall be provided for hose 4.2.2.1 New Transformers. All new transformers connections and filling valves. that contain PCBs shall have a label of adequate durabil 4.2.1.2 Special Containers for Scrap Materials ity, permanently and prominently attached to the tank - 4.2.1.2.1 Drums labeled "SCRAP ASKAREL" by the manufacturer, giving adequate warning and in should be available for handling all spilled and waste structions. A suggested label includes the following: askarel from sumps, failed units, drip pans, sample jars, CAUTION: The insulating liquid in this transformer eic. contains polychlorinated biphenyls (PCBs). Care should 4.2.1.2.2 Open-head drums with suitable clo be taken to prevent entry into the environment. In case sures and labeled "SCRAP BURNABLE ASKAREL of malfunction or leaks, consult the instruction manual WASTE" should be available for handling contaminated or the manufacturer. cellulose insulation, rags, paper pressboard, wood, gas 4.2.2.2 In-Service Transformers. The transformer kets, sawdust, etc. manufacturer should make available suitable labels with 4.2.1.2.3 Separate containers for handling a similar warning as shown in 4.2.2.1 for use on exist steel, copper, and aluminum, each adequately marked, ing transformers. shall be provided for the components of contaminated 4.2.3 Information for Transformer Users core and coil assemblies. These containers are required 4.2.3.1 General. Askarel-filled transformers are for the various materials when repairing or scrapping delivered to customers as sealed units from which there assemblies. is no escape of askarel under normal operation. Although 4.2.1.2.4 Containers for supplies of material certain types of equipment failures can permit loss of for absorbing small askarel spills or cleanup of larger some askarel to the environment, such cases are extreme spills should be provided. ly rare. 4.2.1.3 Conditioning of Askarels 4.2.3.2 Transportation and Receiving. Immedi 4.2.1.3.1 Askarel Conditioning Equipment. ately upon receipt of the equipment and following any The conditioning unit should be located either in the transportation or handling accident that could affect storage tank area or in the main transformer manufac- the integrity of the tank, bushings, or radiators, the ' luring area for filling with askarel. transportation vehicle, tank, and fittings should be 4.2.1.3.2 Fuller's Earth. Conditioning of new examined for any leakage or spillage that may have askarel or recycled askarel requires fuller's earth treat occurred in shipping. If leakage is evident, the cause ment. The spent fuller's earth in cartridges or bags, should be corrected and the spillage soaked up with when replaced, should be allowed to drain thoroughly absorbent materials such as sawdust, followed by a over drip pans to remove as much liquid askarel as pos cleanup of the affected area with rags soaked with kero sible. The cartridge units of steel mesh construction sene or other approved solvent such as perch)oroethy- . should be placed in the "STEEL CONTAMINATED Iene or trichloroethylene. All materials used should be WITH ASKAREL" container for disposition. Cloth collected for proper disposition as described in 4.1.6: bags filled with fuller's earth should be placed in the 4.2.3.3 Installation and Periodic Inspection. Fol "SCRAP BURNABLE ASKAREL WASTE" container lowing installation, the unit should a^ in be inspected for disposition. for any damage or leakage. It is recommended that 4.2.1.4 Teardown of Units for Repair or Scrap periodic in-service inspections be made for any leaks. 4.2.1.4.1 Drain all askarel from the unit either 4.2 J .4 Filling, Filtering, or Drying Askarel. into a holding tank for reuse or into the drum labeled Most askarel units are shipped'with the proper amount "SCRAP ASKAREL" for disposition, and then allow of askarel, but if it becomes necessary to top off a unit, sufficient time for all of the askarel to drain from the the manufacturer's instructions should be followed. core and coils. \ If it is necessary to dry an askarel unit or to treat an 4.2.1.4.2 Remove the core and coO assembly askarel unit with fuller's earth, instructions should be from the transformer. Sufficient absorbent material followed. When filtering or conditioning askarel, all should be placed on the floor to absorb any askarel of the precautions previously described Tot drip pans, Quid that still drips from the transformer. proper disposal of filter media, etc, apply. 4.2.1.4.3 Place all materials in the appropriate 4.2.3.5 Sampling. It is common practice to sam salvage containers during the dismantling for later dis ple askarel from a transformer for periodic maintenance position. testing. As previously described, such samples should be 16 AMERICAN NATIONAL STANDARD C 107.M 974 taken in a manner to avoid .any contamination of the Specific Resistance (Resistivity) o f Electrical Insulating environment. Washings should be collected for proper Liquids, C59.51-1965 (R1973) (ASTM D 1169-64 disposal. Field and laboratory test samples, washings, (1973)) etc. should also be collected for proper disposal. 4.2.3.6 Transformer Disposal. The ultimate dis* [10] American National Standard Method of Test for posal of an askarel-filled transformer may be accom Hydrolyzable Chlorine Compounds in Chlorinated Aro plished in either of two ways: matic Hydrocarbons (Askarels), C59.106-1970 (ASTM D 1820-65 (1971)) (1) Complete drainage and dismantling with the proper disposal of the askarel and askarel-soaked com [11] American National Standard Method of Test for ponents as described in 4.1.6. Thermal Stability of Chlorinated Aromatic Hydrocar (2) Disposition of askarel transformers by means of bons (Askarels), C59.111-1970 (ASTM D 1936-64 junk or scrap dealers. This should be avoided unless a (1971)) transformer is first drained, followed by soaking the interior with a suitable solvent. Accumulated liquids and washings are to be disposed o f as described in 4.1.6. [12] American National Standard Method of Test for Distillation of Road Tars, A37.9-1974 (ASTM D20-72) [13] American National Standard Methods of Testing Electrical Insulating Oils, C59.2-1974 (ASTM D 117-71 (1973)) 5. References 5.1 References to the Text [1 ] Standard Method of Test for Rapid Gas Chroma tographic Estimation of Higher Boiling Homologues of Chlorinated Biphenyls for Capacitor Askarels, ASTM D 3303-74 [14] American National Standard Method of Test for Dielectric Breakdown Voltage of Insulating Liquids Using Disk Electrodes, C59.19-1968 (R1973) (ASTM D 877-67 (1971)) [15] American National Standard Method of Test for Flash and Fire Points by Cleveland Open Cup, Z11.61973 (ASTM D 92-72, IP 36/67) [2] American National Standard Method of Test for Specific Gravity o f AskareJs, C59.68-196S (R1973) (ASTM D 1810-63 (1973)) [16] American National Standard Method of Test for Saybolt Viscosity, Z11.2-1956 (R1971) (ASTM D 8S56(1973)) [3] American National Standard Method of Test for Neutralization Number by Color-Indicator Titration, Z 11.131 -1964 (R 1974) (ASTM D 974-64 (1973), IP 139/65) [17] American National Standard Method of Test for Coefficient of Thermal Expansion of Electrical Insu lating Liquids of Petroleum Origin, and Askarels, C59.57-1963 (RI973) (ASTM D 1903-63 (1973)) [4] American National Standard Method of Test for Neutralization Number by Potentiometrie Titration, Z 11.59-1958 (R 197I) (ASTM D 664-58 (1968), IP 177/64) [5] Standard Method of Test for Density of Rubber Chemicals, ASTM D 1817-66 (1972) [6] American National Standard Method of Test for Inorganic Chlorides in Askarels, C59.55*1963 (R1973) (ASTM D 1821-63 (1973)) [7] American National Standard Method of Test for \ Pour Point o f Petroleum Oils, Z11.5-1966 (R1972) (ASTM D 97-66 (1971), IP 15/67)89 [8] American National Standard Method of Test for Power Factor and Dielectric Constant of Electrical Insulating Liquids, C59.22-1967 (R1973) (ASTM D 924-65 (1973)) [9] American National Standard Method of Test for [18] MUNCH. R. H. Measuring the dissipation factor, dielectric constant, and resistivity of liquids. Jnsuhtionj G rcuin, vol 16, Maj 1970, pp 46-49. [19] Chlorodiphenyls. Hygienic Guide Series. West mont, N J.: American Industrial Hygiene Association, Jan-Feb 1965. [20] Standard Specification for Chlorinated Aromatic Hydrocarbons (Askarels) for Transformen, ASTM D 2283-73a 5.2 General References Aroclor Polychlorinated Polyphenyls (Biphenyls), Technical Bulletin O-FF/IR- St. Louis: Monsanto In dustrial Chemicals Company, Nov 1971. DRINKER, C. K. Further observations on the possible systemic toxicity of certain of the chlorinated hydro carbons, Journal o f IndustriaI Hygiene and Toxicology. vol 21,1939, pp 155-159. 17 AMERICAN NATIONAL STANDARD C 107.1-1974 DRINKER, C. K.; WARREN, M. F.; and BENNET, G. A. The problem of possible systemic effects from certain chlorinated hydrocarbons. Journal o f Industrial Hygiene and Toxicology, vo] 19, 1937, pp 283-311. ELKINS, H. B. 77ie Chemistry o f Industrial Toxicology. New York: John Wiley & Sons. Inc, 1959. GREENBURG, L.; MAYERS, M. R.; and SMITH, A. R. The-systemic effects resulting Trom exposure to certain chlorinated hydrocarbons. Journal o f Industrial Hygiene and Toxicology, vol 21, 1939, pp 29-38. Threshold Lim it Values fo r Chemical Substances and Physical Agents in the Workroom Environment. Cincin nati: American Conference of Governmental Industrial Hygienists, 1973. TREON, J. F.: CLEVELAND. F. P.; CAPPEL. J.: and ATCHLEY, R. W. The toxicity of the vapors of Aroclor 1242 and Aroclor 1254. American Industrial Hygiene Association Quarterly, vol 17,1956, pp 204-213. 6. Revision of American National Standards Referred to in This Document When the American National Standards referred to in this document are superseded by a revision approved by the American National Standards Institute, Inc, the re vision shall apply. 18 Appendixes (These Appendixes are noi a pan of American National Standard Guidelines for Handling and Disposal of Capacitor- and Transformer-Grade Askarels Containing Polychlorinated Biphenyls. C] 07.1-1974, but are included for information purposes only.) ` Appendix A Disposal Services In addition to the supervised dry landfill sites that may be used for the disposal of askarei-contaming scrap, the following additional known facilities and services have been established, and others may be available.1 Chem-Trol Pollution Services, Inc P.O. Box 200 1550 Balmer Road Model City, N.Y. 14107 Phone: 716 754-8231 This organization has facilities and services capable of handling: (1) Liquids. Askarels alone or mixed with solvents or oils. Disposal by high-temperature incineration. (2) Solids (software). Askarel-soaked compounds, rags cartons, absorbing earths, etc. Disposal by incinera tion or scientific landfill. (3) Solids (hardware). Capacitors, transformer tanks, cores, askarel-soaked metals. Disposal by scientific land fill. Has solvent extraction capability. Monsanto Company 800 North Lindbergh Boulevard St. Louis, Mo 63166 Phone: 314 694-3352 This organization has facilities and services capable of handling askarel liquids alone or mixed with other oils or solvents by high*temperature incineration. Liquid is pumped through a gun with atomizing steam into incinerator. Temperatures are maintained at 2000 F 2500F with auxiliary natural gas. Exit gases are quenched to 180F by contact with water. Gas is then passed through a high-energy venturi scrubber for re moval of particulates. Before exhausting to air (1 10F), gases are passed through a packed column scrubber to remove HC1. Nuclear Engineering Company Eastern Division P.O. Box 146 Morehead.Ky 40351 Phone; 606 784-6611 Nuclear Engineering Company Disposal Division Sheffield, 111. 61361 Phone:815 454-2624 This organization provides containerization, trans portation, and disposal services of all liquids and solids' (including hardware). Disposal is in controlled chemical and scientific landfill area. Licensed by Atomic Energy Commission for radioactive waste disposal. The organi zation also has two West Coast locations, in the states of California and Washington. Rollins Environmental Services, Inc P.O. Box 2349 Wilmington, Del 19899 Phone:302 658-8451 This organization has facilities and services capable of handling: (1) Liquids. Askarel alone or mixed with solvents or oils. Disposal is by high-temperature incineration. (2) Solids (software). Askarel-soaked compounds, rags, cartons, absorbing earths, etc. Disposal is by incin eration at combustion temperatures up to 2500F. In cineration gases are scrubbed, and entrained solids are removed before exhausting to air. Rollins Environmental Services maintains disposal facilities in the following areas: Philadelphia/Camden: 'T he liitmg given herein ii representative of some of the sources Rollins Environmental Services, Inc that provide this service, and is. not preumed to be complete. Route 322 ^ Any other organizations that wish to be listed should notify the Standards Institute so that they may be included m the next Logan Township edition of this standard. Bridgeport, N.J. 08014 19 APPENDIX Baton Rouge: Rollins Environmental Services, Inc Scenic Highway & West Cheatham Lane Scotl andville East Baton Rouge Parish, La 7080" Houston: Rollins Environmental Services. Inc Tidal Road & Highway 134 Deer Park, Tex 77536 Cy J Appendix B Analytical Procedures and Laboratory Service Organizations Bl. General Analytical procedures for determining PCBs in air. water, and sediments are given in Sections B3 and B4. B2. Laboratories The following laboratories are representative of those offering services for PCB analyses:' Cams Chemical Corporation 1375 Eighth Street La Salle, 111. 61301 Phone: 815 223-1500 Limnetics, Inc. (Subsidiary of Cams Corporation) 6132 West Fond du Lac Avenue Milwaukee, Wis 53218 Rione: 414 461-9500 GoIIob Analytical Service Corporation 47 Industrial Road Berkeley Heights, N J. 07922 Phone: 201 464-3331 B3. An Analytical Procedure for the Determin ation of Airborne PCBs B3.1 Scope. This procedure is based on techniques used by the Monsanto Industrial Chemical Company 'The Luting given herein is representative of some of the sources that provide this service, and is not presumed to be complete. Any other organizations that wish to be listed should notify the Standards Institute to that they may be included in the next edition of this standard. 20 for the isolation and determination of PCBs in water, soil/sediment, and biological materials. Absolute con firmation of PCB structures is not obtained with this method. Where needed, additional structure proof should be obtained using techniques such as mass spec trometry for further identification of gas chromatog raphy fractions. B3.2 Principle. Airborne PCBs are absorbed in toluene by drawing the air through one or more fritted bubblers or impingers in cylinders filled with toluene. After a suitable amount of air is sampled, the scrubbing solvent is diluted or concentrated, and interfering components, if present, are removed by chemical treatment and column absorption chromatography. The amount and type of PCBs present are determined by electron cap ture gas chromatography (EC/GC). B3.3 Reagents (1) Hexane: Pesticide grade. (2) Toluene: Pesticide grade. (3) Sodium sulfate: Anhydrous, granular, analytical reagent (AR) grade. Heat at 400C for 1 hour prior to use. (4) Alumina adsorption: For chromatographic anal ysis, 80/200 mesh. Heat at 400C for a minimum period of 4 hours and deactivate with 5% (w/w) distilled water. For alumina column preparation fill a chromatographic column with hexane up to the point where the reservoir joins the column, and push a glass wool plug to the bot tom with a glass rod. In a 50-ml beaker measure 35 ml (about 30 grams) of deactivated alumina, and pour this slowly into the column. Tap or vibrate the column to settle the alumina, and top the alumina with 2 to 3 cm of anhydrous sodium sulfate. Wash the column with 50 to 100 ml of hexane prior to the addition of the sample. (5j Distilled water: Extracted with hexane to re- . tu CO Z O CL CO L CC. LU > APPENDIX NOTE: Instrument: Hewlett-Packard 5750 Detector: 41Ni, electron capture Column* 6-ram X 6-foot. 4?; XE-60 on 80,100 mesh. Chromosorb W, HP, AW-DMCS. Column temperature: 200C Injection temperature: 220C Detector temperature: 250C Carrier gas: He, 60 ml/mtn Purge gas: 10K CH/argon. 120 ml/min Pulse interval: 50 ms Injection volume: 5 m1 Standard concentration: l.OOM&'ml Range: 10 Attenuation: 8 AROCLOR 1016 1i 0 12 34 5 '6 7e 9 M IN U TES Fig. B1 Aroclor 1016 Electron Capture Chromatogram move hexane-soluble electron capturing impurities. (6) Sulfuric acid: AR grade, specific gravity = 1.84. (7) Potassium hydroxide: AR grade. (8) Ethanol: Formula 2B. (9) Alcoholic potassium hydroxide, 2.5% (w/v): Dis solve about 12.5 grams of AR grade KOH in 500 ml of ethanol. (10) Sulfuric acid-water, 9:1 (v/v): Carefully add 270 ml of AR grade sulfuric acid to 30 ml of distilled water in a 500-ml iced beaker. (11) PCB standards: Aroclor 1 0 , 1221. 1242, 1248, 1254, and 1260. (See Fig. B1 through B7.) N B3.4 Apparatus (1) Gas scrubbing bottles, high form, ground-glass joint, fritted coarse disks. (2) Separatory funnels equipped with ground-glass stoppers and TFE-fluorocarbon stopcocks, capacities o f,125, 250, 500, 1000, and 2000 ml. (3) Kundema-Danish evaporative concentrators, 500-ml capacity, equipped with three-ball Snyder col umns and graduated S-ml capacity vials. (4) Chromatographic columns, glass, 10 inches X 20 mm (OD), with a 5*inch X 50-mm (OD) reservoir at the top, equipped with TFE-fluorocarbon stopcocks. (5) Flat-bottomed boiling flasks, 125 ml capacity. (6) Liebig condenser, 200 mm in length. (7) Hot plates. (8) Water bath. (9) 10-jd syringes. ; (10) Dry-test meter or wet-test gas meter. (11) Laboratory vacuum pump. (12) Rotating vacuum evaporator. (13) Usual laboratory glassware. B3.5 Sampling. The air to be sampled for airborne PCBs is drawn through a gas scrubber (or scrubbers) and a dry-test meter using a laboratory vacuum pump. See Fig. B8. The sampling flow rate is controlled by bleeding in air via a needle valve located-between the 21 o appendix Fig. B2 Comparison oV-EJectron Capture Chromatograms for Aroclor 1221, 1242. 1248, 1254. and 1260 22 5&1 APPENDIX NOTE: Instrument: Hewlett-Packard 5750 Detector: *' Ni electron capture Column: 6*mm x 6-foot. 4E XE-60 on 80/100 mesh. Chromosorb W. HP, AW-DMCS Column temperature; 170C Injection temperature: 220C Detector temperature: 250C Carrier gas: He, 60 ml/min Purge gas: 103 CH^/argon, 120 ml/min Pulse interval: 50 sis Injection volume: 5 wl Standard concentration: 1.48 ug/ml Range: 10 Attenuation: 4 RELATIVE RESPONSE K -J- o AROCLOR 1221 1 IHI " " ' | -- 1 T OI234 MINUTES XFig. B3 Aroclor 1221 Electron Capture Chromatogram APPENDIX NOTE: Instrument: Hewlett-Packard 5750 Detector: " Ni electron capture Column: 6-mm x 6-foot, 4^ XE-60 on 80/100 mesh. Chromosorb W. HP. AW-DMCS Column temperature: 190C Injection temperature: 220C Detector temperature: 250aC Carrier gas: H e;60 ml/min Purge gas: 10% CH^/argon. 120 ml/min Pulse interval: 50 ns Injection volume: 5 jil Standard concentration: 1.03 ttgfm1 Range: 10 Attenuation: 8 e i RELATIVE RESPONSE MINUTES \ Fig. B4 Aroclor 1242 Electron Catture Chromatogram 24 I APPENDIX ` 10 1 NOTE: Instrument: Hewlett-Packard 5750 Detector: **Ni electron capture Column: 6-mm x 6-foot, 4* XE*60on SO 100 mesh. Chromosorb W, HP. AW-DMCS Column temperature: 190C Injection temperature: 22GC Detector temperature: 250C Carrier gas: He. 60 ml/min Purge gas: 10Ci CH*/argon. 120 mL'min Pulse interval. 50 is Injection volume: 5 jil Standard concentration: 1.31 Mg/ntl Range: 10 Attenuation: 4 O 1 2 3 4 5 6 7 6 9 10 II 12 13 MINUTES F*v B5 Atodor 1248 Electron Capture Chromatogram 25 a p p e n d ix r I NOTE: Instrument. Hewlett-Packard 5750 Detector: **Ni electron capture Column: 6-mm X 6-foot, XE-60 on 80,'100 rpssh. Chiomosorb W. HP. AW-DMCS Column temperature: 205C Injection temperature: 220C Detector temperature: 250C Carrier gas: He. 60 mi/min Purge gas: 10$ CH^argon, l20mL'min Pulse interval: 50 m Injection volume: 5 ui Standard concentration: J.02ji&'ml Range: 10 Attenuation: 8 UJ LO Z o CL tn UJ o: UJ > P < LU IS ( 20 1 10 r " 01 1^ 23456709 MINUTES \ Fig. B6 Aroclor 1254 Electron Capture Chromatogram 10 II 12 26 APPENDIX 20 22 I 26 I NOTE: Instrument: Hewlett-Paclurd 5750 Detector: 4 ,Ni electron capture Column: 6-nun X 6-foot, 4$ XE-60 on 80/100 mesh, Chromosorb W, HP, AW-DMCS Column temperature: 220C Injection temperature: 22QC Detector temperature: 250C Cartier gas: He, 60 ml/min Purge p i : 10% CR*/argon, 120 ml; min Pube interval: SO ns Injection volume: S til Standard concentration: 0.98ng/ml Range: 10 Attenuation: 8 U in z o a. tn liJ cr. LJ > 19 21 I 24 25 o 1 TM I I 1-----------i 4 | i O I 2345 6789 10 II 12 MINUTES Fig. B7 Axodor 1260 Electron Capture Chromatogram 27 i APPENDIX O' - - SAMPLE GAS in l f t -- - SCRUBBER(S) -- DRY-TEST METER -- AIR BLEED I n --- laboratory VACUUM PUMP EXHAUST Fig. B8 Sampling Train > pump and the meter. At the end of the sampling period, the metered gas volumes are corrected for temperature and pressure to cubic metres at 25C and 760 mmHg. It is important to note that neither the capacity nor the efficiency of the gas scrubber(s) for removal of air borne PCBs have been experimentally evaluated. For this reason, it is best to minimize the sampling flow 'rate and maximize the sampling time period to obtain measurable amounts of PBCs. When high flow rates must be employed or a larger capacity may be needed, r- J t is recommended that several gas scrubbers be used in tandem. It is cautioned that until the efficiency and capacity of the toluene gas scrubber have been experimentally established, this procedure should be used only to measure relative PCB levels sampled under equivalent , conditions. .B3.6 Procedure (1) After scrubbing the desired amount of air, re cord the metered volume, pressure, and temperature. (2) Quantitatively transfer the scrubbing solvent to a round-bottomed flask and reduce the volume to approximately 2 ml by rotary vacuum evaporation. (3) Quantitatively transfer the concentrate to a 30-mJ beaker with the aid of several small portions of toluene. (4) Inject a fraction of a microlitre o f the concen trate into the gas chromatograph to check for interfer ences and determine the approximate level of PCBs present. If no interferences are present, dilute or cticentrate the sample to a known volume, as determined by the electron capture chromatogram, and proceed with the gas chromatographic analysis. (5) If interferences are present, proceed with the chemical treatment and column chromatographic cleanup procedures. (6) Transfer the concentrate to a I25-m! extraction 28 flask with the aid of several small portions of solvent. (7) Evaporate the concentrate just to dryness with a gentle stream of dry, filtered air and add 25 ml of 2.5Cr alcoholic potassium hydroxide. (8) Add a boiling chip, put a water condenser in place, and allow the solution to reflux for 45 minutes. (9) After cooling, transfer the solution to a 250-mi separatory funnel with the aid of 25 ml of distilled water. (10) Rinse the extraction flask with 25 ml of hex ane and add it to the separatory funnel. (11) Stopper the separatory funnel and shake vigor ously for at least 1 minute. .Allow the layers to separate, and transfer the lower aqueous phase to a second sepa ratory funnel. (12) Extract the saponification solution with a second 25-ml portion of hexane. After the layers have separated, add the first hexane extract to the second separatory funnel, and transfer the aqueous alcohol layer to the original separatory funnel. (13) Repeat the extraction with a third 25-ml por tion of hexane. Discard the saponification solution and combine the hexane extracts. (14) Carefully add 25 ml of the sulfuric acid solu tion (9:1 concentrated sulfuric acid-water) to the hex ane extracts. (15) Stopper the separatory funnel and shake vigor ously for at least 1 minute. Allow the layers to separate, and discard the lower aqueous acid layer. Repeat this step until the acid layer is colorless. (16) Wash the hexane with a 25-ml portion of water. Discard the water wash. (17) Filter the hexane extract through a 4-uich funnel, plugged with glass wool that is covered with a layer of sodium sulfate, into a Kundema-Danish evap orative concentrator. (18) Add a small boiling chip, put the Snyder col umn in place, and reduce the hexane volume to less APPENDIX than 5 ml by heating the apparatus in a 80C to 90C water bath. (19) After cooling, remove the 5-mJ graduated tube and transfer the hexane extract to an alumina adsorp tion column, washing it in with several 5-ml portions of hexane. (20) Carefully add 100 ml of hexane to the column reservoir, and collect the total, eluent in either a 250-mi volumetric flask or a Kundem a-Danish evaporative con centrator. (21) If the column eluent is collected in a volumet ric flask, dilute to volume with hexane, and proceed with the gas chromatographic analysis. (22) If the column eluent is collected in a KundemaDanish evaporative concentrator, reduce solvent volume, cool, dilute to volume, and proceed with gas chromato graphic analysis. B3.7 Electron Capture Gas Chromatographic Procedure (1) Instrument: Gas chromatograph (for example, Hewlett-Packard Model 5750, or the equivalent) (2) Detector: High-temperature 63Ni, electron cap ture cell (3) Column: 6-mm X 6-foot glass column. 4% XE* 60 on 80/100 mesh, Chromosorb W, HP, W-DMCS (4) Column temperature: I60C to 190C (5) Injection port temperature: 195C to 215C (6) Detector temperature: 300C (7) Pulse interval: 50 ns (8) Flow rates: Helium carrier, approximately 60 ml/min; argon-methane purge, approximately 120 ml/ min Using EC/GC as the determinative step, inject, in duplicate, 1 to 10 pJ of each solution into the chroma tograph. By comparison with standard solutions in jected, in duplicate, under the same operating condi tions, determine the amount and type of Aroclor using the individual or total peak height and area methods, B3.8 Sample Concentration. Concentration of sample extracts is necessary, prior to cleanup by chromato graphic or chemical means, to reduce am ple size and increase sensitivity. The preferred method of concen trating allows minimum loss through volatilization or chemical decomposition and requires a minimum time. The three methods of solvent volume reduction most commonly used are evaporation by exposure to a stream of air, evaporation employing a Kundema- \ Danish evaporative concentrator equipped with a Snyder column, and evaporation under reduced pres sure. All three techniques have been used without en countering any significant losses from volatization or chemical alternation. However, the Kundema-Danish evaporative concentrator and the sirearn-of-air methods are easier to use. B3.9 Column Adsorption Chromatography and Chemi cal-Cleanup. Silica gel, a magnesia silica gel.9 and alu mina deactivated with 0$*c, 1.09c. 1.551. 2.09i, and 57 water were investigated as adsorbams for the elimina tion of interferences. Alumina (59c water) was found to be more effective and reproducible than either silica gel or a magnesia silica gel.9 The activity of alumina varies with age and lot; therefore, 59c water was added to the alumina, after heating for a minimum of 4 hours at 400C, to ensure a reproducible activity. Saponification, and subsequent extraction of the sample with sulfuric acid, is an effective way to remove a number of chlorinated hydrocarbon interferences as well as other matrix interferences. PCBs are not affected. B3.10 Column Performance. Column performance is the key to effective gas chromatographic analysis and. as such, the choice of column materials is particularly important. Ideally, the support employed should be inert, mechanically strong, and of high surface area. Chromosorb W, HP, AW-DMCS fulfills these require ments and is recommended for this work. A variety of polar and nonpolar liquid phases have been investigated. The following columns have been found to provide adequate separation, etc, for use in PCB analysis by electron capture: 4% (w/w) DC-200, SF-96, OV-17, SE-30, SE-54, XE-60, Apiezon L, and 67c QF-1. DC-200 and XE-60 or QF-1 have been found to be the most suitable of these liquid phases. Another important consideration when working with an extremely sensitive detector and. consequently, low levels of materials is column conditioning. With polar phases such as XE-60 and QF-1, operating a new column overnight at a temperature 25C to 50C higher than that to be used during analysis results in a more stable column. A no-flow conditioning technique is employed to condition nonpolar columns. The column is purged with carrier gas, heated for 30 minutes at an elevated temperature without carrier flow, and then cooled to room temperature. At the end of this cycle, the carrier flow is resumed and the conditioning is com pleted as in the case of the polar liquid phase. Two pre cautions should be observed: during conditioning, the column should not be connected to the detector, and the maximum safe temperature of the liquid phase should not be exceeded. Since all liquid substrates bleed to one degree or another and columns eventually degrade, all new col umns should be characterized with two column perfor mance indicators: the number of theoretical plates (V) and a tailing factor (7*). p,p'-DDT is employed to check these parameters because it is known to degrade on *For eximple, Flor. 29 APPENDIX th eo r etic al p lates, N = l6 { * /y )2 t a il in g , T* o /2b PEAK HEIGHT "poor" columns. In this manner, one can determine whether the performance o f a new column is satisfactory and when the column performance begins to fall ofT. A column is considered good if the number o f theo retical plates per foot is o f the order of 400 to 500,, with tailing factors of 1.0 to 13 . Calculation o f these parameters is ahown in Fig. B9 and B10. Additionally, there should be no significant extraneous peaks upon injection o f a pure p,p'-DDT standard. Other chromatographic conditions that can be ad justed are column temperature and flow rates. AN, though resolution of a mixture increases with decreas ing temperature, a temperature should be chosen that allows the elution of all components within a conve-i nient time period. The flow rates shown are optimum for a given instrument, column, and detector system. These should be adjusted if better results can be achieved. 30 Any system o f instrument and column suitable for chlorinated pesticide analysis is satisfactory for PCB analysis. The use of the high-temperacure 63Ni electron capture cell is highly recommended. The ability to oper ate at higher temperatures prevents maintenance prob lems due to contamination from high-boiling compo nents. Glass columns also should be employed. B 3.ll Detection and Measurement. Quantitative deter minations employing the electron capture detector are nonstoichiometric measurements made by comparing peak heights or areas for known concentrations with those for unknown compositions. Three variations of the peak height or area quantification procedures have been employed: Case 1. EC gas chromatogram of PCB unknown, unchanged with respect to standard PCB with no evi dence of interferences i* APPENDIX Case II. EC gas chromatogram of PCB unknown, altered with respect to standard PCB with no evidence of interferences Case III. EC gas chromatogram of PCB unknown, unchanged with respect to standard PCB with evidence of interference The amount of PCBs in Case I samples is determined by preparing a plot o f the major peak height or area versus concentration. With Case III samples, a peak free from interference is used. When dominant interferences are present, one or more of the chemical cleanup proce dures is employed. In all cases, the response o f the electron capture detector must be linear for quantitative analysis. B3.12 Contamination. In determining PCBs in biologi cal materials by electron capture gas chromatography, laboratory sources of contamination can be a major problem. The samples and extracts should never be allowed to come in contact with materials other than glass, TFE-fluorocarbon, or metal. Laboratory glassware should be thoroughly washed with hot, soapy water, and rinsed with distilled water, acetone, and then hex ane. All equipment should also be rinsed again with hexane just prior to use, and blanks should be frequent ly carried through all steps of the procedures to ensure against the possibility of contamination. B3.13 Sensitivity (1) Concentration: 2 ppb (parts per billion) (2) Absolute sensitivity: 0.5 X 10-9 gram (3) Volume injected: 5 pJ (4) Final volume of extract: 5 ml (5) Sample size: 250 ml B4. Analysis o f W ater and Sedim ent for PCBs B4.1 Scope. This methodology is used by the Monsanto Industrial Chemical Company for the determination of the amount and type of PCBs in water and sediment oraples. Absolute confirmation o f PCB structures is not obtained with this method. Structure proof can be ob tained using additional techniques such as mass spec trometry to further identify the gas chromatography frictions. \ B4.2 Principle. The PCBs in water and sediment sam ples are extracted into an organic solvent. Interfering components are then removed from the extracts by chemical treatment and column adsorption chroma tography. The amount and type of PCBs present are determined by electron capture gas chromatography (EC/GC). B4.3 Reagents (1) Hexane: Pesticide grade. (2) Acetonitrile: Pesticide grade. (3) Sodium sulfate: Anhydrous, granular, analytical reagent (AR) grade. Heat at 400C for 1 hour prior to use. (4) Alumina adsorption: For chromatographic anal ysis, 80/200 mesh. Heat at 400C for a minimum of 4 hours and deactivate with 5% (w/w) distilled water. For alumina column preparation fill a chromato graphic column with hexane up to the point where the reservoir joins the column, and push a glass wool plug to the bottom with a glass rod. In a 50-ml beaker mea sure 35 ml (about 30 grains) of deactivated alumina, and pour this slowly into the column. Tap or vibrate the column to settle the alumina, and top the alumina with 2 to 3 cm of anhydrous sodium sulfate. Wash the column with 50 to 100 ml of hexane prior to the addi tion of the sample. (5) Distilled water: Extracted with hexane to re move hexane-soluble electron capturing impurities. (6) Sulfuric acid: AR grade, specific gravity = 1.84. (7) Potassium hydroxide: AR grade. (8) Ethanol: Formula 2B. (9) Alcoholic potassium hydroxide, 2.5% (w/v): Dissolve about 12.5 grams of AR grade KOH in 500 ml of ethanol. (10) Sulfuric acid-water, 9:1 (v/v): Carefully add 270 ml of AR grade sulfuric acid to 30 ml of distilled water in a 500-ml iced beaker. (11) PCB standards: Aroclor 1242,1248, 1254, and 1260. (See Fig. B2 and Fig. B4 through B7.) B4.4 Apparatus (1) Separatory funnels equipped with ground-glass stoppers and TFE-fluorcarbon stopcocks; capacities of 125,250,500,1000, and 2000 ml. (2) Kundema-Danish evaporative concentrators, 500-ml capacity, equipped with three-ball Snyder col umns and graduated 5-ml capacity vials. (3) Chromatographic columns, glass, 10 Inches X 20 mm (OD) with a 5-inch X 50-mm (OD) reservoir at the top, equipped with TFE-fluorocarbon stopcocks. (4) Sintered glan filter funnels, 600-ml capacity, 90-mm disk diameter, medium porosity. (5) Flat-bottomed boiling flasks, 125-ml capacity. (6) Liebig condenser, 200 mm in length. (7) Hot plates. (8) Water bath. (9) Reciprocating variable-speed shakrr. (10) 10-*d syrin^s. (1 1) 32-ci aD-glass mortars and pestles. (12) 8-inch X 12-inch X 2-inch (2-1/2 qt) heatresistant glas baking dishes. 31 APPENDIX (13) U.S. Standard sieve, No. 30. (14) Usual laboratory glassware. B4.5 Sampling. It is to be assumed that a rather wide variety of sampling techniques may be employed in col* leering samples submitted for analysis. For this reason, water and sediment samples should be treated as given in B4.S.I and B4.5.2. B4.5.1 Water. Where possible, the entire water sam ple, including the container in which it was collected, should be extracted with hexane. With larger samples, where this is not physically possible, the containers should be simply agitated and a 250-ml portion used for the analysis. (See B4.6.) B4.5.2 Sediment. Any excess water should be de canted, and the entire sediment transferred to a glass baking dish to air-dry at room temperature. The dried material should be transferred from the dish into a mor tar and ground. The ground sediment should be sieved, remixed, and a 250-gram portion taken for analysis. (See B4.7.) B4.6 Extraction of Water Samples (1) After agitating, transfer the entire aqueous sam ple or a 250-ml aliquot into a graduated glass cylinder. Record the volume of the sample and quantitatively transfer it to a separator)' funnel with distilled water. (2) Rinse the graduated cylinder with two 50-ml portions of hexane and add each to the separatory fun nel. (3) Stopper the separatory funnel and shake vigor ously for at least 1 minute. Allow the layers to separate, and transfer the lower aqueous phase to a second separa tor)' funnel. (4) Extract the water sample a second time with a 50-ml portion of hexane. After the layers have sepa rated, add the first hexane extract to the second sepa ratory funnel, and transfer the aqueous layer to the original separatory funnel. (5) Repeat the extraction with a third 50-ml por tion of hexane. Discard the aqueous layer and combine the hexane extracts. (6) Filter the combined extracts through a 4-inch funnel, plugged with glass wool that is covered with sodium sulfate. Collect the fltrate in a KundemaDanish evaporative concentrator, add a small boiling chip, put the Snyder column in place, and reduce the hexane volume to less than 5 ml by heating the apparatus in an 80C to 90 C water bath. (CAUTION: Solvent vapors must be vemed into a hood.) (7) After cooling, remove the 5-ml graduated tube and transfer the hexane extract to an alumina adsorp tion column, washing it in with several 5-ml portions of hexane. (8) Carefully add 100 ml of hexane to the column reservoir, and collect the total eluent in either a 250-ml volumetric flask or a Kundema-Danish evaporative con centrator. (9) If the column eluent is collected in a volumetric flask, dilute to volume with hexane, and proceed with the gas chromatographic analysis. (10) If the column eluent is collected in a KundernaDanish evaporative concentrator, reduce solvent volume, cool, dilute to volume, and proceed with the gas chro matographic analysis. B4.7 Extraction of Sediment and Soil Samples (1) Decant off any excess water and transfer the entire sediment sample to a glass baking dish. Air-dry at ambient temperature (heat should be applied). (2) When dry, transfer the soil/sediment to a mor tar and grind. Sieve the ground material through a No. 30 mesh sieve and weigh 250 grams (to the nearest 0.01 gram) into a 16-ounce narrow-neck screw-cap (alumi num-foil liner) glass bottle. (3) Moisten the soil with about 10 ml of water and add 150 ml of acetonitrile. Cap the bottle tightly, and mechanically shake it for a minimum period of 1 hour. (4) Quantitatively transfer the acetronitrile extract into a 600-ml sintered glass filter funnel containing a ]/4-inch layer of anhydrous sodium sulfate. Collect the filtrate in a 600-ml beaker (vacuum filtration may be necessaiy). (5) After the acetronitrile has completely drained into the beaker, wash the bottle twice with 50-ml portions of acetonitrile, adding each wash to the funnel after the previous wash has completely percolated through the sediment. (6) Quantitatively transfer the extract to a KundernaDanish evaporative concentrator, add a small boiling chip, put the Snyder column in place, and reduce the solvent volume to less than 5 ml by heating the appara tus in an 80C to 90C water bath. (CAUTION: Solvent vapors must be vented into a hood.) (7) After cooling, remove the 5*ml graduated tube and transfer the concentrate o f extracts to a 125-ml extraction flask with the aid o f several small portions of solvent. (8) Evaporate the extract just to dryness with a gentle stream of dry, filtered nitrogen and add 25 ml of 2.5% alcoholic potassium hydroxide. (9) Add a boiling chip, put a water condenser in place, and allow the solution to reflux for 45 minutes. (10) After cooling, transfer the solution to a 250ml separatory funnel with the aid of 25 ml of distilled water. (11) Rinse the extraction flask with 25 ml of hex ane and add it to the separatory funnel. (12) Stopper the separatory funnel and shake it 32 APPENDIX vigorously for at least I. minute. Allow the layers to (6) Detector temperature: 300*C separate, and transfer the lower aqueous phase to a (7) Pulse interval: 50 is second separatory funnel. (8) Bow rates: Helium carrier, approximately 60 (13) Extract the saponification solution with a sec ml/min; argon-methane purge, approximately 120 ml/ ond ,25-ml portion of hexane. After the layers have min separated, add the first hexane extract to the second Using EC/GC as the determinative step, inject, in separatory funnel and transfer the aqueous alcohol duplicate, 1 to 10 ;tl o f each solution into the chroma layer to the original separatory funnel. tograph. By comparison with standard solutions in (J4) Repeat the extraction with a third 25-ml por jected, in duplicate, under the same operating condi tion of hexane. Discard the saponification solution and tions, determine the amount and type of Aroclor using combine the hexane extracts. the individual or total peak height and area methods. (15) Carefully add 25 ml of the sulfuric acid solu The electron capture detector should also be used to tion (9:1 concentrated sulfuric acid-water) to the hex guide the isolation procedures. Water and sediment ex ane extracts. tracts can be checked for the presence of PCBs or inter (16) Stopper the separatory funnel and shake vigor ferences, or both, by injection of microlitre portions ously for at least 1 minute. Allow the layers to separate, of the extracts at various points in the extraction and discard the lower aqueous acid layer. Repeat this and concentration schemes. In this manner it can be step until the acid layer is colorless. determined whether the sample needs to be concen (17) Wash the hexane with a 25-ml portion of trated or diluted and whether the cleanup procedures water. Discard the water wash. should be employed. (18) Filter the hexane extract through a 4-inch fun nel, plugged with glass wool that is covered with a layer of sodium sulfate, into a Kundema-Danish evaporative concentrator. (19) Add a small boiling chip, put the Snyder col umn in place, and reduce the hexane volume to less than 5 ml by heating the apparatus in an 80C to 90C water bath. (20) After cooling, remove the 5-ml graduated tube and transfer the hexane extract to an alumina adsorp tion column, washing it in with several 5-ml portions of hexane. (21) Carefully add 100 ml of hexane to the column reservoir, and collect the total eluent in either a 250-ml volumetric flask or a Kundema-Danish evaporative con centrator. t (22) If the column eluent is collected in a volumet ric flask, dilute to volume with hexane, and proceed with the gas chromatographic analysis. (23) If the column eluent is collected in a Kundema- Danish evaporative concentrator, reduce solvent vol ume, cool, dilute to volume, and proceed with gas chro matographic analysis. B4.9 Extraction. The extraction of PCBs from water, employing hexane as the extractant, has been found to be quantitative and sufficiently simple and rapid for use as a routine procedure. The evaluation o f this method was based on spiking water samples with standard acetone solutions of PCBs. The spiking method consisted of adding the PCB in 25 to 50 Ml of acetone to 500 ml of tap water in a 32ounce narrow-neck screw-cap jar. After the sample was thoroughly mixed, duplicate 225- to 250-ml aliquots were taken and subjected to the proposed sample prep aration and worked up as outlined. The results were quantified by preparing a calibration curve using stan dard hexane solutions of the PCBs used to spike the water samples. The major isomer peak height was used to construct the calibration plot. The average recovery and deviation achieved sub stantiated the applicability of the method for the quanti tative recovery and analysis of PCBs from water at the ppb-ppm level. No PCB recovery experiments from spiked rediment and soO samples have been performed. Instead, several o f the residual solids representative of some of the B4.8 Electron Capture Gas Chromatographic Proce dure (1) Instrument: Gas chromatograph (for example, Hewlett-Packard Model 5750, or the equivalent) \ (2) Detector: High-temperature 43Ni, electron cap ture cell (3) Column: 6-mm X 6*foot glass column, 4% XE60 on 80/100 mesh, Chromosorb W, HP. AW-DMCS types o f sediment or soO analyzed were reextracted with hexane/acetone (40:60) in a soxhlet extractor to test for the efficiency o f the acetonitrile extraction step. The hexane, after isolation by dilution with dis tilled water, was then carried through the purification steps. Recoveries by soxhlet extraction have indicated that the acetonitrile extraction of PCBs was essentially quantitative in the cases checked. (4) Column temperature: 160C B4.10 Sample Concentration. Concentration of sample (5) Injection port temperature: 195C extracts is necessary, prior to cleanup by chromito- 33 APPENDIX graphic or chemical means, to reduce sample size and increase sensitivity. The preferred method of concen trating allows minimum loss through volatilization or chemical decomposition and requires a minimum time. The three methods of solvent volume reduction most commonly used are evaporation by exposure to a stream of air, evaporation employing a Kunderna-Danish evapo rative concentrator equipped with a Snyder column, and evaporation under reduced pressure. All three tech niques have been used, and no significant losses from volatilization or chemical alternation have been encoun tered. However, the Kunderna-Danish evaporative con centrator and the stream-of-air methods are easier to use. B 4 .ll Column Adsorption Chromatography and Chemeal Cleanup. SQica gel, a magnesia silica gel,9 and alu mina deactivated with 0%, 1.0%, 1.5%, 2.0%, and 5% water were investigated as adsorbants for the elimina. tion of interferences. Alumina (5% water) was found . to be more effective and reproducible than either silica gel or a magnesia silica gel,9 The activity of alumina varies with age and lot; therefore 5% water is added to the alumina, after heating for a minimum of 4 hours at 400C, to ensure a reproducible activity. ' Saponification, and subsequent extraction of the sample with sulfuric acid, is an effective way to remove a number of chlorinated hydrocarbon interferences as well as other matrix interferences. PCBs are not affected. B4.12 Column Performance. Column performance is the key to effective gas chromatographic analysis and, as such, the choice of column materials is particularly important. Ideally, the support employed should be inert, mechanically strong, and of high surface area. For these reasons, Chromosorb W, HP, AW-DMCS is recommended for this work. A variety of polar and nonpolar liquid phases have been investigated. The following columns have been found to provide adequate separation, etc, for use in PCB analysis by electron capture: 4% (w/w) DC-200, SF-96, OV-17, SE-30, SE-54, XE-60, Apiezon L, and 6% QF-1; DC-200 and XE-60 or QF-1 are the most suit able o f these liquid phases. Another important consideration when working with an extremely senative detector and, consequently, low levels o f materials is column conditioning. With polar phases such as XE-60 and QF-1, operating a new column overnight at a temperature 25C to 50C higher than that to be used during analysis results in a more stable column. A no-flow conditioning technique is em ployed to condition nonpolar columns. The column is* *Foi exwaple, Floriiil. purged with carrier gas, heated for 30 minutes at an elevated temperature without carrier flow, and then cooled to room temperature. At the end o f this cycle, the carrier flow is resumed and the conditioning is com pleted as in the case of the polar liquid phase. Two pre cautions should be observed: during conditioning, the column should not be connected to the detector, and the maximum safe temperature of the liquid phase should not be exceeded. Since all liquid substrates bleed to one degree or another and columns eventually degrade, all new col umns should be characterized with two column perfor mance indicators: the number of theoretical plates (AO and a tailing factor (7)- p,p'-DDT is employed to check these parameters because it is known to degrade on "poor" columns. In this manner, one can determine whether the performance of a new column is satisfac tory and when the column performance begins to fall off. A column is considered good if .the number of theo retical plates per foot is of the order of 400 to 500. with tailing factors of 1.0 to 1.3. Calculation of these parameters is shown in Fig. B9 and BIO. Additionally, there should be no significant extraneous peaks upon injection of a pure p,p'-DDT standard. Other chromatographic conditions that can be ad justed are column temperature and flow rates. Although resolution of a mixture increases with decreasing tem perature, a temperature should be chosen that allows the elution of all components within a convenient time period. The temperatures given are optimum for 42% chlorinated biphenyl; temperatures are increased when specifically analyzing for the higher chlorinated biphe nyls; that is, 54%, 60%, etc. The flow rates shown are optimum for a given instrument, column, and detector system. These should be adjusted if better results can be achieved. Any system of instrument and column suitable for chlorinated pesticide analysis is satisfactory for PCB analysis. The use of the high-temperature 63 Ni electron capture cell is highly recommended. The ability to oper ate at higher temperatures prevents maintenance prob lems due to contamination from high-boiling compo nents. Qass columns also should be employed. B4.13 Detection and Measurement. Quantitative deter minations employing the electron capture detector are nonsloichiometric measurements made by comparing peak heights or areas for known concentrations with those for unknown compositions. Except for sharp peaks, peak area measurements are usually more repro ducible than peak height measurements but are extreme ly time consuming unless a recording integrator is em ployed. However, peak height measurement; are as accurate as disk integration of triangulation and, if the 34 . Nk American National Standards The s ta n d a rd in this booklet is one of nearly 5,BOO sta n d a rd s ap p ro v ed to d a te by th e A m erican N ational S tan d ard s Institute, form erly th e USA S tan d ard s In* stitute. The S tan d ard s Institute provides the m achinery for creating voluntary stan* d a rd s. It serves to e lim in ate duplication of stan d ard s activities a n d to w eld con flicting stan d ard s into single, nationally occepted standards under the designa tion "Am erican National Standards." Each stan d ard represents general agreem ent am ong m aker, seller, and user groups as to the best current practice with regard to some specific problem . Thus the com pleted standards cut across the whole fabric of production, distribution, a n d consumption of goods and services. American National Standards, by reason of Institute procedures, reflect a national consensus of m anufacturers, consumers, an d scientific, technical, an d professional organizations, and governm ental a g en cies. The. com pleted standards a re used widely by industry an d commerce and often by municipal, state, and federal governments. The S ta n d a rd s Institute, u nder w hose auspices this w ork is being done, is the United States clearinghouse and coordinating body for standards activity on the n a tio n a l level. It is a fed eratio n of tra d e associations, technical societies, profes sional groups, an d consumer organizations. Some 1,000 com panies are affiliated with the Institute os company members. The American N ational Standards Institute a the United States m em ber of the In tern atio n al O rg an izatio n for S tandardization (ISO), the International Electro technical Com m ission (IEC), a n d the Pan American S tan d ard s Commission (COPANT). Through these channels A m erican industry m akes its position felt on th e in te rn a tio n a l level. A m erican N otional S tan d ard s o re on file in the libraries of the national standards bodies of more than 50 countries. For a free list of all American National Standards, write: American Kitiotui Stewards htrtvfi, he 1490 Broadway Ntw Tori N. Y. 10011 v r t *** - ! I f V / M isc e lla n e o u s Hazard Ho. 2581 A p p lic a t ion Ho. 33C206Q Sap tom ber 2 9 , 1934. RSPOR on LIQUID DIELECTRIC AND COOLING MEDIUMS G eneral E leo tr io Co., S oh en eotad y, H. Y. P L A IN T IF F 'S EXHIBIT I Xi i I 2. Z 2. I ' Page No. d s s c r i? n o n ..................................................................................... 1 CULBIS liADE FOR THS PRODUCTS. .................................. 2 PLAN OF INVESTIGATION.......................................................... 4 SXAHINATION AND TSST R3C0HD............................................ _ HOORD IN S3R V U E .................................................................... 4 21 o THS SU 3M IT T 0R ................................................................... CONCLUSIONS.......................................................................................... 21 22 RS0012NDA.TI0N 1 ir-' .* O J. ' ' I INSTRUCTIONS FOR , * SEARCHING LISTS OF SERIAL NUMBERS FOR PCB TRANSrQRMERS I . INTRODUCTION Recent rulings*by the EPA have put s trin g e n t reg u latio n s on the disposal o f those transform er in s ta lla tio n liq u id s which contain PCBs. ' The General E le c tric Company manufactured many transform ers using an in su latin g liq u id - containing PCBs. We c alle d th is liq u id Pyranol. We have been receiving l i s t s o f se ria l numbers from our customers with the request th a t we id e n tify fo r then those transform ers which were manufactured with PCBs. The General E le c tric Company used no Pyranol in any transform er manu factu red in Hickory o r Shreveport and in no transform er manufactured a t any . location, p rio r to 1930 o r a f t e r Decanter 31 1976. - O . I I . F ir s t PASS AT LIST A. Check c u sto m ers request and id e n tify u n its as requested. B. I f no s p e c ific requests are made, proceed as follow s: 1. Since n e ith er Hickory nor Shreveport ever b u ilt a pyranol f i l l e d transform er, put a "NO" a f t e r each s e ria l number on the l i s t which has e ith e r a "Y" o r "T" a f t e r the usual l e t t e r plus six d ig its . Example: G46389566Y (Hickory 1966) . J539450Y71 (Hickory 1971) . L706425TELA (Shreveport 1975) 2. Since no Pyranol f i ll e d transform ers were ever b u ilt p rio r to 1930 o r a f te r December 31, 1976, i f the date of manufacture can be id e n tifie d as before 1930 or a f t^ r January 1, 1977, put "NO11 a f te r the se ria l number. Example: S erial numbers le s s than 4700000 were b u ilt before 1930. Serial numbers higher than M310000 3. The l i s t w ill usually have some se ria l numbers which are not General E le c tric Company. The GE s e ria l numbers are e ith e r seven d ig its (up through 1956) o r a l e t t e r f o l 1owed by six d ig its {since 1950). (The-coding fo r place and date of manufacture was f i r s t introduced in the la te 1950's and is not to be considered p a rt of the se ria l number.) Any number which does not follow one of the above p a ttern s is not GE. Mark a ll such s e ria l numbers "NOT GE". * *t I I I . NUMERICAL ARRANGEMENT Give the l i s t to Nancy fo r numerical arrangement. She w ill ignore a ll numbers marked e ith e r "NO" or "NOT GE". Nancy's l is tin g gives each number a sequential number which corresponds to i t s positio n on the o rig in al l i s t . This sequential' number may be used l a t e r in locating a number when working back and fo rth between l i s t s . Id en tify the l a s t s e ria l numbers in each column of the o rig in al l i s t with the assigned sequence number to e sta b lis h the range of sequence numbers in each column. Set o rig in al l i s t aside. IV. CHECK PLACE OF MANUFACTURE Check num erically arranged l i s t a g ain st HB 5405, page 2. If se ria l number 1s. lis te d th ere as assigned to e ith e r Hickory o r Shreveport, so in d ic ate on this;.by "Y" o r "T". Also, id e n tify Oakland "K" and Merced "Mu fo r p o ssib le l a t e r convenience. P i t t s f i e l d numbers may be l e f t unmarked. V. MICROFILM SEARCH x A. Oo nothing fu rth e r on the num erically arranged l i s t with the se ria l numbers marked "Y" or "T". -2- tt B. Try to Id e n tify a ll o th ers as e it h e r "OIL" o r "PYR" ( f o r P y ra n o l). As soon as one can be id e n tif ie d as e it h e r o il o r P y ran o l, so mark and proceed to next number. 1. Look fo r s e r ia l number on m icrofilm . a) I f found 1) Look f o r th e word "OIL" o r "Pyranol" somewhere on th e t e s t card o r t e s t re p o rt. 2) Look f o r the l e t t e r "A" before th e P .0 , (production o rd er number). A P .0, number w ith "A" preceding i t meant Pyranol. 3) Look fo r and examine th e form d e s ig n a tio n , which is the l a s t group o f c h a ra c te rs in th e r a tin g . Look fo r the l e t t e r "A" in t h is group, which meant Pyranol. Samples of ra tin g s : HSBA-60-25-2400/4160Y-120/240-W2F /s m o *Az FO**) TWAMZfiO /S o /t.- pQ&A*1 HS-60-25-2400/4160Y-120/240-W2FA QffSJGA/ A T /oaS "A " rt ZAMS PYArfAtOU- fT/CL^O 0AT-60-6Q0-72QQ-48GY-RA 4 ) Look fo r a c ata lo g number or T. S. number. I f one can be found, w rite i t down f o r checking a g a in s t c atalo g number o r T. S. number assignm ents, p y^A + 'c ^ Example of c atalo g numbers: 26H55 6 f h 47X4! '/fuj C UJ (-Lu H U! Mic, Examples of T.S. numbers: 5501gQ225XAL X 70CG045AA I f d a te of manufacture can be e sta b lis h e d as a f t e r January I , 1977, id e n tify u n it as "OIL". b) I f s e r ia l number cannot be lo ca te d on m icro film , w rite "7" on nur.^rical l i s t . (_Ft* HW M p,& ,r$ fu i -rs) *1 " .-T* >*+/r *+ FJ u J pJ X. ^ uo ^X 3- VI. FINAL ACTION ON ORIGINAI LIST (Oralt th is step unless i t 1s s p e c ific a lly requested.) A. Go down through l i s t , addressing each number not previously marked during the " F irst Pass". B. Locate the addressed number on the num erically arranged l i s t . C. Write the following a f te r the number on the o rig in a l l i s t : 1) "NO" i f marked "YMo r "T" on numerical l i s t . 2) "NO" i f marked "OIL" on numerical l i s t . 3) "PCB Transformer" i f marked "PYR" on numerical l i s t . 4) "?" i f marked on numerical l i s t . C DBTiUBtrnON TRANSfORMBQ Serial Numbers V I 5405 Pag \ Apr. 2 1 ,198( Tbis information, which' is approxi The place of manufacture is coded mate and subject to many exceptions, . as follows: applies primarily to distribution trans K-- Oakland, Calif. formers rated 500 leva below. It is in M-- Merced, Calif, (starting 1907) tended to five a rough idea of trans P--Pittsneld. Mass, (includes form former age and place of manufacture. er Holyoke, Mass, plant) T--Shreveport, La. Y --Hickory, N. C. All requests for distribution trans former replacement parts should be directed to Hickory. T f <! w SwteJ Hamhaw M aau/adWad A * ra s Ym t fmomrr Wwtortwd Traaatanaar Sartal N--toin APW* Yaw Pctorr MaiwiiICfura* Traaifemar Sariad(Awert pptmm Y*w faaory o rn o to 2M H 3Q 25494SI to 2CUSSO 2834531 to 3023743 3025744 to 2032800 3032001 to 3037800 3037801 to 31*2300 3103301 to 3191100 3190101 to 3203100 3203101 to 3234100 3334101 to 3333100 3333101 to 3300000 3300001 to 3374099 3374100 to 3377099 3377100 to 3 43409* 1434100 3441099 3441100 to 3333399 SS23400 to 333839* 3330400 to 3 4133*9 3413400 1 3433399 3433400 1 3700000 3700001 3833499 3833700 ) 3843899 3843700 to 3933499 3933700 3934499 3*34700 4040899 4040900 40438*9 4063900 4070899 4070900 to 4071 *9 9 4071900 0 4137379 4137300 to 4137379 4(37300 4 3 3 2 1 *9 4332200 1 4343199 4342200 to 4499499 4499500 to 4309499 4309300 1 4390999 4391000 4391999 4393000 1 4440499 4448300 to 4678499 4478300 1 4731000 4731801 1 4773499 4793300 1 4803499 4803300 (4839700 483*701 4 *1 24 *9 4*12700 to 4133494933700 ( 497419. 4974203 497819V 4973200 to 490180 4983301 4998100 4993101 to 503 0 3 9 3080300 3033300 3033301 1 3034700 3034701 3034700 303470T to 204039* 3040300 1 3094800 3094801 to 3142999 3143000 1 3143800 3165801 la 3167799 316IOOO 1 5196300 5196201 ta 3312999 3211000 la 3216900 521*901 a 5217999 1887-1921 1923 1723 1934 1933 1 *3 4 1938 1924 1933 1924 1928 1736 1923 1924 1938 1934 1928 1936 1934 1934 1927 1934 1 *2 7 -1 9 3 4 1937 1927 1927 1927 1938 1927 1928 1928 1929 1939 1939 1929 1929 1739 1739 1730 1930 1*30 1931 1990 1*31 1930 1931 1932 1933 1*31 1933 1933 1734 1733 1734 1934 1935 1934 1935 1933 1934 t 35328178303040 tloa 3523X073303*93 t f f 3303100 ta83100*9 3310100 8373099 8372100 83770*9 X P 38444433090000 18844444338090* 3444301 13308300 7 3305801 5317899 X 5517900 la 353389* X 5533900 15424899 X 5624900 15634200 3634201 ta 3634899 f X 5434900 la 5446000 3446001 15774499 p X F 3776900 3783300 33778824590010 to33781443839090 X P 3042301 15898387 5898588 3898400 X P P 45819483400010 44114433999*99 4144000 to 4190000 4203000 (6305200 X 4303201 1420799* P X 4304000 to 43534*9 p 4352500 16357481 X 4357482 14431300 4421501 445349* p 4453500 4454154 X p X p 4434157 4457499 4437503 6444399 4444980*460000 1ta64439809133989 X 4389839 to 48*0383 . p X p X 4390383 14704300 46780943300010 146889928939397 6898338 14903799- 7019000 la 7093999 p X 7094000 la 7098200 p 7098301 17319999 p 7320000 to7230410 X 7370411 7234999 - 7323000 to 7333007 p p X p 7335008 la7314200 77331364350010 ttoo77333344453959 X 77333344543040 l1a77333374353909 p p p X X 7337351 73393*9 7777443484430509044*00001000 tt1laoo7777464493443005035099909990 X JC 77469923110404 t'#o77649973019493 p p 7697100 la 7793099 7793100 la 7797134 K 7797333 la 7798108 X p 77875948710019 llaa 71913041710008 p 101109 t# 8106099 X X 106100 la 8213700 318701 la 8349099 1*15 . 11992344 1934 1934 1917 11993344 11993377 111999333177 11993387 1*38 1939 1199338* 1939 193* 119*3399 1939 1940 111999444000 1941 t940 1941 1941 1941 1941 ,1941 1941 11994412 1943. 1942 1943 1943 11994433 1943 11994434 11994434 1943 11199*444444 1944 1943 1944 11994435 11794454 11994454 1946 11994476 P P 18227429413010 118823772440390* 11994467 X X XP 88227744120704 114327764347033 X 8274404 to 8551099 11994477 f X 1947 p XXpp X 8551100 to 88590*9 8575999100010 1la789190090909 481171000000 t1o#944146499999 1947 1199447 11994487 X pp KP p X 998844510000 tlaa 6999814409999 X t t 991300 la 9142999 99117603000000 t1o9921447*999090 11994487 111999444885 C KP K P X Xp p . 99334447990011 1to9237444**9090 99338803700010 99351834790909 194* 111999544049 X 9431300'9*34499 194* P KKP K p Xp 99444433850000 119944444547999* 9433300 9438499 X X 9*48700 T9472473 9472472 to 9473499 194* 11993300 K . 1950 1931 p 478700 to 9483499 Xp p 9708700 9713499 99772111770000 1199773733449999 X 9744700 to 9733499 1931 1951 1931 X 11995322. Xp 99778440770000 l1a99777833649999 x p X 9790700 1* 9793699 99180003770000 11* 99880099999999 1932 11993333 1933 1933 X pe X X X 9810000 lo 9813699 9828300 la 9823299 9443300 la 9833299 9853300 to 9843299 9848300 19X78299 1934 11993344 X 1933 1733 p 9893300 to 9903299 p 9903500 la 9f 13499 XX 99991334350000tlo 99994183449999 X 1pp / 1231914009090 ta3391800*9998 >333273050010 333475909090 p 348100 la 447230 X Xp Xp p 444772313010 11444454009090 444001 (a 1491*99 >583453440000 t1a1558423859999 XX p X X 1778045073104000000 lllaaa 1754440400905999999 971100 la 1960099 *980100 la 941099 111999535446 1936 1930 111999333112 1951 .11993512 1993323 4i 9U 1733 11773332 11773334 I1 \P j P J p p Xp pp CCll0304010000 tlaa CCll4394099999 CC1l4783I0O0O0 llaa CCll7737099999 C300000 to C257599 11773334 1734 1975334 p No chan# t i n M at, 10, I960 iir n t, NA 700. 701. 703. 711.713, 121-733. 731-737 Dato rub/acf fo without notice G E N E R A L ELECTRIC G f1 5405 Pag 2 Apr. 3 1 ,19 *0 DISnOBtmON TRANSFORMERS S end Numbers Tfenrame# Sartal H aran Araras Ysra Pactar? Moaafocltirad Truciomar erial Montan Aspeas Tear Factary Mamaclarad Tramtama# SaelaJ Haasari Aaa#* Yaar Pactar? a i too la 034099 034100 I* 049099 074100 ta 07499 077000 la 079 080300 la 0*37*2 014400 ta <4374*9 C442300 ta C44MJ99 <447400 ta C97394 *<497400 la C430999 011300 ta 0130 013100 ta 0300*9 0*2100 ta 0*3341 0**100 ta CBOMOO ta *0*44000 la 0c*su00tv0*0 073334 *a ;. CI7S333 <*79999 . <97*417 ta <97*434 C97TOOO ta C779400 07*401 taCIM** 0140000 la 0149*99 0130000 ta 020199 0209000 la 033*999 0244000 la 024*999 0270000 ta 0317999 0319000 la B31999* 0321000 ta 0334799 023*000 ta 0444743 0444743 ta 0437999 043*000 la 0441799 0141*00 ta 0311799 0311*00 ta 0317799 - 9317*09 9313300 la ta 031379* 0313799 0313*00 ta 033*414 033*417 la 0349999 0400000 la 042*74*' 043*730 ta 0434999 0744000 ta 0737999 073*000 ta 07*1999 9742000 la 07*3999 0*44000 ta 0*73999 0*74000 0*92913 DI93914 0923999 0924000 ta 0933999 0931000 la 0940299 094000 ta 0941999 0949000 la 09SH22 094*423 0999999 100000 la (I2*9ta E279000 249999 1237300 la 23*999 340000 1 09907* 139907 ta 414799 E4T4000 ta 41719* 1417197 ta 043999* 140000 1 300*47. 30044 la 339999 044000 3*3999 494000 la 4*7113 14*7114 7139*9 I41OOO ta 1*239*9 E129000 la CU2349 1*42330 la 922404 1934 1933 1933 1.934 1934 1933 193* 1933 193 1934 193* 1934 1934 1937t 1934 1937 193 1934 1937 193 1937 1937 1937 193* 193* 193* 193* 1940 193* - 1940 193* 19*0 1939 1940 1941 1937 1991 1937 193* 1937 1931 1931 1939 199* 193* 1939 1939 1940 1940 1939 I960 1941 1942' 1941 1941 " 1940ett 1941 1**#7>.. i 1941 1941 1941 1*41 P* 922403 ta E928999 929000 lo 934299 934300 ta E999999 F100000 ta F128999 f 129000 la P130944 P130947 la 13*999 P P240OOQ ta F239300 F239301 ta F271T99 P373000 F444704 F444773 M F477999 PP F47*000 ta F30193* F301939 ta P324099 P F324100 F312099 P P332100 ta F339332 r F3I2100 F407044 ta FJS4099 F414700 K K F414701 F434100 F434099 F43I099 , F439100 F431000 FM44797099999 P F47BOOO P449000 to HK7999 M974SO F497441 ta 94*99 F403300 ta *12499 F114000 la P924S37 9924*3* i FT33999 P P934000 F933999 0144000 0140000 0301*13 C303000 00001333700131449*3991992979 P G4134*00 ta 043230 0433303 0433399 rTP 0433400 ta 0370399 G370100 0710900 0723901 ta 03901*9 0723900 0730*9* E 0*4740* 0999999 E H20030Q H207999 KJC T- H20M0O MH23S44I H23S442 H234001 ta 234000 H339I41 T E 239143 H34744S H247IM M373999 E 274000 274340 X 374341 te K293444 T K292647 330042 T 330043 w 341999 * T 343000 244000 E 347001 3*930* X 349309 ta 3*9799 P. H37I739 400199 P 430300 4223*9 PP T ` 423290 43349* * 333300 340444 340447 3*3491 T 3*40*0 392119 . * 393120 72*330 r 774331 734999 * 733000 713134 E 713123 la 713444 T C4300 ta *44341 Y 414212 73909 lofi iiiA ru u g v iu i w a ta n i iu M n w n u fflo v n w w ro w ffin d by dash and tha Use two d ig its a / cha year and a Ia tta r-- *T" fo r P tru flald , "Y " for H ickory, "K " for Oakland, and "M M for M srcad, "T " for S hravapart. Zx- am pla: C 97940I-J7K . In 1973 th a la ria i ntunbar suffix was changed to uaa tha G S d ata coda. E xarapU : M 316674TEF A was bu ilt 1941 r H173910 la 178417. 1970 1742 F *300 ta 890042. i9*r M 1943 F 890043 la 893483 1934*4 ta 19*493 194 1970 MM 1944 1941 P E il 00000 WJ21 *999 1742 1942 1943 X E E J33Q193 la J3304I3 J330414 J33Q999 3S1133 J33I249 J44349* J43I499 1949 Y 1972 P 1973 P 1972 P 1971 Y 1943 1944 1944 1943 1944 Y r pp p J714300 J749U0 1749*31 1790700 J790701 J79Q*1* J79QI19 J790904 J791000 JI144O0 1970 1971 1972 1974 1971 11 \1 J 19*3 19*3 194* 1947 19*4 P JS14401 J*14*00 1*191*1 1927000 1933170 1J11*1*9*9113214944341942*99*92999 1970 1970 1971 1971 1972 Mn TT 1944 19*7 19*3 1941 1944 pp E E E140000 K323341 41*07* 0KC24333330949499099 E K43030Q ta 471433 1971 1972 1973 1971 YT P C 1944 E471433 E310011 C E310030 31007* 1972 1973 E E 19*4 T 1943 1*44 1943 19*3 Y E E Y E311213 K330300 E431300 ES43394 831300 K3131*2344491013*44347999*9*39 1973 1971 1*72 1973 1973 E M Y YT . 1944 . 1943 Y* EMI3 00 999*99 1973 Y 1943 S U00000 1141147 1973 Y 1944 19*4 19*4 1944 E Y EC LI41300 1170000 W1L1I47*14499** U71300 U *7000 11*0914 LI92499 1973 1973 TT 1973 1973 ET 1947 1947 E Y LI92321 la LI92974 LLI2*932390707 119*300 122993* 194 194 1949 P 1229*39 L242371 W112244023409* 1973 p 1974 1973 1974 P 1973 T 194* 1949 1240309 144244* 1440300 ta 1440*19* 1974 1973 T P 1442300 L444999 K73 T 1970 1443000 U434I3 1974 T 1949 1442300 W L442999" 1974 r 1970 P 1971 1973 w L443404* 1443403 ta L443444T 1974 975 1972 L443449 U*3*47t F U43IA* L444l<72t 1974. 1977 r 1971 7 1443000 M1472734* 1974 1774 7 ` L473VS3 ta U71473 1974 P 1974 * 1947 U 1471474 14*0727 194 19*7 M U80737 14*0*22 L493000 14930*7 E 14*309* 1493739 1974 1977 1974 ppf 1973 rp 194 K 1443000 1700471 1974 1947 194* Y Y 1700472 1702999 1973 X 1949 194 Y Y 17434*2 1711114 1711117 171*1*9 171*197 17234*1 1949 Y 1773300 17*7429 1944 1949. E K 1717*30 ta 1091130 1191131 la L999974 l 1973 1974 rf 1977 x 1974 r 1973 Y 1974 Y in S hravepart, M ay 1978. T ha final "A" aignifiaa alu m inum w indings. * Som a du plication of w A n has occurred batw aan laclara. W hara th is hoa happ an ad, th a n id ia corracdy indicata tha ppro sima ta y aar of m anufactura and th a factory. t D istrib u tio n Switch**. VOmuad line* Ma. 10, 1900 Ji S ^ B 5 v UI!m i Oses tubiwG ta chenga w ithout naife* GENERAL ELECTRIC DISTRIBUTION TRANSFORM ERS 540* Sriai Numbers Page My 31.19f TRANSFORMER SERIAL NUMBERING SYSTEM Starting with 1957 and thru 1974. all serial numbers were suffixed by a dash and the last two digits of the year and a letter - MP" for Pittsfield. "Y" for Hickory, "K" for Oakland. "M" for Merced, and "T* for Shrevepoa. Example: C979401-57K. In 1975 the serial number suffix was -changed to use the GE date code. For example, M316674TEPA can be interpreted as follows: " 1. T -- Shreveport (see above) 2. 5 = May The month code began with "A" inJanuary 1965 and ended with M in December, excluding the letter T . . This code will be used thru 1965. In 1986, with a new year code, the month code would be then begin with the letter "N" through "Z~, excluding the letter *C and this sequence will run through the year 2006. 3. P = 1979 The year sequence was begun in 1965 with the letter "A", and excluding letters 1 .0 . Q, V and Z. w end in 1985 with the letter "Y". This sequence wi begin again in 1986 with the.letter "A", but with different month code. 4. A = aluminum windings This past history of the numbering system and what can t expected in the future should be of assistance in determinin properwarranty procedures, and should also eliminate constantupdating instructions on the serial number sequences. T iw M rn w S n a lN u n *M M000001 to MO 13933 M039QQ1 to *4039183 M 039184 ta *4039334 M039355 to M039499 *4049300 to M I304 4 M 130485 to M 295I75 M300000 la M300392 M300393 taM 303496 AC03571 to *4312770 M312771 to M3226S9 M 323100to *4333450 . M323S00 to *4409959 M4G9960 to M3734S6 M S73501to *457355* *4573557 ta M573800 M 573I01 to *4574337 A457433*to M573700 M m tm n d Aporax. Y*ar Foaary 1975-. 1973 1976 1977 1976 T Y 7 Y 1977 1976 1977 1977 1978 1976 YY Y T T T 1977 1978 1977 1978 1977 1978 Y T Y Y Y T TVamtomw Sara! Nwntoan Mmmwwd A v o n *, 'toar fao ory MSBS700 la M i06199 *4386200 ta M5B9717 M390001 to M393173 M593174 to *4606001 M6C4200 ta *4406967 1978 1978 1978 1979 t9 7 l Y T T T Y M 60696I ta M606989 *4607000 ta *4701185 M 701186 ta *006951 *0 0 7 0 0 0 ta M I07573 *4607374 to M807773 *00 7 8 0 0 ta M 80I099 1978 1978 1979 1978 1978 1971 Y Y Y Y Y Y *01 3 1 0 0 ta M i 13280 M i 13281 ta M il5366 *0 1 3 5 0 0 ta *4993569 M993572 to M999964 N000001 ta *4001355 N001S0Q ta **002093 1978 1979 1979 1960 1979 1979 Y Y Y Y r Y Troraformar Sonoi N taftaw i MumAomirad Aoorax. Yor Fooory **002094 to N02299 **002300 ta **007704 **007705 ta **001744 N 010001 ta *4020362 N020S43 ta N022299 N022300 ta N02302S 1980 1979 '1980 1980 1981 1979 Y T T T r Y N022Q29 ta N 199026 N 199027 ta M223392 N223650 ta **224311 N224312 ta *4223499 N223300 ta N229878 N2300Q1 ta **234963 1980 1981 1980 1981 1981 1981 Y Y Y Y T T WN234964 M N 2432I4 N243300 ta *4414941 W N414942 ta N439703 N445300 ta N 446I36 #**446137 ta NS44S96 #**646300 ta N646797 1992 1981 1982 1981 1982 t9S2 T Y Y Y Y Y -7 n- K. tJ Tf- P * TP- k - 79 5 to CA - t i V) - * 3 +Add*i or chantjvdwwcwFub. 22. 1992hum. 700. 7 0 1. 702. 711.713, 72 *7 2 3 , 73 (-737 (m/c) Oortj tubiarf ta naru GEHERAL UECTRIC r  SELECTED PCBs (AROCLOR1260, -1254, -1248, -1242, 1232, -1221, and -1016) Agency for Toxic Substances and Disease Registry U.S. Public Health Service \t CONTENTS FOREWORD .......................................................... LIST OF FIGURES ................................................... LIST OF TABLES .................................................... 1. PUBLIC HEALTH STATEMENT ..................................... 1.1 WHAT ARE PCBs? .......................................... 1.2 HOW MIGHT I BE EXPOSED TO PCBs? ......................... 1.3 HOW DO PCBs GET INTO MY BODY? ........................... 1.4 HOW DO PCBs AFFECT MY HEALTH? ........................... 1.5 IS THERE A MEDICAL TEST TO DETERMINE IF I HAVE -BEEN EXPOSED TO PCBs? ....................................... 1.6 WHAT LEVELS OF EXPOSURE HAVE RESULTED IN HARMFUL HEALTH EFFECTS? ........................................ 1.7 WHAT RECOMMENDATIONS HAS THE FEDERAL GOVERNMENT MADE TO PROTECT HUMAN HEALTH? ................ '......... 2. HEALTH EFFECTS SUMMARY ...................................... 2.1 INTRODUCTION ........................................... 2.2 LEVELS OF SIGNIFICANT E X P OSURE ................ .'........ 2.2.1 Key Studies and Graphical Presentations ......... 2.2.2 Biological Monitoring as a Measure of Exposure and Effects ............................ 2.2.3 Environmental Levels as Indicators of Exposure and Effects ............................ 2.3 ADEQUACY OF DATABASE ................................... 2.3.1 Introduction.................................... 2.3.2 Adequacy of the Database for Health Effect End Points ...................................... 2.3.3 Adequacy of the Database for Other Information Needed for Risk Assessment .......... 3. CHEMICAL AND PHYSICAL INFORMATION ........................... 3.1 CHEMICAL IDENTITY ...................................... 3.2 PHYSICAL AND CHEMICAL PROPERTIES ....................... 4. TOXICOLOGICAL D A T A .......................................... 4.1 OVERVIEW .................................. 4.2 TOXICOKINETICS .%............................. 4.2.1 Absorption ...... '............................... 4.2.2 Distribution.................................... 4.2.3 Metabolism ...................................... 4.2.4 Excretion ....................................... iii vii ix 1 1 1 2 2 2 2 3 7 7 8 8 20 27 28 28 29 32 35 35 35 41 41 43 43 44 46 48 v 4.3 TOXICITY .................................... 4.3.1 Lethality and Decreased Longevity ...... 4.3.2 Systemic/Target Organ T o x i c i t y ...... . 4.3.3 Developmental Toxicity ................. 4.3.4 Reproductive Toxicity .................. 4.3.5 Genotoxicity ........................... 4.3.6 Carcinogenicity ........................ 4.4 INTERACTIONS WITH OTHER CHEMICALS ............. 5. 'MANUFACTURE, IMPORT, USE, AND DISPOSAL ............. 5.1 OVERVIEW ...................................... 5.2 PRODUCTION ............... ..................... 5.3 IMPORT ........................................ 5.4 USES .......................................... 5.5 DISPOSAL ...................................... 6. ENVIRONMENTAL FATE ..... ............................ 6.1 OVERVIEW ...................................... 6.2 RELEASES TO THE ENVIRONMENT................... 6.3 ENVIRONMENTAL FATE ............................ 6.3.1 Transport and Partitioning ............. 6.3.2 Transformation and Degradation ......... 7. POTENTIAL FOR HUMAN EXPOSURE ...................... . 7.1 O V E R V I E W ............................. ......... 7.2 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT 7.2.1 Air .................................... 7.2.2 Water ................................... 7.2.3 Soil ................................... ^ J 7.2.4 Other .................................. 7.3 OCCUPATIONAL EXPOSURES ........................ 7.4 POPULATIONS AT HIGH RISK ...................... 8. ANALYTICAL METHODS ................................. 8.1 ENVIRONMENTAL M E D I A ........................... 8.2 BIOMEDICAL SAMPLES ... ..........:.............. 9. REGULATORY AND ADVISORY STATUS ..................... 9.1 INTERNATIONAL ................................. 9.2 NATIONAL ...................................... 9.2.1 Regulations ............................ 9.2.2 Advisory Guidance ...................... 9.2.3 Data Analysis .......................... 9.3 STATE ......................................... 10. REFERENCES ......................................... 11. GLOSSARY ................................. .......... APPENDIXES A. PEER REVIEW ............... \.................... B . FEDERAL REGISTER ANNOUNCEMENT .................. 49 .5 0 52 62 6665 66 73 75 75 75 75 76 76 77 77 77 78 78 79 81 81 81 81 82 82 83 85 87 89 89 89 93 93 93 93 93 94 95 97 123 129 131 vi c Vi '* \ DRAFT TOXICOLOGICAL PROFILE FOR SELECTED PCBs (Aroclor-1260, -1254, -1248, -1242, -1232, -1221, and -1016) Date Published -- November 1987 Prepared by: Syracuse Research Corporation under Contract No. 68-03-3228 for Agency for Toxic Substances and Disease Registry (ATSDR) U.S. Public Health Service in collaboration with U.S. Environmental Protection Agency (EPA) \ Published by: Oak Ridge National Laboratory under DOE Interagency Agreement No. 1425-1425-A1 DISCLAIMER Mention of company name or product does not constitute endorsement by the Agency for Toxic Substances and Disease Registry. \ .V, FOREWORD The Superfund Amendments and Reauthorization Act of 1986 (Public Law 99-499) extended and amended the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA or Superfund). This public law (also known as SARA) directed the Agency for Toxic Substances and Disease Registry (ATSDR) to prepare toxicological profiles for hazardous substances which- are most commonly found at facilities on the CERCLA National Priorities List and which pose the most significant potential threat to human health, as determined by ATSDR and the Environmental Protection Agency (EPA). The list of che 100 most significant hazardous substances was published in the Federal Register on April 17, 1987. Section 110 (3) of SARA directs the Administrator of ATSDR to prepare a toxicological profile for each substance on the list. Each profile must include the following content: n(A) An. examination, summary, and interpretation of available toxicological information and epidemiologic evaluations on the hazardous substance in order to ascertain the levels of significant human exposure for the substance and the associated acute, subacute, and chronic health effects, (B) A determination of whether adequate information on the health effects of each substance is available or in the process of development to determine levels of exposure which present a significant risk to human health of acute, subacute, and chronic health effects, and (C) Where appropriate, an identification of toxicological testing needed to identify the types or levels of exposure that may present significant risk of adverse health effects in humans." This toxicological profile is prepared in accordance with guidelines developed by ATSDR and EPA. The guidelines were published in the Federal Register on April 17, 1987. Each profile will be revised and republished as necessary, but no less often than every three years, as . required by SARA. The ATSDR toxicological profile is intended to characterize succinctly the toxicological and health effects information for the hazardous substance being described. Each profile identifies and reviews the key literature that describes a hazardous substance's toxicological properties. Other literature is presented but described in less detail than the key studies. The profile is not intended to be an exhaustive document; however, more comprehensive sources of specialty information are referenced. iii ' l- .) Each toxicological profile begins with a public health statement, which describes in nontechnical language a substance's relevant toxicological properties. Following the statement is material that presents levels of significant human exposure and, where known, significant health effects. The adequacy of information to determine a substance's health effects is described in a health effects summary. Research gaps in toxicologic and health effects information are described in the profile. Research gaps that are of significance to protection of public health will be identified by ATSDR, the National Toxicology Program of the Public Health Service, and EPA. The focus of the profiles is on health and toxicological information; therefore, we have included this information in the front of the document. The principal audiences for the toxicological profiles are health professionals at the federal, state, and local levels, interested private sector organizations and groups, and members of the public. We plan to revise these documents in response to public comments and as additional data become available; therefore, we encourage comment that will make the toxicological profile series of the greatest use. ! This profile reflects our assessment of all relevant toxicological testing and information that has been peer reviewed. It has been reviewed by scientists from ATSDR, EPA, the Centers for Disease Control, and the National Toxicology Program. It has also been reviewed by a panel of nongovernment .peer reviewers and was made available for public review. Final responsibility for the contents and views expressed in this toxicological profile resides with ATSDR. ( 0' James 0. Mason, M.D., Dr. P.H. Assistant Surgeon General Administrator, ATSDR iv o ~i \ ^ L IS T OF FIGURES 1.1 Health effects from breathing PCBs .......................... 1.2 Health effects from ingesting FCBs .......................... 1.3 Health effects from skin contact with FCBs ........... :...... 2.1 Effects of FCBs--inhalation exposure ........................ 2.2 Effects of FCBs--oral exposure .............................. 2.3 Effects of FCBs--dermal exposure ............................ 2.4 Levels of significant exposure for PCBs-inhalation .................................................. 2.5 Levels of significant exposure for PCBs-oral ...................................... ................. 2.6 Levels of significant exposure for PCBs-dermal ...................................................... 2.7 Adequacy of the database on health effects of FCBs (human data) ................................................ 2.8 Adequacy of the database on health effects of FCBs (animal data) ............................................... 4 5 6 9 10 11 12 13 14 30 31 v v ii L IS T OF TABLES 2.1 PCB levels in blood of exposed workers (Aroclors 1016, 1242, 1248) ............................ 2.2 PCB blood levels (Aroclor 1254) and duration of exposure 2.3 Serum PCB concentrations in U.S. populations with out occupational exposure to PCBs and in subpopulations consuming fish from PCB-contaminated waters ............ 2.4 Serum PCB concentrations in populations with occupational exposure ........................................... 3.1 Chemical identity of the Aroclors ...................... 3.2 Physical and chemical properties of PCBs ............... 3.3 ^Approximate molecular composition of PCBs ..!........... 4.1 Acute oral LD^q S Aroclors ........................... 4.2 -Acute dermal LD^q values of Aroclors in rabbits ........ 4.3 Genotoxicity of PCBs in vitro ........................ 4.4 Genotoxicity of PCBs in vivo ........................... 7.1 Aroclor residues in raw domestic agricultural commodities for fiscal years 1970-1976 ............................. 7.2 Estimated dietary intake of PCBs for adults, infants, and toddlers (^g/kg/day) ................................... 8.1 Analytical methods for environmental media ............. 8.2 Analytical methods for biological samples .............. 21 23 24 26 37 38 40 51 53 67 68 84 86 90 91 \ ix 1. PUBLIC HEALTH STATEMENT L.l WHAT ARE PCBs7 The abbreviation PCB refers to polychlorinated biphenyls. PCBs are a family of man-made chemicals that contain 209 individual compounds. Because of their insulating and nonflammable properties, they have been used widely as coolants and lubricants in transformers, capacitors, and other electrical equipment. The industrial manufacture of PCBs was stopped in the United States in October 1977 because it had been discovered that PCBs would accumulate and persist in the environment and could cause toxic effects. Some commercial PCB mixtures are known in the United States by their industrial trade name, Aroclor. 1.2 HOW MIGHT I BE EXPOSED TO PCBs? Although PCBs are no longer manufactured, human exposure to these compounds is still occurring. Many of the transformers and capacitors that were filled with fluids containing PCBs when they were made still contain PCBs and are still in service. The useful lifetime of many of these transformers can be 30 years or more. The two main sources of human exposure to PCBs are environmental and occupational. PCBs are very persistent chemicals that are widely distributed throughout the entire environment. Background levels of PCBs can be found in the outdoor air we breathe, on soil surfaces, and in water. Consumption of contaminated fish is a major source of PCB exposure to humans. Fish become contaminated with PCBs by exposure in water, which results in a very high accumulation of PCBs in the fish tissue. Most of the PCBs in the outdoor air we breathe may be present because of an environmental cycling process. Compared with the intake of PCBs through consumption of contaminated fish, exposure to PCBs as a result of breathing air containing PCBs is negligible. PCBs in water, or on soil surfaces, evaporate into the air and are then returned to earth by rainfall or settling of dust particles containing PCBs. Reevaporation repeats the cycle. Once in the air, PCBs can be carried long distances; PCBs have been found in snow and seawater in the Antarctic. PCBs can be released into the environment from the following sources; Poorly maintained toxic waste sites which contain PCBs Illegal or improper dumping of PCB wastes, such as transformer fluids Leaks or fugitive emissions from electrical transformers containing PCBs * r t 2 Some consumer produces that may contain PCBs are: Fluorescent lighting fixtures made before PCB use waTs stopped Electrical devices or appliances containing PCB capacitors made before PCB use was stopped Occupational exposure to PCBs can occur during: Repair or maintenance of PCB transformers Accidents or spills involving PCB transformers Disposal of PCB materials Contact at hazardous waste sites 1.3 HOW DO PCBs GET INTO MY BODY? PCBs can enter the body when food containing PCBs is eaten, when air that contains PCBs is breathed, or when skin comes in contact with PCBs. Most exposure of the general population is by consumption of fish* and shellfish from PCB-contaminated water. Exposure from drinking water, is minimal. Infants can be exposed to PCBs from breastfeeding if the mothers have PCBs in their breast milk. 1.4 HOW DO PCBs AFFECT MY HEALTH? Occasional skin irritations, usually acnelike lesions and rashes, and liver effects are the only significant adverse health effects that have been observed in PCB-exposed workers. Workers experience PCB exposures that are much higher than those received by the general public. Adverse health effects have not been observed in people in the United States with nonoccupational exposure. Effects of PCBs in experimentally exposed animals include liver damage, skin irritations, death, low birth weights and other reproductive effects, and cancer. 1.5 IS THERE A MEDICAL TEST TO DETERMINE IF I HAVE BEEN EXPOSED TO PCBs? PCBs can be detected in the blood, body fat, and breast milk. Blood PCB levels are the best indicator of recent exposure to PCBs, and levels in the fat are the best indicators of long-term exposure. These tests are not routine clinical tests, but they could be used to detect PCBs in members of the general population as well as workers with occupational exposure to PCBs. Although these tests indicate if there has been exposure to PCBs, they cannot be used to predict potential health effects. x 1.6 WHAT LEVELS OF EXPOSURE HAVE RESULTED IN HARMFUL HEALTH EFFECTS? The graphs on the following pages show the relationship between exposure to PCBs and known health effects for the PCBs that are covered by this profile. Other PCBs may have different toxic properties. In Che first sec of graphs, labeled "Health effects from breathing PCBs," I ' r\ I f- 3 exposure is measured in milligrams, of FCBs per cubic meter of air (mg/m^). In all graphs, effects in animals are shown on the left side, effects in humans on the right. In the second set of graphs, the same relationship is represented for the known "Health effects from ingestion of or skin contact with products containing FCBs." Exposures are measured in milligrams of FCBs per kilogram of body weight per day (mg/kg/day). Figures 1.1, 1.2, and 1.3 show the relationship between exposure to FCBs and known health effects. The scales represent exposure levels. The first column on the graphs, labeled "Short-Term," refers to known health effects from exposure to FCBs for 2 weeks or less. The columns labeled "Long-Term" refer to PCB exposures of longer than 2 weeks. The level marked on Fig. 1.1 as the TLV (threshold limit value) is an average level recommended as a limit for workers over an 8-hour workshift and 40-hour workweek. The levels marked on the graphs as anticipated to be associated with minimal risk of developing health effects are based on information generated from animal studies; therefore, some uncertainty still exists. Based on information that FCBs cause cancer, in animals, the Environmental Protection Agency (EPA) considers PCBs to be probable cancer-causing chemicals in humans and has estimated that ingestion of 1 microgram of PCB per kilogram per day for a lifetime would result in 770 additional cases of cancer, in a population of 10,000 people and 770,000 additional cases of cancer in a population of 10,000,000 people. It should be noted that these risk values are plausible upper-limit estimates. Actual risk levels are unlikely to be higher and may be lower. 1.7 WHAT RECOMMENDATIONS HAS THE FEDERAL GOVERNMENT MADE TO PROTECT HUMAN HEALTH? The government has made recommendations to limit exposure to FCBs in the workplace and exposure of the general public to PCBs in drinking water and food. The National Institute for Occupational Safety and Health (NIOSH) recommends an occupational exposure limit for all FCBs of 0.001 milligram of FCBs per cubic meter of air (mg/ra^) for a 10-hour, workday, 40-hour workweek. The American Conference of Governmental Industrial Hygienists (ACGIH) recommends limits of 0.5-2 rag/m^ for occupational exposures to specific FCBs (see Fig. 1.1). EPA recommends that levels in drinking water of 0.0035 milligram PCB 1016 per liter of water (mg/L) for adults and 0.001 mg/L PCB 1016 for children are probably safe. These health advisories are for a specific PCB (1016) because other FCBs have not been detected in drinking water; an exposure period of approximately 7 years is assumed. With respect to cancer, however, it is assumed that "any exposure involves some risk" in the absence of information to the contrary. The Food and Drug Administration (FDA) specifies PCB concentration limits of 0.2 to 3 parts per million (milligrams PCB per kilogram of food) in foods such as infant foods, eggs, milk (in milk fat), and poultry (fat). i. $ < 4 SHORT-TERM EXPOSURE (LESS THAN OR EQUAL TO 14 DAYS) EFFECTS IN ANIMALS CONC. IN AIR (mg/m3) EFFECTS IN HUMANS QUANTITATIVE DATA WERE NOT AVAILABLE QUANTITATIVE DATA WERE NOT AVAILABLE LONG-TERM EXPOSURE (GREATER THAN 14 DAYS) EFFECTS IN ANIMALS CONC. IN AIR (mg/m3) EFFECTS IN HUMANS 10 8 SKIN IRRITATIONS AND UVER EFFECTS - 2 LIVER DAMAGE-------- 0 Fig. 1.1. Health effects from breathing PCBs. RANGE OF TLVs FOR SPECIFIC PCBs r , f Si 5 SHORT-TERM EXPOSURE (LESS THAN OR EQUAL TO 14 DAYS) EFFECTS IN ANIMALS DOSE (mg/kg/day) EFFECTS IN HUMANS nPATH ... 750 I ? 1 15 f QUANTiTATIVE DATAWERE NOT AVAILABLE EFFECTS ON ^ UNBORN LONG-TERM EXPOSURE (GREATER THAN 14 DAYS) EFFECTS IN ANIMALS DOSE (mg/kg/day) EFFECTS IN HUMANS LIVER AND SKIN _ 0.1 DAMAGE. DEATH * 0.09 QUANTITATIVE DATA WERE NOT AVAILABLE 0.08 0.07 0.06 EFFECTS ON UNBORN AND 0.8 NEWBORN 0.05 0.6 0.04 0.4 LIVER DAMAGE 0.2 ( 0.002 ______MINIMAL RISK FOR EFFECTS OTHER THAN 0.001 CANCER 0.03 0.02 0.01 MINIMAL RISK FOR EFFECTS OTHER THAN 0.0001 ___ CANCER Fig. 1.2. Health effects from ingesting PCBs. SHORT-TERM EXPOSURE (LESS THAN OR EQUAL TO 14 DAYS) EFFECTS IN ANIMALS DOSE (mg/kg/day) EFFECTS IN HUMANS 1400 DEATH__________ 1200 QUANTITATIVE DATAWERE NOT AVAILABLE 1000 eoo LONG-TERM EXPOSURE (GREATER THAN 14 DAYS) EFFECTS IN ANIMALS DOSE (mg/kgftJay) EFFECTS IN HUMANS 1400 HEALTH EFFECTS FROM SKIN CON TACT INCLUDE SKIN IRRITATION AND LIVER 1200 EFFECTS. BUT DOSES ARE NOT KNOWN 1000 600 600 600 400 400 200 200 LIVER AND KIDNEY DAMAGE_____ 00 Fig. 13. Health effects from skin contact with PCBs. \ 2 . HEALTH EFFECTS SUMMARY 2.1 INTRODUCTION This seccion summarizes and graphs data on the health effects concerning exposure to FCBs. The purpose of this section is to present levels of significant exposure for PCBs based on key toxicological studies, epidemiological investigations, and environmental exposure data. The information presented in this section is critically evaluated and discussed in Sect. 4, Toxicological Data, and Sect. 7, Potential for Human Exposure. This Health Effects Summary section comprises two major parts. Levels of Significant Exposure (Sect. 2.2) presents brief narratives and graphics for key studies in a manner that provides public health officials, physicians, and other interested individuals and groups with (1) an overall perspective of the toxicology of PCBs and (2) a summarized depiction of significant exposure levels associated with various adverse health effects. This section also includes information on the levels of PCBs that have been monitored in human fluids and tissues and information about levels of PCBs found in environmental media and their association with human exposures. The significance of the exposure levels shown on the graph may differ depending on the user's perspective. For example, physicians concerned with the interpretation of overt clinical findings in exposed persons or with the identification of persons with the potential to develop such disease may be interested in levels of exposure associated with frank effects (Frank Effect Level, FEL). Public health officials and project managers concerned with response actions at Superfund sices may want information on levels of exposure associated with more subtle effects in humans or animals (Lowest-Observed-Adverse-Effect Level, LOAEL) or exposure levels below which no adverse effects (No-ObservedAdverse-Effect Level, NOAEL) have been observed. Estimates of levels posing minimal risk to humans (Minimal Risk Levels) are of interest to health professionals and citizens alike. Adequacy of Database (Sect. 2.3) highlights the availability of key studies on exposure to PCBs in the scientific literature and displays these data in three-dimensional graphs consistent with the format in Sect. 2.2. The purpose of this section is to suggest where there might be insufficient information to establish levels of significant human exposure. These areas will be considered by the Agency for Toxic Substances and Disease Registry (ATSDR), EPA, and the National Toxicology Program (NTP) of the U.S. Public Health Service in order to develop a research agenda to provide this information. 2 . 2 LEVELS OF SIGNIFICANT EXPOSURE To help public health professionals address the needs of persons living or working near hazardous waste sites, the toxicology data summarized in this section are organized first by route of exposure-inhalation, ingestion, and dermal--and then by toxicological end points that are categorized into six general areas--lethality, systemic/target organ toxicity, developmental toxicity, reproductive toxicity, genetic toxicity, and carcinogenicity. The data are discussed in terms of three exposure periods--acute, intermediate, and chronic. Two kinds of graphs are used to depict the data. The first type is a "thermometer" graph. It provides a graphical summary of the human and animal toxicological end points (and levels of exposure) for each exposure route for which data are available. The ordering of effects does not reflect the exposure duration or species of animal tested. The second kind of graph shows Levels of Significant Exposure (LSE) for each route and exposure duration. The points on the graph showing NOAELs and LOAELs reflect the actual doses (levels of exposure) used in the key studies. No adjustments for exposure duration or intermittent exposure protocol were made. Adjustments reflecting the uncertainty of extrapolating animal data to man, intraspecies variations, and differences between .experimental vs actual human exposure conditions were considered when estimates of levels posing minimal risk to human health were made for noncancer end points. These minimal risk levels were derived for the most sensitive noncancer end point for each exposure duration by applying uncertainty factors. These levels are shown on the graphs as a broken line starting from the actual dose (level of exposure) and ending with a concavecurved line at its terminus. Although methods have been established to derive these minimal risk levels (Barnes et al. 1987), shortcomings exist in the techniques that reduce the confidence in the projected estimates. Also shown on the graphs under the cancer end point are lowlevel risks (10"^ to 10-7) reported by EPA. In addition, the actual dose (level of exposure) associated with the tumor incidence is plotted. 2.2.1 Key Studies and Graphical Presentations Dose-response-duration data for the toxicity and carcinogenicity of the PCBs discussed in this profile are displayed in two types of graphs. These data are derived from the key studies described in the fpllowing sections. The "thermometer" graphs in Figs. 2.1, 2.2, and 2.3 plot exposure levels vs NOAELs and LOAELs for various effects and durations of Inhalation, oral, and dermal exposures, respectively. The graphs of levels of significant exposure in Figs. 2.4, 2.5, and 2.6 plot end point-specific NOAELs, LOAELs, and/or minimal levels of risk for acute (14 days), intermediate (15-364 days), and chronic (>365 days) durations for inhalation, oral, and dermal exposures, respectively. Dermal exposure contributes significantly to occupational exposure, but the relative contributions of dermal and inhalation exposure in occupational settings has not been discerned (Wolff 1985). Furthermore, occupational exposure levels are expressed as concentrations of PCBs in air, making it difficult to quantitate dermal exposure doses. For this ANIMALS (mg/m3) O RAT.MOUSE. RABBIT, GUINEA PIG, CAT, NO DEATHS, 24 OAYS. INTERMITTENT RAT, MOUSE. RABBIT, GUINEA PIG, CAT. LIVER TOXICITY. 213 OAYS. INTERMITTENT 0.1 HUMANS (rog/m1) CHLORACNE * AND LIVER EFFECTS 0.1 _ 0.01 001 LOAEL O NOAEL Fig. 2.1. Effects of PCBs-- inhalation exposure. \ ANIMALS (mgAg/day) 1000 RAT. LOsq, SINGLE DOSE MINK. LD50. SINGLE DOSE O MOUSE. DEVELOPMENTAL TOXICITY, 1 DOSE MOUSE. DEATH, 14 DAYS. CONTINUOUS 100 O MOUSE, DEATH, 14 DAYS. CONTINUOUS RABBIT, DEVELOPMENTAL TOXICITY. 28 DAYS. CONTINUOUS 10 -- O RABBIT, DEVELOPMENTAL TOXICITY. 28 DAYS. CONTINUOUS MINK. DIETARY IT 50.2B DAYS. CONTINUOUS HUMANS QUANTITATIVE DATA WERE NOT AVAILABLE RAT, DEVELOPMENTAL TOXICITY. 21 DAYS. CONTINUOUS MINK, DIETARY LD50. 9 MONTHS. CONTINUOUS; RAT. DECREASED LONGEVITY. 104 WEEKS, CONTINUOUS 1 _ RAJ, REPRODUCTIVE TOXICITY. 1-2 GENERATIONS. CONTINUOUS RAT. UVER TOXICITY. 4 DAYS. CONTINUOUS; MINK. REPRODUCTIVE TOXICITY. 170 DAYS. CONTINUOUS RAT. UVER TOXICITY. 2 -6 MONTHS. CONTINUOUS O RAT. UVER TOXICITY. 4 DAYS, CONTINUOUS: RAT, REPRODUCTIVE TOXICITY. 1-2 GENERATIONS, CONTINUOUS 0.1 -- MONKEY. UVER AND SKIN TOXICITY. 173 DAYS, CONTINUOUS MONKEY. DEVELOPMENTAL TOXICITY, 87 WEEKS. CONTINUOUS O RAT. UVER TOXICITY. 4 WEEKS. CONTINUOUS 0,01 l-- 0 MONKEY. DEVELOPMENTAL TOXICITY. 87 WEEKS. CONTINUOUS LOAEL O NOAEL Fig. 2.2. Effects of PCBs--oral exposure. ANIMALS (m g/kg/day) 0,000 1.000 RABBIT, LDjo. SINGLE DOSE HUMANS OCCUPATIONAL EXPOSURE IS ASSOCIATED WITH UVER EFFECTS AND CHLORACNE, BUT DERMAL DOSES ARE NOTAVAILABLE 100 -- RABBIT, UVER. KIDNEY. ANDSKINTOXICITY. 38 DAYS. INTERMITTENT 10 *-- LOAEL Fig. 2*3. Effects of PCBs--dermal exposure. 12 Q ACUTE (S14 DAYS) INTERMEDIATE (15-364 DAYS) CHRONIC 365 DAYS) (mg/m3) DECREASED LONGEVITY TARGET ORGAN TARGET ORGAN 10 r QUANTITATIVE DATA WERE NOT O g . h . m . r . c AVAILABLE (AROCLOR 1242) O g.h,m,r,c (LIVER) (AROCLOR 1242) (LIVER AND SKIN) (AROCLORS 1242 AND 1254) g. h,m, r,c(LIVER) (AROCLOR 1254) 0.1 A 0.01 > - LOAEL INANIMALS O NOAEL INANIMALS IRANGE OF EFFECT FOR HUMANS * g GUINEA PIG h RABBIT m MOUSE r RAT c CAT Fig. 2.4. Levels of significant exposure for PCBs--inhalation exposure. o ? < r> 13 ACUTE (S 14 DAYS) INTERM EDIATE' (1 9 -4 6 4 OAYS) c h r o n ic (2365 OAYS) DEVELOPLETHALITY M ENTAL TARGET DECREASED ORGAN LONGEVITY TARGET REPROORGAN DUCTlON DEVELOP- DECREASED MENTAL L O N G E V IT Y (m gfogtfiy) 1000 r 9* rn((AARROOCCLLOORR11229241)) 100 - O D I (AROCLOR 1254) *111 (A RO CLO R 1254) ' CANCER 10 0.1 0.01 >II (A R O C L O R 1 2 5 4 ) i f (A RO CLO R 1254) *f (LIVER) n (AROCLOR 1254) IA R C C L O R 1254) r (LIVER) r (A RO CLO R 1254) p n (AROCLOR 1254) If (AROCLOR 1254) Mt (LIVER) (ARO CLO R 1248) (A R O C L O R S 12*2, 1 2 4 8 ,1 2 3 4 ,1 2 6 0 ) Mi (A R O C L O R 1 0 1 6 ) M (AROCLOR 1260) 0.001 0.0001 0.00001 0.000001 0.0000001 IO"4 - , IO-5 - e s t im a t e d HUMAN CANCER RISK LEVELS IO-6 - 0.00000001 *- 1 M NIM AL RISK LEVEL I POR EFFECTS OTHER vL THAN CANCER I MINIMAL R IS K LEV EL ! EXTRAPOLATED FROM IN T ER M ED IA T E EX PO SU R E DATA t RAT n MNK m MOUSE k MONKEY n RABBIT LOAEL ONOAEL \<r7- i LOAELAND NOAEUN SAME SPE C IES Fig. 2J5. Levels or significant exposure for PCBs--oral. ACUTE (<;14 DAYS) LETHALITY . (mg/kg/day) 10,000 f-- INTERMEDIATE (15-364 DAYS) TARGET ORGAN CHRONIC 365 DAYS) QUANTITATIVE DATA WERE NOT AVAILABLE 1,000 h(AROCLOR 1221) 100 h(LIVER, KIDNEY. SKIN) (AROCLOR 1260) 10 *-- LOAEL\ h RABBIT Fig. 2.6. Levels of significant exposure for PCBs--dermal exposure. 15 reason, effects of occupational exposure are discussed under inhalation exposure and plotted in Figs. 2.1 and 2.4 (graphs for inhalation exposure). 2.2.1.1 Inhalation exposure Lethality and decreased longevity. Data regarding inhalation exposure levels that produce death in humans were not available. Exposure to near saturation vapor concentrations of heated Aroclor 1242 (8.6 mg/m^) 7 h/day, 5 days/veek for 24 days was not lethal for cats, rats, mice, rabbits, or guinea pigs (Treon et al. 1956). This concentration represents a NOAEL for lethality for intermediate inhalation exposures (see Figs. 2.1 and 2.4). No data were available regarding lethality/decreased longevity of animals due to acute or chronic inhalation exposure to PCBs. Target organ/systemic toxicity. Oral toxicity studies have established that the liver and cutaneous tissues are primary target organs of PCBs. Occupational exposure to PCBs has been associated with alterations in serum levels of liver enzymes and dermatological effects such as chloracne (Meigs et al. 1954; Ouw et al. 1976; Fischbein et al. 1979, 1982; Baker et al. 1980; Smith et al. 1981a,b,c). Although monitoring data were reported in some of the studies, exposure levels were not adequately characterized. Furthermore, although inhalation exposure is considered a major route of exposure, the contribution of dermal exposure to total occupational exposure is also significant. Fischbein et al. (1979) reported that occupational 8-h time-weighted average (TWA) concentrations of Aroclor 1242 and 1254 ranged from 0.07 to 11.0 mg/nH in workers who had increased SGOT levels and skin effects; the range is plotted on Figs. 2.1 and 2.4. In the only animal inhalation study of PCBs, degenerative liver lesions, a frank effect, occurred in cats, rats, mice, rabbits, and guinea pigs that were exposed to 1.5 mg/nH Aroclor 1254 vapor for 7 h/day, 5 days/week for 213 days (Treon et al. 1956). This FEL is plotted on Figs. 2.1 and 2.4. Histologic effects were not produced in those species exposed to Aroclor 1242 (1.9 rag/m^ 7 h/day, 5 days/week for 214 days, 8.6 rag/m^ 7 h/day, 5 days/week for 24 days). The higher NOAEL of 8.6 mg/m^ for intermediate-duration inhalation exposure is plotted on Fig. 2.4. Since the FEL for Aroclor 1254 is lower than the NOAEL for Aroclor 1242, a minimal risk level cannot be derived. Developmental toxicity. Pertinent data regarding developmental effects of PCBs via inhalation exposure in animals were not located in the available literature. Slightly lowered mean birth weight and gestational age was observed in infants b o m to mothers with occupational exposure (dermal and inhalation) to PCBs, but monitoring data were not reported (Taylor et al.1984). Reproductive toxicity. Pertinent data regarding reproductive effects of PCBs via inhalation exposure in humans or animals were not located. - -M 16 Genotoxicity. The PCBs have produced generally negative results in in vivo and in vitro genotoxicity assays (Sect. 4.3.5 on genotoxicity in toxicological data section). Carcinogenicity. An increased incidence of malignant melanomas was reported in a group of workers exposed occupationally (considered inhalation, although dermal exposure is also considered to be likely) to Aroclor 1254 (Bahn et al. 1976). These and other data provide inadequate evidence of carcinogenicity in humans (Sect. 4.3.6 on carcinogenicity in toxicological data section). Data regarding the carcinogenicity of inhaled PCBs in animals were not available. 2.2.1.2 Oral exposure Lethality and decreased longevity. Data regarding oral exposure levels that produce death in humans were not available. Single-dose oral LD50S for PCBs have been reported for rats and mink. The lowest values are 750 mg/kg for Aroclor 1221 in mink (Aulerich and Ringer 1977) and 1010 mg/kg for Aroclor 1254 in rats (Garthoff et al. 1981). These FELs are plotted on Figs. 2.2 and 2.5 for lethality due to acute oral exposure. In mice fed diets containing 1000 ppm Aroclor 1254 for 14 days, 3 of 5 died by day 15 (Sanders ct al. 1974). No mice fed diets containing 250 ppm Aroclor 1254 for 14 days died. Thus, 250 ppm is a NOAEL, and 1000 ppm is a FEL for lethality in mice for short-term oral exposure. Assuming that a mouse consumes a daily amount of food equal to 13% of its body weight (EPA 1986a), the NOAEL is equivalent to 32.5 mg/kg/day, and the FEL is equivalent to 130 mg/kg/day. These levels are plotted on Figs. 2.2 and 2.5 for lethality for acute oral exposure. Homshaw et al. (1986) determined LC5 0 S of Aroclor 1254 for dietary exposure in mink to be 79-84 ppm for 28 days and 47-49 ppm for 28 days followed by a 7-day withdrawal period. In mink fed Aroclor 1254 for 9 months, the LC50 was 6.65 ppm (Ringer et al. 1981). Assuming that mink consume 150 g of feed per day and weigh 800 g (Bleavins et al. 1980), 47 ppm is equivalent to an LD50 of 8.8 mg/kg/day (see Fig. 2.2), and 6,65 ppm is equivalent to an LD50 of 1.25 mg/kg/day. This FEL is plotted on Figs. 2.2 and 2.5 for intermediate exposure. Reduced survival occurred in rats fed diets containing >25 ppm Aroclor 1254 for 104 weeks (NCI 1978). Assuming that rats consume the equivalent of 5% of their body weight per day in food (EPA 1986a), then 1.25 mg/kg/day represents a FEL for chronic oral exposure in rats (see Figs. 2.2 and 2.5). NOAELs for increased mortality were not identified in these studies. Target organ/systemlc toxicity. The liver and cutaneous tissues are primary targets of PCB toxicity in orally exposed animals. Increased relative liver weight hccurred in rats fed diets containing >8 ppm but not 4 ppm Aroclor 1254 for 4 days (Carter 1985). The 4- and 8-ppra levels, which correspond to 0.2 and 0.4 mg/kg/day, respectively, if rat food consumption is assumed to be 5% of body weight per day, represent a NOAEL and LOAEL for acute oral exposure (see Figs. 2.2 and 2.5). The NOAEL is the basis for the minimal risk level for o acute oral exposure (see Fig. 2.5). 7; ; 17 In Intermediate-duration studies, hepatic microsomal enzyme activities were Increased in rats treated with <iiet concentrations of 0.5, 5, or 50 ppm Aroclors 1242, 1248, 1254, or 1260 for 4 weeks (Litterst et al. 1972). Dietary exposure to 5 ppm Aroclor 1242 for 2 to 6 months produced increased liver lipid content in rats (Bruckner et al. 1974) and >20 ppm Aroclor 1254, or 1260 for 28 days (Ghu et al. 1977) or 8 months (Kimbrough et al. 1972) produced frank degenerative liver , alterations in rats. Dietary concentrations of 0.5 ppm Aroclors 1242', 1248, 1254, and 1260 and 5 ppm Aroclor 1242, therefore, represent the highest NOAEL and lowest LOAEL, respectively, for intermediate-duration hepatic effects in rats. Asstiming that rats consume 5% of their body weight in food per day, the NOAEL and LOAEL provided 0.025 and 0.25 mg/kg/day, respectively (see Figs. 2.2 and 2,5). Two monkeys Chat died from dietary exposure to 2.5 or 5.0 ppm Aroclor 1248 for 173 or 310 days, respectively, had frank liver lesions (Barsotti et al. 1976). Although this study is limited by the number of animals, other studies with monkeys corroborate these FELs, as chloracne and gastric lesions were also associated with intermediate-duration exposure to 2.5 or 5.0 ppm Aroclor 1248 (Barsotti and Allen 1975, Barsotti et al. 1976, Thomas and Hinsdill 1978). The lowest monkey FEL (2.5 ppm) is equivalent to 0.105 mg/kg/day (see Figs. 2.2 and 2.5) if it is assumed that monkey food consumption is 4.2% of body weight per day (EPA 1986a). Chronic feeding studies with rats (NCI 1978; Morgan et al. 1981, Ward 1985, Norback and Weltman 1985, Kimbrough et al. 1975), conducted at concentrations (>20 ppm) that were higher than the lowest FELs in the intermediate-duration monkey studies, did not produce non-preneoplastic or nonproliferative liver lesions. Chronic (12 to 16 month) feeding studies were conducted with 2.5 and 5.0 ppm Aroclor 1248 in monkeys (Barsotti and Allen 1975, Barsotti et al. 1976), but skin lesions and other effects (as indicated above and in subsequent sections) occurred after several months of exposure. Therefore, it is inappropriate to identify effect levels for systemic effects resulting from chronic oral exposure because of the types of liver lesions (preneoplastic) in rats and the short latency for cutaneous and other effects in monkeys. Developmental toxicity. Slightly decreased birth weight, head circumference, and gestational age were observed in newborns of mothers who were consumers of PCB-contaminated fish, but the effects were not associated with specific levels of intake (Fein 1984, Fein et al. 1984). Rogan et al. (1986) found that levels >3.5 ppm PCBs in milk fat were significantly correlated with decreased muscle tone, decreased activity, and abnormal reflexes in human infants. Jacobson et al. (1985) found that consumption of PCB-contaminated fish by mothers and serum cord levels of PCBs were predictors of poor visual recognition memory and fixation to novelty in infants. The doses of PCBs consumed by the mothers cannot be determined in these studies. Collins and Capen (1980a) fed diets containing Aroclor 1254 at 0, 50, or 500 ppm to female rats during gestation and lactation. Significantly (P < 0.001) reduced litter size occurred at 500 ppm. At 3 both 50 and 500 ppm, the neonates and weanlings had ultrastructural ? 18 lesions in the thyroid follicular cells and reduced serum levels of thyroid hormone. Thus, 50 ppm is the LOAEL for fetotoxicity due to oral exposure in rats. Assuming that a rat consumes a daily amount of food equal to 5% of its body weight (EPA 1986a), 50 ppm is equivalent*to 2.5 mg/kg/day. The LOAEL is indicated on Figs. 2.2 and 2.5 for developmental toxicity in rats. Gestational exposure to Aroclor 1254 by gavage produced fetotoxic effects in rabbits exposed on days 1-28 at doses >12.5 mg/kg/day but not <10 mg/kg/day (Villeneuve et al. 1971). The dose of 10 mg/kg/day, therefore, represents a NOAEL for developmental effects in rabbits (see Figs. 2.2 and 2.5, acute exposure). The dose of 12.5 mg/kg/day represents a FEL for developmental effects in rabbits because it produced fetal deaths. Haake et al. (1987) reported that treatment of pregnant C573L/6 mice with Aroclor 1254 by gavage at 244 mg/kg on day 9 of gestation did not result in any fetuses with cleft palate. This dose is plotted on Figs. 2.2 and 2.5 as a NOAEL for developmental toxicity in mice. Monkeys that were fed diets containing 1.0 ppm of Aroclor 1016 for approximately 7 months prior to mating and during pregnancy delivered infants with reduced birth weights, but this effect did not occur at 0.25 ppm (Barsotti and Van Miller 1984). Assuming that a monkey consumes a daily amount of food equal to 4.2% of its body weight, the daily dosages in the 1.0 ppm (LOAEL) and 0.25 ppm (NOAEL) groups were 0.04 and 0.0105 mg/kg/day, respectively. The NOAEL serves as the basis for the minimal risk level for intermediate and chronic oral exposure as derived by EPA (1987a). Fetal mortality, a frank effect, occurred at >2.5-ppm (0.1-mg/kg/day) dietary concentrations of Aroclor 1248 in other studies .with monkeys (Allen and Barsotti 1976; Allen et al. 1979, 1980). Reproductive toxicity. There are no studies regarding reproductive effects of PCBs in humans. Diets that provided >2 ppm of Aroclor 1254 for 4 months prior to macing and during gestation were lethal to fetuses and .caused reproductive failure in mink (Aulerich and Ringer 1977, Bleavins etal. 1980). Assuming that mink consume 150 g of feed per day and weigh 800 g (Bleavins et al. 1980), then the 2-ppm FEL provided 0.38 mg/kg/day (see Figs. 2.2 and 2.5). Reduced litter sizes occurred at Aroclor 1254 dietary concentrations of >20 ppm but not <5 ppm in one- and two-generation reproduction studies with rats (Linder et al. 1974). The dietary concentrations of 5 ppm (NOAEL) and 20 ppm (FEL) provided 0.25 and 1 mg/kg/day, respectively, if rat food consumption is assumed to be 5% of body weight per day (EPA 1986a). These levels are plotted on Figs. 2.2 and 2.5 for reproductive effects of intermediate oral exposure in rats. Genotoxicity. The PCBs have produced generally negative results in in vivo and in vitro genotoxicity tests (Sect. 4.3.5 on genotoxicity in toxicological data section). Carcinogenicity. EPA (1987a) used the Norback and Veltman (1985) study as the basis for a quantitative carcinogenicity risk assessment for PCBs. The dietary level of 100 ppm Aroclor 1260 was converted to an intake of 5 mg/kg/day by assuming that a rat consumes food equal to 5% of its body weight per day. This dosage was converted to a TWA dosage of \ 19 3.45 mg/kg/day (see Fig. 2.5) to reflect the fact that rats received 100 ppm for 16 months, 50 ppm for 8 months, and 0 ppm for the last 5 months. The rat dosage was converted to an equivalent human dose of 0.59 m g / k g / d a y on the basis of relative body surface areas. Incidences of trabecular carcinomas, adenocarcinomas, and neoplastic nodules in the liver were combined to produce total incidences of 45/47 in treated females and 1/49 in controls. Using these data, EPA (1987a) calculated a human q.* of 7.7 ( m g / k g / d a y ) D o s a g e s corresponding to risk levels of 10"\ 10"^, 10", and 10"^ are 1.3 x 10'^, 1.3 x 10"" , 1.3 x 10"^, and 1.3 x 10' mg/kg/day, respectively. The 10"^ to 10" risk levels are indicated on Fig. 2.5. 2.2.1.3 Dermal Occupational exposure to PCBs is considered to be by the inhalation route in this profile, since air levels are commonly monitored in the workplace setting. It is clear, however, that under occupational conditions dermal exposure would also occur. This was recognized by ACGIH (1986) when a skin notation was placed with the TLV. Dermal adsorption and exposure can occur from contact of the skin with the vapors of PCB as well as actual dermal contact with the compound or with contact with dust or surfaces to which the PCBs are absorbed. Although it is realized that dermal exposure may be a major route of exposure in the occupational setting, quantitation of the relative contribution to body burden of absorbed PCBs from the inhalation and dermal routes is not possible. Lethality and decreased longevity. Human data are not- available. Median lethal doses for single dermal applications of PCBs to rabbits ranged from >1269 mg/kg for Aroclors 1242 and 1248 to <3169 mg/kg for Aroclor 1221 (Fishbein 1974). As only ranges of median lethal doses were reported, the lowest dose (1269 mg/kg) is indicated on Figs. 2.3 and 2.6. Systemic target organ toxicity. Occupational exposure to PCBs involves dermal contact, but, for reasons discussed previously, occupational exposure data were discussed under inhalation exposure. Dermal application of Aroclor 1260 to rabbits on 5 days/week at a dose of 118 mg/day for 38 days (27 total applications) produced degenerative lesions of the liver and kidneys, increased fecal porphyrin elimination, and hyperplasia and hyperkeratosis of the follicular and epidermal epithelium (Vos and Beems 1971). As body weight appeared to be approximately 2.7 kg (Vos and Beems 1971), the FEL of 118 mg/day is equal to a dose of 43.7 mg/kg/day (see Figs. 2.3 and 2.6). Developmental and reproductive toxicity. Pertinent data regarding developmental and reproductive effects of dermal exposure to PCBs' were not located in the available literature. Genotoxicity. The PCBs have produced generally negative results in in vivo and in vitro genotoxicity tests (Sect. 4.3.5 on genotoxicity in toxicological data section). Carcinogenicity. Occupational exposure to PCBs,^ which involves inhalation as well as dermal exposure, provides inadequate evidence of carcinogenicity in humans (Sect. 4.3.6 on carcinogenicity in \ 20 toxicological data section). Aroclor 1254 has shown weak tumor initiator but not promoter activity in two-stage carcinogenesis studies with mouse skin. Dermal studies of FCBs as whole carcinogens have not been conducted in animals (Sect. 4.3.6.3 on carcinogenicity of dermal exposure in toxicological data section). 2.2.2 Biological Monitoring as a Measure of Exposure and Effects 2.2.2.1 Exposure FCBs are pervasive environmental contaminants that are found in body tissues and fluids of the general population, including adipose tissue, blood, and breast milk. In the National Human Adipose Tissue Survey (NHATS)-, 46 composite adipose tissue samples collected during surgical procedures or during autopsies during fiscal year 82 were analyzed for organochlorine compounds (EPA 1986b). Of the 46 samples, 83% contained FCBs as follows: 22% contained trichlorobiphenyl, 53% contained tetrachlorobiphenyl, 73% contained pentachlorobiphenyl, 73% contained hexachlorobiphenyl, 53% contained heptachlorobiphenyl, 40% contained octachlorobiphenyl, 13% contained nonachlorobiphenyl, and 7% contained decachlorobiphenyl. EPA (1985a) performed a statistical analysis for baseline estimates and time trends for PCBs in human adipose tissue in the NHATS for 1970-1983. The findings indicated that 5.5% of the population had a FCB level >1 ppm compared with the historic percentage of 28.9%. The percentage of people who had >1 ppm PCB levels increased with age and was greater in males than in females, but there was no significant race difference. Historically, the Northeast Census Region has had the greatest percentage of people with levels >1 ppm, but, in recent years, the difference between the northeast and other regions no longer exists. Although 100% of the samples contained detectable levels of FCBs, there was a steady decrease over time in the percentage of people with >1 .ppm. Anderson (1985) discussed the use of adipose tissue biopsy in assessing human exposure to FCBs. Because adipose tissue is the primary storage site of FCBs, adipose tissue samples have been the preferred biological specimen. Analysis of FCBs in adipose tissue provides a direct measure of body burden, but has disadvantages over analysis of serum levels because collection of samples is invasive and timeconsuming. Based on data that adipose tissue levels of FBBs (polybrominated biphenyls) and DDT are directly correlated with serum levels of FBB and DDT, it can be predicted that FCB adipose levels will also correlate with serum levels. Anderson (1985) recommended that whenever an adipose tissue sample is obtained at biopsy, a paired serum sample should be collected and the two tissues be analyzed for FCBs. Once the correlation is characterized, blood samples may become the preferred choice for monitoring, unless identification of low exposures is required. Wolff (1985) reported data on blood levels of PCBs in workers in relation to exposure levels (Table 2.1) and blood and adipose tissue \ \ 21 Table 2.1. PCB levels in blood of exposed workers (Aroclors 1016, 1242, 1248) A ir levels (m g /m 3) Blood levels (ng/m L ) Mean High N 0.3-2 0.05-0.275 0-0.26 0.1-1 1060 440 130 355 149 89 118 48 3500 1400 407 3330 1500 370 2530 604 19 'Inside"0 14 "Outside"0 60 26 High exposed 55 Low exposed 140 Never exposed 110 High exposed 180 Other Workers who were exposed inside or outside the impregnation room. Source: Wolff 1985. V o 22 C7 o levels of FCBs in workers in relation to duration of employment (Table 2.2). Generally, higher exposure levels result in higher blood and adipose tissue levels of FCBs, but because FCBs accumulate in the body, exposure duration is at least as important as exposure level. Kreiss (1985) reviewed available data, including unpublished Centers for Disease Control (CDC) data, for serum PCB concentrations in U.S. populations without occupational exposures for 1968-1983. Mean serum levels were usually between 4 and 8 ng/mL, with 95% of the individuals having concentrations <20 ng/mL (Table 2.3). Cross-sectional data concerning PCB levels in a representative sample of the U.S. population are not available because the various groups were monitored during investigations of pesticide residues, food chain contamination, hazardous waste sites, and occupational exposure in which a nonexposed control group was necessary. Subpopulations consuming fish taken from contaminated waters have mean serum FCB levels that are several times higher than those in other general population groups and comparable to those usually associated with occupational exposure (Table 2.4). Interpretation of the data in Tables 2.3 and 2.4 is complicated by differences in analytical methodology and methods of population selection and data reporting (Kreiss 1985). FCB levels in adipose tissue and in human milk fat are 100 to 200 times higher than serum levels (Kimbrough 1987a). PCB concentrations averaged 1.5 ppm in the breast milk of 1057 women in Michigan (Wickizer et al. 1981). These levels are relatively high and apparently due to consumption of contaminated fish. 2.2.2.2 Effects Several studies of general population subjects attempted to correlate serum PCB levels with health indices. Baker et al. (1980) found that plasma triglyceride levels increased significantly with serum PCB concentrations in residents of Bloomington, Indiana, including workers occupationally exposed to PCBs. Chloracne or systemic symptoms of PCB toxicity were not noted, and there were no significant correlations between PCB levels and hematologic, hepatic, or renal function indices. Kreiss et al. (1981) reported that serum PCB levels were positively associated with serum cholesterol levels, gamma-glutamyl transpeptidase (GGTP) levels, and measured blood pressure in residents of Triana, Alabama, that were exposed via consumption of contaminated fish. The associations in the above studies were independent of predictors of FCB levels such as age, sex, and/or consumption of alcohol and fish. Although FCBs may be related to elevated blood pressure (Kreiss et al. 1981), the effect has not been validated and has uncertain relevance to PCB exposure because the fish also contained high concentrations of DDT residues. Steinberg et al. (1986) determined that five serum analytes (-glucuronidase, 5'-nucleotidase, triglycerides, cholesterol, and total bilirubin) correlated positively and significantly with log concentrations of serum total PCBs in residents who lived or worked in the vicinity of an electrical manufacturing plant. Aroclor 1260 was significantly and positively correlated with several of the analytes, Table 2.2. PCB blood levels (Aroclor 1254) and duration of exposure Mean duration Mean blood Mean adipose of employment concentration concentration (years) (ng/m L ) N U g/g) N 12 6 16 8 17 3.8 4.3 238 80 24a 258 17 53 6* 32 4 8 33tf 86 5.6 36 14' 15 1.4 5 12' 19 1.3 9 ''Persons with more than 5 years employment; geometric means; geometric mean of S3 plasma samples which matched the adipose samples was 54 ng/m L. ^Persons with less than 5 years employment; geometric means. `Persons exposed. 'Persons nominally exposed. 'Noncxposcd. Source: Wolff 1985. Area and sampling method Table 2.3. Serum PCB concentrations In U.S. populations without occupational exposure to PCBi and In mbpopulatlons consumine fi*h from PCB-conlamlnated waters Number of subjects Year PCB level, ng/mL Arithmetic mean Geometric mean, median" Arithmetic 95% standard confidence deviation interval Range References Charleston County, S.C, volunteers Lake Michigan random non-fish eaters Bloomington, Ind., volunteers and controls Michigan PBB cohort Populations without occupational exposures, 1968-1983 616 1968 4.9 -- ---- 29 1973 17.3 15" ---- 110 1977 18.8 -- 10.8 17-21 1631 1978-79 7.7 6.4 Billings, Mont., random packinghouse workers Franklin, Idaho, volunteers Random unexposed workers Newton, Kans., volunteers Lake Michigan random non-fish eaters Canton, Mass., volunteers Old Forge, Pi., volunteers 17 1979 103 1979 19 1979 7 1979 416 1980 10 1980 138 1981 7.5 5.8 ---- 12 -- 4.9 4.2 -- 6.6" 7.1 5.2 3.6 1 6.8 4-11 "-- ---- 3.1 2-8 ---- 5.2 3-11 - '" 0-29 <5-41 Finklea et al. 1972 Humphrey 19B3a 6-79 <1-57 2-30 <5 10-27 2-11 <3-60 Baker et al. 1980 Kreiss et al. 1982 Drotman et al. 1961 Drotman et al. 1981 Chase et al. 1982 Vernon et al. 1981 Humphrey 1983a 1-18 <3-43 Condon 1983 Reid and Fox 1982 Area arid sampling method Jefferson, Ohio, volunteers Fairmont, W. Va,, vblunteers Norwood, Mass., volunteers take Michigan volunteer sporlfishcrs Triana, Ala., volunteers Lake Michigan volunteer sporlfishcrs New Bedford, Mass., volunteers 'Median. Source: Kreiss I98S, Table 2.3 (continued) Number of subjects Year 59 1983 PCB level, ng/mL Arithmetic mean Geometric mean, median0 Arithmetic standard deviation 95% confidence interval Range References 5.8 4.4 6.5 4-8 1-45 Welly 1983 40 1983 6.7 5.0 5.3 5-8 1-23 Welly 1983 990 1983 4.9 4.2 3.5 4-6 2-30 Condon 1983 Populations without occupational exposures consuming PCB-conlamlnated fish 90 1973 72.7 56a ---- 458 1979 572 1980 22.2 -- 17.2 21.4 22.3 "-- 20-24 -- II 1981 31.4 23.6 29.3 13-50 25-366 Humphrey |9B3b 3-158 Kriess cl al. 1981 <3-203 Humphrey 1983b 5-101 Condon 1983 26 OJ Table UL S eraa PCB coaceotntfoos in populations with occupational exposure PCB levels, og/mL Facility Number of subjects Arithmetic mean Geometric mean 95% confidence interval Range References Railway car maintenance Capacitor plant Capacitor plant Capacitor plant Capacitor plant Public utility Private utility 86 34 290 80 221 14 25 33.4 394a 124* 48e 342a -- -- -- - - 67a 2 ttf - 119* 25.3* 24* 24* 22* 29c 234-554 98-150* 38-58* -- 151617-25* 20-43* 10-312 Chase et al. 1982 trace-1700 1 Ouw et a l 1976 6-2530* Fischbein et aL 1979 1-546* Wolff et aL 1982a 41-1319 Maroni et aL 1981a 1-3330* Smith et aL 1982 1-250* 39* 5-52* Smith et aL 1982 33* 7-24* 9-48* Smith et al. 1982 7-250* 'Blood level `Lower PCB homologs. 'Higher PCB homologa. Source: Kreiss 1983. o 27 but Aroclor 1242 was correlated significantly and negatively only with )jr HDL-cholesterol. Umbilical cord serum levels of PCBs have been correlated with reduced birth weight and size, shorter gestation, and neonatal behavioral effects in a few reports (Fein 1984; Fein et al. 1984; Jacobson et al. 1984a, 1985; Rogan et al. 1986). Although increased levels of FCBs in cord blood may be predictors of these kinds of effects, the effects are not well validated. Cord serum levels associated with these effects are reported in Sect. 4.3.3 (developmental toxicity in toxicological data section). Workers with occupational exposure to FCBs (see Table 2.4) have also-been evaluated for subclinical associations with serum'lipids and other health indices (Kreiss 1985). Significant correlations between plasma PCB and serum triglycerides (Chase et al. 1982), plasma triglycerides (Smith et al. 1982), SGOT (Chase et al. 1982, Smith et al. 1982, Fischbein et al. 1979), SGTP (Ouw et al. 1976), and GGTP (Smith et al. 1982, Maroni et al. 1981a, Fischbein 1985) have been reported. Measures of liver enzyme induction (e.g., GGTP) are not commonly associated with PCB levels, and possible hepatocellular damage (as indicated by SGOT, SGTP) has been demonstrated only in occupationally exposed groups with higher ranges of PCB levels (Kreiss 1985). Maroni et al. (1981a) examined the health condition and PCB blood levels of 80 electrical workers exposed to PCBs (42% mean chlorine content) for many years. They found that hepatic involvement was associated with blood concentration of trichlorobiphenyls (Student t test, P < 0.001), but the association with pentachlorobiphenyls was not as great (P < 0.01). Individuals with abnormal liver findings had average blood trichlorobiphenyl concentrations of 215 /xg/kg (range 77407 Mg/kg), while workers without abnormal liver findings had average concentrations of 92 ig/kg (range 13-345 /xg/kg). The abnormal liver findings include hepatomegaly and altered liver enzyme levels, with well-defined liver failure noted in a few cases. The authors suggested that trichlorobiphenyls may reflect current PCB exposure levels more closely than pentachlorobiphenyls. 2.2.3 Environmental Levels as Indicators of Exposure and Effects 2.2.3.1 Levels found in the environment The purpose of this subsection is to summarize available data that suggest that levels of PCBs found in environmental media (primarily soil, drinking water, and food) are associated with significant human exposure and/or effects. Schwartz et al. (1983) found a significant positive correlation (P < 0.001) between fish consumption measures and PCB levels in maternal serum and.milk. The specific PCBs present were not correlated with the various Aroclor mixtures. From their data, Schwartz et al. (1983) determined that serum PCB levels increase by 0.15 ng/mL and milk.levels increase by 0.12 ng/g for every 0.45 kg of PCB-contaminated fish consumed. The rate of fish consumption was not stated. Drotman et al. (1983) found a positive correlation between Che PCB concentration in human breast milk and the number of contaminated eggs consumed by lactating women. I 28 2.2.3.2 Human exposure potential The purpose of this subsection Is to discuss the chemical-specific issues involved in human exposure of FCBs from water, soil, and food. Experimental monitoring data have shown that PCB concentrations are higher in sediment and suspended matter than in the associated water column, and this is in agreement with the high soil adsorption constants for FCBs. The partitioning between suspended matter and water will be isomer specific and should correlate with the octanol/water partition coefficient of individual isomers. Thus, lower chlorinated FCBs should have a greater tendency to partition to the water than higher chlorinated FCBs. This implies that human exposure to the higher chlorinated isomers from whole water (water + sediment) will be greater than from settled water. Therefore, the human exposure potential to higher chlorinated FCBs from contaminated waters will increase as exposure to sediment and suspended matter increases. The exposure of lower chlorinated FCBs from drinking water from contaminated sources should remain about the same whether the water is filtered or not. In general,' FCBs are strongly adsorbed in most soils; therefore, leaching will not generally occur. This implies that the exposure will be greatest at the point of initial adsorption. In many instances, this may be at or near the soil surface. The principal route of human exposure to FCBs from a spill in soil at a restricted outdoor site is through inhalation of air (EPA 1987b). Soil ingestion and dermal contact with soil would not be expected to be significant routes of exposure at a limited access site. Nonetheless, ingestion is considered the primary route of exposure from spills at a nonrestricted residential site, although it is anticipated that some exposure would occur through inhalation also. Although dermal exposure can occur at soil sites where access is possible, it is expected that the FCBs will adsorb to the soil particles, reducing the rate of dermal absorption. The bioavailability of FCBs through inhalation may be higher for the lower chlorinated congeners since their tendency to volatilize from soil is greater than the tendency of the higher chlorinated congeners to volatilize. 2.3 ADEQUACY OF DATABASE 2.3.1 Introduction Section 110 (3) of SARA directs the Administrator of ATSDR to prepare a toxicological profile for each of the 100 most significant hazardous substances found at facilities on the CERCLA National Priorities List. "(A) An examination, summary, and interpretation of available toxicological information and epidemiologic evaluations on the hazardous substance in order to ascertain the levels of significant human exposure for the substance and the associated acute, subacute, and chronic health effects. (B) A determination of whether adequate information on the health effects of each substance is available or in the process of development to determine levels of exposure which present a significant risk to human health of acute, subacute, and chronic health effects. i* 29 (C) Where appropriate, an identification of toxicological testing 1 needed to identify the types or levels of exposure that may present significant risk of adverse health effects in humans.11 This section identifies data gaps in current knowledge relevant to developing levels of significant exposure for PCBs. Such gaps are identified for certain health effects end points (lethality, systemic/target organ toxicity, developmental toxicity, reproductive toxicity, and carcinogenicity) reviewed in Sect. 2.2 of this profile in developing levels of significant exposure for PCBs, and for other areas such as human biological monitoring and mechanisms of toxicity. The present section briefly summarizes the adequacy of existing human and animal data, identifies data gaps, and summarizes research in progress that may fill such gaps. Specific research programs for obtaining data needed to develop levels of significant exposure for PCBs will be developed by ATSDR, NTP, and EPA in the future. 2.3.2 Adequacy of Database for Health Effect End Points * 2.3.2.1 Introduction and graphic summary The adequacy of the PCB database for health effect end points in humans and animals is depicted on bar graphs in Figs. 2.7 and 2.8, respectively. The bars of full height indicate that there are "adequate" data to meet at least one of the following conditions: 1. For noncancer health end points, one or more studies are available that meet current scientific standards and are sufficient to define a range of toxicity from no effect levels (NOAELs) to levels that cause effects (LOAELs or FELs). 2. For human carcinogenicity, a substance is classified as either a "known human carcinogen" or "probable human carcinogen" by both EPA and the International Agency for Research on Cancer (IARC) (qualitative), and the data are sufficient to derive a cancer potency factor (quantitative). 3. For animal carcinogenicity, a substance causes a statistically significant number of tumors in at least one species, and the data are sufficient to derive a cancer potency factor. 4. There are studies which show that the chemical does not cause this health effect via this exposure route. Bars of half height indicate that "some" data for the end point exist but do not meet any of the criteria for "adequate" data. 2.3.2.2 Descriptions of highlights of graphs Data concerning effects of PCBs in humans that are useful for quantitative risk assessment are not available. The available data pertain primarily to intermediate- or chronic-duration occupational ,Ni }. exposures in which the exposures are inadequately monitored and do not j l r\. HUMAN DATA A ADEQUATE V - DATA J A y SOME DATA J NO DATA Uo l L E T H A L IT Y ACUTE IN TE R M E D IA TE CHRONIC Z_______________________________________________/ SYSTEMIC TOXICITY DEVELOPMENTAL REPRODUCTIVE TO X IC IT Y TO X IC ITY C A R C IN O aE N IC IT V Fig. 2.7. Adequacy of the database on health effects of PCRs (human data). . 'T ``O - ANIMAL DATA LETHALITY ACUTE IN TE R M E D IA TE CHRONIC Z ______________________________________________ / SYSTEMIC TOXICITY DEVELOPMENTAL REPRODUCTIVE TO X IC IT Y TO XIC ITY CARC1NOQENICITV Fig. 2.8. Adequacy of the database on health effects of PCBs (animal data). A ADEQUATE V * DATA J A SOME DATA J NO DATA u u> i correlate with duration and intensity-of exposure. Occupational exposures to PCBs involve significant dermal exposure, but, as discussed previously, occupational concentrations are expressed milligrams per cubic meter of air (mg/m^). For this reason, occupational exposure data were discussed under inhalation exposure. Children b o m to mothers who consumed PCB-contaminated fish had some developmental effects, but the effects cannot be directly attributed to PCBs; therefore, the bar for developmental effects due to oral exposure indicates that there are some data. The toxicity and carcinogenicity of the PCBs in animals by the oral route are reasonably well characterized. Determination of toxicity effect levels for chronic oral exposure is precluded by occurrence of proliferative/neoplastic alterations. Effects of acute oral, inhalation, and dermal exposures to the PCBs in animals have not been extensively investigated because concern for effects in humans is centered on intermediate/chronic-duration oral exposures. 2.3.2.3 Summary of relevant ongoing research J.L. Jacobson of Wayne State University is conducting a study sponsored by the National Institute of Environmental Health Sciences to evaluate the impact of PCBs on physical, cognitive, and neurological development in early childhood. The children, examined at'age 4, were exposed to moderate levels of PCBs, or maternal serum PCB levels were high near the time of their birth (NTIS 1987). W.J. Rogan of the National Institute of Environmental Health Sciences is conducting a follow-up study of children exposed to PCBs through breast milk. The children under study are a cohort of 856 North Carolina children exposed to relatively low levels of PCBs and a cohort of 108 children from Taiwan exposed to relatively high levels of PCBs (NTIS 1987). 2.3.3 Adequacy of the Database for Other Information Needed for Risk Assessment 2.3.3.1 Pharmacokinetics and mechanism of action Quantitative data concerning the pharmacokinetics of PCBs following inhalation and dermal exposure are lacking. Such data could greatly assist efforts to evaluate health effects resulting from inhalation and dermal exposure to PCBs. Further studies should be conducted concerning the distribution of PCBs, especially regarding the distribution of PCBs In the plasma compared to adipose tissue. Ongoing studies concerning pharmacokinetics and mechanisms of action were not located. 2.3.3.2 Monitoring of human biological samples PCBs can be measured in serum, adipose tissue, and milk. These measurements can indicate elevated exposure but do not provide information concerning the route of exposure. Although biological monitoring is useful for documenting exposures, it cannot be used for predicting health effects. 33 Biological monitoring methods indicate body burden of PCBs that have accumulated over a lifetime. Adequate methods are not available to distinguish exposure routes, short or intermittent exposures, or lowlevel exposures due to the bioaccumulation and slow excretion of FCBs. Several studies concerning monitoring of biological samples are ongoing. The Massachusetts Department of Health (population survey in Mew Bedford, Massachusetts) and the Indiana State Department of Health (population survey in Monroe County, Indiana) are conducting studies that will provide information on PCB body burden levels in conjunction with selected health outcomes. Several smaller studies are being conducted by the CDC. 2.3.3.3 Environmental considerations Methodology of sufficient sensitivity and specificity to measure FCBs in the environment exists. The bioavailability of FCBs from environmental media appears to be fairly well understood. There appears to be a fairly good understanding of the environmental fate and transport of FCBs; however, more experimental data are required to understand the potential importance of photolysis in degrading the more highly chlorinated PCBs,..which are more persistent in the environment. In addition, a better understanding of the environmental cycling of FCBs is needed to assess future exposure from' current environmental sinks such as FCBs adsorbed to sediments. No studies were found that involve the environmental interaction of PCBs with other pollutants. There are no known ongoing experimental studies pertaining to the environmental fate of PCBs, which would help to fill the data gaps as mentioned above. \ -^ V1-'' -o 3. CHEMICAL AND PHYSICAL INFOBliATION 3.1 CHEMICAL IDENTITY Data pertaining to the chemical identity of the Aroclors are listed in Table 3.1. Aroclors are mixtures of chlorinated biphenyls. The general chemical structure of chlorinated biphenyls is as follows: (where n and n' may vary from 0 to 5). The numbering system for the biphenyl structure is also shown above. Aroclor products are identified by a four-digit numbering code in which the first two digits (12) indicate that the parent molecule is biphenyl and the last two digits indicate the chlorine content by weight. Thus, Aroclor 1242 is a chlorinated biphenyl mixture with an average chlorine content of 42%. The exception to this designation method is Aroclor 1016, which retained the 1016 designation by which it was known during development (Mieure et al. 1976). Aroclor 1016 is a mixture that contains primarily mono-, di-, and trichloro isomers and has an average chlorine percentage (41.5%) that is very similar to Aroclor 1242. 3.2 PHYSICAL AND CHEMICAL PROPERTIES Selected physical and chemical properties of the Aroclors are presented in Table 3.2. Table 3.3 identifies the approximate molecular composition of the Aroclors. Data pertaining to the pyrolysis of PCBs which results in the formation of polychlorinated dibenzofurans (PCDFs) have been reviewed (EPA 1987a). Several studies involving pyrolysis of specific PCB isomers have found that the pyrolysis products include PCDFs, chlorinated benzenes, naphthalenes, phenyl ethynes, biphenylenes, and hydroxy PCBs. There appear to be four major paths for production of PCDFs from PCBs: (1) loss of two ortho chlorines, (2) loss of ortho hydrogen as well as chlorine, (3) loss of an ortho hydrogen as well as chlorine but involving a shift of chlorine from the 2- to the 3-position, and (4) t loss of two ortho hydrogens (EPA 1987a). The formation of PCDFs from the pyrolysis of PCBs occurred when an electrical transformer in an office -J t -r C D f building in Binghamton, New York, accidentally caught fire on February 5, 1981 (Schecter and T i e m a n 1985, Tiem a n et al. 1985)^ i' V -J Tifale 3.1. Oiemlcil Ideality of (be Aroclors Aroclor 1016 Aroclor 1221 Aroclor 1232 Chemical name0 Aroclor 1242 Aroclor 1248 Aroclor 1254 Aroclor 1260 References Synonyms Trade names Chemical formula Wiswesser line notation* Chemical structure PCB-1016 Polychlorinated biphenyl with 41.5% Cl b . See Table 3.3 NA See text PCB-I22I Polychlorinated biphenyl with 21% Cl b See Table 3.3 NA See text PCB-1232 Polychlorinated biphenyl with 32% Cl b See Table 3.3 NA See text PCB-1242 Polychlorinated biphenyl with 41.5% Cl 6 See Table 3.3 NA See text PCB-1248 Polychlorinated biphenyl with 48% Cl b See Table 3.3 NA See text PCB-1254 Polychlorinated biphenyl with 54% Cl b See Table 3.3 NA See text PCB-1260 Polychlorinated biphenyl with 60% Cl Chlorodiphcnyl (60% Cl) b See Table 3.3 NA See text SANSS 1987 Identification Nos. CAS Registry No. NIOSH RTECS No. EPA Hazardous Waste No." OHM-TADS No. DOT/UN/NA/IMCO Shipping No. STCC No. Hazardous Substances Data Bank No. National Cancer Institute No. 12674-11-2 T Q 1351000 3502 8500400 UN23IS 4961666 Unknown Unknown 11104-28-2 TQ 1352000 3502 8500401 UN2315 4961666 Unknown Unknown 11141-16-5 TQ 1354000 3502 8500402 UN2315 4961666 Unknown Unknown 53469-21-9 TQ1356000 3502 8500403 UN23I5 4961666 Unknown Unknown 12672-29-6 TQ1358000 3502 8500404 UN23I5 4961666 Unknown Unknown 11097-69-1 TQ 1360000 3502 8500405 UN23I5 4961666 Unknown C02664 11096-82-5 TQ 1362000 3502 8500406 UN23IS 4961666 1822 Unknown SANSS 1987 SANSS 1987 EPA 1980a EPA-NIII 1987 Chcmlinc 1987 *4 Slone 1981 I1SDB 1987 NCI 1978 "These are the current chemical names as indexed by the Chemical Abstracts Service1(CAS). ^Aroclor is the trade name for chlorinated biphenyls used by Monsanto. *Wiswesscr line notations are not applicable for mixtures. " Designation prior to May 19, I960. ^ '*> r >. 'A ` / J Molecular weight0 1016 237.9 Color Physical state Odor Melting point, *C Boiling point, aC (distillation range) Auloignilion temperature Solubility Water, mg/L ^ Clear Oil Unknown Unknown 323-336 Unknown 0.42 Organic solvents Density, g/cm1 at 2S'C Partition coefficient Log octanol-water^ Vapor pressure, mm Hg at 25"C Henry's law constant, Btm-mVniol at 25"Cc Refractive index Very soluble 1.33 3.6 4 X 10~4 2.9 X I0-4 1.6213-1.6233 (2 5 'C ) Table 3.2. Physical and chemical properties of PCBs 1221 200.7 Clear Oil Unknown Unknown 275-320 Aroclor designation 1232 1242 1248 232.2 266.5 299.5 Clear Oil Unknown Unknown 290-325 Clear Oil Unknown Unknown 325-366 Clear Oil Unknown Unknown 340-375 1234 1260 References 328.4 Light yellow Viscous liquid Unknown Unknown 365-390 375.7 Light yellow Sticky resin Unknown Unknown 385-420 Hotzlnger et at. 1974 Monsanto 1974 Monsanto 1974 Monsanto 1974 Unknown Unknown Unknown Unknown Unknown Unknown 0.59 (24"C) Very soluble 1.15 Unknown Very soluble 1.24 0.24 0.34 0.10 <24"C) Very soluble 1.35 0.034 0.06 (24` C) Very soluble 1.41 0.012 0.057 (24*C) Very soluble 1.50 0.0027 Very soluble 1.58 Monsanto 1974, Paris et al. 1978, llollifteld 1979 EPA 1985a Monsanto 1974 4.7 6.7 X 10"* 3.5 X I0 "1 1.617-1618 (20C) 5.1 5.6 6.2 6.5 4.06 X JO"1 4.06 X I0"4 4.94 X |0~4 7.71 X 10"* Unknown 5.2 X 10"4 2.8 X 10"1 2.0 X I0_l Unknown 1.627-1.629 Unknown (20 C) 1.6375-1.6415 (25C) 6.8 4.05 X 10"* 4.6 X 10" 3 b Monsanto 1974, Callahan el al. 1979 c% Unknown 1ARC 1978 1 uo>o s > - -> r  ^r v Tibie 3.2 (continued) Aroclor designation 1016 1221 1232 1242 1248 1254 1260 References Flash point, *C (Cleveland open cup) s' Flammability limits Conversion factors Air(25*C)rf Water Unknown 176 238 None None None Unknown Unknown Unknown Unknown' Unknown Unknown 1 mg/m1 0.095 ppm ppm (w/v) mg/L - ng/mL 1 mg/m1 -- . 12 ppm Same 1 mg/m1 " 0.105 ppm Same 1 mg/m1 0.092 ppm Same 1 mg/m* 0.08 ppm Same 1 mg/m1 " 0.075 ppm Same None Hubbard 1964 Unknown 1 mg/m1 " 0.065 ppm Same 'Average mass from Table 3.3. These log K,,, values represent an average value for the major components of the individual Aroclor. Experimental values for the individual components were obtained from Hansch and Leo 1983. `These Henry's law constants were estimated by dividing the vapor pressure by the water solubility. The first water solubility given in this table was used for the calculation. The resulting estimated Henry's law constant is only an average for the entire mixture; the individual chlorobiphcnyl isomers may vary significantly from the average. Burkhard ct al. (1983) estimated the following Henry's law constants lulm-mVmol) for various Aroclors at 25C: 122) (2.28 X 10"'), 1242 (3.43 X 10"*). 1248 (4.4 X I0_<), 1254 (2.83 X 10"*). 1260 (4.15 X 10"*). `These air conversion factors were calculated by using the average molecular mass as presented under molecular weight. G> VO f. Table 33. Approximate molecular composition of PCBs (percent) Arod or designation Hmpincal formula 1016 1221 1232 1242 1248 1254 1260 C |2H io c 12h 9c i C 12HsC12 C l2H 7Cl3 c 12h 6c i4 C ,2H 5CIs C l2H 4C lj C i2H 3Cl7 C i2H 2C18 C ijH tC Ij Average molecular mass <0.1 1 20 57 21 1 <0.1 ND ND ND 257.9 11 51 32 4 2 <0.5 ND ND . ND ND <0.1 31 24 28 12 4 <0.1 ND ND ND 200.7 232.2 <0.1 1 16 49 25 8 1 <0.1 ND ND 266.5 NDa ND 2 18 40 36 4 ND ND ND 299.5 < o .i <0.1 0.5 1 21 48 23 6 ND ND 328.4 ND ND ND ND l 12 38 41 8 ND 375.7 aND * none detected. Source: Hutzinger et al. 1974. n , i j 4. TOXICOLOGICAL DATA 4 .1 OVERVIEW Evaluation of the toxicokinetics and toxicity of PCBs is complicated by the fact that PCBs are mixtures of a variety of different congeners and impurities, each with its own characteristics. Impurities include the highly toxic PCDFs. Aroclor PCBs are the subject of this profile, but toxicokinetics studies often examined specific congeners, and many toxicity studies used mixtures of PCBs other than Aroclors, particularly Kaneclors. Kaneclors are similar to Aroclors but are produced in Japan rather than the United States and differ in method of production, chlorine content, and PCDF contamination. The reported range of PCDFs in Kaneclors and Aroclors is 5 to 20 ppm and 0 to 2 ppm, respectively. Reference to Kaneclors is made occasionally to support statements about Aroclors because effects produced by Aroclors and Kaneclors are similar. Kaneclor toxicity data are not considered in detail because of the aforementioned differences in composition and because reported lowest effect levels are lower for Aroclors than Kaneclors. The general population is exposed to PCBs primarily by the oral route (through food, particularly fish). Inhalation and dermal exposure are the primary routes of occupational exposures, but the relative contribution of these routes is unknown. Studies of the absorption of PCBs following oral exposure indicate that gastrointestinal absorption of most isomers is >90%. The limited data concerning the absorption of PCBs following inhalation and dermal exposure indicate that PCBs can be absorbed via these exposure routes. Distribution of ingested or injected Aroclors follows a biphasic pattern. During the first day following dosing, the PCBs distribute to the liver and muscle tissue. The compounds are then redistributed to fat, skin, and other fat-containing organs. Heavily chlorinated congeners redistribute to adipose tissue to a greater extent than the less chlorinated congeners, although the type of chlorine substitution is also a factor. A number of studies indicate that PCBs can cross the placenta and locate in the fetus. PCBs also concentrate in milk. Higher PCB levels may reach the offspring through nursing than through placental transfer. The metabolism of PCBs is dependent on the number and position of chlorine atoms, with lesser chlorinated isomers metabolized more readily than more chlorinated isomers. PCB metabolites tend to be 3- or 4hydroxy compounds produced via an arene oxide intermediate. The presence r ' s of vicinal unsubstituted carbon atoms at the 3-4 positions may be helpful but not essential to this process. 41 i V" < X>'.*' ` t-iv\r,, vri" 42 PCBs that are metabolized with more difficulty tend to be excreted almost exclusively through the biliary route, while the metabolites of mono-, di-, and trichlorinated Isomers are also eliminated through the urine. Urinary metabolites are in the form of conjugates, including glucuronides and sulfates. Glutathione conjugates have also been identified. Higher chlorinated PCBs tend to persist in the body longer than lower chlorinated PCBs. For example, biological half-lives in the rat range from 1.15 days for 2,2'-dichlorobiphenyl to 460 days for 2,2',4,4'-hexachlorobiphenyl. Aroclors appear to have a low order of acute lethality. Data for non-Aroclor PCB mixtures and specific PCB isomers suggest that mice and guinea pigs are more sensitive than rats. Aroclors are lethal at much lower total doses when administered subchronically or chronically than acutely, indicating that PCBs bioaccuxnulate to concentrations that are toxic. Animal studies have shown that the liver and cutaneous tissues are the major target organs for Aroclors. Aroclors have also been shown to produce stomach and thyroid alterations, immunosuppressive effects, and porphyria in animals. Animals are sensitive to repeated exposures to Aroclors as a result of rapid bioaccumulation to toxic levels. Monkeys are particularly sensitive to the toxic effects of Aroclors. Gross toxic effects other than reversible skin lesions have not been associated with Aroclor exposure (occupational) in humans. Biochemical effects, however, such as increased liver enzyme levels, have been associated with Aroclor exposure in workers and in the general population. More serious health effects were observed in humans who consumed rice oil chat had been contaminated with Kaneclors in Japan ("Yusho" incident) and Taiwan ("Yu Cheng" incident). Although there is an historical linkage between Yusho and PCBs and some regulatory documents ascribe health effects from these incidents to PCBs, effects from the incidents are not reviewed in this report because exposure was to Kaneclors and because the effects cannot be attributed specifically to the Kaneclors. The Kaneclors were heated in thermal heat exchangers before the rice oil contamination and during cooking and contained relatively high concentrations of PCDFs and polychlorinated quaterphenyl contaminants. There appears to be general agreement that the PCDF contaminants, particularly the more potent isomers, contributed significantly to the health effects observed in the Yusho and Yu Cheng patients. Please refer to Kuratsune and Shapiro (1984) for a more complete discussion of this topic. Aroclors appear to be fetotoxic but not teratogenic In various species of animals, including rats, mice, rabbits, and monkeys, but the possibility that contaminants (e.g., >PCDFs) may be responsible for the effects should be' recognized. Effects such as decreased birth weight, shortened gestation age, and neonatal.behavioral alterations have been associated with PCB exposure in humans. Oral exposure to Aroclors produced deleterious effects on reproduction in monkeys, mink, and, at higher doses, rodents. 43 PCBs have produced generally negative results in in vitro and in vivo mutagenicity assays. Feeding studies In laboratory animals demonstrated the carcinogenicity of several PCB mixtures, but it is not clear which components of the mixture or metabolites are actually carcinogenic. The liver is the primary target of PCB carcinogenicity. 4.2 TOXICOKINETICS 4.2.1 Absorption 4.2.1.1 Inhalation Human. Inhalation exposure and dermal exposure are the primary routes of occupational exposure to PCBs, but the relative contribution of each route has not been discerned (Wolff 1985). Animal. Six rats were exposed to an aerosol of a PCB mixture (Pydraul A200, 42% chlorine) at a concentration of 30 g/w? (0.5 to 3 /m particles) for 30 min (Benthe et al. 1972). PCB concentrations in the liver 15 min after cessation of exposure were >50% of the maximum concentration attained after 2 h (70 /xg/g tissue). These data indicate that the PCBs were readily absorbed. 4.2.1.2 Oral Human. The general population is exposed to PCBs primarily by the oral route (primarily by consumption of contaminated fish). Schwartz et al. (1983) found elevated levels of PCBs in the serum and breast milk of women who ate PCB-contaminated fish from Lake Michigan. Humphrey (1976) reported blood levels of PCBs in people who consumed contaminated sport fish from Lake Michigan in 1973. Annual consumption of 24 lb resulted in a mean blood level of 0.073 ppm, while annual consumption of 6 lb resulted in a mean blood level of 0.020 ppm. Blood levels of PCBs in persons who ate no fish averaged 0.017 ppm. These studies indicate that PCBs are absorbed by the gastrointestinal tract, but do not provide information regarding the extent of absorption. Animal. Drill et al. (1981) and EPA (1985a) reviewed a number of animal studies indicating that PCBs, including Aroclors, are absorbed readily from the gastrointestinal tract following oral administration. Albro and Fishbein (1972) examined the absorption of 19 PCB congeners and unchlorinated biphenyl in rats treated by gavage at doses of 5, 50, or 100 mg/kg. Determination of PCBs in feces collected for 4 days indicated that absorption of all congeners was >90%. Using rhesus monkeys, Allen et al. (1974a,b) determined over 2-week periods that >90% of a single oral dose of 1.5 or 3.0 g/kg Aroclor 1248 was absorbed. Bleavins .et al. (1984) determined over 5 weeks that European ferrets absorbed 85.4% of a single dose of [^C]-labeled Aroclor 1254 (0.05 mg) given in food. In contrast to the above studies, Norback et al. (1978) claimed that 59.3 to 87% of a single oral dose of 2,4,5,2*,4',6'-HCB passed unabsorbed through the intestine of monkeys during the first week after dosing. It was unclear why relatively little of this isomer was 44 absorbed. There are no data on Che effect of Che environmental matrix or vehicle on Che bioavailability of specific PCBs and ?C3 mixtures. Studies with 2,3,7,8-TCDD indicate that the vehicle may play a significant role in the relative bioavailability of 2,3,7,8-TCDD and related compounds (e.g,, FCBs) (EFA 1985b). 4.2.1.3 Dermal Human. In a study of occupational exposure of electrical workers to PCBs (Pyralen*3010 and Apirolio, 42% chlorine content), Maroni et al. (1981b) concluded that absorption of FCBs occurred mainly through the skin. Quantitive data were not available. Animal. Hiller (1944) reported the deaths of guinea pigs and rabbits treated dermally with a mixture of FCBs containing approximately 42% chlorine. The guinea pigs were treated with 34.5 mg/day for 11 days, while rabbits were treated with 86 mg every other day for 7 doses or 172 mg every other day for 8 doses. Lesions observed in guinea pigs and rabbits included fatty degeneration and centrolobular hepatocellular atrophy of the liver. Using tritium-labeled PCBs (40% chlorine), Nishizumi (1976) found evidence for dermal absorption of PCBs in rats via follicular diffusion. Quantitative data were not provided. . 4.2.2 Distribution 4.2.2.1 Inhalation Human. Wolff et al. (1982b) examined the relative concentrations of FCB congeners in plasma and adipose tissue of 26 persons occupationally exposed to FCBs (20 to 54% chlorine). Exposure was not discussed, but it probably included both inhalation and dermal exposure. The results indicated chat FCB congeners with chlorines in both 4positions were the major components in plasma and adipose tissue. FCBs with unsubstituted 3,4- positions on at least one ring were observed at lower concentrations in plasma and adipose. The adipose-plasma partition ratio calculated for Aroclor 1248 residues was 185, while the partition ratio for Aroclor 1254 residues was 190. In a more recent study of 173 workers from the same population, adipose-plasma partition ratios of 210, 190, and 200 were determined for Aroclors 1242, 1254, and 1260, respectively (Brown and Lawton 1984). Animal. Maximum FCB concentrations in the liver and brain of rats occurred 2 and 24 h, respectively, after a single 30-min exposure to 30 g/w? of Fydraul A200 aerosol (42% chlorine) (Benthe et al. 1972). Concentrations in these tissues subsequently declined, while adipose concentrations reached a maximum after 48 h. 4.2.2.2 Oral x Human. A number of studies reviewed by EPA (1987a) indicate that PCBs concentrate in human breast milk. Exposures in these studies were most likely oral, 'but may have included both Inhalation and dermal exposure. Wolff (1983) reported the half-life of PCBs (percentage chlorine in compounds not stated) in breast milk at 5 to 8 months and found that the concentration of PCBs In breast milk was 4 to 10 times 'y 45 that In maternal blood. Similar results were reported by Jacobson et al. (1984b). Ando et al. (1985) examined the PCB concentration in maternal blood and milk and the placenta of six Japanese women. They found that the congeners present were more typical of Kanechlor 500 than Kanechlors 300, 400, or 600. The results indicated that as the chlorine content of the PCB congeners increased, the correlation between the placental content of congeners and maternal blood and milk also increased. PCBs were detected in the umbilical tissues, umbilical blood, amniotic fluid, and baby's blood from a woman who was occupationally exposed to Kanechlors 300 and 500 in a capacitor factory (Yakushij i et al. 1978). PCB levels in these tissues and fluids were considerably less than in the mother's blood. Maternal serum concentrations of PCBs were also higher'than cord serum concentrations in women who resided in western Michigan (Jacobson et al. 1984b) and upstate New York (Bush et al. 1984) (i.e., in regions with easy access to fish from the Great Lakes). Kraul and Karlog (1976) determined PCB levels in abdominal fat, brain, and liver from necropsies completed in 1972 and 1973 in Copenhagen, Denmark. The ratios of PCB levels were reported as 1:3.5:81 for brain:liver:fat, indicating that adipose was the site of greatest bioaccumulation of-the tissues studied. Animal. Following absorption, PCBs, including Aroclors, are distributed in a biphasic manner. The compounds rapidly (minutes to hours) clear from the blood and accumulate in the liver and muscles (Drill et al. 1981). PCBs may be translocated from the liver to adipose tissue for storage or be metabolized in the liver, with metabolites excreted in the urine or bile. Muehleback and Bickel (1981) treated rats by gavage with a single dose of 0.6 or 3.6 mg/kg [^-^C]-2,4,5,2',4',5'-hexachlorobiphenyl. The rats were examined 1 h, 24 h, 6 weeks, 20 weeks, or 40 weeks after dosing. The results showed the highest levels of PCBs in muscle, liver, fat, and skin early in the study. By the end of the study, the highest PCB levels were found in adipose tissue followed by skin, muscle, and liver. During the 40-week study period, only 16% of the total dose was excreted. Gage and Holm (1976) determined concentrations in abdominal fat of mice 7 and 21 days after the mice were dosed by gavage with a single dose (13-165 /g/mouse) of 1 of 14 PCB congeners. Relatively low levels (<10 ng/g//ig dose) were found at 7 days for 4,4'-, 3,2',4',6'-, and 2,3,4,2',4',6'- isomers, with relatively high levels (>100 ng/g/^g ;dose) for 2,4,5,2',4',5-, 4,2'4'6'-, and 2,4,2*4'- PCBs. * l Kurachi and Mio (1983a)\exposed mice to Kanechlor-400 at 100 mg/kg in the diet for 5 to 20 days. Analysis of tissues at the end of the feeding period indicated high levels of PCBs in the gonads. High levels of PCBs were also found in skin, adipose tissue, adrenals, and kidneys. A second group of mice were kept on the PCB diet for 20 days in a rotation cage to cause fatigue. Mobilization of fat deposits was observed with liver PCB levels in fatigued mice 10 times greater than in j mice fed the same diets but allowed to rest. 46 A number of animal studies have demonstrated that FCB mixtures and specific congeners and isomers can cross the placental barrier and accumulate in fetuses (EPA 1987a). High levels of PCBs also accumulate in the mammary gland where they are secreted in the fat portion of the milk. Masuda et al. (1979) fed PCBs to pregnant mice through the first 18 days of gestation and found the highest levels of serum PCBs in offspring 1 to 2 weeks old. In studies in which monkeys were exposed prior to and during gestation, signs of PCB-induced intoxication in nursing but not newborn offspring were observed (Allen and Barsotti 1976, Iatopoulos et al. 1978). Results such as these have led some investigators to conclude that transfer through nursing may account for higher exposure of young than does placental transfer. This conclusion may be inappropriate, as it is often based on the fact that the absolute quantity of PCB residues is substantially higher in breast milk than cord serum; relative to fetal body weight, even low-level prenatal exposure can cause substantial concentrations (Jacobson et al. 1985). Groups of 24 rhesus monkeys were maintained on diets that provided Aroclor 1016 at doses of 0, 4.5, or 18.1 mg/kg/day throughout gestation and a 4-month gestation period (Barsotti and Van Miller 1984). At birth, the concentrations of the PCBs in the skin of infants were similar to concentrations in the subcutaneous fat of the mothers. At weaning, the FCB content in the mesenteric fat of the infants was 4 to. 7 times greater than in the subcutaneous fat of the mothers. Gas chromatographic patterns showed chat the adult adipose tissue did not include the total spectrum of peaks observed in the Aroclor 1016 standard, that all of the peaks observed in the standard occurred in the neonate skin, and that the peaks in the mesenteric fat at weaning and 4 months after weaning were qualitatively similar to those in the adult adipose tissue. These data suggested an inability of the fetus to metabolize and excrete certain congeners that are more readily metabolized and eliminated by adults and older infants. Bleavins et al. (1984) fed female European ferrets a single dose of [^C]-labeled Aroclor 1254 in the diet (0.05 mg) early (day 14) or lace (day 35) in gestation and determined the placental transfer of PCBs. They found that placental transfer to the kits was 0.01% (per kit) of the maternal dose when dams were exposed early in gestation and 0.04% (per kit) when dams were exposed late in gestation. Placental transfer of PCBs was considerably less than mammary transfer, with the ratio of placental to mammary transfer at 1 week of lactation 1:15 and 1:7 for offspring of dams dosed early and late in gestation, respectively. 4.2.2.3 Dermal Data concerning the distribution of Aroclors following dermal exposure of humans or animals were not located. Because PCBs are lipophilic, the compounds should concentrate in adipose tissue regardless of the route of exposure.\ 4.2.3 Metabolism 4.2.3.1 Human 2,2',4,4*,5,5*-Hexa-CB was the PCB congener found in the highest concentration in human adipose tissue, while 2,2',4,4',6,6'-hexa-CB was