Document dQ4OJeXdYXw5BrMvvDOE6LZ46

EFA 560/6-7*405 PCBs IN THE UNITED STATES INDUSTRIAL USE AND ENVIRONMENTAL DISTRIBUTION TASK I FEBRUARY 25,1976 FINAL REPORT U.S. ENVIRONMENTAL PROTECTION AGENCY OFFICE OF TOXIC SUBSTANCES WASHINGTON, O.C. 20460 HONS 208959 EPA 560/6-76-005 ?C3s IN THE UNITED STATES INDUSTRIAL USE AND ENVIRONMENTAL DISTRIBUTION Task I EPA Contract No. 68-01-3259 EPA Project Officer: Thomas Kopp For Environmental Protection Agency Office of Toxic Substances 4th and M Streets, S.W. Washington, D. C. 20460 February 2S, 1976 HONS 208960 REVIEW NOTICE This report has beer reviewed by the Office of Toxic Substances, era and approved for publication. Approval does not signify that the aor.ter.ts necessarily reflect the views and policies of the Environmental Protection Agency, nor does mention of trade names or ccrmercial products constitute endorsement or reuLiiuendation for use. HONS 208961 ABSTRACT This docmant presents tha currant stats of knowledge about tha production, usage, and distribution of polychlorinated biphenyls (PGtl in the Unitad States, The infocrnation presartad is derived frtxn detailed studies on tha production and first tier user industries, the pest and present gwiaration and disposition of ?C3aontairung wastes, envlromental transport and ctmilativa loads# potential alterna tives to PGJa usage, inadvertent lessee to and potential formation in tha environ ment, and current regulatory authorities for ?CBi control. Theaa results indicated that, although PCBa oortant of industrial wastes can be reduced through various approaches (treettnant, substitution, etc.), there exists a potantially severe future hazard in tha fora of large mounts of PCBa currently contained in land disposal sitae. Further definition of this and other aspects of the POs prcblen, and deteaninstion of ways to minimize tha hazard, are reoemnanded. MONS 208962 TABLE OF CCNTOrrS Page SECTION I - INTRODUCTION.............................................................................................. j_ 1.0 cvniviEw or the pcbs problem..................................................... 2.0 OBJECTIVE AW) SCOPE OF THE REPORT.......................................... i 2 SECTION II - SXHMX....................................................................................... 4 1.0 PRODUCTION, USMZ, AW) DISTRIBUTION OF PCBa....................... 4 1.1 Overview of PCBa Industrial Usage in ths United Stataa.................................................................... ... 1.2 Cunulatiwa PCBs Production and Usage in the United States ................................................................................... 1.2 Currant Distribution of PCBs Usage and Associated wastes............................................................................. a 1.4 Land Disposal and OTvirormantal Load.................... a 1.5 Foreign Production of PCBa....................................... lo 4 5 2.0 CHARACTERIZATION CF INDUSTRY PRACTICE AW) WASTE HANDLING FOR THE PCBa PRCOU2R AW) MAJOR FUST-TIBl USERS............... 10 2.1 Manufacture of PCBa and PCB-Ccrrtaining Capacitors and Transformers................................................................. 10 2.2 Tresanant and Disposal of Industrial wastes Containing PCBS................................................................................. 12 2.2.1 incineration...................................................... 12 2.2.2 Treatment of PCB-Contaminated wastewater... 12 2.2 Characterization of the Investment CastingIndustry . 15 2.4 Transformer Service Industry.................................. 16 2.0 SUBSTJ1V1BS AM) USE AI3BWAXIVES FOR PCBs........................... 16 2.1 Sttstitueae far PCBs in Capacitors........................ 2.2 Si&stltutas far PCBs in Transformers............ ...... 2.2 Alternatives to Other PCBs Applications................ 16 17 19 4.0 SOURCZS or aKfVBOBfr ENTRY CF PCBS INTO THE ENVIROMENT. 19 4.1 Paper Recycling.............................................................. 19 4.2 Effluent Contamination by PCBa in OtherIndustries . 20 4.3- Xhadv*rtn& Production of PCBs in the EHvironnant . . 20 ii. MONS 208963 TABLE cr caraNTS (Con't) ` section n tcon't) ^2 5.0 TRANSPORT AND DISTRIBUTION OF PCB* THE mVGOWENT ... 21 6.0 REGULATORY ACTICNS CN PCBs............................................................. 23 SECTION III - CONttUSICNS At RBOaMNDATICNS........................................ 25 1.0 CCNCIitSKKS....................................................................................... 25 2.0 RSCCTMMKriCNS............................................................................. 23 SECTION IV - CHEMICAL At PHYSICAL PROPERTIES Of GttORDOOTD BIPHENYLS 31 1.0 DtlSOOUCtlCN...................................................................... 1.1 The Chnnistry of tha Otlorinatad Biphenyls................... 1.2 CamarcUl Production and Chanical Makst of ths Aroclora.......................................................... 1.3 Physical Properties of ths PCS Aroclora...................... 31 39 1.3.1 Physical Properties of Industrial and Technical Interest..................................................................... 39 1.3.2 Physical Propartia* of Brwironnantal Intarast . 41 1.4 Chanical Properties of tha QilnrttoipharyLa...................... 1.5 Photochanlcal Raacticna Involving tha PCSa...................... 1.6 Metabolic Omnistry of tha Qilorcbiptanyla...................... 49 49 51 SECTION V - INDUSTRIAL OtAMCHRIZASICNS...................................................... 54 1.0 QRRCDUCnCN................................................................................... 54 2.0 WNUnCIVIUNS PROCESS - PCt.YCHL0(UNA3ZD BIPHENYLS (PCSa) . 54 2.1 Prooaaa Description........................................................... 2.2 Mar HSstaa................................................................................ 2.3 Plant Water Usage . .............................................................. 2.4 'laatamrair Treatment and Housekeeping............................. 54 57 59 60 2.4.1 Tiaaiaant Facility for tha Effluent fran Saugat Coolant........................................................................ $4 2.5 Plant Effluents................................................................. 3.0 P3 USE* ............................................................................................. 65 3.1 Aakarel Capacitor Manufacturing Industry......................... 65 31 34 ill. HONS 208964 table or auriNrs (con't) 3.1.1 Askarel Capacitor Manufacturing Plants....................$7 3.1.1.1 3.1.1.2 3.1.1.3 3.1.1.4 3.1.1.5 3.1.1.$ AaJcarel Handling.............................................?q Process Description ................................. 71 Raw Wastes......................................................... 7$ water Us*......................................................... 76 Wairswetar Treatment...................................so Effluent Caiposition.................................. so 3.2 Askarel Transformer Manufacturing Industry....................... 34 3.2.1 Transformer Manufacturing Plants............................... 33 3.2.1.1 Askarel Handling. .............. .......................... 38 3.2.1.2 Process Description..................................... 91 3.2.1.2,1 Assaably and Aakaral Filling Procedure for the Distribution and Power Transformer ... 92 3.2.1.3 Raw Wastes......................................................... 98 3.2.1.4 Meter Use......................................................... 98 3.2.1.5 Wastewater Ttsatmuit................................. 101 3.2.1.6 Effluent Corpseiticn................................ 103 3.2.2 Aakaral Transformer Repair Industry......................103 3.2.2.1 3.2.2.2 3.2.2.3 3.2.2.4 3.2.2.5 Transformer Inspection andMaintenance. 103 tapeir of Felled Transformers.................. 108 P9 Usage in the Transformer Repair Induatry....................................................... 114 TtanafoEmar Service Life......................... 115 Usage Rate of PCTe in Transformer Repair........................................................... 115 3.3 Xnueetmmit Casting...................................................................... U5 3.3.1 Badcground...................................................................... 116 3.3.2 Iiwastmurt Casting Tadmologias............................. 118 3.3.2.1 Princlplss of Investment Casting ... 118 3.3.2.2 FOaidry Proueae - Use of PCT and PCS rilled Mures................................................122 3.3.2.3 Masts Streens................................................ 125 3.3.3 Mai Mnufacturing........................................................... 127 3.3.4 RaBcnandstions...............................................................124 3.4 Seamdary fiber Reoovary {Paper Recycling) ...................... 128 iv. HONS 208965 TABLE OF CONTENTS (Con't) ' Page 3.4.1 Historical Use of PCBs in the PaperIndustry. . 129 3.4.2 Fiber Recovery Mill Process 135 3.5 Industrial Use of PCBs as Hydraulic and Heat Transfer Fluids.................................. ^0 3.5.1 General................................................................... 140 3.5.2 Use of Irrported PCBs by Joy Manufacturing . . , L41 3.6 Recent Use of PCBs in Product Development Activities . L41 SECTION VT -WASTE TREATMENT TECHNOLOGIES................................................... 145 1.0 INTRODUCTION......................................................................................... 145 1.1 Sisimary of Waste Management Problait Areas................... 145 1.1.1 Waste Liquid PCBs and ContaminatedScrap Oil . 1.1.2 PCBs in Wastewater . . . ....................................... 1.1.3 PCB-Contaminated Solid wastes ............................... 145 146 146 1.1.3.1 1.1.3.2 Burnable Solid Waste Materials Con taining PCBS.............................................. Nonbumable Solid Waste Materials Containing, or Contaminated with PCBa 146 147 1.1.4 Air Emissions of PCBs........................................ 147 1.2 Stannary of current PCBs waste Control Practices ... 147 1.2.1 1.2.2 1.2.3 1.2.4 Control of Waste Liquid PCBs and Contaminated Scrap Oils............................................................ 147 Control of FQs in wastewaters.................... 148 Control of Solid Wastes Contaminatedwith PCBa 149 Control of Air Emissions of PCBa................. 150 2.0 CMCIDKCE PCBs WASTE TREATMENT TECHNOLOGIES CONSIDERED. . . 151 2.1 Treatment of Waste Liquid PCBa and Contaminated Scrap Oils............................................................................................. 152 2.1.1 Incinaraticn........................................................ 153 2.1.2 Sanitary or Scientific Landfill..................... 154 2.2 Treatment of Wastewaters containing PCBa........................... 154 2.2.1 Carbon Adsorption.................................................... 154 2.2.1.1 PCBa Adsorption Testing by _ Carborundum Carpany........................... ... . 156 v. MONS 208966 TABLE OF CCNTOrrS (Cots'C) Pace SECTION VI (Con't) 2.2.1.2 PCBs Adsorption Testing by ICI-US ... 133 2.2.1.3 POs Adsorption Testing by Calgon Corp. 160 2.2.1.3.1 2.2.1.3.2 2.2.1.3.3 2.2.1.3.4 Adsorption Treattnent of Wastewater................................... 164 Reactivation of the Granular Carbon...........................................165 Carbon Transport ....... 166 Materials of Construction . 166 2.2.1.4 Carbon Regeneration Alternatives - wet Catalytic Oxidation................................... 166 2.2.1.5 Further Applications Data........................... 163 2.2.2 Ultraviolet-Assisted Ozenation...............................168 2.2.2.1 2.2.2.2 2.2.2.3 2.2.2.4 Molecular Responses to Ultraviolet ESisrgy................................................ 169 Photodegradation of FCBe............................170 Experimental Factors in UV-Assisted Ozone Oxidation of PCBe............................172 Destruction of PCBs and Refractory Organirs at Houston Research, Inc. . . 173 2.2.2.4.1 PCB Destruction Data .... 173 2.2.2.4.2 Operating Data Obtained frezn Refractory Organics Taste . 173 2.2.2.5 Destruction of PCBs and Refractory Organics at Mastgate Research Corp.. . 177 2.2.2.5.1 2.2.2.5.2 PCBs Destruction Data. ... 177 Pilot-Scale Tests of Re* fractory Organics Decorposi- tion..........................................191 2.2.2.6 Laboratory Test Results from AiResearch Corp................................................................... I85 2.2.2.7 Conmnea on UV/OaoneTests........................1S 2.2.3 Non-Carbon Adsorbsnta forPCBs.....................................I88 2.2.3.1 The Amberlita XAD Series of Macroretieular Resins......................................................I87 vi. HONS 208967 TABLE OF CONTENTS (Can't) SECTION VI (Con't) 2.2.3.1.1 PCBs Adsorption Testing . 2.2.3.1.2 Process Concept for Resin Adsorption of PCBs . . , 2.3 Treatment of PCBs - Contaminated Solid Wastes. , , , 2.3.1 Incineration..................................................................... .... 2.3.2 Sanitary Landfill.............................................................iso 2.4 Treatment of Air Emissions......................................................... 190 2.4.1 2.4.2 2.4.3 Condensation Methods..................................................... 190 Granular Adsorption Methods..........................................190 Catalytic Oxidation of Organics in Evaporatsd Effluents......................................................................... 191 2.5 The Potential for Zero Discharge.............................................. 191 3.0 RATIONALE AND SELECTIONS OF CURRENTLY REOOMGNDED WASTE TREAT MENT METHODS........................................................................................... 192 3.1 Incineration Recanoendad for Liquid FCBa and scrap Oils. 152 3.2 Carbon Adsorption and UV-Assisted Ozonation fieumtnanded for PCBs in Wastewater................................................................ 193 3.3 Incineration and Landfill Reooitnended for Contaminated Solids............................................................................................... 194 3.4 Dry Carbon Filter Adsorption Recommended for Control of Air Emissions................................................................................195 SECTION VII - PRODUCTION AM) DISTRIBUTION...................................................... 198 1.0 PRODUCTION AM) CURRENT USE.................................................................... 198 1.1 Domestic Production of PCBe and PCTs...................................... 198 1.2 Foreign Production and Distributionof PCBe.........................207 1.3 Swnery of Reeent PCBe and PCTs Inserts........................... 207 2.0 FUTON YEAR EXTRAPOLATIONS FOR PCB PRODUCTION AM) USE IN ELECTRICAL EQCTPMNT............................................................................310 3.0 OVERALL MOSttAL BALANCE....................................................................315 sanra vm - suaemuiES tor PCBe.................................................................... 220 1.0 INTRODUCTION. . Vll* HONS 208968 TABLE OF OONTE2JTS (Can't) Pace SECTION viii (can't) 2.0 ELECTRICAL CAPACITORS............................................................................. 220 2.1 Function of the Dielectric Material..................................... 221 2.2 Practical Capacitors ................................................................. 224 2.3 Required Properties of Dielectric Liquid ........................... 225 2.4 The Use of PCBe in Capacitors...................................... .... . 226 2.4.1 2.4.2 2.4.3 Properties of PCB Capacitor Dielectric Liquid ..226 ^vantages and Disadvantages of PCBe in Capacitors.................................................................. 228 Usage of PCBa in Capacitors..........................................228 2.5 Alternatives to the Use of PCBa in Capacitors.................. 228 2.5.1 Substitutes for PCBa...............................................229 2.5.1.1 Phthalate Esters .......................................... 230 2.5.1.1.1 Dioctyl Phthalate:(DOP) ... 230 2.5.1.1.2 Diiaononyl Phthalate .... 230 2.5.1.2 2.5.1.3 2.5.1.4 2.5.1.5 ADcylated POB...............................................231 ADcylated Oilorodiphenyl Oxide............ 232 Silicones.......................................................233 Diaryl Sulfone........................................... 233 2.5.2 Elimination of Dielectric Liquids in Capacitors . 233 2.6 The Use of PCB Capacitors in Electrical Equipment. ... 235 2.6.1 Power Factor Correction........................................... 235 2.6.1.1 High Voltage Power Factor Capacitors . . 239 2.6.1.2 Low Voltage Power Factor Capacitors . . 239 2.6.1.3 Lighting Ballast Capacitors................ 240 2.6.2 Motor Starting Circuits........................................... 242 2.6.3 Electronic Filter capacitors.................................. 244 2.7 Institutional Barriers to Substitutes for PCBs in Capacitors........................................................................................244 2.7.1 Performance Acceptability........................................245 2.7.2 Fire Safety.................................................................. 246 2.7.2.1 2.7.2.2 2.7.2.3 Utility Use of Power Factor Correction Capacitors................................................... 246 Industrial Use of Power Factor Correction Capacitors............................ 247 Lighting and Appliance Capacitors ... 247 viii. HONS 208969 TABLE OF CONTENTS (don't) SECTION VIII (Can't) *as* 3.0 ELECTRICAL TRANSPOIWERS.....................................................................248 3.1 Heat Generation in Electrical Circuits............................248 3.2 The Nature and Purpose of Transformers............................250 3.3 Desired Properties for Transformer Heat TransferFluids. 251 3.4 Use of PCBa in Electrical Transformers............................252 3.5 Present Alternates to the Use of PCBs in Transformers . 254 3.5.1 Mineral Oil-Filled Transformers....................... ... . 254 3.5.2 Open Air Cooled Transformers....................................255 3.5.3 Closed Gas Filled Transformers............................ 257 3.6 Current Alternatives to the Use of PCB Cooled Trans formers ........................................................................................... 258 3.6.1 Vault Usage Requirements for Transformers . . ..258 3.6.2 Vault Construction Requirements for Transformers. 259 3.6.3 Transformer Vault Construction Costs.................... 261 3.7 Substitutes for PCBs in Transformers............................... 263 3.7.1 3.7.2 3.7.3 3.7.4 Fluorocarbons.............................................................. 264 Silioones...................................................................... 264 High Flash Point Mineral Oils................................267 High Flash Point Synthetic Hydrocarbons.............267 3.8 institutional Barriers Co the Use of Substitutes for PCBS............................................................................................. 263 3.9 Relative Merits of Alternatives to Nan Askarel Transformers..........................................................................271 3.9.1 3.9.2 3.9.3 3.9.4 Distribution Transformers........................................ 271 Power Transformers....................................................... 271 Precipitator Transformers........................................ 273 Railroad Transformers............................................... 273 3.10 Replacement of Askarele in Existing Transformers.... 274 3.10.1 PCS Losses Dus to Transformer Failures.............274 3.10.2 Owirormental Effects of an Askarel Replacement Program.......................................................................... 275 3.10.3 Effect of Leaving Askarel Transformers inService 276 4.0 INVESTS*! CASTING 4.1 Function of the Filler Material........................................... 277 4.2 Use of PCBs in Invesbnent Casting....................................278 4.3 Advantages and Disadvantages of the Use of Deka PCBs in Investtnent Casting.................................................................. 278 ix. HONS 208970 TABLE Of CONTENTS {Can't) Pace SECTION VIII (Can't) 4.4 Alternatives to the Use of Oeka PC3s..................................279 4.4.1 Replacement Filler Materials........................................ 279 4.4.1.1 Isophthalic mid............................................. 279 4.4.1.2 Polystyrene........................................................280 4.4.2 Unfilled waxes...................................................................280 4.5 Conclusions - Substitutes for PCB in Invesbnent Casting. 280 SECTION IX - PCBs RELEASE MO CLKJLATIVE ENVUOWENTAL LOADS............... 296 1.0 ESTMTES OF FREE PCBs IN THE ENVIROHENT.................................. 286 1.1 PCBs Losses to the Enviroment Since 1930, by Use and by Chlorine Content of Molecule................................................. 286 1.2 Total PCBs Aeeunulation and Current Rates.......................287 1.3 Currant PCBs Disposal in landfills and Duips................... 291 1.4 Release of PCBs via Industrial Effluents (Waterborne). . 294 1.5 Spills of PCBs airing Transport............................................. 294 SECTION X - INADVERTENT A*HNT REACTIOE AS ROUTES OF QfTRY OF PCBs INTO THE ENVUOMNT................................................................ 297 1.0 intrcoxticn....................................................................................... 297 2.0 OCM43CXAL BAOOOUO, FRCOUCnCN HD PROPERTIES OFBIPHENYL. 297 2.1 Origins and Camnarcial Usage Background.............................. 297 2.2 Production Methods and Rates for Biphsnyl....................... 298 2.3 Properties and Characteristics of Biphsnyl....................300 3.0 PROVEN BIPHENYL REKTIOS YIEIDING PCBs...................................301 3.1 Chlorination of Biphenyl..................................................... 301 3.2 Reactions Containing Phanyls to Produce Biphenyls .... 302 4.0 BIPHENYL USM2 IN HEAT TRANSFER FLUIDS, DYES HDPACKAGING. . 303 4.1 Hast Transfer Fluids.............................................................303 4.2 Dye Carriers for Polyestsrs and Polyolefins....................... 303 4.3 Biphenyl as a Mold Preventive in Packaging.......................304 4.4 Gwenl Biphenyl Occurrence in the ESrvircmsnt............... 305 5.0 POe (aNERAXICN HD VASTEJATER EXPERIMNIS IN A IWOR U.S. S1FBNYL USMZ LOCALITY.................................................................305 6.Q POTENTIAL OB3WOATICN HD SUBSEQUENT REACTICN OF COT AM) ROJttZD CCMPCLND6 IN THE ENVUOWENT TO FCSM PCBs................... 307 X. HONS 208971 TABLE Of CCNTENTS (Can't) SECTION X (Can't) 7.0 CCtffARISCN OF POTENTIAL INADVERTENT AMBIENT REPCTICNS .... 308 8.0 K3s FOUND IN THE EFFLUENTS CF THE MACHINnOf AND MECHANICAL PROOUCTS MANUFACTURING INDUSTRY...................................... ino SECTION XI - MWEMENT OF PQs IN THE QJVTRCNMENT - GENERAL DISTRIBU TION MODEL...................................................................................... .... 1.0 INTRODUCTION.......................................................................................... .... 2.0 RATIONALE FOR MODEL DEVELOPMENT........................................................315 2.1 Tim Dependence of the PCS Input Rate [B(t)|................... 316 3.0 APPLICATION OF THE KDQEL TO LAKE MXQiXGAN..................................... 317 4.0 RESULTS AMD CONCLUSICNS...................................................................... 319 4.1 Results............................................................................................. 319 4.2 Conclusions......................................................................................320 SECTION XII - REGULATORY ACTIONS ON PCBs........................................................ 322 1.0 nmcoucncN............................................................................................. 322 1.1 Measures Token by the Manufacturers.........................................322 1.2 Measures Taken by the U.S. Goverrmartt..................................... 323 1.2.1 1.2.2 1.2.3 1.2.4 1.2.5 1.2.6 1.2.7 1.2.8 1.2.9 Food, Drug and Cosmetic Act (21 (J.S.C. 301 et sag.).................................................................................. 323 The E)jg, Meat and Poultry Acts................................. 324 the Clean Air Act (42 U.S.C. 1857 et sag.). ... 324 Federal Water Pollution Control Act (33 U.S.C. 466 et seg.) ................................................................ 325 The Refuse Act of 1899 (33 U.S.C. 407)................... 326 The Occupational Safety and Health Act (29 U.S.C. 651-678)........................................................................ 326 Act to Regulate Transportation of Explosive* and Other Dangerous Articles (18 U.S.C. 831-835) 326 Federal Insecticide, Fungicide, and Rodenticide Act (FURA) (7 U.S.C. 135-135K)................................. 327 Needs for Federal Control............................................ 327 1.3 International Decisions and Agraanant..................................... 328 1.4 Hmmtem Taken by Foreign Government!................................. 330 1.4.1 Measures Token by Manufacturers - Limitations of ..................................................................................330 xi. HQNS 208972 TABLE OF CONTENTS (ODll't) SECTXCN XII (Con't) 1.4.2 Measures Taken by Sans Governments.............................131 1.4.2.1 P<3 Producing Countries.................................331 1.4.2.2 Mon-Preducing Countries................................. 332 1.5 U.S. Custans Regulations........................................................ 333 APPENDIX A APPENDIX B APPENDIX C APPENDIX D APPENDIX E APPENDIX F - PCS AE60FPTICN TESTING BY XAJ3-4 EESIN.....................................A-l - MAOOCTICEIAR EESINS FROM ION AND HAAS 03............................3-1 - NCN-CARBCN AEGOREfTICN AND OTHER RESEARCH STAGE P<3 TJCMMENT TECHNOLOGIES.................................................................C-l - vASS BALANCE MDCQ. FDR PODISTRIBUTION................................... 0-1 - BJOEHXND DATA USES TOOOJSTIBCT THEMOCEL FOR PCEs IN LAKE MICHIGAN................................................................................-1 - TOXICOLOGICAL ASPECTS.................................................................... f-1 xii. HONS 208973 SECTION II 1.2- 1 1.3- 1 SECTION rv 1.1- 1 1.2- 1 1.2- 2 1.3.1-1 1.3.1- 2 1.3.2-1 1.3.2- 2 1.3.2-3 1.3.2- 4 1.3.2-5 SECTION V 3.1.1- 1 3.1.1.3- 1 3.1.1.3- 2 3.1.1.6-1 3.1.1.6- 2 3.1.1.6- 3 3.2.1- 1 3.2.1.3- 1 r.r.gr nF -abtes Pace Estimates of emulative K3s Production, Usage, and Gross Environmental Oistribution in the United states Over the Period 1930-1975 in Millions of Pounds ... Estimated Production, Usage, and Losses of PCBs in the United States During 1974 in Millions of Pounds ... 7 9 Empirical Formulation, Molecular weights and Chlorine Percentage in PCBe .............................................................. 35 Approximate Molecular Ccnposition of SelectedAroclors 36 High Resolution Gas Chromatography of Aroclor 1248 . . 37 Chemical and Physical Properties of Representative Aroclors................................................................................. 40 Electrical Properties of Sane Aroclors....................... 42 Solubility, Vapor Pressure and Halflife for Vaporization from Water of Selected Aroclors at25*C.......................... 43 Vaporization Rates of Aroclors ........................................... 45 Percent Loss in Area of Seven Chrcratogram Peaks of Aroclor After Heating.......................................................... 46 Solubility of Qilorobiphenyla in water...................... 47 Relative Peak Heights (Peak 5 100) in Saturated Aqueous Solutions of Aroclor 1254................................... 48 U.S. Capacitor Manufacturing Industry Using PCBs ... 69 No^Product PCB Discharges............................................. 77 Quantity of waste loads..................................................... 78 Range of Flow Rates & PCS Concentration in Effluents frail Capacitor Manufacturing Plants............................... 81 Conparison of Discharges ....................................................... 82 Intake water PCB Concentration...................................... 83 U.S. Transformer Manufacturing Industry Using PCBs . . 89 Non-Product PCB Discharges............................................. 99 x L i. i . HONS 208974 T-TST TM tmtab rraw-H SBCTICN V (Con't) race 3.2.1.6-1 3.2.1.6-2 3.4-1 3.4.1-1 3.4.1-2 3.4.1-3 3.4.2-1 PCB Concentration in Effluents fran Transformer Manufacturing Plants........................................................ Influent and Effluent Ccrpositiora of Plant 103 ... PCB Concentrations in Wisconsin Paper Plant Effluents. History of Aroclor 1242 Constnpticn in the Manufacture of NCR Carbonless Paper for the Years 1957 through 1971....................................................................................... History of NCR Carbonless Paper Production for the Years 1957 through 1971................................................. Ratio of Aroclor 1242 Consurption for Carbonless to NCR Carbonless Estimated Production.............................. Corpoeition of Raw Water and Claifier Effluent .... 105 L30 131 132 133 139 SBCTICN VI 2.2.1.1-1 2.2.1.2-1 2.2.1.3-1 2.2.2.5.1-1 2.2.2.5.2-1 Carborundum Co. Tests of PCBe (Aroclor 1254) Rsncval fran Water by an Experimental Activated Carbon . . . ICI-US Tests of PCBe (Aroclor 1254) Removal from Water by The Types of Camnsrcial Carbons.............................. Results of Calgon Corp. Laboratory Isotherm Tests for Carbon Reeosvel of PCBs..................................................... UV Ozonolysis Destruction of Typical Capacitor and Transformer PCBe at westgata nasairrh........................... Simulated Two-Stage, Continuous uv-Ozcneticn of a 5 Gcaponent Mix at Westgata nsssirrh Corp....................... 157 159 162 130 134 SBCTICN VXX 1.1- 1 1.1- 2 1.1- 3 1.1- 4 PCB t PCT Mmifacture and PCB Sales Monsanto Industrial Chmnicsls Qapany (1957 thru 1964)............................. PCB PCT Mnufacture and PCB Sales Monsanto Industrial Hrtrsls Copany (1965 thru 1974) PCI Mnufacturs and Sales Monsanto Industrial Chemicals . Gapany (First Quarter - 1975)...................................... Bd-Osm of PCTs and PCBe by Type................................... 199 205 206 xi v. HONS 208975 LIST OF TABLES (Con't) SECTION VII (Con't) Pace 1-2-1 1- 1-1 2- 1 Production, Trade and Use of PCBs OECD Matter Countries (1973) ................................................................. Preliminary Sirtmary of PC3s Import Data for 1971-75 Versus Monsanto Production and Sales Data................... Ttotal PC3 Breakdown by Use (1966-1975)............................. 203 209 212 SECTION VIII 3.3- 1 3.9-1 Properties of Transformer Liquids Tested by FTE Corporation. ............... ................ Relative Merits of Alternatives to the Use of Askarel Transformers in Applications .......... 270 272 SECTION IX 1.1- 1 1.1- 2 1.1- 3 SECTION X 2.3- 1 8-1 SECTION XI 2.1- 1 3.0- 1 3.0- 2 PC3 Environmental Load by Aroclor Type ........ Cimiiative Environmental PCB Load by Chlorine Content. Carputad Spectrun of Chlorine Content for Wild PCBs. . 288 289 ' 290 Physical Constants of Biphenyl ............ POBs Concentration in the Effluents of the Machinery & Mechanical Products Manufacturing. ........ 300 311 Sunniary of PQ3 Input Sources (1973-1974) to Lake Michigan ........................... .............. Overall POs Balance for Lake Michigan Area During tlie Period 1930-1975 ................................................................. Derived PCB Concentrations in Lake Michigan Water and Biota Over the Period 1930-1975.......................... 317 318 313 xv. HONS 208976 LISTCFFI<XIHES SECTICN II Paqe 1.0- l U.S. Production and Usage of FCBs Sutmary over 1972-75 ................... ............ SECTICN rv s 1.2-1 Moiaties f ran mid Principal Qilorobiphmyl leaner* are Ehrmsd .................................................... 33 SECTION V 2.1- 1A Preparation of Crude chlorinated BiphanylsNbneanto Krunmrid Plant......................................... 55 2.1- IB Distillation of Qrude ProductsMtnsanto Krvmnrid plant.................. 55 2.2- 1 Non-Product PCS Dischargee at Monsanto's Knmnrid Plant........................................................ 59 2.4-1 Process Flow Diagran of the John Zink Incinerator at Msissnto's Knrtrrich Plant.............................. 61 3.1.1- 1 Median Size Industrial Capacitor.............................. 69 3.1.1.2-1 Generalized Flow Diagren for the Manufacturing of Large Capedton..................................... 72 3.1.1.2-2 Generalized Flow Diagran for the Manufacturing of Snell Capedton........................................................ 73 3.2.1- 1 Substation Transformer................................................. 90 3.2.1.2.1- 1 Transformer Filling With Vapor Phase Predxying of Intsrion................................................................ 93 3.2.1.2.1- 2 Transformer Filling With Oran or VSauan Charter Predrying of Transfixser Intemala....................... 96 3.2.1.2.1- 3 Traneformer Filling operation With Oran Predxying of AsMnbled Hardware............................................. 97 3.2.1.3*1 Non-Product PCB Discharges.......................................... 99 3.2.1.W Process Flow Qiagm for Thermal Ocidizer Incinerator at Plant 103......................................... 102 *vi. HONS 208977 LIST OF FIGURES (Continued) SECTION V (Qsntinued) ?x;e 3.2.2.2- 1 Transformer Maintenance & Servicing................... 3.2.2.2- 2 Transformer Pepair.............................. iio m 3.3.2.1- 1 Investment Shell Process ... ............................................. 3.3.2.2- 1 Flew Chart of PCBs Usage in Investment Casting . . >;j 3.3.2.3- 1 Idealized Flow Chart for an Investment Casting Foundry, Shewing Waste Streans ......... 126 3.4.2-1 Mill Fiber Recovery Process and Water Effluents . . 136 SECTION VI 2.2.1.3-1 Equilibriun Carbon Adsorption of PCBs Fran Water at Low Concentrations {Calgon Data)................... . 163 2.2.2.4.1- 1 Lab Scale J^paratus for Reaction and Mass Transfer Studies at Houston Research, Inc. ........ 174 2.2.2.4.1- 2 Aroclor 1254 Destruction by UV-Aisisted Ozonation......................................................... 175 2.2.2.4.2- 1 Ozone Oxidation of Acetic Acid, Effect of UV and Taigarature (Initial Of.COOH-lOS mg/1, 0.(1) 3.5 mg/1)....................... J............................ i ... . 176 2.2.2.4.2- 2 Ozoie/UV Oxidation of Acetic Acid? Effect of Increased Radiation Input.......................................... 138 2.2.2.5.2- 1 The Effect of UV Path Length on TOC Destruction . . 182 2.2.2.5.2- 2 Schematic of Bench Reaction Systan at Westgate Dasaardi Corp................................................................... 133 2.2.3.1.2- 1 PCBs Renoval Ptooess Concept Flew sheet by Rohm and Haas Ctnpany.......................................................... 338 SECTION vn 1.1- 1 U.S. Production of PCBs and PCTs and Domestic Sales and Brports of PCBs...................................................... 1.1- 2 U.S. Damstic Sales of PCBs by End Use Applications 201 202 xv i i. HONS 208978 LIST OF FIGURES 'Continued) SECTION VII (Continued ?age 1.1-3 U.S. Domestic Sales of P<3s by Type.......................... 20 3 2-1 unbiased Extrapolations of Least-Square Linear Curves for PC3 Prediction and Use m Electrical Equipment ........ .........................................214 xviii. HONS 208979 AadowLEXQCJrs . The preparation of -his report was accomplished through the efforts z: the staff of Versar -to., Springfield, Virginia, under the overall direction of Dr. Stebert L. Durfee, Vice President. The oonsiderable aid furnished by personnel of the Environmental Protection Agency, Office of the Toxic Substanoes, is acknowledged. Mr. Tom Kcpp served as Project Officer and provided guidanoe for the project effort. Appreciation is extended to The Electric Industries Association, The National Electrical Manufacturers Association, The Investment Casting Institute, The wisacnsin Paper Council, and the many individual oarparu.es who gave us invaluable assistance and cooperation in this program. Appreciation is also extended to the individuals of the Staff of Versar Inc., for their contributions and assistance during this program. Specifically, our thanks to: Mr. Janes D. Barden, Ehvirormental Engineer Mrs. Gayanah Y. Contos, Senior Qiemical Engineer Dr. E. Ellsworth Hadcnan III, Senior Scientist Dr. Mohanmal N. Khattak, Analytical and Ehvironnental Chemist Miss Susan A. Perlin, Envircnnental Engineer Mr. Bennett Y. Ryan, Eaologist Mr. Robert A. Mestin, Senior Oamical Engineer Dr. Frank C. Whitmore, Senior Scientist Also our acdcxvlodgement and appreciation is given to the secretarial staff of Versar Inc., for their efforts in the typing of drafts, neaessary revisions end final preparation of this document. Qir special thanks to: rtrs. Nancy C. Downie Mrs. B. Lym Waller Mrs. Lillette A. Steevee xix. HOMS 208980 SECTION I ' 1CTROOUCTION 1.0 CVEWLcW OF THE PCBs PROBLEM The tarsi polychlorinated biphenyls (PCBs) refers to a family of organic chamcals which have been produced and marketed in this country for 45 vears as a series of relatively complex mixtures under the trade nan* Aroclor. Each of these mixtures contains a nurtoer of chlorinated biphenyl isomers out of an overall range of chlorine content from one chlorine to ten chlorines per molecule. In general, higher chlorine content corresponds to greater resistance to chatucal (and biochemical) degradation. PCBs are among the stable organic coipounds known, and, in addition, they exhibit other properties which render than extranely advantageous for use as dielectric and heat transfer fluids. These properties include low solubility in water, low vapor pressure, low flammability, high heat capacity, low elactrical conductivity, favorable dielectric constant, and suitable viscosity-temperature relationships. Because of these properties, and also bscauss KBs exhibit little acute toxicity (toxic effects fron high level, short term exposure), this family of materials has been extensively used in marry industrial applications, primarily in "closed" or "seni-closed" systems such as electrical transformers and capacitors, heat transfer systeme, and hydraulic systems. Most of the PCBs marketed to L'.S. industry are still in service, primarily in electrical equiprant. The ronainder has ottered the general envircmane; a significant fraction of this amount is present in air, water, soil, and sediment, but most of the PCBs in the environment are believed to be in landfills and dtnpa across the country. In the late 1960's it h*c*n apparent that, although PCBs exhibit little acute toxicity, they are aocunilated in the tissues of many biological species and do esdiibit dixcnic (long-term) toxicity to marry species even when the exposure is to very Low oanosntraticns. The effects of chronic PCB ejgxwure may be con sidered m roughly oaparable to those of DOT. HONS 208981 Thm recognition of this problem resulted in a major program designed to lessen the envorornwntal stress arising from widespread use and dissemination of PCBs; by mid-1971, tie Monsanto Industrial Chemicals Co., the sole u.s. pro ducer, had roluntarily terminated sales of Aroclors (PCBs and polychlorinated tnphenyls, or PCXs) for all but closed electrical systwe uses, ,'tonsanto also, in the sane time frare, offered incineration services far waste liquid PCBs and terminated production of the most highly chlorinated Aroclors. During 1972 and 1973, the fbed and Drug Adninistraticn developed Limita tions on P<3a concentrations, designed to eliminate interstate transport of P<3 aontaninated foodstuffs, far a nunber of important dietary item and packaging matarials used for foods. These limitations also reinforced the elimination of P<3* usage in the U.S. except for closed electrical systens. After approximately five years of the voluntary industrial restrictions, and about three years following the FDA limitations, a National Conference cn PCBs was held in Chicago during Novmnbar, 1975, under the joint sponsorship of ESA and other aovarnnent agencies. By that tias it had bteaue apparent that, although dietary intake of MBs had declined (apparently as a result of the FDA actions plus oooperaticn of the food and food pedcaging industries), inproved anelytioal tedniquaa plus more extensive monitoring efforts had revealed PCBs cantsanation at envirommtally significant levels to be more widespread than originally thoi^ht. Results presented at the Chicago meeting indicated PCB levels in the environment, on an overall basis, to have bean mote or lass constant since 1971, although there were local instances of both increases and decreases in PCS levels. It thus appears that, inlika COT, elimination of POs from dissipative uses has not resulted in a significant radio-inn in snviromental load. 2,0 OUECTZVE AW S03R OP THE tCPORT It was against the jfeove background that the work upon whidi this report is based was performed. The abjective of this report is to present the current state of knowledge about P9a production, distribution, usage, and losses to -2- MONS 208982 the envirarant in th* Unitad States. Many, but not all, of the facets of the PG3s prcblen are addressed; many of the estimates presented are on engineering and scientific judgement instead of hard data, simply because hard data in these areas are not available. Me hope that all assunpticns and judgements in the report are clearly identified as sudi, and that sufficient supporting information, where available, is presented to justify the choices made. while this report attarpts to shad sane light an the possible reasons why PCS levels in the environment are not decreasing as rapidly as had been hoped, its scope also includes a detailed presentation of past and present production and usage of PCBs in the united States, an analysis of PCS distribution and environnental ranspart as applied to Lake Michigan* a treatment in detail of potential substitutes and use alternatives, a discussion of the technical aspects of substitution* and discussions of various other aspects of the over all probln. Toxicological and hunan health aspects are not addressed; ror are the various current activities of ETA, other Government agencies, ani individual states' toward reducing entry of FOa into the environment. The information and data contained in the report were collected from personal interviews and telephone conversations with representatives of many of the firms handling or using POa* from trade associations, frcn the open literature, and from local* state* and Federal Govemnent personnel* researchers, and other parties having interest in and information concerning the PCBs problem. Ten visits to plants 're maos; these cowred the categories of FOs product!cn, small and Large capacitor manufacturing, trans former manufacturing, investment casting, and waste disposal contracting (wests PCTs). The degree of cooperation, and therefore the accuracy of the data obtained, varied widely frcm industry to industry. Electric utilities provided key information, as did also other users or distributors of products containing FQa. -3208983 hons sitticn ii SM*WDf 1.0 PRXUCTICN, USAGE, AND DISTRIH/TICN Of K3a 1.1 Overview of PCBs Industrial Usage in the Unitad States Over the past four years the donaatic production aid use of polychlo rinated biphenyls (PCS*) have bean approximately constant with averages of 40 million pounds per year for production and 33 million pounds per year for dcrestic sales. During this period Monsanto Industrial Qmicals Carp., the sole daiestic producer, has supplied approximately 99 per cent of the danestic market. Monsanto sells several PCS mixtures under the generic trade name Aroclor, aid purchase has been limited to intended use in nominally closed electrical systsns (transformers and capacitors) since 1971 under voluntary restrictions inposed by Monsanto. The renoinder of the domestic usage depends an imported PCSe, nest of which originate in Italy and the maunder in France. Decachlorobiphenyl is imported fron Italy Car use in investment casting wax, and the notarial import*! fran France is used in cooling systans of mining machinery. Of the domestic sales of POe, 63 to 70 per cant are to manufacturers of capacitors, aid the meiider to manufacturers of transformers. Transformers, which contain 2,000 to 2,500 ponds of PCBs on the average (present as a 60 to 70 par cant conponait of mixtures with tridilontenrane called Askarels) are used primarily to chenge voltega* during the traiwnission aid distribution of elsctrical power. Approximately five per cent of the transformers in service in this country certain POst seat transformers contain mineral oil instead of PC3*. Capacitors containing PCTs are of M general types; small capacitors vdiidi axe built into electrical applianoae sort os fluorescent lights, TV ssts aid small rotors, and large capacitors dildi axe used as separata units in electrical pe**r distribution syetans and with large industrial machinery sudi as alactric rotors and welding neridpee. roe wed in about 95 par cant of U.S.-produced liquid impregnated capacitors (net -- ti capacitors in radios and othar slsctronic equipment are aolid-atata wits). HONS 208984 P3s *r typically used in transformers whan protaction against fire is of ptnrourt importance. use of p<3* in capacitors is an a. number of factors', but fin protaction and service lifs appear to be the nest important. Industry codes, such as the National Electrical Code, specify the use of PC3- filled transformers and capacitors under a nunber of oor^itions. These codes will serve as institutional barriers to rapid reductions in FOs usage, but at present there are also technical barriers to substitution of other materials for PCBs in electrical equipment. The above overview of current PCBs usage in the U.S. is suimarlzsd by Figure 1.0-1, which traces domestic PCBs production and importation through first tier usage and distribution of PC3e - containing products. 1,2 Oi"M*tive 33s Production and Usage in the united States Estimates developed for total P<3s production and utilization in the U.S. since their introduction to industry in 1929-30 are presented in Table 1.2-1. These data define the estimated proportions of PCTs used in various applications, and an acoouiting, based on available data plus estimates, of the current distri bution of this material. Of the roughly 1.25 billion pounds purchased by U.S. industry, it is estimated that only 55 million pounds, or 4.4 par cent, have been destroyed by incineration or by in the environment. About GO per cent of the total dramatic eales is still in service, almost all in capacitors and transformers. The reminder, about 44 million pounds, are in the environment: it is estimated that 290 million potnla are in landfills or dwps and ISO million pounds axe "free* in the general awlrrarnent (air, vatar, soil, sediments) and prasimnebly available to the biota. Sens of the values in Table 1.2-1 are relatively well-established, while others are gross estimates resulting frea a leek of date in the area. The esti mated reliability tot each value presented is shown on the table. For instance, the POs usage in carbonless copy paper is a firm value obtained fren the only produmr (tot), whet* as the anoint of POs ervirornentally degraded could con ceivably range fxm a low value to the total of mw, di-, and trictUorobiphenyl utilised bat not still in service. The value for U.S. production could not be -5MQNS 208985 riOM l.ft-l. Ui PRODUCTION ANO USAGE Of PCS* SUMMRY OVER 1972-79 MQNS 208986 Table 1.2-1 n<^Elti'"teS oJ= Production, Usage, Gross OwiroroentAl Distribution in the United States Over the Period 1930-1975 in Millions of Pounds ti.s. fa mteiiai TOUl u,i. fa lj^aoru U-S. K3 DONtw IM-T Taul U.I. fCf Ocaru CO by Uh Cit^cyi IwtrOlM HMt TrHtc/ Hiae* indubtriAl crtpm ifytfnalics *i U Ctlwr Pluckcisar Urn Cj|eittn Tnmtnmo UM <** tta CUsuml fa B*VM or mclnnadi EnvujwiiiUy ib^rcM [fCUMTMad Undfilla m in ouytt C4p, Tra. Tnteun *1W rWtlvt* n. Gtfu(Mft AJerr (;*m, tc.l rm rOi in tha binraaM ioil( w*crf ur, wIimmI Toca OOMRUl Presetit* I.4M 1 ].w L.2U tM 1,44) fl E. Inhatrul pa* cumntly pcbi Qtmntlf Ot KM kn kraa La Dwiramc pa* i 34 ft 4% m i * 494 m is Cttusiud tan/lkV*aill,i--cy 41 - 20% ; Ml it - 201 i 20% t US t lot t 15f t 51 tm t 1H im t 20% t Ml l 70% i 10* l.AI no t 20% 0 l 40% 104 ! 40% i t M% 744 M M HONS 208987 nuch ow 1.45 billion pounds nor less than 1.1 billion pounds, based on analysis of other available or estimated data: '.vence, the estimated confidence interval for this value cn Table 1.2-1 of +5 per cant and -20 per cent. One of the more important conclusions frtsn this work is the estimation of abcut two times the amount of PCBe in landfills and dinpa as catpared to the xnount of PCS* already free in the envirotmant. The material in land sites may be considered a threat to bacons widely dispersed over a Ion; period of time. The length of time required can only be guessed at, but is probably short in oaipariacn to the time required for degradation of the PCTs by natural pro cesses. Thus, relsase of the land disposal material through slow vaporization and leaching could very well worsen an already severe ervironnantal problen. 1.3 current Distribution of PCTs Usage and Associated Wastes A material balance for PCTs production, sales, distribution, and wastes in 1974 is presented in Table 1.3-1. Reliability of the values were estimated as for the previous table. The emxnts estimated to be land disposed, totaling 1,18 million poinds, do not include land disposal of previously used PCTs. However, the arcunts listed under scrap PCTs incinerated account for all PCTs incineration in the U.S. during 1974 at the rarximerdad teipsrtur*-time conditions (> 2000*7: > 1.5 seconds residue* tima). Of ths total of 2.61 million pounds incinerated, the Monsanto facility accounted for over half, other <j.ineniaa currently providing incineration services include General Electric, Rollins Biviramontal Services, and Chao-Trol Pollution Services, but the total nvsber of such facilities to to be available in the U.S. is six. 1.4 Lard Disposal and Bivlrcmntal Load The 1.18 million poinds per year of land-destined wastes estimated above is only a snail portion of the total PCTs altering landfills and duips yearly; the currant estimated yearly rate of PCBa entering land disposal sites is about 12 million poinds. The largest source of this material .is capacitors which have failed or bancma obsolete, or tdiich are contained in obsolete equipment, other important sources are industrial pi*** wastes from PCTs production and first-tier usa^, and the total of other (non-electrical) muucipal and industrial solid testes. -8- HONS 208988 Table 1.3-1 Estimated Production, Usage, and losses of POs in the United States . during 1974 in Millions of Pounds Proddisi or irporu Omttic PradwtMi toul! *por% ifainco OBHaatac hiw 0|VR IlpOCf Um fn Liwttory, cc. ran uhp by rn*n Cramy Ctpaeiten Ttwfaafi III HUH CAatLHf *m. Ouar KM to Ur* [uua ran to bn m a( ml slid <0*1 rn PCM iwuftcturo m vetor uOouy rtv vnfmr in*uy m* immnt otoui* Inslmnuoi o< lcr* non rtv KM andietm rt pm uttray rn innlanni uiritny HdMnoi Bmnii ipM to *mtm * toot < paw m no aiiteui fn ranuiar nSniiy fn innlm uirttny yn* teuo TtMprc ItuLl 40.444* 0.4i tf.tU Co*tm.4l &*lc 14.404* 5.J95* On 45 0,445* to.ftU Irdufttrul Pwgsi by C4t*%ory 22.0 U.O 0.4 0.09 15.4$ *iit Dupma or laat rjcwud Ot Vlluu , --------------------- 1 : iOt - Ml : 101 t Wt s 104 t JOt t 20t t 20t t TOt 0.01 0.41 o.n 0.4 o. 1.4$ 0.44 O.Otll** o.ooai** 0.0001** 0.01 l.K : sot : 504 T sot t 19% t 194 *m t 10% t 40% 1 40% t 40% t 50% ntUM Ui -9HONS 208989 . The total current environmental load of Tree" PCBs mi estimated to b* about 150 million pounds. An analysis of envirormant load (Fraa PCBs) average chlorine content per molecule indicated that, if mono-, di-, and trichloro isorers v--* drsregarded, the average chlorine content of Free PCRa would be within seven per cent of the value for Aroclor 1254. 1.5 Foreign Production of PCBs Known current producers of PCBs besides the United States include the United Kingdan, Czechoslovakia, France, Germany, Spain, and the U.S.S.R. Japan was a producer until 1972. In 1973, total foreign production of PCBs is estimated at 43 million ponds, corresponding to a 50 per cant reduction since 1971. On this basis, the U.S. production appears to be about half of the world totalUsage of PCBs in all cotntriss is expected to decrees# further as a result of re cant findings on adverse environmental effects and potential human health hazards from PCBs, and this usage is expected to be essentially confined to use in capac itors and transformers. 2.0 OOUtM^StlZATTCM 0T PCU5TRY PRACTICE AM] WASTE HMOLSC FOR THE PCBs PRODUCER AM) MhXK FIRST-TIER USRS 2.1 Manufacture of PC3a and PO-Oxttaininq Capacitors and Transformers PC3s ere produced den--finally only by Monsanto at Sauget, Illinois. The process inwlvee the batch chlorination of biphenyl and subsequent separation and purification of the deeired chlorinated biphenyl fraction#. Tha degree of chlorination is detanuinad by the oontact time in the reactor. Depending on tha distanoe and aixa of shifBSRt, transport is vis tank car, tank truck, or canton carrier (drew). There are 17 capacitor plants and 18 transformer plants utilizing PCBs in tha United Statae. Manufacture of both types of units involv-- initial pre paration of internal --d --cases, filling with PCBs under vacuun, cleaning and dagnaain?' d performance tasting. The greatest PCT west-- occur in tha filling opantlora. Filling of snail capacitors (less than 2 panda of PCBs) and moat large capacitors is performed in chanters holding many snail capacitors or fser large cnaa. The chanter and tha capacitors are evseuatad and than floodfilled with tha PQ) liquid. Ft"''-- liquid is rsieved from tha chanter, tha filled -10- HQNS 208990 unit* an cleaned and sealed, and then the sealed units are degreased, painted, and tested. Transformers and the largest types of capacitors are filled individ ually after evacuation; this produces relatively less chance of PCBs loss than the flood-filling process. Of the 38 plants in the above categories, 10 discharge their effluents into the water ways while the remainder discharge into the sewage treatment plants All plants in these categories have discharges under heavy rainfall conditions. There are three types of waste materials genarated at these plants that require treatment and proper handling in order to minimize the PCB into the environner.t. These are: (a) waste waters containing trace quantities of PCB* (10 to 500 ppt> PCB*); (b) wasts PCBs, scrap oils and snail quantities of process water highly contaminated with PCBs; and (c) Burnable and nen-burnable solid materials contaminated with PCBs. Quentitative estimates of these wastes are given below: Waste Loads, Daily Average PCB Distfiarge in Waterways or Sewers Land-Destined PCB wastes PCB Mnufecturer 3.06 lbs 301 lbs Capacitor industries 5.86 lbs 4440 lb* Transformer Industries 0.17 lbs Unknown Scrap Oils to Incineration 1425 lbs 3968 lbs 1750 lbs The above waste loads represent current industrial practice. It may be assunad that, prior to taowledge of the adverse envirorrental effects of PCBs, Rush of the types of material curmtly landfilled or incinerated was not disposed of properly and thus entered the environwnt directly. As yet. very little is being done at these plants to control air missions. The gesnl industry assunption is that the vapor pressure of PCBs is so low that thsre will be essentially no air contamination. A few facilities, however, ware located to be filtering and chilling exhaust air fran PCBs inpragnation areas. -11- HONS 208991 and plant personnel are beginning to realize that evaporation of PCBa may neke a significant contribution to general contamination of the plant area. Since most water used at these facilities is for non-contact cooling purposes, at most plants it is possible to significantly reduce the effluent volute by segregation of wastewaters, recycling and proper housekeeping measures. Most user plants and the PCB producing plants have already undertaken PCBs contain ment programs in order to minimize the entry of PCBs into the envirorrrent. While the emissions of PCBs to water are expected to decrease due to improved pollution abetment of waterborne wastes, the release of PCBs to air and land may increase. Cne potential source of increasing air missions is the increase in incineration due to proper handling of wastes which were previously discharged into the water ways or sewers. The quantities of land-destined vostas are expected to increase due to improved housekeeping measures. Rivers receiving PCBs discharges for a muter of years vary greatly in PCBs content with time, apparently depending upon PCS content in storm water run off and the degree to which contaminated bottom sediments are agitated and sus pended, tftezeever there have been PCB operations in the past, there are probably high concentrations in local tatarweys bottom sediments. Over the past 45 years, waste PCBs from transformer and capacitor opera tions have been used as local road oiling compounds. Sometimes they were discarded in dutpe adjacent to manufacturing facilities. These are sources of long term leeching of PCBa into waterways, particularly with storm water runoff. 2.2 Treatment and Dispoeal of Industrial Wastes Containing PCBs A study was performed to determine and ccRpaze the methods available for the treatment of PCB-aontaining wastes from the PCBS production, capacitor manu facturing, and transformer manufacturing industry categories. A full treatment of this technology, including cost estimates for treatment, may be found in the Task II Report wdsr Contract 68-01-3259. Mich of the technical portion of this work is rspco&ioad herein and msmarized below. -12- HONS 208992 2.2.1 Incineration . The nost advanced treatment technology in use is incineration. The PCBa manufacturer and one user have plant scale facilities capable of destroy ing PCBa with very high efficimcy. There are at least two oonmercial services available, with four incinerator locations in the Eastern and Southern U.S., for PCBs incineration. Incineration is primarily applicable to waste PCBs and scrap oils contaminated with PCBs. Incinerators for PCBs destruction have the capacity of "burning" sore contaminated wastaMter but, of course, the proportion of that water to the exothermic oil burning must be leapt low. Cnly one oomercial incin eration service (Rollins) can routinely handle all kinds of PCBs contaminated transformer and capacitor ocmpcnsnts, sludges, fuller's earth and other solids, as long as they can be contained in a 47 gallon fiber drun. Cne FCB user oerpany incinerates transformer internals for purposes of metal recovery. Wests liquid PCBs and scrap oils (contaminated PCBs) are best handled, as a guideline, by high taepermture (2000-2400*F) and long residence time (2-3 seconds) incineration. However, heranse of incinerator design variables, the conditions should be chosen in each case to lead to 99.9994 destruction. The beet incinerator combination for handling wastes fran these industries is a rotary burner fired by a burner, and followed by an afterburner and scrubber systen for HC1 and particulate control. The rotary burner can be designed to handle a variety of solid metarials, and the liquid burner can handle both the oily and water type westaa. 2.2.2 TTaaiaent of PO-Oontamlnatad wastewater 9m is no ocmmrcial scale wastewater treatment for PCBs removal being prectioad beyond thoaa of gravity settling of the heavy PCBa layers as a sludge fran the bottom of svmpe or tanks, and skinning of a contaminated oil-layer froa the vetar surfaoee. Mequete methodology is available for those plants wishing to con trol th release of FOs to the mvirotmant. Currently available technologies can -13- M0NS 208993 be appi to the efficient removal of PCBs from wastes, or their destruction with the. other wastes. The PCBs content of wastewaters can be lowered to the 1 ppb level or below by renoval of solids (and oil layers, where applicable), followed by adsorption of PCBs onto cartoon, macroreticuiar polymer resins or possibly other adsorbents. Carbon adsorption is currently the best available technology for plant scale treatment of PCBs wastewaters. This conclusion is based on laboratory tests with PCBs in water, and on the long background of plant scale use of carbon adsorption for rsroval of organics fran water. Polymeric resins WBraLTTES) were found in laboratory tests to be approximately as effective as carbon in removing PCBs fran water. Further pilot scale testing is needed with this newer (than cartoon) technology to accurately assees its potential. Ultraviolet catalyzed ozonation wee datamined to be the beet method, demonstrated on a laboratory scale, for destruction of FCBe in wastewaters when the stream oocur in large volute, on a relatively continuous flow basis and with PCBs at the ppb concentration levels. This technology has the potential for conversion of PCBs to CO^, H^O and HC1. However, significant developnmt and optimization work would be required before application of the process becomes practical. In aUitim, the potential exists for production of toxic degradation predicts by UV-ozonation. Although still in the laboratory stage, catalytic reduction of PCBs offers the possibility of reduction to biphenyl and HC1; and catalytic oxidation is another process which offers a potential for destruction of PCBs to C02, H20 and tCl. It is believed that wastewater treatment systems employing acti vated cartoon and poesibly UV-ozonaticn could produce effluents which would be at or below the limits of detectability for PCBs with currant analytical techniques. However, since no full scale systmns for the treatment of PCBs are in operation at this tine, this roesability cannot be confirmed. 14- MONS 208994 Unfortunately, no methodology is presently available which can guarantee "zero discharge" of PCBs to the envirorrent. "Zero discharge" objec tives can be best met now by eliminating discharge streams and developing recycle systems. All streams that are high in pollutants and cannot be treated for reuse, including rainwater runoffs, could be collected and incinerated under a "zero discharge" Objective. 2.3 characterization of the Investment Casting Industry Investment casting is a lost-wax process by \4iich metal castings which are of intricate shapes or which require close dimensional tolerances are massproduced. The pattern wax, sane of which aontains PCB filler, is molded and then used to make a ceramic shell (inveatmeit) whose internal dimensions are those of the desired product. The wax is typically melted from the shell, and the shell is fired (sintered), which rrnmvea the last traces of the wax. Then nolten metal is poured into the noId (shell) and coclad to foot the castings. Than an currently 135 investment casting foundries and four major investmwt casting wax manufacturing plants in the United Statu. The Yates Manufacturing Ccspany, Qiicago, 111., is the sole lorn U.S, supplier of dacachlorobiphenyl (daka) waxes. The daka content is 30 per out of the total wax by weight. Yates currently imports daka from Italy and ttenufeetuns begun 1 and 1.5 million pounds of daka vex annually. Very little is tawwn about the wax manufacturing process, wax manufacturers are also believed to use polychlorinated terphenyls (PCTs) imported from francs. The major losaoe of the virgin and used waxes appear to ooeur during the dewaxing of the ceramic neld. The noId is fired in a furnace to set the sold and ranove the wax. expanding on furnace conditions, the daka or PCT in the wax is either burned or released to the atnosphers. The magnitude of these mnissions is not taiown. Most fasidries recover the drained pattern wax and reuae it several timee, It is estimated that the purchased wax is used an average of 2.5 times. Little of the wax is destroyed in the process; therefore, it is considered probable that the investment casting foundries store or of relatively large anounts of used PCB- or PCP-oontaining wax. -15- MGNS 208995 2.4 Transfearer Service Industry Meat servicing of tranafosnars is performad by electrical repair shops rather than by the utility or the owner of the transformer. Thirteen ccrpames were identified as offering transformer service at a total of 131 locations. Servicing of asfcarel- filled transformers may include the filtering of the askare* to renove degradation products and moisture or the replacement of the askarel with new liquid. PCB wastes include filter media, scrapped askarel, and miscellaneous solvents, rags, etc. The proper disposal of these wastes is specified by a volun tary NEMA standard. Liquid PCBs ara incinerated in most, but not all, cases. The total usage of PCBs by the transformer repair industry is about 800,000 Ib/year, or about seven per cent of the amount used to nanufacture new transformers. 3.0 SUBSTITUTES AtB USE ALTERATIVES FOR PCBS Potential substitute materials and use or process alternatives which would eliminate or reduce the current requiranenta for PCBs were investigated. Inportant points fran this study are swmarized below. 3.1 Substitutes far PCBs in Capacitors PCBs (primarily Aroclor 1016) are currently used in almost all U.S.-made capacitors far AC service (liquidfilled capacitors) and are uniquely suited for this application because of their high dielectric constant, high resistance to current flow and electrical breakdown, chenicel stability, and non-flamebUity. A msber of different liquid materials now under development or tasting have been j.iL'opoeed as substitutss far PCBs In capacitors. Including phthslsts asters, synthetic hydrocarbons, alkylated chlorodiphanyl oxide, alkylated PCBs, diaryl sulfcnas, and silicones. Since eeh of these materials is relatively more flamtable than Aroclor 1016, it appears that use of any liquid substitute will probably pose more of a fire hazard than use ot PCBs. Vulnerability of capacitor manufacturers to lia bility for dmoegaa fran capacitor failure is a major factor in industry acceptance of a substitute capacitor fluid. The conservative code structure now in force oould also pose significant barriers to reduction or elimination of PCBs usage in -16- HONS 208996 capacitors. In addition, data on electrical performance, toxicity to hanans, and ertvironwntal effects of the potential substitutes are not presently sufficient to allow meaningful carparisons with FC3s. Dry AC capacitors (film-type) are in the development stage. These capacitors are significantly larger than liquid-filled capacitors and are limited to a maxitun of 280 volts. Satisfactory dry film capacitors will not be available until there are separate technological breakthroughs: 1) the development cf a plastic film that carbines a high dielectric constant with a low loss-tangent: and 2) the development of winding techniques that exclude all air fran the winding of the capacitor. Although it is considered probable that satisfactory substitutes for pcbs will be developed within the next S years, no such material is presently available and nuch additional research remains to be done. Qn the other hand, a significant portion of the large capacitors used by utilities, and sane in industry, are situ ated out-of-doors. These could be replaced by capacitors containing a more flam mable fluid without significantly increasing ths risk of fire. Although direct replacement of existing PO-filled capacitors with units containing substitutes appears possible for many large capacitors, anticipated sire differences will present severe problems in retrofitting. Ths naw fluids a) n cannot be directly substituted for PCBs in existing capacitors. In addition, of obsolete or replaced units will probably be in landfills for many years to ocme. it is probable that ths best replacanant softens for capacitors, assorting cessation of PCS* production and use, would be use of ren-PCT replacements as units become obsolete or fail. 3.2 Substitutes far PCBs in Transformers Aroclors 1242 and 1254 are currently used in about five per cant of U.S.built transformers; met transformers are cooled with mineral oil. Transformers filled with askarel (60-70 per cent PCBs) are often specified for use in buildings and in hasardous locations Where minimiration of the fire hazard is of paramount important. Ths National Fire Code requires that oil-fIliad units, and aakarelfilled tBits rated for service over 35 kv, be enclosed in fireproof vaults when -17- HONS 208997 used in buildings. For units b*lw 35 kV, the higher cost (by 20 to 30 per cent) of an askarel unit is rare than offset by the savings on vault construction. Open, air-cooled transformers are limited to a clean, dry environments, but are being increasingly used m oumercial buildings. Closed, gas-cooled transformers are more expensive than askarel units, aoth of the above types have voltage limitations and much less overload capacity than the askarel-filled type. Several substitute liquids have been suggested for use in transformers which are less flarmable than the currently used mineral oil, but which are nore flamable than askarel. The nest premising are a silicone oil and a synthetic paraffinic hydrocarbon. These liquids are characterized as being self extin guishing - i.e., they do not continue to bum after being ignited by a momentary electrical arc. Proposals have been submitted to the National Electrical Code to allow the use of these self extinguishing materials under those conditions where askarals are presently specified. Because of the relative lack of service experi ence with these liquids, it is unlikely that these proposals will be accepted. The next Coda revision (1978) will probably continue to recognize only askarel and "oil filled" transfaimers. It is likely that the "self extinguishing" liquids will prove to be satis factory alternatives to PCBs. Substantial experience on the performance of the liquids will be required before the code requirsmnts will be changed to allow their use. The restrictive Electrical Code, which has ben incorporated into the OSHA Standards, may act to inhibit the accixnulation of this data and thereby act to postpone the general acceptance of these substitutes for PCBs. The major conclusion frtxn this portion of the study was that technically acceptable alternatives to the use of PCBs in transformers exist and that their use should not result in s significant increase in fire hazards from transformer failure. At present tha salaction of P3 (askarel) transformers appears to be based primarily on cost rather than technical considerations. As with capacitors, direct replacement of PCBs in existing transformers would preset potentially severe problems. These include the extreme difficulty of moving more than 90-95 per cent of the PCBs, even by repeated flushing with -18- MONS 208998 a ocnpatibla solvent (trichlorcbsnzane), and the raquiranants of incmarat.u'.g such large quantities of FQi and contaminated solvent. 3.3 Alternatives to Other PCBs Applications On a preliminary basis, there appear to be no overriding technical (or institutional) barriers to the use of alternatives to decachlorobrpheiyl filler in investment casting waxes. (This also appears to be the case for the poly chlorinated tarphenyls.) Potential alternatives include use of materials such as isophthalic acid as the filler and uee of the new low-shrinkage unfilled waxes. A coet increase of about ten per cent is projected for each of the above altern atives. Since the voluntary restriction by Monsanto in 1971 of FCBs sales for uee in closed electrical system only, PCBs have largely bean eliminated fran usage in hydraulic and heat transfer system. Adequate substitutes were generally available at the time of the Monsanto restriction, and the present usage of PCTs (believed to be minor) should be replaceable by alternatives with minimi dis advantage. 4.0 sources cr cAovsaarr amor cf pcts into the emvhomut 4.1 Paner Recycling Over the period 1957 to 1971, approximately 45 million pounds of Aroclor 1242 was used by a single producer (NCR) in the production of carbonless copy paper. Seme fraction of this material has entered the paper recycling stream and is apparently a major source of observed PCBe contamination of effluents fran the secondary fiber recovery industry. PCBs were also added to paper in inks and possibly in other additives; this material wee probably Aroclor 1254. Thus, in its effort to conserve resources profitably, the secondary fiber recovery (paper recycling) industry is inadvertantly releasing previously used and "stored" PCBs into the gearal environment, primarily to water. Reliable estimates of the enaiite of PCBs so released are not available, and, although the significance of this nelMee should diminish as office files are snptied, the amounts renaming to be released are not team. -19- MONS 208999 Results Cron an analysis of PCS* entering Lake Michigan, d<imfr| later in Section 5.0, indicate Chat, although there is a significant concentration of paper recycling activities in the area of this lake, the contribution of ppr mills to the total POSs input to Lake Michigan is snail in corparison to atmos pheric fed.lout. However, affluents containing amounts of PCTe which are very snail compared to the total envirormsntal load can be extremely important on a local basis, and further investigation of this problem is urged. It should be noted that water usage in the paper recycling irxlustry is high and effluent K2 concentrations are typically S to 10 ppb. The ooat of FC3s removal would therefore probably be higher par unit of profit than for the other industry categories described herein. 4.2 Effluent Contamination by PCBa in Other Industries High concentrations of PCS* were recently reported in effluents fron a mnbar of plants engaged in the manufacture of machinery and mechanical products. These maasumants have not been verified to data. PQs were, in the past, used extensively in hydraulic and heat transfer systsme, in lubricants, and in paints and plastics, so that it is not inconsistent that effluarts from the machinery manufacturing industry contain PCBa. PCB aontaninaticn of effluents is known to have ocuuired via slow release of old deposits in sewers and elsewhere, although industrial usage in smni-opan applications is believed to be continuing at a low level. 4.3 Inadvsrtmt Production of PCBs in the Enviroment Three general types of reactions were considered as potential sources of inadvertent production of PCSs. Of the three, the one considered most likely to occur is chlorination of biphnyl in wastewater during treatment. This refers specifically to the discharge of wastewater containing biphenyl to a municipal sewer and the subsequent dilorlnetion of the materiel in the treetenant plant. Biphenyl is used extensively as a dye carrier for the dyeing of synthetic fibers; in this application, much of the biphenyl leaves the process as *ste. The sstiaetad U.S. industrial usage of biphenyl is about 50 million pounds per year, of which at least half is usad in dyeing operations. Although chlorination of -20- MONS 209000 biphoiyl in sewage traabisnt appears likely, the extent of neither the initial chlorination nor further chlorination is knewn. Further investigation of biphenyl chlorination as a possible source of POs is reccmended. Chlorinated biphenyls have been produced by the deccrposition of DOT, although this requires recent)inatian of phenyl radicals from cleavage of two DDT molecules. Significant production of FQi in the environment by this mecha nism is considered unlikely. Formation of PCBs via chlorination of the product formed fran the combination of tare substituted benzenes is also considered of less potential significance than direct chlorination of biphenyl in wastewater. 5.0 TRANSPORT AND DISTRIBUTION OF PCS* IN THE ENVUCtWENT A first order mass balance model was developed and used to study the trans port and distribution of PQJs in the envirorment. The total environmental load of "free" PCBs was regarded as a "pool" of mixed PCBs. In applying the model, the pool was assumed to exhibit properties roughly similar to those of Aioclor 1254. The model was applied to lake Michigan; the boundaries of the region studied were taken to be the drainage basin of the lake. Lake Michigan is a nearly closed body of water of sufficient size to allow averaging of properties and of sufficient interest that sane pertinent data ware available. The estimated total input of PCBs to Lake Michigan (1973-1974) was 13,400 lb/yr, of which 1,600 lb/yr came from point sources (smmation of industrial and municipal discharges reaching the lake), 6,400 lb/yr represented fallout directly onto the lake, and 5,400 lb/yr was derived from fallout on the drainage basin (assumed to be 50 per cant of total fallout on the basin). Thus, it is estimated that about 88 per cant of the PCBs currently entering Lake Michigan arise fran fallout. Application of the model produced the following emulative values for the period 1930 to 1975 (input function assured proportional to danestic sales): Total input Total in solution Total in biota Total in sediments 1.49 x 105lb 1.0 x 105 lb 3.64 x 103 lb 1.7 x 104 lb -21- MONS 209001 Tbtal in outflow Total evaporated 9.07 x L33 lb 1-93 x LG'' Lb Since degradation of PCBs in the Lake was assured to be zero, the closing of the material balance depended upon total evaporation fror. the lake being L.93 x 104 pounds, or about 13 per cent of the total input. This value is m excellent agreenent with values derived both fran kinetic theory and from co distillation theory; this result substantiates both the .tcdel form and the material balance above. Average water and biota concentrations derived from the analysis (using a bioconcentration factor over water of 4 x 10 S are, for recent years: 1960 196S 1970 1975 Water Cone, (ppt) 1.60 2.92 5.35 9.10 Siota Cone 64 117 214 364 The above agrees well with available data on lake and biotic concentrations since 1970. Mean residence times of PCBs in air and wetar, and ths transport mechanists which operate at ths various phase interfaces, are very important to ths under standing of anviroraantal transport and distribution. Lifetime values are extremely sensitive to ths asswptiona required for their calculation (required because of the lack of adequate exparimntel data). Estimates derived fran work by others range fran 20 days to eight years for ths average lifetime to fallout of airborne PCBs. Residence times to evaporation in Lake Michigan appear to be on the order of ten hours, based on theoretical calculations, whereas residence times to evapora tion fran sea water may be one to two orders of magnitude lower. The picture of grose PCBs transport consistent with all of the above findings 'L 'the one doninated by air transport. Tarrestial conponsnts, including fresh water, are partial sinks responding primarily to input fran fallout. Lossas are to evaporation and to rivers, which snter the oceans where further (possibly rapid) -22HONS 209002 evaporation occurs. Degradation of FCBs, which was acsvned zs re zero va lake Michigan analysis, appears too slcv to lave a significant effect, frc-ostriil and .municipal effluents and air emissions are sources cf both old and r.ew ?C3s.large antxmts enter landfills and a snail fraction enters the cycle through laacnmg and evaporation. If the above is even partially correct, then one possible answer to the question of why the restriction on uses beginning in 1971 has not caused t'.e hoped for diminution in rC3s distribution is as follows: (1) The systems which cause concern with regard to PCBs (fresh water systems and associated biota) serve as sinks for PCBs; (2) Other possible sinks are not available or are ineffective in retaining PCBs; and (3) The environmental degradation of POi is too slow to be significant over a five year period. Further work in many aspects of PCBs transport and distribution are needed m order to estimate the real magnitude of the future environmental problem from these materials. Such work should also assist in identifying potential methods for re ducing the environnsntal load of POs. 6.0 REGULATORY ACTIONS CM PCBs Four government agencies, the Monsanto Catpeny and NEMA comprise the regulatory forces currently restricting the use and distribution of PCBs. EBA, OSHA, FDA and USQA have, between them, authority to regulate and monitor food levels, disposal into waterways, industrial housekeeping, and safety practices in the work place, Each of these available authorities has a limited focus and is inadequate to pre vent sore PCBs from entering the snvixonment. There are currently no regulations to restrict the importation of PCBs as a disucal for use in applications banned by the Monsanto Cotipsny. As a result, PCB is being imported by a few ocnpanies for use in several "open-end1' or "naiunallyclosed" applications. -23- MONS 209003 Several producing natrons have voluntarily limited sales of PCS*, sue* 1972, japan has banned production and importation of PC3e. Tbs united Kingdom has barred sales of ?C3s to all applications except usage as dielectric fluids, while Genreny has lessened this restrictive measure to include use in heat transfar and hydraulic systems. Among nor-producing countries, Sweden and Norway have stringent regulations. In Sweden, only the Environmental Protection 3oard can authorize the use of PQe or ouepounds containing PGSa, while in Norway only the Ministry of Social Affairs can authorize the use of PCBe. -24- MONS 209004 SECTION III CCNCLUSICNS AND RECCMJDA,TICNS 1.0 Conclusions Conclusions which have resulted directly fron the work reported herein are presented below. Sane of these have been discussed briefly lt. the preceding section, but each is believed to be justified by information contained in the text of the report and ths appendices. (1) It is estimated that approximately 1.25 billion pounds of PCBs have been sold for industrial use in the U.S. since initiation of production around 1930. (2) Of this amunt, at least 95 per cent are still in existence; most is in service in capacitors and transformers, but about 290 million pounds are believed to reside in landfills and dunps and about 150 million are believed to be ''free" in the environment. The magnitude of these values indicates that there is a strong future threat from PCBs present in land disposal sites. (3} In 1974, U.S. usage of FOi sold by Monsanto, the sole domestic producer, was distributed between capacitor manufacture (22 million pounds) and transformer manufacture (12 million pounds), Imported materials smuntad to about one per cant of I'.S. industrial purchases of POs in 1974; about 400,000 pounds (of decachlorobiphenyl) were used in investment casting and and an estimated 50,000 pounds of new material were used in specialized hast transfsr systems. (4) Waterborne effluents from PCBs production and first-tier use currently release siounts to the enviromsnt which are very snail in caparison to the amounts entering land disposal sites fra these industries. However, these efflusnts can have sewer* local impacts, as evidenced by the currant POs problM in the Hudson River. -25- MONS 209005 (5) Monsanto and portions of the electrical equipment industry - utilizing PCBs have greatly reduced PCB releases to water and land over the past few years, primarily through improve ment of plant housekeeping, improved waste collection and handling, and disposal of liquid wastes through incineration* (6) There is no plant-scale process used at present for the specific purpose of rsnoving PCBs from industrial wastewater. (7) the best available treaonent technology for removal of PCBs fron wastewater is carbon adsorption coupled with solids and oil/grease rsroval, Carbon treaewnt can produce end-of-pipe PCBs concentrations of one ppb or less. Other adsorbents, such as resins, also appear effective to this extent* (3) The most premising method, of those water treatment technologies under development, for PCBs destruction is ultraviolet-catalyzed ozonation. (9) Incineration is an effective method of disposal for liquid PCBs. Landfilling is the only generally available disposal method for PCBs-oontaminated solid wastes, but incineration of these wastes is technically feasible. (10) "Zero discharge1* to water of PCBs fron production and firsttier use is available only through extensive water reuse plus extensive incineration of lightly contaminated wastewaters, (11) Significant amounts of solid PCB (decachlorobiphenyl, or deka) wastes are stored or disposed of on land by the investment casting industry. Air emissions of deka may also be significant in amount, but no evidence of potential health hazards from this material has bean reported. (12) The total present usage of PCBs for open and semi-closed applic ations is not known but is believed to be small in caiparison to closed electrical system usage. A few capacitor manufacturing -26- MONS 209006 plants report recent use of POs in vacuun purp*, and a significant aircunt of carbonless copy paper containing PCBs must still be in inventory and in files, (13) Chlorination of waste biphenyl in industrial wastewaters discharged into rrunicipal sewers is a potential mechanist for inadvertent production of PCBs. (14) PCBs are uniquely suited to the requirements of capecitors for AC service. Although a nurber of potential substitutes for this application are under development and test, they are all more flamnable than Aroclor 1016 and neither their performance in service nor their potential toxicity to nan and other species have been evaluated sufficiently to allow a definitive oenparison with 1016. (15) Alternatives to PCBs usage in new transformers are available. In addition, tasting of premising substitute fluids (termed "self-extinguishing") is underway; these fluids may gain industry-wide acceptance within three years as substitutes for PCB fluids. At present, specification of PCS-filled trans formers appears to be based primarily on oost considerations. (16) No technical barriers to substitution for PCBs (deice) in investment casting waxes are apparent. Several potential alternatives have been previously used by this industry. (17) Atmospheric fallout is a major source of PCBs input to fresh water systens. In Lake Michigan, the PCBs contribution at present appears to be rtueh larger then the total of PCBs inputs from point sources such as nunicipal sewage treatment and paper recycling. (18) The importance of atmospheric transport of PCBs relative to other potential inputs to water indicates that the availability of anvironnantal sinks from PCBs is limited, possibly due to short residence times to evaporation in sea water. -27- MONS 209007 (19) At present, regulatory authority over PCSs in the United State* is insufficient to significantly reduce future PCSs inputs to the environment, although inputs directly to the waterways fron industrial sources can be reduced from their present level. Current disposal practices, except for in cineration, tend to delay instead of prevent the PCBs entry into the "free" (available to the biota) state, and these practices are regulated only minimally. 2.0 REOCPMENSATIONS During Decnber, 1975 and January, 1976, ETA AAninistrator Russell Train called for a cooperative effort between Government and industry to eventually eliminate PCBs from production and usage in the United States. The recormendations listed below ware developed with this objective in mind, although each reoannendation also reflects the still existing needs for further definition of the current and future PQa problem and for the develojnent of methods for reducing the potential damage bo tauten health and the environrent. (1) The current distribution and losses to the wvixcnnsnt of PCSs should be defined more accurately, study is needed for the following aspects of past and presant usage: (a) Present extant and distribution of usage in semiclceed systems such as heat transfer and hydraulic systems (dissemination of information concerning PCBs affects end available substitutes will result in wluntaiy reduction of PCBs usage); (b) Definition of pest and present usage in investment casting, including quantification of air eniaaiona, disposal on land, and waterborne ocntaminatlont (c) Preemit distribution and projected future trends for PCBs in the pulp and paper industry, especially the secondary fiber reoovery portion; and -28- MQNS 209008 (d) Extent of inadvertent PCBs contamination in . effluents from other industries which are currently not purchasers of PCBs. (2) The basic transport properties of PCBs, particularly those re lating to evaporation and atmospheric fallout, should be studied in depth. This and other information should be used to investi gate global transport characteristics of PCBs and to predict the potential magnitude of the global PCBs problem. Potential sinks and destruction methods for PG3s should be investigated. (3) The type of analysis presented herein for Lake Michigan should be further expanded and refined for application to other important fresh water systsns. The model should be extended to a prediction of future effects and the influence of possible reductions in PCBs usage. (4) Transport of PCBs from landfills should be investigated; in particular, potential methods for delaying or reducing PCBs release from landfills should be studied. (5) Development and testing of potential substitutes for PCBs in capacitors, transformers, and investment casting vxn should be encouraged strongly. Technical and institutional barriers to the use of alternatives should be attacked on all possible fronts as soon as possible. Extensive toxicological testing of proposed substitute materials should be performed prior to acceptance. (6) Methods for treatment of PCBs-contaminated water effluent should be developed and applied. Research and development activities on directly destructive treattnent methods, such as UV-assisted ozonaticn and catalytic oxidation or reduction should be encouraged, but further work on adsorptive techniques is also needed. -29- MQNS 209009 (7) Alternative approaches and schedules for PCBs elimination ' from U.S. mmietfoa should be evaluated with regard to technical feasibility, institutional acceptability, and eoonanic and environmental iirpact. Based on these considerations, an optimized path to PCBs elimination should be developed. (8) Possible inadvertent formation of PCBs in the environment should be studied; in particular, it is rsoamanded that the chlorina tion of biphenyl in wastewaters be evaluated as a potential source of PCBs. -30- HONS 209010 SECTION TV CHEMICAL AND PHYSICAL PROPERTIES OF CHLORINATED BIPHENYLS 1.0 INTRDDUCnCN The purpose of this section is to present a precis of cl* salient charac teristics of the ccnmercial preparations of the polychlorinated biphenyls 'which have generated concern as environmental pollutants. The eiphasis is directed to those properties that have led to the relatively widespread use of these materials. In addition, attention will also be directed to those physical and chemical properties that contribute to the environmental effects arising from the general distribution of these materials. The discussion is not meant to be exhaustive, but rather to offer the basic technical information that is used to support the other sections of the total report. The most ootplets oonpilation of the relevant infoanetion that has been published to date is that by Hutzinger et al (0. Hutzinger, S. Safe, and V. Zitto, "The Chenistry of PCBs", CRC Press, 1974} and the authors express their debt to this publication. 1.1 The OMmistcy of the Chlorinated Biphenyls The polychlorinated biphenyls (PCBs) constitute a large class of caipounds produced by the pertial (or conplsts) chlorination of the biphenyl mole cule. Since their introduction in 1929 in ccrtnercial quantities, these compounds, or rather ccrtnercial mixtures of various matters of the class, have been applied in a considerable variety of industrial applications. The unique physical and chemical properties of these carpounds, including low vapor pressure at artoient toiperatures: resistance to centalstion; markable chemical stability; high dielectric oonstant and high specific electrical resistivity have been utilized in such applications as electrical insulating fluids; fire resistant heat trans fer and hydraulic fluids; lubricants for use at high toiperatures and pressures in critical applications and as a constituent in a variety of elastomers, adhesives, paints, lacquers, varnishes, pigments and waxes. -31- MONS 209011 PCS* and mixtures of chlorobiphenyls have bean prodLc*d in a nuiber of countries and marketed under several trade names including Arcelor, clophen, Phenoclor, Kanachlor and Fenclor. The essential characteristics of all these mixtures, which depend in detail on the specific mixtures of chlorobiphenyls that make up the specific preparation, are sufficiently alike that it will suffice to discuss all in terms of the Aroclors, which is the trade name of the preparaticr.s of Monsanto Qwnical Ccrpany. In those special cases wherein there is sera particular property peculiar to one of the foreign PCB mixtures, a note will be made. A great deal of confusion has appeared in the literature because of the ncmnclatuxe that is used to describe the ccnmercial preparations and the individual authenticated chlorobiphenyls. In order to clarify the ncranclature to be used herein, it is appropriate to digress briefly as follows. The biphenyl irolecule has a total of tan (10) carbon-hydrogen bonds at which chlorine sub stitution can be accommodated. A schmstic representation of the biphenyl mole cule with the various positions at which substitution can be acocnplished lumbered in the American Qtnical Society standard notation is presented belcw: 5* 6* 23 3* 2' 6S ACS Convention for Numerical Assigtmsnts of Biphenyl Substitution In the interest of a ocranon usage, the following rules will be followed in this report; a, Vhsn referring to a mixture of different species, as occurs in the conmarcial products, v will use the term polychlorinated biphenyls or the acronym PCB. -32- MQNS 209012 b. Those species of chlorinated conpounds that arise frcm a specified marfaer of chlorine substituents on the biphenyl molecule will be referred to as chlorobiphertyls with a suitable numerical prefix to define the miter of sub stituted chlorines: i.e., dichlorabipher.yl. Thus, there are a total of ten (10) chlorobiphertyls that might appear in the earnerical mixtures. c. Those specific ccnpounds that represent the class of oerpeunds formed by a specific nuter of substituent chlorine atone but differ in the locations at which substitution has taken place are referred to as isomers. Thus, in terms of the above, the proper manner of referring to a camercial PQ3 mixture is as a "mixture of chlorobiphenyls containing various proportions of ths iosners of each". To illustrate the utility of the mitering system indicated pre viously, the correct names of the compounds shorn belo* are: Cl Cl 2,3',5,5'-tetrachlorobiphenyl NH. Y Cl Cl 3',4,4',S-tetrachloro-2-biphenylamine 33HONS 209013 The tan chlorobiphenyls and son* of the salient chenical data are listed in Table 1.1-1; note that the total of all the isomers of the chlorobiphenyls are 209 separate ccrpounds. 1.2 Cemercial Production and Chemical MaXeup of the Aroclors The camercial process by which the PCBs are made involves the chlorination of biphenyl with anhydrous chlorine in the presmca of a catalyst which may be either iron filinos or ferric chloride. The crude orodict is cenerallv purified to remove aolor, tracee of hydrogen chloride, and the catalyst by treeonent with a)Jli and subsequent distillation. The resulting product is then a mere or less aonplex mixture of the chlorobipheryls, the precise opposition depending on the conditions under which chlorination was carried out. The approxi mate oenpoeition of selected Aroclors is given in Table 1.2-1. By way of aoqslanatien, the products made by ftonsanto under the trade name Aroclor are designated as to the starting material, with biphenyl represented by the 12 prefix, and with the approximate chlorine percentage by the second set of digits; i.e., Aroclor 1248 is s chlorinated biphenyl containing approximately 48 percent chlorine. Fim the data prtaantad in Table 1.1-1 and 1.2-1, it might be inferred that all of the isomers of the individual chlorobiphenyls are to be found in each of the aomnerclal mixtures. Tb illustrate the actual situation, Aroclor 1248, v4iich is made primarily of the di-, tri-, tetra-, penta- and haxa- chlorobiphenyls, Gould be expected to contain something of the order of 140-150 separata isaners. In point of fact, there are leea than 50 identifiable peaks observed in the high resolution gaa duomatogm of typical specimens of Aroclor 1248 as is illustrated in Table 1.2-2. Tlw observations relative to the high resolution studies of the ccmnercial Aroclor mixtures have been sumerized by Hutzingar, at al (ibid), in the fans of Figure 1.2-1 whidi indicates the structural units of which the signi ficant isoeae are oonstruetad. -34- MONS 20901V Table 1.1-1 Empirical Formulation, Molecular weights and Chlorine Percentage m ?CBs Empirical forrtiula chlorobiphenyls C12H10 cI2H9CI C12H8C12 C12H7C13 C12H6C14 C12H5C15 C12H4C16 C12H3C17 C12H2C18 C12lC19 C12C110 Baaed cn Cl35 Molecular weight* 154 138 222 256 290 324 353 392 426 460 494 Percent chlorine* 0 18.6 31.5 41.0 48.3 54.0 58.7 62.5 65.7 68.5 79.9 '<2. c: iscners 1 3 12 24 42 46 42 24 12 3 1 -35- MONS 209015 Tabic 1.2-1 Approximate Molecular Composition of Selected Axoclors Chlorobiphenyl C12H10 C12H9C1 C12H8C12 C12H7C13 C12H6C14 C12H4C16 C12H3C17 C12H2C18 C12H1C19 C12ai0 1221 Aroclor Type or Grade 1242 1248 1254 1260 (Ercent ce.uposition) 1016 U <0.1 51 1 32 16 4 49 2 25 0.5 8 M3 1 ND <0.1 M3 M3 M3 M3 M3 M3 2 18 40 36 4 <0.1 <0.1 0.5 1 21 48 23 6 M3 M3 M3 12 38 41 8 1 <0.1 1 20 57 21 1 <0.1 M3 M3 M3 M3 36HONS 209016 Table 1,2-2 High Resolution Gas Chranatoqraphy of Aroelor 1248 Peak nutter* 1 2 3 45 6 7 3 9 10 11/12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41/42 43 44 45 46 NO. Of Cl 2 3 2 3 3 3 3 3,4 3,4 3,4 3 3 3 3,4 3,4 3,4 3,4 4 4 3,4,5 4,5 4,5 4 4 4 4 4 4,5 4,5 4,5 4,5 5 5 6 4 6 5 5,6 6 6 6,7 % In Aroelor 1248 0.4 1.0 3.2 11.2 3.2 3.1 2.0 1.4 1.4 0.8 8.5 9.7 2.1 7.4 7.4 6.0 4.5 3.1 2.6 0.8 1.2 1.0 0.2 5.0 3.3 2.0 2.1 1.0 0.5 0.5 0.8 1.0 0.4 <0.1 <0.1 0.2 0.3 0.2 <0.1 0.2 (0.7) % In fatty tissue 0.9 1.4 0.9 2.4 0.5 0.2 4.8 0.8 0 1.6 1.6 0.8 0.5 - 7.0 4.1 0.3 0.4 - 1.0 - - 5.3 2.0 0.4 0.5 2.9 29.0 1.4 - 1.7 1.4 0.1 0.1 11.0 1.1 8.0 5.3 0.9 (1.1) -37- MONS 209017 Figure 1.2-1 Moieties fran which Principal Chlorobiphenyl Isomers are Formed The moat cannon subrtitution pattern* for the chlcrobiphenyls fond In PCS preparation*. Only one phenyl-ring is shewn. The moat abundant tetraehlorobipberryls, for exxrple, are those fran the dichLozophenyl-noieties shown. One di- and one trichlorophenylwould give neat abundant penta-chlorobiphanyls, etc. 38-- HONS 209018 Several carments are necessary at this point: The rrportance of such detailed determination and identification of the isaners characteristic of the conrnercial PCBs lies in the observations, to be discussed below, that bioaccunulated chlorobiphenyls shew what appear to be significant differences in the distribution* of the individual isorters from the source materials. The nest pro bable explanation for these observations seem to be that at least sate of the chlorobiphenyls are metabolized principally to hydro-chlorotoiphenyls. Only after very aaiplete isawric spectra are available can such effects be properly studied. Secondly, the detailed study of the PCBs has shewn that there are no major oenpeunds in these mixtures aside from the chlorobiphenyls. On the other hand, products formed by the addition (rather than by substitution) of chlorine to the biphenyl molecule in laboratory studies, yield significant con centrations of partially saturated structures. These structures are apparently either not formed under the conditions of chlorination that preveil during the industrial processing or alternatively are destroyed during the purification steps of tht process. In contrast to ths Arodors, sens of ths foreign products have shorn traces of polychlorinated naphthalenes and polychlorod ibenaofurans ? a fact that may have oonsiderabls toxicological significance in view of the rather more toxic nature of these latter products. However, recent information published by FDA indicates that iiqpurities of ehlorodibensofurans have been also detected in Aroclors. 1.3 Physical Properties of the PCT Aroclors The relevant physical properties of ths Aroclor mixtures naturally separate into two groups; those properties that have led to the widespread in dustrial use of these msterials, and those properties that result in the intro duction of these materials into the enviroment with what appears to be con siderable potential danger. 1.3.1 Physiol Properties of Industrial and Technical interest The most useful ccrrpilation of the physical properties of the various Aroclors that has so far appeared in the literature is that given by Hutzinger, et al (ibid), a portion of which is herein reproduced (with minor changes) as Table 1.3.1-1. -39- HONS 209019 ~0 HONS 209020 In addition to the chenical stability and resistance to oorrbustion illustrated in Table 1.3.1-1, the electrical properties of the PC3 Aroclors are of extrane significance in the utilization of these materials. aonpilation of the relevant data is presented as Table 1+3.1--2, which illustrates the nature of the prablen that is encountered when one undertakes a search fcr a suitable substitute for these confounds in such segments of the electrical in dustry as the manufacture of capacitors. Specifically, the dielectric constants for most dielectric liquids lie in the range up to perhaps half of that of the polychlorinated biphenyls. 1.3.2 Physical Properties of Ehvirormental Interest The essentially world-wide distribution of the chlorinated hydrocarbons such as the PCBs suggest that a major route by which such ocrpounds are transported is through the atncsphere either in the form of vapor or perhaps sorbed onto dust particles. In addition, it is observed that there is a wide spread accumlation of these uoipounds within the biota ranging frem the smallest an up the food chain until truly enormous loeda are found in the highest mothers of the chain. Sinoa this bioaccuiulation also includes the aquatic biota, the possibility of aonaiderabla transport via the solubility of these ocrpounds in water mist also be taken into accoimt. Table 1.3.2-1 lists sane of the vapor pressure and solubility data for several of the Aroclors (0. MacKay and A. w. Wblkoff, Env. sci. and Tech., T_, 611 ff (1973)). The analysis of co-evaporation (MacKay, ibid) of dilute solu tions of the Aroclors by equilibrium thantodynamics suggests that, because of the vary high activity coafficients of the chlorobiphsnyls in water, the potential for evaporation is quite high enough that this mechanism is a major portal by which such uonpounda enter the atmosphere. The fourth oolutn of Table 1.3.2-1 indicates the theoretical time for a fifty percent reduction in the concentration of the Arcelor fran a saturated water solution (pure water plus PCBs), assuning the water depth to be 1 meter thick. Clearly, the results of this analysis need to be ex perimentally verified. -41- MONS 209021 Table 1-3.1-2 Electrical Properties of Sam Aroclors Aroclor Dielectric constant at 1000 cycles* 7PZ--------- 100 Volume res, ist.ivity, b 8 an at 100C 500 V, de 1232 1242 1248 1254 1260 1268 5442" 5460* 5.7 5.8 5.6 5.0 4.3 2.5 3.0 2.5 4.6 4.9 above 500 x 109 4.6 above 500 x 109 4.3 above 500 x 109 3.7 above 500 x 109 4.9 acove 500 x 109 3.7 '' T Dielectric strength,0 w >35 >35 >35 >35 -- PCTesr ! actor,a 100C, 1000 cycles, \ <0.1 <0.1 <0.1 <0.1 -- *ASrm MSO-47T bASTM D-257-46 CASIM >-149-44 Polychlorinated terphenyls 42- HONS 209022 Table 1.3.2-1 Solubility, Vapor Presure and Halflife for Vaporisation from Water of Selected Aroclors at 25SC PCB Type Aroclor 1242 Aroclor 1249 Aroclor 1254 Aroclor 1260 Solubility (mg/1) 0.24 5.4 x 10"2 1.2 x 10~2 2.7 x 10"3 Vapor Pressure (ntn Hg) 4.06 x lO-4 4.94 x 10-4 7.71 x 10"S 4.05 x 10-5 Theoretical halflife for vaporization frcn 1 m. water 5.96 hr. 59.3 min. 1.2 min. 29.9 min. -4> HONS 209023 As pointed out above, not only is each of the Arcclors a mixture of several chlorobiphenyls, but there are a number of isomers present for each of the chlorcbiphenyls. Thus, the solubility of an Arcelor, or the vapor pressure of an Aroclor, represents an average over the various species that make up the mixture. Tto illustrate the effect of the structural complexity, Table 1.3.2-2 (Hutzinger, ibid) details the measured vaporization rates of the several Aroclors. Ch the other hand, the changes in the mixture corresponding to Arcelor 1254 on extended heating are displayed in Table 1.3.2-3 (Hutzinger, ibid). The possible implications of these data lie in the fact that nuch of the Aroclor that is found in typical enviroimental samples sear* to demonstrate lesser amounts of the lc*er chlorine number chlorcbiphenyls than is characteristic of freshly manufactured samples. This observation has frequently been attributed to possible metabolism of the more lightly chlorinated species coupled with enhanced fixation of the higher chlorinated species. A partial listing of the measured solubility in water of identified authentic chlorobiphsnyls is shOMi in Table 1.3.2-4 (Hutzinger, ibid) and the effect of the solubility differences of the individual chlorcbiphenyls cn the constitution of Aroclor 1254 solutions is illustrated in Table 1.3.2-5 (Hutzinger, ibid). A factor that is meet probably of considerable importance in tht admission of such oenpounds aa the PCBe into the environment is a measure of the partition coefficients between such interface systmm as soil-air; soil-water; lipids-water; and, more generally, water-solid particles. At the present time there seers to be very little actual data available in direct form, although nuch should be possible to infer from the effects of various combinations of stationary phase and support in gas chromatography cn the retention index. An interesting and probably significant point of datum has ban presented by 0. R. Branson of the Dow Oaedcal Co., tds reports that the distribution of 2,2',5 triehlorobiphenyl beaiesn elirjgs uatsr eir wes 92l-3t-5t, respectively. -44- MONS 209024 Table 1.3.2-2 Vaporizetier Rates of Aroclors Aroclor (Surface area: 12.28 an2) 1221 1232 1242 1248 1254 1262 1260 1270 (Decs) wt. loss <g> 0.5125 0.2572 0.0995 0.0448 0.0156 0.0039 0.0026 0.0015 Exposure at 100#C (hr) 24 24 24 24 24 24 24 24 Vaporization rate (g/an2/hr) 0.00174 0.000874 0.000338 0.000152 0.000053 0.000013 0.000009 0.000005 -45MONS 209025 Table 1.3.2-3 percent Lose in Area of Seven Chrcmatogran Peaks of Arcelor After Heating Aroclor 1254 peak 1 2 3 4 5 6 7 % Peak Remaining After Heating with water without water 25 min 60 min 10 min 34 17 59 26 78 27 60 46 86 49 100 85 100 67 13 15 20 20 27 28 16 -46- MONS 209026 'able 1.3.2-4 Solubility of Chlcrobiphenyls in Water Ccrrpound Monochlorobiohenylj 2- ' 3 4- Dichlorobi phenyls 2,4 2,2' 2,4' 4,4'- Trichlorobiphenyla 2,4,4' 2',3,4- Tfctracftlorobiphanyls 2,2',5,5' 2,2',3,3' 2,2',3,5'2,2',4,4'2,3',4,4'" 2,3',4,53,3',4,4'- Pentachlorobiphenyls 2,2',3,4,5' 2,2',4,5,5'- Hexschlorobiphenyl 2,2',4,4',5,5'- Oetachlorobiphenyl 2,2',3,3',4,4',5,5'- Decachlorobipheryl 4,4'-Oichlorobiphenyl +Tween 90 0.11 -^^Vaen 80 18 -Htadc acid extract Solubility mg/1 (ppm) 5.9 3.5 1.19 1.40 1.50 1.39 0.09 0.095 0.079 0.046 0.034 0.170 0.068 0.058 0.041 0.175 0.022 0.031 0.0098 0.0070 0.015 5.9 >10.0 0.07 -47- MONS 209027 Table 1.3.2-5 Relative Peak Heights (Peak 5 * 100) in Saturated Aqueous Solutions off Aroclor 1254 Peak No. 1 2 3 4 5 6 7 8 9 10 11 12 13 Saturated aqueous solution (26*0 172 91 47 14 100 33 57 5 21 8 4 11 6 Saturated aqueous solution (4*0 Aroclor 1254 starriard 144 35 72 16 41 30 91 100 100 28 23 59 55 5 10 24 25 13 31 46 24 so 10 11 -48- HONS 209028 1.4 Oisniral Properties of the Chlorobiphenyls Considerable detail on the rest important chemical reactions that are known to occur with the chlorobiphenyls is presented in Chapter 5 of the treatise on "Hie Chemistry of the PCB" by Hutzinger, et al. Suffice it to say here that oxidation and hydrolysis can be carried out, but only under corditions which are considerably more rigorous than would be obtained in industrial applications. This relative stability is, of oourse, one of the most attractive features of these carpounda in technological practice. The class of reactions to which the chlorobiphenyls are susceptible and which is of most interest in terms of their possible toxioological significance are those which result in cyclization. Of particular interest in this context is 2,2' dichlonobiphanyl, which on cyclization yields the ccrpound dichlorodibenzofuran The toxioological data on these two occpounds indicates the nature of this change: the L0q for oral doses to rats is of the order of 250 mg/kg for the dibenzofuran whereas the corresponding toxicity for the chiorobipherty1 is in excess of 4000 mg/kg. (Data from the "Toxic Substances List", HEW, 1973). The close proximity of the 2 and 2' substituents on the biphenyl molecule facilitates intermolacular cyclization reactions under a variety of con ditions. Of special interest is the observation that alkali fusion of 2-chioro21 -hydroxybiphenyl and the dehydration of 2,2' -dihydrcxychlorobiphenyl yield the corresponding chlorodibnsofurans; hydroxylation of the chlorobiphenyls is the aamm initial step in the metabolism of these aonpounds. The immediate biological significance of thia is untaiown at this time since the chlorodibanzofurans have not ben isolated from animal experiments. 1.5 Photochsnical Reactions Involving the PCBs A great deal of effort has ben directed to the study of the effects of ultraviolet (W) radiation on the chlorobiphenyls since photodestruction is believed to be a major mechanism for the nvixornental decay of chloro- hydrocazbon pesticides such as DDT. There has ben much speculation as to the role that W photaodlsintegration might play in terms of the chlorinated biphenyls. The --work ei carried out using mercury vapor UV sources with the result -49- HONS 209029 that, bscauss of the significantly harder radiation (mercury source 250 ran, solar radiation at surface of the earth with an effective cutoff at 290 nm), cross section and reaction paths are difficult to extrapolate to environmental situations In rtcra recent times, such irradiation studies have been carried out using General Electric "Black. Light" sources which nuch note nearly approximate the spectral distribution of solar radiation, A niTiber of types of effects have been observed including partial dechlorination and even, in sane cases, the formation of very viscous semi-solids that apparently arise from carpiex polymerizations. Again, the extension of the experimental results to environiental conditions is somewhat limited in value since the majority of the irradiation studies have ben carried out in solvents other than water. The very low solubility of even the least chlorinated chlorobiphenyls in water makes the experimental study of aqueous solutions especially difficult, particularly whan the information of concern is the quantitative evaluation of the reaction products that are formed. It nust be said, at this time that the probability of UV disaseociation being a major source for the environ mental decay of the dUorobiphanyls seam to be significantly less than that for the chlorinated hydrocarbon pesticides. Since it is assured that a major portion of the chlorinated biphenyls are transported and distributed throughout the world through the median of ad sorption on dust particles or as a vapor, it follows that studies of the stability of thin sorbed film or of vapors of the dilorinatsd biphenyls against long term UV irradiation are of importance. The earlier attsnpts to discover the presence of reaction products resulting from long term exposure of selected chlorobiphenyls to solar rsliation were svbject to the differential evaporation of the lass chlor inated species; this result seriously biased the observations. The recant experi ments that ham been conducted within quartz containers seen to obviate evaporation problens and, further, seam to indicate that the mono- and diohlorobiphanyls are essentially ocapletely destroyed whan exposed to herd w for times of the order of weeks or months. Problems of detection sensitivity continue to plague attempts to elucidate the detailed mechanists and oathways. -50- HONS 209030 Studies of thin films of chlorobiphenyls sorbed onto appropriate surfaces ham also been carried out within a quartz enclosure. TO date, the major objection to such experiments, in terms of extrapolation to environnental conditions, aeena to be that the concentration, or rather the absolute density of the surface layer, is sufficiently high that the activated species retain in contact for sufficiently long times as to allow the formation of products that might well be vary rare events in corresponding environmental concentrations. At this timt there appears to be significant research being directed to the determination of the stability of chlorobiphenyls against ultraviolet radiation and that it is to be expected that the situation which obtains in typical environnsntal renditions will be greatly illurinated in the near future. 1.6 Mehniir Qimistry of the Chlorobiphanyle The vary oenbination of physical and chemical properties that have made the chlorobiphenyls and their tedwical mixtures of such wide technical interest also result in these oonpounds being of significance as environmental pollutants, especially in terms of their inject on tha biota. The very low chanucal activity, coupled with high lipid-weter partition coefficients, ap parently contribute to the bioaocwulation whereby the chlorobiphenyls, pecially the more highly chlorinated species, tend to beoape fixed within the body fats and particularly in higher umbers of the food chain. There is evidence that this fixed load of refractory chlorinated organic materials, or the circulating levels of ths sane oespounds that oust aooocpany such fixed loads, represents a serious hazard to the bearer or progeny. The tootle consequence* of body burdens of chlorobiphenyls is note fully iliannsed in the section of this report concerned with toxicology of the chlorobiphenyls. Ths mechanist* by which an organisn can deal with ingested refractory ccrpounds are naturally separated into physical and dwical processes. The physical prooasses are primarily associated with tha requirements of free energy across the boundary between differing phases such as a water-lipid boundary, or a cell well, etc. Since there does not exist a significant body of partition coefficient data for various oenbinations of interfaces, little of a quantita tive nature can be stated as to the biological significance of such physical processes. -51- HONS 209031  On the other hand, as is pointed out in Section 2.4, hydroxylation is a rather easily accaiplishad process for at least the less chlorinated chlorobiphenyls, Thus, it might be assumed that one should observe the hydroxylated chlorobiphenyls as intermediate metabolic products in a variety of organists. Ebqserimental data is available to indicate that such hydroxylation processes are indeed exhibited by a wide variety of organiars. The principle species re lated differences seen to be in the rate at which such processes are found to occur -- very rapidly in rodents and vary slowly in fish. In addition, once the target chlorobiphanyl has bean hydroxylated to a more or less degree, there appear to be available a wide variety of species-specific addition processes which oould make use of the hydroxylated molecule. Interestingly, there is to data no evidence of biologically or metabolically induced eyeliration; it thus appears likely that the chlorodibenzofurans are not biologically formed. The salient observations to date on the metabolism of chlorobiphenyls might beet be sumarized as follows; a. Mian the challenge to the animal is a technical mixture of chlorobiphenyls, there is a preferential storage of the tore highly chlorinated species, with the result that the hcnologue spectrun of stored PCBe often rapeesmts a more heavily chlorinated mixture than the original test mixture. b. There is conflicting and often species-dependent date aa to the mschanisn by which the less chlori nated species are differentiated; whether the pro cesses involve mstabollsn, physical partitioning, or eoa combination of such processes has not bean settled. -52- MONS 209032 c. Conflicting and confusing evidence exists indicating - marked differences in accunulaticn and differentiation between specific isaners especially at the middle levels of chlorination. These differences also seem to be species^dependent in a nurber of cases. d. There is significant evidence that P(3 metabolian proceeds through an intermediate step of hydroxylation {often this appears to be the terminal step whereby the increased aqueous solubility of the hydroxylated species acconplishes the end of its ranoval). e. There are several observations indicating that iso merization can be accomplished during metabolic reactions. In this oantext, the results of Bagley and Cranartie (Baglay, G.E. and E. Cranartie, J. Chron. 75, 219-226, (1973)), with the elimination of Aroclor 1254 in the Babwhite, axe most pertinent. In conclusion, there has bean nuch work directed to the study of the mechanise whereby living organise are able to eliminate chlorinated biphenyls frcm their system. In spite of this effort and because of the inherent cmplexity of this sv&ject, tha nature of these mechanise raoains a mystery. -53- HONS 209033 SECTION V INDUSTRIAL CHARACTSUZATICNS 1.0 INTRODUCTION This section discusses polychlorinated biphenyls (PCTs) production and each PC3s user (capacitor, transformer, investment casting, paper recycling and miscellaneous) manufacturing process, when known, for each operation the following information is given: . Name and the location of oanpanies in each category; . A description of the processes at the facilities studied and pertinent flow diagrams, where appropriate: . Ra* waste load data per ton of PCS used and souroes of these wastes; . Water usage data in tame of gallons per day; . Treatment and housekeeping measures practiced at the facilities and on-going PCS ccntaiment program; . Plant waste effluents found and their opposition. 2.0 t*NUE3CTORDC PROCESS - PCLYOttORDMII) BIPHENYLS (PCBe) 2.1 Process Description Monsanto, the sole domestic manufacturer of PCBe, manufactures this chemical in their Saugst, Illinois plant. The basic raw material is biphenyl which is menufactured from pure benzene in another Monsanto plant. The PCS manufacturing operation is conducted in two steps. First, biphenyl is chlorinated with anhydrous chlorine in the presvwe of ferric chloride to produce <*"*<* PCBe and then the crude PCBe are distilled to obtain the finished product. A schematic flew diagram of this process is gi\mn in Figure 2.1-1A and B. -54- MONS 209034 ?IXRi 2.1-LA. PREPARATION OF CRUDE CHLORINATED BIPHENYLS-MONSANTO KRUMMRICH PLANT MRHPffL M). ATCH CHLOR1NATOR wa ui m AMCOR LOWfA TANK RAW AROCLOR STORAAC Ftaxe 2.1-IB. OtSTtLATTON OF CRUDE PROOUCTS*MONSANTO KRUMMRICH PLANT 55- HONS 209035 ' The reaction section consists of 6 reactors (3 batch and 3 cascade). Currently, Monsanto manufactures fair different types of Aroclors (1242, 1016, 1254 and 1221). For the manufacture of any given product, the chlorinator is charged with prefer quantities of biphenyl and catalyst and heated above the melting point of biphenyl. The flow of valorized chlorine is then started and the charge is circulated with a puip. Throughout the chlorination, the tstperature is kept above the melting point of the mixture, but below 150*C to avoid excessive sublimation and plugging of the lina discharging the hydrogen chlorine produced by the chlorination. Tha reaction pressure is maintained near atmos pheric. Tha degree of chlorination is principally determined by tha time of aontact with anhydrous chlorine. The contact time varies front 12 to 36 hours for the manufacture of different Arcelor types. The degree of chlorination is measured by tha specific gravity of the mixture or the ball and ring soften ing point when the product is viscats. The vapors fra tha chlorinator (HC1 containing PCBe) are scrubbed with liquid Aroclor and the gaseous HC1 is sent to ansthsr plant at the Sauget complex for purification. The crude predict is held at an elevated toperature and blown with dry air for several hours, after vfeich it is sent to the raw Aroclor storage tank where a few tanthe of 1 percent of alkali are stirred with the material bo react with any remaining hydrogen chloride or ferric chloride. The air from the blower tank is scrubbed with water and vented bo the atmosphere through a demister. The raw Aroclor is subsequently batch distilled under reduced pres sure to move the color, and the traces of hydrogen chloride and ferric chloride. The methods of puri fixation are different for the different types of end pro ducts. Raw Aroclor 1254, 1242 and 1221, each are distilled in stills under re duced pnssura, adiisved vis steam jet ejectors; tha oendanssta fra tha still is tha finished product v4iile the bottoms are the Montars which are drunned and sent bo incineration. The *l--"mjti"" section for the 1016 predict consists of a gas fired retort and a vacuum distillation tower. The latter is used bo allow the separa tion of the higher chlorinated, less biodegradable compounds from the relatively -54- HONS 209036 lower chlorinated and rrore biodegradable ones. The raw Arcelor (42* chlori nated meterial) is fed into the reboiler. The vacuum in the tower is maintained at about 100 im fig by stean jet ejectors. The steam is partially ^ the condensate is discharged into the plant discharge sutp. The first cut frem this tewer is recycled back to the retort. At a preset overbad taiperature the 1016 product is collected and sent to the product storage. The high boiling residue from the tower is sent to a subsequent chlorination cycle and tltt re sulting raw Aroclor is distilled in a still. The overhead from this still is the finished product. The bottoms from this tower axe the Mentars. The spent ferric chloride catalyst, used in PCB manufacturing, is sent to incineration with Mcntar residues. Far special orders, in order to increase electrical resistivity, the Arodors are stirred at an elevated toiperature with a few tenths of 1* of well-dried fuller's earth and then filtered through paper. All Arodors are stored at 150*F. Steam coils ere used on the storage tanks for heating these tanks. 2.2 Raa wastes The raw wastes from the manufacturing area consist of the liquor from the scrubber, the aondmate from the stems jet ejectors, water used for showers and eye bathe, miscellaneous floor wash downs, waste oil collected in drip pans and drum, and montars which are the bottom cut from their stills. The and the quantities of the individual waste stream are not moni tored. All efflumit streams generated in the manufacturing area are directed into the smpe in this area. The waste oil aollectad in the drip pans and the Mentars are enptied into 55 gallon druns and sent to incineration. The raw wastes gsnsrated in the incinerator cmaiat of the venturi w-mhtw i ] the water phase from the separator s\zp in the incinerator axaa. Thm of the axfcinad stream is monitored. However, the oont- of the individual streams is not known. Nan-product PCB discharges are 4wn in Figure 2.2-1. It has ben estimated that this plant generates -57- MONS 209037 FTGDW 2.2-1. NON-PRODUCT PCB DISCHARGES AT MONSANTO'S KRUMMRICH PLANT VAPOR PROM JET EJECTORS-----------------------EXHAUSTS FROM THE SCRUBBER---------------SURFACE AREA EVAPORATION (IN GENERAL) CONDENSATE FROM STEAM EJECTORS NON-CONTACT COOLING WATER-----------SCRUBBER LIQUOR ------------------------------------ MONTARS ---------------------------------------------------------BOTTOMS FROM SEPARATOR SUMP-----COLLECTION FROM ALL DRIP PANS RAQS FOR CLEAN INS------------FLOOR DRY--------------------------------SPENT FILTER PAPERS FULLERS EARTH -------------------- AIR TO SEWERS INCINERATION -50- MONS 209038 about 25 lbs of scrap oil and Mcntar per ton of PCB produced. Additionally, the quantities of material sent to landfill approximates to 5.4 lbs per ton of PCB produced. Further, t'fcnsanto reports that the plant's PCB contribution to the air is under 1 lb/day. 2.3 Plant water Usage On the average, the PCB plant uses a maxinun of 338,300 gallons of water and a maxittun of 360,000 lbs of steam daily, water is used for nonoontact cooling purposes in shell and tube oondensers, in a water scrubber, for floor washings, for showers and in eye baths. Steam is used in the steam jet ejectors and for steam tracing purposes. The plant uses ramicipal water and purchased steam. The process water from this facility oonsists of the liquor from their scrubber and the steam condensates which are discharged in one of the tare stripe in the manufacturing eras* Additionally, 273,600 gallons of water are used in the incinerator daily for quenching the hot gaees from the fire box. The resulting weak muria tic acid in the quench pot is used in the venturi scrubber and in the packed tower. The type and quantities of water used and discharged at this plant are stnmerisad belowi Water Balance . Manufacturing Plant Process weter in water scrubber mime, floor Meta down* condensate from stems jet ejectors Quantities, GPP Used Discharged 14,400 7,200 14,400 7,200 14,400 -59- MONS 209039 Water Balance (Con't) * Manufacturing Plant Mon contact cooling water showers, eye bath condensate iron steam tracers Total . Incinerator water used for hot gasquenching water phase from the simp Total Quantitiea, GPP Used Discharged 360,000 7,200 -- 388,800 360.000 7,200 28,300 432.000 273,600 -- 273,600 273,600 14,400 288.000 2.4 wastewater Treatment and Ho~ieatrearing Monsanto report* significant anviromantal controls at their Krtmnrich, Seuget plant. Sinoe 1969, they have invested more than 22 non-years of trade and minims of dollar* in this prograa. The in-houae gi have re duced the PCS dischargee into water bo about three pounds par day. A JOhn Zink deeignad incinerator was erected at Sauget in 1970 to safely dispose of PCBs. A achmtlc flow diagram of this operation is given in Figure 2.4-1. Aroclor is steam atomised and fad into the fixe box. Natural gas is used far aoefeueticn and the feed is incinerated at taqperature above 2200*F at 5 percent encase oxygen with a tatentim time of 2-3 seconds. The gases are quanchad with watar and the exhausts fren the quench pot ax* passed through a hi^i energy venturi scrubber, that through a packed aoltan which is irrigated by the weak autistic add originating from the quench pot. Exhausts ax* ttwi vented to through a danistar. These exhausts as well as ths effluent fm toe incinerator section are monitored. In toe Incineration area, drainage is directed to trenches and piping which flow into a 10,000 gallon vmdsrground concrete basin. The water -60- MQNS 209040 FIGUIB 2.4-1. PROCESS FLOW DIAGRAM OF THE JOHN ZINK INCINERATOR AT MONSANTO'S KRUMMRtCH PLANT 9i t HONS 209041 layer from this basin is pimped continuously, combined with the scrubber liquor, metered, monitored and discharged into the sanitary sewers of the Sauget com plex and frem there it is sent to the East St. Louis municipal sewers. The organic phase from the simp is periodically pimped into waste storage tanks for incineration. ' The incineration unit has a rated design capacity of 10 million pounds par year. However, since the start of its operation this unit has achieved a servioe factor of about 0.60. Monsanto reports that this incinerator can achieve a maxiirun of 6 million pounds of capacity annually; the unit is plagued with various mechanical problem. Monsanto uses their incinerator to process both their own wastes and as a service to other industries. The service charge for incineration is an average of 5C per lb of material, but the aost appears bo be increasing. The incinerator feed is brought into the plant either by truck in 55 gallon sealed dnaae, by talk tricks or by rail. The drum are opened, picked up by a fork lift and enptied into a concrete pit. The tank truck carrying the waste liquids enters the incinerator area end the 1 iguirf waste is than pimped from the truck into the pit. The material in this pit is periodi cally pimped via a vertical certrifugal pimp into one of the four 20,000 gallon incinerator waste feed tanks. The rail car is brought into a designated area close to the incinera tor site. The from the rail ear is normally pimped into a long term, 500,000gallon storage tank. The material fraa this tank ia puiped into the incinerator feed tanka located an the incinerator pad when required. Drainage is provided along the rail tracks. These drains enpty into the 10,000 gallon simp located index the incinerator pad. Xn the nmfeeturlng area, Monsanto has taken a nimfaer of significant steps to prevent lose of POe to the envlrorment. Drainage is directed to trendies and piping, and then to one of two concrete 3,000-gallon underground settling basins. This insures PQ acntairmnt in case of accidental spill or MONS 209042 -62' aquigrant failure. Relief valve lines and atmospheric vents are routed through catch tanks, or are redirected to settling basins. When stall quantities of PC3* are collected in tbs settling basins of the manufacturing area they are later puiped into SS gallon drurs, ard eventually incinerated. The overflow fran these stripe is entbirwd with the rencontact cooling water used at the plant, monitored aid then discharged into tl Sauget complex's sanitary sewer and from there to the East St. Louis municipal system. PCB* are pecked and shipped in galvanized'-steel 55 gallon dnme, or in railroad tank cars. All tank cars are top loaded. In the drvm filling area spills are cleaned via rags or floor dry and these materials are druimed and sent to landfill located in the town of Sauget. In the PC3 truck or rail car Loading area, drainage is directed into a small concrete pit. The material accumulated in this pit is periodically purped into the basins located in the menufacturing area. Nitrogen blanketing is provided on storage tanka to eliminate any "breathing" of the tanks and resultant PCB escape. Mist eliminators have been installed in vnpar lines to eliminate the possibility of PCBe leaving the manufacturing area through these lines. Finally# undargrowd sswezs have b*n replaced with abow-ground sewers, ami repaired or acefcined with others, so that the effluant from the department can be monitored. In addition, this step will prevent any unknown buildip of PCBe in the saner system or any oentamnatien of PCBe into other A high housekeeping level is maintained in the plant itself, nmiaelreeplnrj leyrralhlllrlee which the operators have assured are as follon: . All purpe are checked for leakage on every shift. Drip pans that collect leeks are aeptiad into scrap FOB druie. -63- MONS 209043 . All leaks or* reported and docunentad so that collections con be made and settling basins observed. , "Floor Dry" is used to absorb any PC3s that have spilled or leaked. If it beaomes recessary to flush K2s to the settling basin, a minimm amount of water is used. . Sampling drums and scrap PCT dries are quickly palletized, labelled and transferred to the in cineration area. 2.4.1 Treatment Facility for the Effluent fran Sauget Ccrplex The processing and incineration departments' aqusous efflisnt enters the plant sewer system, and this systsn discharges into the Sauget Village wests sewer systsn. Hie oenfeinsd streams than flow to the village primary treatnsnt plant. Hie village treatment plant is wonder expansion to a secondary chemical treatment plant, scheduled for 1976 aorpleticn. Additionally, evaluatiens are being conducted to include the village plant discharge in a projected regional biological treatment plant. 2.5 Plant Effluents This plant hae no point source discharge from their operation. There is a single disdisrge from the manufacturing operation (the ccnbinad stream of pmreee and non-contact cooling water) to the mein somst syaton of the Sauget rypi-- an! there is a aaoond discharge from the incinerator area to the sane sewer system. Hie "TieiH'n of theee streams as reported by Monsanto are as follows! Effluent from the Manufacturing Operation Effluent from the Incineration area flow rats, gpd PCBs, ppa PTSs, lba/day 422,000 0.75 2.70 288,000 0.15 0.36 64- MO NS 209044 It has been reported that these effluents are clear liquid with essentially no suspended solids. The incinerator effluent may contain sera anwnts of diloride. Ho*ver, no information is available on the chloride content. 3.0 PCB USER INDUSTRIES 3.1 Askarcl Capacitor Manufacturing Industry Presently 90-95 percent of all impregnated capacitors manufactured in the U.S. are of the POi type. Two important types of capacitors are phase correctors an power lines and ballast capacitors for fluoresoent lighting. Aroclor 1016 is the principal PCS used in this application; at sane plants Aroclor 1242 and 1221 are also being used in limited quantities. The principal types of Aroclor impregnated capacitors and their applications are given below. A. High Vbltaga Power Generally AC capacitors are used to improve the power factor of a circuit. Power factor is the ratio of true power in watts to the apparent poMr as ob tained by multiplying the current flowing to the load by the circuit voltage. The power factor correction can be made directly at the load or at utility sub station. In the latter case high voltage mits will be designed for 4,800 to 13,800 volt service. Tb the utility engineer the use of capacitors is purely a natter of eooRmica. T3 main benefits that result from the use of capacitors are 1. Reduction of losaae associated tilth the delivery of electrical power to the point of use. 2. Reduction of the Investment required in equipment far delivering electrical power to the point of use, which may be broken down into; a. Refection of line euurt for the same kilowatt load. b. Induction of the kva rating of equipment required to handle the sane kilowatt load. -65- MONS 209045 c. deduction of the transmission line voltage drop for a given kilowatt load. d. Control of delivered voltage if the capacitor kva is varied. Electric utilities also use capacitor banks in series with distribution circuits to iupruvs voltage regulation. B. Low Vbltage Power Capacitors installed in industrial plants at the demand site (typically large motors and welders) are designed for 230 to 575-volt service. Capacitors installed near the loads are the most efficient way to supply the magnetizing current to produce the flux necessary for the operation of inductive devices. Bates for the sals of power are generally structured to encourage power factor correction at the site, eliminating the need for the electric utility to trans mit both power-producing current and magnetizing current all the way fron the generator to the plant site. Che same considerations apply to induction heating applications, the principal difference being that capacitors for this application are designed for operation at 960 to 9600 Hz. C. Lighting Capacitors improve the efficiency of lighting syetens. A fluorescent or mercury vapor lap can be ballasted without the use of a capacitor, but the peter factor of the lighting systea would then be in the range of 50 to 60%. For uuuuercial or industrial lighting with either fluorescent or high intensity discharge laps, the use of a capacitor in the circuit provides part of the lap ballasting and brings systoai power factor into the range of 90 to 95%. D. Air Conditioning M la the lighting applications, the capacitor improves systai sfficimcy. Air conditioners could be made to operate without capacitors, as do hone re frigerators, but because of the higher capacity required for air conditioners. 66-- MQNS 209046 the resultant line current would virtually eliminate heme "plug-ins" and would still further overburden a seriously threatened national power network. Almost all air conditioner purrp motors are of the split-winding type on which the capacitor provides phase differential for the so-called start winding, thus delivering jxxi starting torque. The proper size capacitor permits high (90%) power factor after start-19. 2. Industrial Electronics This market catenary is a catchall covering many varied applications, two important ones being motor run and power supply applications. Motor run appli cations are for pupa, fans, and farm feed equipment, and do not differ signifi cantly firm air conditioning applications. The power supply market uses capacitors principally to provide high power factor, but through careful design the capacitor can also provida wave shaping where desired. 3.1.1 Askarel Capacitor Manufacturing Plants Then an seventeen oerpanies in the U.S. which manufacture aekerel capacitors at nineteen plants. The nane and the location of these plants are given in Table 3.1.1-1. Seme plants manufacture industrial capacitors only and others menufactun power capacitors. Tei major onryanies wen contacted. Detailed information was obtained cn six plants. Four plants wen visited. The data herein represents approximately 50 parent of 1974 Fa usage in capacitor application. The PCS usage in this category wee approximately 22,000,000 lbs. in 1974. The FCB usage in individual plants is consldsnd by then ocrgwnias to be confidential infor mation. The range of Fa usage at thaaa plants was 64,000 fold in 1974. Plant ages range from fin to thirty sewn yean. C^aeitara used in lighting and air conditioning applications aontaia (K0S to 1.0 lba. of Aroclor. The largest power capacitors contain about 77 lba* ot Jtooclor. The most size contains 36 lbs. A sketdi of a site atpadtor is *hrwn in wioure 3.1.1-1. <"^n*citors are not rebuilt and returned to sexvioe after failure. They are disposed of and replaced by raw units. G.E. reports that high voltage utility capacitors, lev voltage -67- MQNS 209047 FIGJm 3.1,1-1. MDILM SIZE snOTKOL CAWCITOR -68-- HONS 209048 Table 3.1.1-1 U.S. Capacitor Manufacturing Industry Using PCBa Coopany Name (In order of PCBa (Jsaga) General Electric Caipany Westinghouse Electric Corp. Aerovcac Universal Manufacturing Corp. Cornell Dubilier P.R. Mallory 6 Co., Inc. Sangaro Electric Co. Sprague Electric Co. Electric Utility Co. Capacitor Specialists Inc. JAFD Corp. York Electronics MoGra*-Edison RF Intaronics . Axel Electronic, Inc. TObe Deutschtnem Labe. Cine-Oirone Lab, Inc. Location of the Plant Hudson Falls, N.Y. Ft. EArtrd, N.Y. Bloaningtcn, Lnd. New Bedford, Mass. Bridgeport, Ccnn. Totowe, N.J. New Bedford, Mass. Waynesboro, Term. Pickens, S.Carolina North Adana, Mass. LaSalle, 111. Escondido, Calif. Bennington, Vt. Brooklyn, N.Y. Greenwood, S. Carolina Bayshore, L.I., N.Y. Janeice, N.Y. Canton, Mass. Palo Alto, Calif. HONS 209049 power capacitors, and induction heating capacitors are manufactured at a rate of 200,000 per year, about 2 to 3% of which are repLaewents; the balance are for no* installations. The current market for capacitors used in lighting appli cations is about 44,000,000 units annually of which 10% are estimated to be replacenent ballasts. The current market for capacitors in air conditioning application is above 12,000,000 units annually, with 5% of these estimated to be for replacement usage. The market for capacitors in industrial electronics applications is estimated at 23,000,000 units per year with no estimate as to the relative size of the replacwent market. 3.1.1,1 Askarel Handling In most plants PCBs are shipped via tank car to a sail siding several miles from the plant. Individual plants provide a de signated tank truck for the transfer of the PQe from the rail yard to the manu facturing plant. TO large plants, PCBs are brought via rail cars into the plant, site. In most plants PCBs are unloaded and transferred to the PCS storage tank without the benefits of any curbs or dUoee. At a very Imt plants, the unloading operation of the PCTs from the tank ear to the storage facility is aonfinad and the recaivlng area is roofed and diked. PG3s from the rat storage POI tanks are filtered through fuller's earth and stored in finished product storage tanks. PCBs are next pugad from the storage tanks to the ispregantion areas for use. Excess PQs from these areas are recycled back to a designated tank and fran there either filtered and reused or, if defective, are puneed into the scrap storage tank. Spent fuller's earth employed at theaa plants is either dnamd and stored at the plant site or is sent to a landfill. -70- MONS 209050 3. Ll.2 Process Description ^ Most plants in this category manufacture either large power capacitors or snail (including less than 2 lbs. of PCBs) industrial type units. The large capacitors are either flood filled or manifold filled. All stall capacitors are flood filled either in a vacuun tank or in an autonatic "carousel'* arrangement where loading and unloading occurs at one station, and the capacitors in each cell are progressively dried, evacuated and filled. A generalized schsnetie flow diagram for the manu facture of large capacitors and snail industrial capacitors are given in Figures 3.1.1.2-1 and 3.1.1.2-2, respectively, the basic manufacturing operation at these plants can be divided into two major operations. a) Non PS related operations consist of the following steps: . Fabrication of capacitor cans, covers and brackats from sheat aliiDinua or ateel. aneller plants, however, purchase capacitor caslnga, capacitor taminals, connectors and foil. . vapor degreasing or detergent washing of metal ocnpcnants. At same plants, ultrasonic cleaning is ussd to clean aneller . Poll winding the capacitor pager or polypropylene film with alunlnisi foil. . Qmplete asssibly of capacitor ocnpcnsnts and sealing the covers, m same units fill holes are provided for PC3 intro duction; in others PCTs are introduced through bushings or a valve. . T+apg vie osas spectrometer and pressure testing prior to vacua drying. b) 9^ related operations 4fca*oc^lstaly different iapregpating techniques are siployed *' Egrtfils lnduetry. 71MONS 209051 I I Mam 3.1.1.2-1 OBUUZED FLOW DUfitAU FOW TIC MANUFACTUMM OF UUNC CAFAC1T0A* i * HONS 209052 -73- CMXT< - *! nmcAim ar'.ntn * > COVCtt [tST^ i TBiouwa IMM AECOVCAIM r . .i , tt.uaMteC jOCTIMEMT WAJHweV CAFACITO* asseBmbly SOLOCAIM t CMTIC. mtoi Minium I m JO ULRU,fll |~WEM j KB nai BUL CAB 1 MXUM* ! Tcf5t pcTto FlUl. BAD* "~1 I .i*i*srOo iaco m | i iinwiuMou VACUUM Vt VACUUM 1 T r^ Ki STOAASE FILTRATION SECTION L____I riUVlUNIa IMFACSMAT K>N, CMVUTOM. FLOOO FILL 1PCBT rwiiiY uni) CWKTItMWMIATtLOI Bnj OB. TO BAM OB M Mimmegmatiom, j CAltOUSEL I rrri rums fill i rOWcBofLBMOAOUB 1[> uum MAUM i 1 ! MTHHmT OMYIMB B**J u iMfCM HKhM "t L -- i H FAuinwB E CAMOTOM IB mrt id terra lmbs kwi* mutmm FLgm 3.1.1.2-2 atWBWUZIP FLOW QUURAM FOR THC UANUFACTURIM OF SHALL CAMCITORS HONS 209053 (1) Conventional flood filling of capacitors Ibis type of filling operation is used for impregnating large power and small industrial capacitors. Here the capacitors are arranged in baskets or in large tanks which are subsequently transferred into vacuum chambers. Vacuum is then drawn and the capacitors are kept under vacuum at an elevated temperature for a specific period of time in order to evaporate the moisture from the capacitor interiors. The tarperature of the tank is next lcfcmred and FQs are introduced under vacuum. The capacitors are alloed to soak for sane time after which they are transferred to the seeling or criziping station via sobile car, sealed, and excess PCBe are thrni drained. The sealed capacitors are next sent to vapor degreasing or detergent washing for cleaning the exterior of thaaa units, the clean units are heat soaked and heat **< in an oven and th*i sent to 100% electrical tasting. Subsequent to electric tasting, the capacitors with stsal casings are peetreeted prior to painting, the pretreatment is either vapor degreasing for painting in an electro-static field or it is several stages of phoaphatizing and rinsing operations, prior to automatic spray painting, where water is usad to scrub the vapors grated during painting. Mast capacitors with almimn casings are marketed unpaintad. However, at sane plants a portion of capac itors with alixninua casings axe fluoride treated and than spray painted. The capacitors are next either air dried or dried in an infrared oven prior to packaging and shipping. (2) Automatic Flood Filling Operation (Carousel) In this method of capacitor impregnation, the assmibled units are piTM* in ovens for the removal of noistura from the capacitor interiors. 13m baskets containing these cspacitors are next trans ferred to the carousel chaiber. which is at the loading position, the carousel paaaaa through 13 subsequent cycles consisting of -74- HONS 209054 HONS 2 0 9 0 5 5 tha majority of tha PCBs ara retrieved through the fill valve - under vacuum. The rejects are next transferred to tha salvage operation. Mechanical pimps are used throughout the syston os achieve vacuum. 3.1.1.3 Raw Wastes Tha raw wastes originating ffran these plants consist of scrap PCBs collected in suxpa, drums and drip pans, contaminated vacuum pimp oils, tha fractionator bottoms frcm tha trichloroethylene recovery, tha caustic bath used, at seme plants, for purposes of paint stripping, spent detergent wash and rinse water from capacitor or opponent cleaning operations, rinse water used in the welding and plating operations, steam condensate firm jet ejectors, tha seal water used in vectasn pimps, water used in phosphatiring and fluoride baths, water spray used in tha paint booths, boiler blow downs and cooling tower blow downs. Furthermore, in at least one plant in tnis category, water infiltrating at a upgrade elevator ahaft creates an additional wests stream. Solid wastes firm these plants consists of scrap capac itors or capacitor interiors, floor dry and rags and newspapers used for cleaning spills, spit fuller's earth and other filtering media used for PCBs filtration and waterless cleanses used at sane plants for hand cleaning purposes. Men-product PCB dischargee, their source and disposition are given in Table 3.1.1.3-1. Mequata data to quantify tha various tastes generated at these plants is not nailabla. Information on waste loads reported by sane plants are given in Table 3.1.1.3-2. 3.1.1.4 water Use ' The water used at these plants is in ths rang* of 12,500 to 1,200,000 gallons par day. In most plants, watar is used primarily for aooling in vapor degreaser*, in pimps and in vacuum tanks. Plant 101 xecyelae their rcnroontect cooling watar through a cooling tower. -76- MONS 209056 TABLE 3.1.1.3-1* NON-PPOOUCT PCB DISQtAOES i l*t wip d j*t i K gBTlnwJ i ftfcinUU r (n i in i *1QsntxolLad uik drain Aim* mm*t 1A tte ffir I k tmU Pta^MUiUif but ( rkM 4Sa^ oii tfl drip pun. m * ipcm fuU*r`* Mnfc. day * SUta* Oear ttf < i itt Air Air Air Air cry U 102 Air Air SWopnucc Utwf** Air Air tncmarauai* TtMHK plw* chan rivwr TTfcfcl 1IH4T pUat hw U*rJ pLaat Mn* D*Wlt than t* Aiwr Ai*ar Cocwit than to rir (Aeimnua Incuantioi iKumtioi Socni hi Air Air Air MMLanrwaci/acauai1 l.itfl (iiid 4JIK T Hlr mm HM ttn* hw MM Ai*tr tneinarauon Stand an nu lidfUl lAdtiU lAdfUl ladflil Inc manual )fil iita Stond ilta llCMNtlOl Stond ait* Stond ut* Air Air So*tr KNoonna* S+mt Scot* Non* Maw Nam Non* Nww Maw Maw Incuianunn LindfiLl Nan* bciaiitia Landfill Undfill 'I III ! ua ililnl i v^ily lisiiA tn ttu to i MfUl< HONS 209057 TABLE 3.1.1.3-2 QUAffTTIY OF WASTE LOADS (lbs/ton of PCB used) Land Dastinad Waste Wastes to Incineration Spent Puller's Earth to Incineration 100 73C1) 100 4.1 Plants 101 102 104 105 129 65 J4) 106 _(5) 56 98 Nona{2> J3) 109 - 127 300 - UnJmown Notaei (1) (2) (3) (4) (5) Reported as POSe. Ms estimate an 175 lbs/ton of PC3 ocrt- teninated solid matsrial which j_g bsing landfilled locally. PQSs an flltand through pecked tarooall cylindrical 11tars. The filter media has an estimated life cycle of 20 jtirs This plant uses clay for PC3 filtration. The quantity of spent clay sent to incineration is not known. These plants store their solid wastes consisting of spent fuller* s earth, rejected capacitors, rags and floor dry, cn site. Plant 104 tan 55-gallan drum of wests and plant 10S forty 55-gallon drum of waste each weak. The weight of materials sent to landfill is not Jraown. However, this ompany reports that during 1974 approximately 650 capacitors were rejected. The rejected unite were drained and than sent to a landfill. -78- MONS 209058 Process water used at variou* plant* consists of water .art in detergent washing, in ultrasonic washing, condensate fron the stem ]et ejector*) seal water from the vacuun futpe, water used in phosphatizing and in fluoride bath* and rinses, and vater used in caustic treatment and painting opera tions. Additionally, water is used for sanitary purposes and in sane plants it is also used as boiler feed. are given below: the quantities and types of water used at these plants Plants Intake oallons/dav 130 740,000 water L'saqe in osllsns/dsy .'tor.-tmtact cooling 655.000 Process wstsr airs# water tm hot solder lip 200 D*t*r**nt rawing t - Phosphatixing baths - water used in tin plating - fluoride bath a rinse - wator used in painting Pirp nal wstsr & stsse condensate Sanitary 44,40 Boiler feed nake-ve 40,000 101 12.500 3.000" 1.000 - 1,500 - 102 104 1.000.0001 2 1,260,000 105 4*0.000 3i#,ooo3 4 1.195,000 3*7,000 .. - 52,000 - 25,000* - 10,000 30.000 200 400 12.000 50 50 44.000 65.000 15,000 Notts: (1) 560,000 gaHara/day of this water is used as pieces* rinse water in non P9 associated, eloetmlytic rsperitar operation (2) Katen* water (1) It hse been eetimted that only ISO,000 pollens of this teter is associated with the plsnts rcn operation. The balance is used ui the manufacture of Kies csparicpi-3 (4) It includes totnr utod in paint stripping and welding operations. 106 336,S00 326.500 5,000 - 5.000 * -79- MONS 209059 3.1.1.5 Wastewater Treatment The major in-plant PCT wastas which readi water strew* originate in tha impregnation areas. Due to tha nature of watar requirements in this industry, at sera plants it is possible to significantly reduas tha quantities of wastes entering tha watar syst*na by adoption of proper housekeeping measures. Since than is no donerstrated tedmology available for tha taanlnal treatment of PG9s in waetawatars, there are no PCB wastewater treatment tedmlquaa currently in use at any facility. Details cn wastewater treatment tedmiquee used at various facilities for purposes of oil recovery or neutralization and an-going aontaiment program undertaken by same plants to prevent tha entry of FCBe into the envirenrent an given in Task H report, "Assessment of Wastewater Management, Treatment Technology, and Associated Oast far Abetansnt of FCBe Concentrations in Industrial Effluent', February 3, 1976, pages 46 thrcu^i 53. . 3.1,1,6 Effluent Oarposltlon . Effluent fra plants in this category range from 3500 to 1,360,000 gallons par day. As indicatad in tha wasts treatment section, thaaa effluents an sant aithar into noaiving watarways or into nuiicipal sewers without ary PC3 treatment. Available information an effluent flaw rates and their PC3 oontwtts, for most plants in this category, an given in Table 3.1.1.6-1. More detailed effluent Information wan obtained on four plants and Table 3.1.1.6-2 aenpans the dischargee fra these plants. Table 3.1.1.6-3 lists PCS concantraticn of tha plant intake watar fra various sources. It is of interest to note that one plant (plant 100} reported large variations in tha PCS content of the receiving waten even at tha time whan tha plant was not in operation. They attributed the variations to storm conditions, stirring-up the sediments from the bottom of the river and greatly increasing tha PCS concentration in tha watar phase. -90- MONS 209060 Plant NOi 100 101 102 104 105 106 107 108 109 no 111* 112* 111 126 TNU 3.1,1.6-1 mKZ of flow SATES t PCB ccaNTHATrcN ra ancon's FROM CAWCITQR .'ftNUTACTURING PCAWIS Outfalls 001 Effluent Flew Rata oai/uay 300,000 Effluent PCB Content av!?S* lbs/day avq/rax 17/55 0.1134/0.3670 Nena 9,000 161/161 0.0121/0.0121 001 807,000 9 0.0605 002 165,000 3.2 0.0044 003 36,000 3.4 o.ooio Maqor outfall 1,060,000 Cool my water 6 roof drains loo.ooo Lab t roof drams 32,000 Carvrrsajor moling wttsr 72,000 Paint strip rinse 50 21 7.8 4.4 3.7 4800 0.1856 0.0065 0.0011 0.0022 0.0002 Major outfall Fran pray punt. booths Nona 650,000 370 1,500* 13,300 316,500 26.6 2.0058 U.lb64 0.075 Disposition of affluent River 5*wtr River River River River River River River River River River Sewer Mona 150,000 1900/4000 2.3769/5.7546 Cooluyj water t toiler bltMdoun Cooling water Hoof nnoff Storm runoff 001 48,000 129,000* 2,900 unknown 100,000 45/108 0.0180/0.0432 338/705 0.3636/0.7585 1360/2370- 0.3290/0.0573 3/11 " " 57/83 0.0475/0.0692 Mona Mona Nona 2,570 18,000 10,224 821 8.7 130 0.0176 0.0013 0.0110 001 Nona 12,000 14.3 580 6200* 0.0014 0.03 Severs River Sower River River River Sewer sewer sewer River sewer NotMi tl] 0iJchar9Od eoce avery 4-3 weeks. (2) Certain* 10,000 gpd sanitary sewaqa and 0000 qpd of surface water infiltration O) These facilities recycle rest of the nen-eonton aooling vatcr used at the plant. Those effluents emsist of a snail frru-rinr\ af da onoLimr water plus chair sanitary discharge. -01- MQNS 209061 Plant Outfall [* TSS, mq/\ PCB, pptj Oil fc Ctmm, aq/1 Allan W, ag/1 Lud. Uj/1 CDfpar, mq/l Ozoaiia, ^/1 Ptunola, ag/1 Ini ag/1 BCD, mq/l 100 001 7.3 3 17 UK UK <.03 <.003 <.003 <.001 <19 001 7.4 16.6 9 3.10 M> UK UK UK UK UK 4.37 TMU 3.1.1.6-2 tanrim of Dladiarqea 102 104 002 003 002 0O3A 003B 7.3 7.2 6.5-12.0 s.5-9.a 4.0-9.1 1*54 2.S 5.2 4.7 4.0 3.2 3.4 21 7.8 4.4 3.38 2.18 7.20 14.40 30.70 M> K> 0.15 0.06 0.11 UK UK UK UK UK UK UK UK UK UK UK 0.03 0.003 JK 0.02 M> UK 0.04 M> UK UK UK 0.29 0.30 0.34 2.45 1.7 UK UK UK 006 6.S-11.6 3.1 3.7 2.66 2.0 UK 0.03 K> UK 1.66 UK 105 004 5.5-8.6 9.5 370 12.8 UK UK 0.03 ux 0.52 LX K> - Hon Jatartahla (X - U*mn MONS 209062 Table 3. LI.6-3 IntaXa water PCS Concentration Plant Source PCX, ppb 100 Minicopal 0.09-2.5 101 Hnicipal 4-7 104 River 57.0 105 Well Water 40.0 106 Municipal 0.25 111 Mmicipal 1.0 112 Hrucipal 1.0 -03- MONS 209063 3. 2 Transformer Manufacturing In&iatry All plane* in this category manufacture transformers using mineral oil a* the dielectric fluid. This dielectric fluid is the principal impreqnant used at ttwse facilities. PCB transformer oils (blends of 60 to 70 peraent Aroclor 1254 or 1242 and 40 to 30 percent trichlarcbertzene) are used in only 5-10 peroent of these plants' manufacturing volume. In general, a transformer consists of a core and coil iirmersed in a dielectric fluid. There are two broad classifications of transformers: distri bution transfoncers, whidi are used to step down voltages, and power transformers, whi<di are used primarily to step up voltages. The precipitation power supply units can be actually classified as a third class of asJcarel transformer. However, the larger plants in this category have only two manufacturing departments -- distri bution and power; and they manufacture the precipitator transformers in their distribution transformer department. The following types of asfcarel transformers are iwnufactured at these plants: A. Askarel Distribution Transformers 1. Network (Receive iq> to 14,400 volts and deliver 120, 240 and 480 volts> 2. Pad - mouited (Receive tp to 14,400 wits and deliver 120 , 240 and 480 wits) 3. Pole - mouited (Receive tp to 14,400 wits and deliver 120 , 240 and 480 wits) The appl leaf-inn of these trans formers in power distribution systems places a great prudiw upon their reliability and high overload capability. 4. Precipitator power supply (Receive 480 AC wits and deliver SO-W kilovolt* low average DC) These units are generally installed close to hot gas stacks in an atnoaphere that would be a fire hazard to oil-insulated transformers and a corrosive hazard to open dry-type transformers. .Seeled dry-type transformers are impractical far hlghrwltsge DC. -84- MONS 209064 Voltages listed cover tha majority of aakarel distribution transformars. Product scope includes up to 34,500 primary volts in1 virtually any secondary voltage, 34,SOO and below. Cuantitiee of asJcarel used in this class of transformers are in the range of 500 to 5,000 lbs. in each unit depending on the rating ard the size of the transformer. A great majority of distribution type transformers have pro vision for venting. Many of thaae units are equipped with spring venting devices which vent upon a pressure excursion, and diaphra^n rupture discs are offered as a customer option. B. Askarel Rower Transformers 1. Secondary mbetaticn (a) Load oantar units (b) Seoondaxy sttetetion generation units (c) Switchboard units (d) Internal inits (e) Jtotor oonerol tnita Theta 5 gurries the largest gnxp of askazelinsulatsd transformers and tlay find widespread application in tha automobile, paper, dwnical, tactile, steel, nonfsrxous metal, cement, mining and patrolaun industries. They are used In canmstcial and putol 1c buildings, such as schools ard hospitals; in dsfense and nuclear anargy installations; and by privets and public utilities. 2. taster init stbetatlon 3. Primary mlt mbetation 4. aspen mbetetlon 5. Industrial furnaos -85- MQNS 209065 Furnace transformers used in the hot, dirty aUJop**re in pmsdnity to glass melting and induction furnaces, which require high current, low voltage power supplies (reoeiva up to 15,000 volts and aontain 2000 to 4000 lbs. of askarel each) - Existing technology does not permit construction of seeled dry-type transformers for these power ratings. 6. Rectifier Rectifier transformers used for large rolling mills and rc industrial power sipplies (receive ^ to 15,000 wits PC ard deliver low voltage high amperage DC. Each wit contains about 19,000 lbs. of askarel). These units are covered by the sane consents given for industrial furnace transformers. 7. Transportation Railroad transfarnars used on-board in electric looototives or nultlpls wit electric railroad cars (receive iq> to 25,000 wits and contain 700 to 2400 lbs. of askarel in each wit depending on the rating and size of the transformers). (a) Third rail These transformers are used for rapid transit syetns, and are basically serving a rectifier function (b) incentive Prior to 1932, all on-board transformers were open dry type. Bacmise of problm with then, railroads went to aakarsl-lnaulatad transformers. The changes in Incentive design sinoe the 1930's would not nw open dry-type transformers as replscamants far askarel wits. A raowt trwd has bean to replace askarel by oil wits, and this will continue unless w Dspartsent of Ttsnaportaticn regulations require ncnflesnbility. -86- MONS 209066 Hcwvr, since a tunnel fin in 1940 causmi by an oil filled locomotive transformer, Penn Central will not allow any oil aontaining transformer equifpad looatptive into New York City. (c) Miltiple-unit car (MJ) Tiieee transformers are muted under the flat-bed of passenger ears. They ride along in this location, about 8 inches above the rail, at speeds up to 150 nph. The transformer mist be ruggedly built to with stand the iapact of flying debris and aonstant vibra tion. Pomr to the cars is brought in through an overhead catenary and is fed to ttw wderside of the car where the transformer, controls, and propulsion equipnsnt are located. Space and vmight are critical in this application. There are only about 33 inchee above the nil. The width of the transformer is 1 fmited by ttw width of the car. Only oil- or aakarel-insulated units would provide the required performance levels in the speoe avail able. As with looantive applications, present Department of Transportation regulations do not restrict ttw use of finable liquids, and the use of aakarel units has beat dictated largely by the r oonslderetions of fire insurance rates, and by Pann-Ontral safety regulations. 8. naartnn Hiaae units provifr reactance (receive up to 15,000 volts urder nonal qpKating oonditiens. During normal operating conditions, they deliver volte and as reoaived. During power surges they choke the voltage and deliver the normal output). 9. Grouraiing,transformers (receive up to 15,000 volts). -87- MONS 209067 3.2.X Transformer Manufacturing Plants There are thirteen ccnpanies in the u.S. which manufacture aakarel transformers at eighteen plants. The name and location of these plants are given in Table 3.2.1-1. Same plants manufacture various types of transformers above and others manufacture only one specific line of transformers. All plants in this category were contacted to obtain infornetion on their waste water. Detailed information va, obtained on two plants which wars visited. The Largest U-S. transformer plant (based on quantity of PCB use) was not visited because of lade of cooperation. The data base represents approximately 20 percent of the 1974 PCB usage for transformer application. The PCB usage in this category was 12.000,000 lbs. in 1974 (equivalent to 15.0 to 17.0 million lbs. PCB transformer oil). The PCB usage in individual plants is considered by these oarpanies to be oonfidwtial information. The range of plant PCB usage was 975 fold in 1974. Plant ages range from three to eighty-five years. The assit of askaxel used in individual transformers ranges fron 40 to 1500 gals. (516 to 19,350 lbs.) with an avera^ of about 232 gals. (3,000 lbs.). A sketch of a large substation transformer is shown in Figure 3.2.1-1. G.E. estimates that the total aikaiel-insulated units that have ben put into service In the united States since 1932 is 135,000, and virtually all of these unite are still in service. The lifetime-before-failure is often longer than 30 years, and airiest all units that do fail are rebuilt and returned to service. TI bu wit production rate of askaxel transformers is abort 5,000 units par year. 3.2.1.1 Aakarel Handling . Pw plants in this category purchase PCBe and tri- chlorcbanzene and do their oiei expounding. Most plants purchase pre-oenpoundad aakarel from Maneanto. Smeller plants purchase their aakarel in 55 gallon drone, filter ttw aakarel and pup directly into the transformer tanks. Tb large plants askarel is dipped vie cars. Ball cars enter in a designated area at the pint alts, nalraral is than pumped from tte rail cars into the raw aakarel storage tank. Any spillage In this area is cleaned by rags or floor dry. The rw aakarel -88- MONS 209068 Table 3.2.1-1 CJ.S. Trans former Manufacturing Industry Using PC3a Corpany Mam* westinghouse Electric Corp. General Electric Carpany Reseaxch-Cottrell Niagara Transformer Corp. Standard Transformer Co. Helena Corp. Hsvi-Duty Electric Kuhlman Electric Co. Electro Engineering Wbrks Envirotech Buell R.E. Uptegraff Mfg. Co. H.K. Porter Van Tran Electric Co. Location of the Plant South Boston, Va. Sharon, Pa. Rone, Ga. Pittsfield, Mass. Finderne, n.J. Buffalo, N.Y. Warren, Ohio Medford, Oregon Helena, Alabama Goldsboro, N.C. Crystal springs, Miss San Leandro, Calif. Lebanon, Pa. Scottsdale, Pa. Belmont, Calif. Lynchburg, Va. Vandalia, 111. Meoo, Texas -89MONS 209069 -90- FXSJR 3.2.1-1. StfiSrXriCM TRMGFORCR HONS 209070 is next Altered through attapulgita dry or fuller's earth and is often through a plate and frane type filter for final deaning and then stored in the finished product storage tanks. Spent day or fuller's earth fran this opera tion is ditmned and stored an site or sent to a landfill. In sane plants, the entire storage area is located within dikes and curhe designed to contain at least the contents of the largest single tank plus sufficient free board to allow for precipitation. At most plants the askarel is distributed from the tank fan area to the filling station, but at one plant (Plant 103) tte finished askarel is next trudeed fran a covered/curbed storage area to an uncovered/ banned tank faun area. Here the trude enters a shelter area, and the askarel is then ptmped fran the trude into distribution storage tank. Recycled askarel fran the manufacturing operations is generally returned through pwpa into a storage tank or into 55 gallon drums and fran there it is either filtered for reuse cr is sent to incineration if it is proved to be defective. 3.2.1.2 Proosee Description Most plaits manufacture all the hardware and cuipunants necessary for the transformer asaotbly. The transformer interiors and the container* are brought to the askarel filling stations where transformers are aeseobled, Hiiet and sealed. The filling operetlan is done in a designated station. At plaits when snail quantities of askarel are handled, spills and drips are cleaned via floor dry or rags. At plants when large quantities of askarel are handled, filling operation is acn&rcted on gratings located on rape. All drainage is directed into these stops. The stops are inspected and cleaned periodically. All ses^t askarel fran stops is ptoped into drune and sent to incineration. Various transformer assoifeling and filling prooedirea are being poetised thxot^iout this inckistxy. In general, all tranaformar assem bling and filling operations consist of a predrying step for moving moisture 91- MONS 209071 fran the transformer interiors, stwal stages of aakarel filling and askarel topping, addition of electrical connections and bushings, electrical testing art sealing. At plants where relatively snail quantities of askarel are used, the assotbly and filling procedure for distribution and power trans formers are alike. Sane plants manufacture only a given sirs of transformers (single tank size operations). At larger plants different assentling and askarel filling procedures are enployed for various transformer sufacategories. Sene of the askarel transformer aseerbling and filling procedures practiced within this industry are described below. 3.2.1.2.1 AsssBbly and Askarel Filling Procedure for the Distribution arid 'Power Transformers A. Vapor Phase Prying Prior to Filling This procedure is primarily used in the filling of rwtwork and ped-neuited transformers. The drying of the transfirmr internals is a vapor phase treatment with a karrisere 'like petroleus distill ate. A schematic flow diagram depicting this systaa is given in Figure 3.2.1.2.1-1. Tha asseefeling steps for these transformers include the followings . First the trensfosner interiors are placed in large vacuus chanters heated with stems coils. The petzolsua liquid is adnittad, vacuus and hast axe applied. The petroleus vapors rise to be oondensed on the interiors, eedianging latent heat for sensible heat and raising tha tsepareture of tha interiors. After a specific time the i is purpart out; vacuus and hast are continued to dry the internals. . The Internals are next nomad and placed in their own containers and flushed with aakarel at attnoapheric pressure. The aakarel is kept in the tank uxfcil tha liquid tmventure is lowered to a pceeet level at which time it is puiped out of the tank. The purpoee of aakarel flushing is to chill the transformer interiors prior to final filling. -92- MONS 209072 -C6 I Flgum 3.2.1.2.1-1 TRAMratUCR HULUN WITH VAFOR PHASE PREDRTtNO of interiors HONS 209073 HONS 2 0 9 0 7 4 Most transformers in this subcategory have gasketed covers with barrel band type connections. Subsequent to the fil ling operation, the transfosnezs are sealed and pressure tested for leaks. The large units are liquid pressure tested while the snaller ones are air pmsure tested. A sdwnatic flow diagram depicting this systma is shown in Figure 3.2.1.2.1-:. The contsninated oil fron the vacuum puip is treated as waste askarel and is sent to lncineratien. C. Oven Drying of Aaserbled Uhits Prior to the Filling This procedure is used primarily in the asenbly of the precipitator tranafosners. Here the transformer internals are placed in their own casings, the covers are welded on the casings and tha assmblsd tank is placad in the acnvection wen all sealed. At an elevated tanparatuxe, veosss is applied at predetermined intervals. The tank is thMt transferred to the filling station where askarel is added through an ipper pipe opening under vseuxa. Both the top piping and the drain valve are next sailed end the unit is than pressure tested. A schanstlc flow diagrmn depicting this systmn is shown in Figure 3.2.1.2.1-3. D. Pr<**a far Assembling the Askarel filled Power Tranafacrers The sane pcoaedixe is used to asssmbls all types of askarel filled power transformers. Tha transformer internals are dried in sealed vaeixa tanks, then they are placed in their own containers and the cover is welded and ---1--* Tha unit is th pressurized and diedcad for leeks by a helius detector. The tank Is next transferred to the filling station fchaza low vacua is dram for a period of 24 hours. The askarel line is then ocmectad and tha *--* la wiies slowly while under vacua up to the operating level. The unit la then sealed d sent to electrical testing. After the tests the 11 Uni-- is returned bade to tha filling station whare it is nitrogen ^measure tested just prior to dripping. The sdwatic flow diagrmn depicting this aystma la down in Figure 3.2.1.2.1-2. -95- HONS 209075 -96- Pigura 3.2.1.2.1-2 transformer fiujno with oven or vacuum chamber predrying of transformer mternals HONS 209076 KW UK MIL tMT KUU.CK'1 tMTN lUtf 0l* Figura 3.2.1.2.1-3 TRANSFORMER FILLING OPERATION WITH OVEN PREDRYING OP ASSEMBLED HARDWARE HONS 209077 All pcwer transfanosrs hra air sp*x on the top md an equipped with an air cooLad circulation systan. Additionally, each unit has a spring loaded relief valve as standard equipment. Tteae trans formers have a greater potential for envirotmantal contamination through the vent aystan, via leaks cn the purp and the valves. 3.2.1.3 Ra* Waste* In general, the process re wastes fran these plants consist of waste aekazel collected in suipe or pans at the filling staticns, centanirvated vaann pup seel oil, contaminated kerosene-like petroleun distillate (used in at least one plant in the vapor phase drying operation), contaninated askarel used for transforms interior flushing and contaminants in ths plant effluent. Additionally, plant 103 has a inique waste stream con sisting of oontaninated ground water vhich is being pimped ffron three caissons at tha plant site, plant 103 also has a bleeefcvter discharge from their incineration systmn. Solid wastes fron these plants consist of rags and floor dry used for miscellaneous cleaning purposes and spant clay used for Arcelor filtration. Additionally, at plant 103 it includes ths sludge from oil/ water separators. Ncn-prodict PCS dischargee are shown in Table 3.2.1.3-1. Estimates cn the quantities of rat waste generated in tw plants whidi were visited are giwi below. Quantities of wests Loads 103 Plants HI Wastes to incineration, lbe/ton of PCS used 115 98.0 Solid waste material stored an site in 55 gallon dm 135 units ihknom 3.2.1.4 water use Water is not an essential ceupcnsnt of ths transfomar manufacturing proxies. PCB wastes which readi water streams at them plants are foe to inadvertent occaeionel loee foring handling and residuals aoamiiated -98- HONS 209076 THU 3.2.1.3-1 WK-PJCOLCT Pta QISOttMES Souroa . Plane axhauat Incinerator axhauat Personal hy?ima and sanitary uatar Ground wear purped through caiaacna Katar uaad at plane Ooneamlnatad oila and waata PCBa Floor a wapInga and raga uaad Cor elaaning Rejected transformer interiors for acppar recovery Osntnninatad and defective aipey dz\na Sludga froa tha oil aaparatar Clay uaad for aakaral filtrati 103 Air Air TO Oil than rivar To oil separators than rivar incineration dacapaulatcr dacapaulater To ataal furnaee in ataal aill Sfeorod an miec Stocad an aita 114 Air hom r/rivar Incinaration IndnaratlA Stocad on aits Shipped to tha conpany vtiieh handlaa chair oontaainatad oila Nona none -99- MONS 209079 around the drainage systems from past operations when no precautions were taken in handling and disposal of PCSs. This category uses water primarily for non-contact cooling purposes in vacuian puipa, ccnpreseors and at same plants as contact ooolmg in their welding and plating operations and in phosphatizing of the steel surfaces prior to painting. All contact cooling operations listed above are primarily non- PCS related operations. Only plant 103 has a PCS related process water which con sist# of the water used in their waste incineration syston for quenching the hot gases fron the reaction section. Plant 103 is also the major water user in this category. In nest atelier plants all cooling is acocnplished by air. At these plants water is primarily used for hygiene and sanitary purposes and for ampressor or pimp cooling purposes. The only water that cones into contact with PCSs at these latter plants is that used for personal hygiene. The types anl quantities of water used at two plants visited axe given below. Water Usage in Gallons/day Non-contact cooling Process water . Contact cooling . Detergent washing . Incineration quench Hygiene Boiler make-up Sanitary Nan PCS related . water used in a lab . water taad for eternal cleanups Plant No. 103 1,646000 183,000 2,000 122,000 unknown Unknown Unknown Unknown None Breatafawn of the water usage was estimated. 114* 38,000 None None None 300 200 9,000 500 4,000 -100- HONS 209080 3.2.1.5 Wastewater Treatment _ there are no effluent treatment techniques in practice at ary plant in this cate^ry for the rsrwal of PCBs. However, in 1972, a John 2ink designed thermal oxidation incinerator was erected at plant 103 to safely dispose of POs. A schematic flw diagran of this unit is given in Figure 3.2.1.5-1. this unit consists of two stean atomized burners and a long cylindrical chanter to provide residence time for thermal degradation. Follow ing the chamber is a water spray quench pot and a counter current packed scrubber aolum located at the base of the stack. The waste oils are brought into the incinerator site in 55 gallon dnzns or by trudc trailers. These waste oils are next puiped fran the drvm* or fran the trailers into the incinerator feed tanks. The steam itemizing burners inject the canbustible liquid wastes into the combustion section with air, in such a manner to create a vortex type turbulence. This produces high heat release and effective ccnbusticn pronoting the thermal degra dation proaesa. After cxnbusticn, the waste gases proceed through the oxidation dabsr whidi provide* 3 to 12 seconds of residence time at temperatures 1600 to 1BOOF for the degradation reactions to go to cotpletion. The flue gases from the disbar pan through a quench pot which aontaina a serin of water sprays to cool the gases. An induced draft fan than forces the oooled gases through the parked bed scrubber aolum. Here, acidic ions produced during the fMTrtateHfn process are absorbed in the scrubber liquor. The scrubber liquor is than neutralized and disposed into the sewer. A high tamperstore decapsulator has been incorporated in the thermal oxidizer unit for solid incineration and copper raoovary. The exhaust of this unit is routed to the ippar end of the oxidizer chamber. Details an wastewater treatment techniques utilized at one facility (plant 103) for purposes of oil recowry and on-going contain ment j. 111 nj i -- undertaken by two plants (plants 103 and 114) in order to prevent the entry oC KBs into the envireraent are aoversd in the Task II report, "sessir of West swat si Management Treatment Technology, and Associated Oasta -101- MONS 209081 SOLID WASH OCCAPSULATOR EXHAUST RECOVERED COPPER AIR ]_____ WASTE OIL WASTE OIL ~r BURNER THERMAL DESRAOATlDN CHAMBER i 0M1 STEAM QUENCH FEED WATER--* TO STACK i NEUTRALIZED TANK --WATER EFFLUENT Flflww 5.2.1.5-1. PROCESS FLOW DIAGRAM FOR THERMAL OXIDIZER INCINERATOR AT PLANT 103 HONS 209082 far Abatement at P(3s Concentration in Industrial Effluents", February 3, 1976, pages 71 through 75. 3.2.1.6 Effluent Caipoeiti.cn Effluent flaw rates and PCB contents are available fraa the three plants which disdiarga into the rivers and from two plants which discharge primarily into sanitary sewers. Detailed effluent conposition is available only cn Plant 103. This information is given in Tables 3.2.1.6-1 ard .3 2.1.6-2, respectively. The remaining plants in this category which discharge to sanitary sneers report that their water usage, fra: reasons other than for sanitary purposes, is minimal. However, they have no data avail^le cn the quantities and aaipositicn of water discharged. 3.2.2 Aakarsl Trans farmer Repair Induetrv A total of 13 ccnpenies repair transformers containing PCS* at a total of 131 locations. The current industry structure has been identified, and sararal potential problems were noted. Ho eetlmetee have been made of the pollution tdiidi occurs fron this industry. 3.2.2.1 Transfbcnsr Inspection and Maintenance Aakarel transformers are very reliable and have life time that range up to 40 year*. Tha failure rate of aakarel filled transformers has been estimated by tha manufacturers to be 0.2 parent per year. Failure occurs primarily due to tha degradation of tha PCS fluid cm mart by electrical arcing within tha transformer. Nina electrical utilities were contacted to determine their inspection and repair procedures. All of these ncrpeniite have some type of program, usually informal, for tie checking of ttwir transformers. In meet cases omelets of a alapis annual inspection which may include a general -i---4aw> of the facilities adjacent to the hardware (e.g., tha vaults may be rlesnarl and vaoasnsd). inspection involves locking for evidence of leaks. One utility pexfosas an annual power factor bast an the windings, and if this teat Indicates a problem in the transformer, than its dielectric fluid -103- M0NS 209083 Plant Ha, 103m 111 113 U6(3) 117 TASLZ 3.2.1.6-1 pcs cwconRAnw m ejttishts frch twhstopwr WHVJCnJWMj PLANTS Discharga Designation 003 OOC Nona Nona 002 003 004 11 12 13 Batch disOiarge Effluant flow Rate Cal/Dty 1,310,000 330,000 30,000. 2,000' 36,000 24,000 150,000 252,000 371,720 504,000 13,300 Effluent PCB Content AvS^/r*tax lh^dav Av<j7'ax DispOSltJ Of iff I'll 4.9/120 7/75 0.0335/1.311 0.0321/0.344 River River unknown unknown tMJewwn Urdcnown River <1/2 2/113 <V3 <0.0003/0.0006 0.0004/0.0226 0.0013/0.0039 River Piver River 3.4/11 2.1/3.I 4/19.1 0.0071/0.0231 0.006o/3.0120 0.0336/0.0803 River River River 21.6/unknown 0.0032/unknown Sewer Neteei (1) This plant haa other dischargee out of their properties. Discharge* listed above an those atsoriirari with PCS related operations. (2) Estimtad. (1) Discharges designated aa II, 12, and 13 an tha cotfeinad affluents frtxa thair power house, and ona each from their wo manufacturing areas, respectively. According to tha plants' Corps of Engineers permit application fbm, filed in July 1971, this plant has 13 outfalls. -104- MONS 209084 TW 3.2.1.6-2 smirar and anuarr cavcsmais cf plwt 101 IMrp flow rat* million <jpd pi yaarly avarspa f min.-max. Iiasoalr^ nnicipal watar 1.1* 6.4 Outfall oos 1.31 7.7 6.4-t.O outfall 006 0.5S 5.5 3.1-7. 1 Alkalinity, ag/1 B0D> 5-day. aq/1 Chaaicai oocyjan, wq/1 . ttq/l IDS, a*/l TSS, aq/1 TVS. */l Mi. aq/X <m KjsldatU Mierogan, a^l Nitrata AN, rq/1 fboapncua Total, mj/1 Color {As P) Turbidity, aq/1 Ibtal hardnaaa, sq/1 Crqmlc Hitrogan, aq/1 SttUtMi aq/1 Stll/ldt, Zq/\ Otlorldt. Cyanida, ug/1 71ucrida, rqfl Aliarima - total. vt/X Sore* - total, u*/l rslctaa - total, s/l fhwrfw - total, vq/l 14 2 * (I 1 34 0.03 0.43 0.13 0.01 30 <33 44 0.3 3.0 <0.1 <0.00 0.14 100 70 *.s <10 Avg/Max Oonc. 23/25 1/3 23/34 70/70 *7/47 3/3 13/22 <0.2/1.0 1*3 lba/day 273 24 231 763 733 31 201 <2 Avq/Max Avg Cere. lba/day 13/20 69 27/30 124 75/32 344 3*4/497 1671 341/413 1563 23/30 10* 43/3* 401 2.1/3.0 13 0.4/1.0 3 0.33/0.3 0.04/0.03 <1 23/30 - <2V<23 - 31/44 340 0.4/0.7 *.l 14/11 133 <0.1/0.1 <1.0 1/1 *1 0.00/<0.01 0,04 -" 300/330 3 -- 7.0/7.S 77 30/30 0.3 4.S/3.1 21 0.91/1.02 3 34/124 241 30/30 <25/<23 33/44 152 1.1/2.0 9.0/3.0 41 <0.1/<0.1 <0.3 11/13 50 <0.00/<0.00 <0.02 9.5/12.0 44 200/200 0.9 9/70 0.04 7,7/1.0 33 310/330 1.4 105- HONS 209085 Ttt 3.2.1.6-2 (CCN'T) Inonin? MitLeipal Wittr Cotaalt. total, jq/1 <7 Qjppar - total, uq/1 500 Iron - total, u<j/l 030 Laad - total, uq/1 mgnaaiJB * total, uq/1 <30 7 - total, uq/1 200 Marcury - total, lkj/1 <1 ttolybdann - total, ug/1 <7 Nicfeal - total, uq/I 100 Botaaaim - total, nq/1 1.1 Silw - total, u <10.0 - total, nj/1 5 Tin - total, uq/l <7 Titaniiaa - total, u 2 Sine - total, uq/1 30 011 6 (2MM, hq/1 1.0 HMrola, uq/1 3 Surfactant*, aq/1 <0.02 QUerlnatad hydrocarbon*, nj/l <1.000 (Moapt paatirlilaa) KBa, uo/lltar - outfall 005 4/4 0.04 20/500 0.2 150/330 l.C <10/30 <0.1 3/7 36 50/200 0.5 <1/<1 <0.004 -- <10/100 <0.1 0.66/1.10 9.6 -- C/10 66 7/10 0.07 -- 70/75 0.76 2/10 21 101/110 1.1 0.11/0.15 1,2 1.000/5.000 U Outfall 006 -- 30/500 0.13 3200/3500 15 80/90 0.36 3/7 16 120/200 0.55 2/2 0.01 90/95 0.41 10/100 0.04 0.99/1.1 4.5 2.0/2.0 0.009 25/30 117 -- 3/3 0.01 730/600 3.4 3.0/9.0 13.7 166/160 0.77 0,22/0.30 1.0 l.OOOA.OOO 4.6 4.9/120 0.05 7/75 0.03 -106- HONS 209066 is tested - at least this is the theoretical method of operation since the aorpany has only two PO-type transformers in use and neither has ever failed the power factor test. Another oonpany measures the operating tsnperature of the tsiits and makes a visual inspection for leaks; this aarpany claiirs that transformers located in the generating facility are inspected daily (visual inspection) and that units located in vaults are chedced at least weekly, vhile meet major inspections are carried out annually, the range of tine intervals between inspections is 6 months to 13 months, with ere company saying that they inspect at least once every 2 or 3 years, awl another saying that substation transformers are inspected weekly. These oanpaniea perform no smpling and analysis work on their askarel transformers. Ore aoipany has annual inspection of all trans formers, but only the mineral oil-type vnits have series withdrawn for analysis to see if there is deterioration or contamination. A company which used to perform power-factor tests until about 8 years ago has since abandoned such tests and does not withdraw askarels for analysis. Servicing of transfoonexs is only rarely performed in-house. The response of most oenyanies was that servicing of aakarsl-type transformers had yet to be required. One ampany did its awn servicing up until 8 or 10 years ago, but since than, became of the special handling problone assort atad with askarels, such work has been famed out to G.E. and Mastinghouse service centers. The general trend seams to be that major servicing is more likely to be dona at special facilities outside the utility orapanias while minor servicing, sudi ae the repair of nail leaks is taken care of at the tracts foster site by the utility. More than half of the mryvles have not scrapped transformers in the past five years, and most have not scrapped any in the past 10 years. Che utility ampany has had no transformer failures in 20 years (except for a minor leak of less than 1 gallon tan years ago). These companies have no ^edLfie methods for such instsness. One oonpany said that scrap transfomers are handled through a local junk oonpany and that askarel disposal is the junk aopany's problem. A ccrpany which says it has scraped no transfoanixs says that whan the PCS capacitors fail they are shipped back to 107- HONS 209087 the manufacturer; presumably, though it was not stated directly, fallal eransformers would also be returned to their manufacturers. Cne aonpany whiih is prcud of its disposal practices has disposed of 200 to 400 gallons of askarel per year since 1970 (most of it canes from failed capacitors); until this year it was all sent to ftmanto for incineration, but starting this year they have been sending it to Sheffield, 111., where it is duped in a landfill that has been approved by n>A for the disposal of radioactive wastes. This catparry stated that many utility acnpanies dump their PCB-related wastes in local landfills. There has been little PCB lost to the envirorment through the safety relaaee valve on the transformers. The oonsensus response was that if the valve released there would be askareis "all over the place". The spaceman for one utility did not know whethar the transformers they used had safety val\s. Cne ccnpany said that a transformer vented several years ago whan a fuse that was suppoead to protect the transformer did not protect it. Very seldcm is a failed transformer scrapped. However, sonatinas the repair work needed la a failed unit could be rather extensive and very costly. The owner of the unit may requeet to scrap hie unit. If the repair shope scrap a transformar, they follow the procedure isuLumanJad by NQft. How ever, if the owner of the transformer decides to handle the disposal of the unit himself, the unit is shipped bade to the owner. Disposal is than usually made through a local junk dealer. 3.2.2.2 Rapair of Failed Transformers In talking with a major transformar manufacturing coipany which specializes in the servicing of transformers, it was learned that PCBa used by service shops are primarily for refilling the units which have failed and have to bs repaired. Apparently, very tw* facilities handle their own servicing. Jfcjar service work is almost always handled by repair sheps while adnor serviaa work, sudi as changing a gasket, to prevent a minor leak, may bs taki care of by the owner of the transformer. Additionally, the repair 108- HGNS 209088 steps often handle askarel conditioning sexviaes. In such a case, the servicemi carries ths filter press to the aoatemer's site and performs this service on site. Several gallons of tO*s axe used in this service for topping the unit and sijusting the level. The procedure for the npair or disposal of failed transfourers and the handling of the PCB liquid in those transformers is suimarized in Figures 3.2.2.2-1 and 3.2.2.2t2. - A nirrber of potential sources of environmental oontanination ham been identified, and are <11 soissert in detail in the following notes to the figures. 1) Testing and analysis of PCB transformer fluid has been largely discontinued due to the strict re quirements imposed cn the disposal of the saiples. This change in procedure may be ejected to in crease the probability of major failures of trans formers aon&aining PCBs. 2) Aoeidmttal spills of PCBs from trnsfosners can occur due to leaks, venting raised by short droiits, or medimlcal dmnege to the transfooner case. In most cases, the trnfonner is ocntained in a vault or is surrounded by dikes which will limit the spill to a controlled area. Cnly in the case of railroad tmsfbsners would the leakage resulting from an accident be sqpectad to be uncontrolled. 3) Ttrnisfccmexs which are scrapped by the ownar/user may be a serious potential source of pollution. Those transformers built during the past several years are well marked with the hazards of the PCTs which they contain. Disposal of junked trans formers by electrical repair shops is gowned by a detailed specification of the National Electrical HONS 209089 109- TRAN3P0RMC* IN JCNVICI RCMMC0 OR SCRAPNCO TOOHB 3.2.2.2-1 TRANVORNCR RKTURWO TO KDVKt TRANSTORCR MONimMKS i SERVICED 110- hons 209090 (T) (B) MBS0 HYONQCAHION FUCL FICUW 3.2.2.2-2. TJWtSTOWER IEPAIR -111- HONS 209091 Manufacturers Association (N&W. However, the disposal of transfonrers through small local junk yards may result in significant pollution because: a) The junk yards are not familiar with P<3 handling procedures. b) The older transfonrers are not marked with special instructions. c) 90 to 95 percent of the transfonrers seen by the junk yards would contain mineral oil. and the occasional transformer containing PCS would be noted only as containing non-flam mable transformer oil. This would not result in any sperjal handling of the PCBs. d) Disposal of PCBs by open burning in a trash incinerator will not omplately destroy the PCBs, but will vaporize this material and dis perse it into the atmosphere. This is only s potential probloa at this time, as uncontrolled scrapping of transformers has not been docmentsd. However, several responses to the questionnaire claimed that oteontiollad trailing of PCB filled transformers by junk yards was thought to have oacurzed in the pest. 4) Ooneidsrtole PCS is shipped in 55 gallon druns to repair shops and users. The residue in aato drun after it is emptied may contain tp to i pound of PCB. Bpty ditzne whidi are recycled to drun re claiming facilities or scrap yards would introduce this relatively small, but significant, onount of F(3 into an uncontrolled anvirennant. All druns presently in use haw detailed handling instruct ions painted at the drvas, and this information -112- HONS 209092 should minimize any potential problens from this source. 5) Filter residues and losses are in general treated as any other waste containing PCBs and are being plaaed in druis and held for controlled disposal. S) Scrap PCB is packaged in 55 gallon druns. The NEHA instructions are very specific as to the re quired disposal procedures for this material. Small repair shops which do not have access to controlled disposal sites or services have been known to mishandle the scrap PCB by disposing into uncontrolled landfills (note 7) or through oil recovery services (note 8). 7) Landfills axe a satisfactory disposal method for scrap PCS transformer oil if the leach water is untutored. In a few cases scrap PCS and PCS con taminated material is sent to s nunicipal Airp. 8) At least ora case is suspected where PCB trans former oil may have been sent to an oil reclaiming ocrtpany whidi mixed it with other hydrocarbon wastes and sold it to a power ccnpany as fuel. It should be noted that the mineral oil used in 90 to 95 percent of the transformers presently in serviae. P roblame may result whan PCS transformer oils are mixed with mineral oils and handled in this manner. 9) New and conditioned PCS transformer oil is normally stored in large surface or underground tanks at the repair shop. leakage may occur fran -113- HONS 209093 these tanks into ground waters. No standards have been established for cheating for such losses, 10) The scraping of unrepairable transformers is covered by the NEMA standard (ANSI 0.07.1-1974). This standard requires that the transformer be drained and then flushed with solvent to isicve PCS residues before the metal values are reclaimed. Possible sources of contamination would be inoenplata flushing and the mixture of used solwit with hydrocarbon rather than with P<3 residuee. This is considered unlikely in the major transformer repair shops. 3.2.2.3 PCB Usage in the Transformer Repair Industry The PCB usage figures far the transfosner manufacturing and repair industries are swnsrlsed below. PC3a Use, Ibe 1971 1972 1973 1974 1st half1975 New PSs used to repair transfaoners 590,000 580,000 440,000 780,000 480,000 PS reclaimed anl reused in repair of tmfoimacii 2,000 64,000 160,000 110,000 78,000 PS shipped to user to rsplaae transformer losses PS ill qineeil in tiane1 former repair PS used la trmfonnar sennfacturing 3,000 3,000 4,000 2,000 2,000 570,000* 11,000,000 Tbtal PS in sarvios in tmfannaxe 270,000,000 * This figure say include PC3a aonteainatad wastes as well ae PS. -114- HONS 209094 3.2.2.4 Transformer Servioe Life There have been relatively few failures of pa filled transformers, and statistically significant data is not available to support service life estimates. General estimates by transformer manufacturers indicate the foilwing expected service life of this equipment: Servioe life of subetatian transfosiers 40 years Service life of power trans formers , including those an railroad locanotives 30 years Transfosnere exhibit a snail but significant infant mortality rate (failure within the first year of service). Overall transformer failure rate estimates are in the range of 0.2 peraent per year. 3.2.2.5 Usage rate of PCSs in Transfoimar Repair The total PCB used in 1974 in the repair of tramformers was approximately 0.3 percent of the estimated total POs in servioe in tram footers. This figure is consistent with the estimated failure rate of 0.2 peroant per year far in-service tramfenters. The usage of PQJ in the tram footer repair industry is approximately 7 percent of that of the transformer manufacturing industry. 3.3 Investment ranting The investment meting industry produces precision-cast natal parts and shapes for the aircraft and other mwdvinery manufacturing industries. Approximately 25 of the 135 investment casting foundries in the United States currently use PCB filled vexes in the manufacture of natal caetings. The R3 incorporated in the waxaa is deoadUorcbiphanyl (daka). The remaining foundries use either polydilodnated tarphanyl (PCT) filled waxes or unfilled waxes. This --presents a review of tha usaga of daka filled waxes in the industry, in cluding available infonnation on use history, process technology, and potential -115- MQNS 209095 FCT-bearing waste streams. Currently available information on PCTs usage in the industry is also included. 3.3.1 Background There are currently 135 investment casting (IC) fcurdries and five investment casting wax manufacturing plants in the United States. The ic industry had its start in the United Statea during World War II when urgent demands for aims and aircraft parts required more efficient nethods of prodicing finished, precisian parts than standard machining techniques offered. During the war the waxes used by IC foundries consisted of a bleni of camauba wax, beeswax, paraffin, and rosins. However, over the last tecade wax fomilationa haw evolved which consist of a variety of polymeric compounds and otter fillers such as decadilorcbiptenyl and PCTs. By reducing the wax content through low-shrinkage fillers (such as P<3a and PCTs) volumetric shrinkage of the aeranic mold is controlled. This allws the production of metal castings with smaller dimensional tolerances than were available with the original in filled waxes. 'Sis major wax manufacturing aaipanies are: 1. Yates Manufacturing Cfcnpany, Inc. 2. M. Arguaso and Company, Inc. 3. Freeman tenufacturing Company 4. J. F. MsOoughlin Company Tte Yates Manufacturing Company, Chicago, 111., is tha sola known U.S. supplier of deka waxes. Tte dscachlorcblptenyl cmtant is 30 peraant of the total wax by weight (Solanon, P., Yates Manufacturing). Yates curmtly inparts deka fran Csffaxo S.P.A., Italy, at a rate of 300,000 to 500,000 lbs. par year, which corresponds to tte manufacture of betueen 1 and 1.5 million pounds of deka wax, annually. At a cost of SO.70 par pound, (Lewis, W.H., Signicast Cdrp.) the annual volune of salse of deka wax should be in the range of $700,000 to $1 mm per year. All the wax manufacturers listed previajely are beliewd to use boosted PCTs as pattern wax fillers. Since the general properties of tte cteca and PCTs are similar, it is believed that the wax prodiction and use -116- MQNS 209096 proowM an similar also. Contact* with industry indicate that tha voltm of FCT* in wax ia probably about tha sane as or greater than that of dak* PCBs Monsanto was tha loading (and probably only) u.s. producer of pcts prior to their voluntary oessation of prodnrtion in 1972. Derastic production of PCTs by Monsanto through 1972 was as folls: Year 1968 1969 1970 1971 1972 Million of Pounds Aioclor 5460 8.87 11.60 17.77 20.21 8.13 It is believed that a relatively snail fraction of this producticn was used in easting waxas, probably on tha order of a million or so pounds par year. Aroclor 5460 (Monsanto's trade naoe far their 60-percentdilorine PCTs) was used primarily in adhesives, lubricmt* and paper coatings. The current source of inserted FC is believed to be Prodslec (France), which markets the material as Electxophenyl T-60 ( 60 peroant chlorine), which, it should also be noted, my aentain PCB oantsninants. In susnary, tha inveetraant casting process, whidi is described more thoroughly in Sections 3.3.2.1 md 3.3.2.2, is a lost-wax casting proms* in which the to be cast is molded froa wax and than insisted or surrounded by a slurry of refractory aeranic. After the aeranic mold has hardened to an appropriate strength, the wax is malted or burned out leaving a added cavity. Molten metal ia then poured into the cavity, and aoolad to form the casting. Tta major lreiaa of the virgin and used waxes occur during the dwexing of tha oiraic sold. As tha aeranic mold is heated to ranewe the wax, a small portion of the wax diffuses into pores of the mold. later, the mold with the IV4 waxm is fixed in e furnace to set the mold and remove tha wax. pending an furnace aonditions, the decachlorcbiphanyl in the wax may be burned or --r~* to the aonoaphare. At laaet several peroant of that used is believed to be adtted via this route. -117- MGNS 209097 It is a normal praction by many fomdries to recover the drained pattern wax and reuse it several times in sprues and gates. Purchased wax is apparently used an average of 2.5 times. During the dAxing process t virgin wax (used to font the pattern) and the old wax (used to Earn the gates and spnies) are collected as one mixture. Little of the wax is destroyed in the process: therefore, it is considered probable that the investment casting foundries store or dispose of relatively large anounts of used PCTcontaining wax. 3.3.2 Investmsit Casting Technologies 3.3.2.1 Principles of Investment Casting The principles of investment casting are the same for both the solid mold and shell processes, but the method of faming the oeramic mold differs scnrahat between the two. Both require a pattern, gating to a central sprue, raaoval of the pattern by melting, pouring metal into the cavity left by the melted pattern, removal of mold material fron the cast cluster, ani cutting of castings frcn the sprue. 3.3.2.1-1. The investment shell pcoaess is deleted in Figure The Pattern: The presses begins with production of a one piece heat-disposable pattern. This pattern is usually mada by injecting wax or plastic into a metal die. Dies range fron simple, hand-operated single cavity tools to fully automated railti-cavity dsvioee, depending on production quantitiee and narylaxity of the parts to be cast. A heat-disposable pattern is required for each unit being cast. Bach pattern has the exact geometry of the required finished part, but they are mada sli^ttly larger in order to oenpaneata for wlunatric shrink age dicing the pattern prediction stage and diring solidification of the ratal in the mold. The pattern carries one at more gates whidi are usually Located at tha heaviest casting section. The gate haa three functions! -118- MQNS 209098 Figure 3.3.2.1-1. INVESTMENT SHELL PROCESS HONS 209099 (1) To attach pattern* to the centrally- located sprue or runner, thus forming a tree-shaped cluster; (2) To provide a passage for the draining of pattern wax once the mold is sufficiently hardened and has been heated; ard (3) To guide noltan metal entering the ncld cavity in the pouring operation. Clustering; Petteme are fastened by the gate to one or ncrv runners. The nruisrs are attached to a pouring cup. All of these parts are usually made of wax. Patterns, runners and pouring cup aoiprise the cluster or tree upon vrtiich the aeranic ncld is farmed. The nanber of runners and their arrangement cn the pouring cip may vary considerably, depending cn alloy type and the size and configuration of the casting. >toHlnqi Up to the point of farming the aeranic ncld, ell foundries operate in essentially the sane manner. After assert;ling the pattern to e tees, however, they may form the ncld by either the inveeteent flask proaese or the investment shell process. Solid told cc Investment Flask Process: There are two investment flask techniques, depending cn the type of alley to be poured. Ferrous alloys require hi^ily refractory materials and binders. The entire cluster is dipped into e oerenic slurry, drained and stuccoed with fins aeranic sand. This step is usually repeated after tha first costing has dried. This ooatad cluster is than placed in an open srl metal can (the flask) which is filled with e coarse slurry of aeranic badoq> material (investment). The in- wshnnt hardens to aonpclaa e green ncld. vtm the flask with its contents are placed into an autoclave, the whole duster (consisting of wax patterns, runners and sprues) melts and rm out through the pouring 09. The resulting mono lithic mold contains cavities of the desired casting diape, with passage lead ing to thou Nonferrous alloys are cast in aeranic molds bended with piaster of peris. The entire tree (heat-disposable patterns, gates, runners, and pouring ctp) is pieced in an open-end metal flask without a first 120- HONS 209100 oermic ooating. Investment slurry is poured into the flask, oaipletely sur rounding the cluster. Before the binder sets up, the flask is pieced under vacuun to remove all air entrapped during mixing of the investment. When the investment beames hard, patterns are melted out exactly as in ferrous casting. The Investment Shell Process*. This technique, as desffibed in Figure 3.3.2.1-1, involves dipping the entire cluster into a ceramic slurry, draining it, then coating it with fine ceramic sand. After drying, the process is repeated several times, using progressively coarser grades of aeranic material, until a self-supporting shell has been formed, the thickness of the shell is usually hetman 3/16 and 5/8 inch. The coated cluster is then placed in a stem auto clave vhere the wax melts and runs out through the gates, runners, and pouring cup. The resulting oeranic shell contains cavities of the desired casting shape, with passages leading to than. Casting; Monolithic shell rrolds and solid molds imst be fixed to bum out the last traces of pattern material and to attain a degree of permeability before the molds can be filled with metal, in the case of solid rrolds, this heating has to proceed slowly, in a controlled cycle whim stretdas over 12 to 18 hours, to avoid cradcing of the noId. The shell molds, node of ceramic material with an axtcantly low coefficient of expansion, can be placed intnediately into a hot furnace. Because the shall rrolds have relatively thin walls, they can be fixed and ready to pour after only a few hours in the furnaces. The hot molds may rely an gravity alone to carry the molten metal into the intricacies of the trold, as is cannon in sand casting, cr the process may use vacua, pressure and/or centrifugal foroe in order to faithfully reproduce intricate details of the wax pattens. Malting equipment arployed depends on the alloy. For ncnferrous allays, gas fixed or electric crucible furnaces are usually used. For ferrous alloys, hi^i frequency induction furnaces and indirect arc furnaces are cannon. -121- HONS 209101 Cleaving: After aooling, mold materials at* reroved from the casting cluster with vibrating equipment. Individual casting are usually rwnoved from the clustar by meats of cut-off wheels, ani any rmainim protrusions left by gates or runners are removed by belt-grinding. Generally, castings are sand blasted for anooth finish, then they are ready far sudi secondary cperatlons as heat treating, straightening and machining. Reclaiming of Pattern Waxes; The present cost of virgin pattern wax is approximately $.79/lb. In the future, it nay be more economical to reclaim wax for use as pattern waxes, in addition to its present use in gates and runners. Furthermore, through a precipitation method, it is possible to remove fillers, including PCBs, from used wax in order to prepare unfilled vox. Improvement of Investment Casting Processes; Several improvements in the investment casting techniques and procedures have been suggested by TIW Metals in Minerva, Ohio, whidi developed them throt^h a twoyear Air Faroe contract (AElffr'IR-74-237). The areas of improvement were in wax pattern formation, nold production processes and metal pouring. Max pattern formation techniques were improved through simultaneous niltipla injections of the gates and rvmnars. The usual procedure requires separate atape. TWo suggestions far inprovenents were mads for the rtcld production process: (1) elimination of the drying cycle between slurry dipping and sand ooating, and (2) the use of microwave own to melt pattern wax out of the oentdc mold or shell. The use of microwave dswaxars would have the ad vantage of reducing wax vdasions in flue gas and drain condensates of auto clave ovens. However, microwave dewaxing may not eliminate wax lessee occurring during mold firing as a result of wax trapped in the pores and cavities of tbs oeraic mold.. 3.3.2.2 Fotavh*y Prr - Use of PCT and PCS Filled Waxes A flow chart which typifies the use of PCBs and PCTs in inveetsant casting is presented in Figure 3.3.2.2-1. PCT filled waxes are -122' HONS 209102 naftMTCB K$| WAI ---------- PATTERN WAX PRODUCTION WAX POOOCTION 011 AATTCM MCEAfilM AMO SHt'ICMT (-30% PCO, 1M ELASTIC 0A6) INVUTIgNT casta* moctsi FIGURE 3.3,2,2-1 FLOW CHART OF PCS* USAGE* IN INVESTMENT CASTING HONS 209103 [iin hi--1 gran wax manufacturers in bulk quantities of 1.0,000 or nere poureis, in plastic bags and contained in boxes far shipment. The received pattern wax is stored in a stodcroan at the foundry until imlted far the production of wax patterns. Ones melted, the wax is injected into a pattern die where the wax is allowed to solidify. The pattern die is then dsassfcled and the wax pattern moved. Several wax patterns are produaed before forming the tree. The fonnaticn of the tree entails attaching tha individual wax patterns to the sprues and gates, and after the trees are asswfcled, the sprues are aaated with a dip-seal wax to fill the voids on the rough sprue surfares. The next step in the process is the formation of the oeranic mold. This is accorplished by dip-coating the wax trees in a oeranic slurry and a fluidized bed of silica, and air drying of the tree. This process is repeated several times before the wax is nelted out of the mold. Dewaxing is aooonplishsd by one of three techniques: steal autoclave, mioewawi oven, cr flash firing in a mold furnace. Hast foundries apparently use the autoclave technique, which involves subjecting the oeranic aosted tie-- to stssn until the wax within Che mold is melted out, leaving the oeranic shell. The melted wax is either disposed of or reclaimed for use as qpruee and gate wax. the new microwave tedwiqua involves heating the molds with miooweme energy* Microwave wits of 5- and 10-kilowatt output are cuuuerdally available for this application. The third technique of flash firing conbinss dewaxing and mold firing in cne step. The oeranic coated wax trees are placed in a furnace where all the wax is removed fran the tree by flmh firing. Mast of the wax is vaporized and leaves the furnace with the stadc gas--. It is not known how many facilities use flash firing. if the fovndzy dewaxes the tress using ajtodave or microwave techniques, the daairert oeranic molds oust be fired in the mold funuwae to etr--jthsn the and to move wex residues. The oeranic moi,4 am raieal to tenperatures of between 1900 and 200QF for approximately two hoots. The vaporized wax residues leave the furnace with the stadc gases, the fouwliim that only 1 to 2 percent of the wax mains in the nolde before mold firing. This estimate of trapped cr wall abeoifaal wax appears tc be low for two reasons: -124- MONS 209104 U.) The porosity of the ceramic mold can be as high as 30 percent/ and (2) Trapped waxes in the cavities of the pattern vary in amount, depending on the pattern's geometric configuration. After firing, the oeranica are ready for metal pouring. The steps involved in pouring, and the subsequent recovery of the castings are evident in Figure 3.3.2.2-1, starting with metal pouring. The high oost of pattern wax has stimulated foundries to reclaim used wax. FOr axarple, the PCB filled waxes sell for approximately 70 aents per poud. The average weight ratio bebesi pattern wax and wax in sprues and gates is about 40:60. Therefora, reclaiming of used wax, especially far use in sprues and gates, ahs become a very important part of the foundry prooets. Reclaiming Involves placing the used wax in open kettles or tanks and heating it above the boiling point of water vntil all the water (from the steam autoclave) is eliminated. After dewatering, the re claimed wax is reconstituted by adding paraffin and other additives until certain melting-point specifications are net. it is claired that wax fillers are not added to adjust the filler content (Vtarster, W., Consolidated Casting Oup.). For those foundries which praceioa wax roclanau.cn on their used wax, it is estimated that 5 to 10 peroett of the wax is deliberately 1i Tpneari of. The major source of the discarded wax is probably the dregs from the dewatering kettles. 3.3.2.3 Waste Stream Idealized waste streams (containing PCBa and PCTs) 1 awlnj an inuastamt casting foundry are shown in Figure 3.3.2.3-1. The broken lines within the procasa box in Figure 3.3.2.3-1 indicate potential PC3 and FCT aery routes via emissions fran the foundry unit processes. The solid lines betnem the processes indicate the production routes of the waxes. -125- MOMS 209105 fsj I 1(1 nam 3.3*2.3-1 _ IDEALIZED FLOW CHART FOR AN NVESTMENT CASTING FOUNDRY, SHOWING WASTE STREAMS- HONS 209106 The solid lines at the top of the figure indicate the two general ambient air escape routes, namely the stadc gas fran the nold firing furnace and the fomdry exhaust air system. The two solid lines leaving the foundry (at the bottan of the figure) represent PCB and PCT escape routes: solid waste, -which is usually sent to landfills, and rav sewage, -which goes to nunicipal sewage treatment in most cases. The broken line outside the facility (at the top of the figure) indicates the possibility for inadvertent recycling of escaped PCBs or PCTs in stadc gas or foundry air eidiaust bade into the foundry facility. PCB-PCT-oontaining waxes enter the foundry as pattern wax packaged in plastic lined bQMBS which an stored until needed in the casting process. During rrcld production, when the wax is melted and injected into metal dies, wax ftmss may escape. The type of dewaxing method enployed by the foundries has a direct effect cn the amount and mode of PCB or PCT less to the envirorment, not only during dewaxing but also during proaess steps that follow. Far exarple, the use of a steam autoclave, in addition to its own potential emission of PCBs or OCXs, also inparts moisture to the wax, and this water nust be removed before the wax can be reused. Dewtaring by evaporation at high tetperature also likely contributes to air emissions. Flash firing, whidi carabines mold firing and dewaxing into cne step, probably anits high levels of PCBs or PCTs, and so far as is known, amissiai controls are not used. Solid wastes can include unreclaimed used wax, excess reclaimed wax, bottans fran reclamations, and wastes from spills, equipment clearout, etc. Althoucb process water doss not appear to be used, sane plants may use cooling water. The steam autoclave appears to be a scurae of water vapor only. 3.3.3 Manufacturing To date, very little is known about the wax manufacturing process. Hrweiier. it is known that in the process PCB or PCT earpounds are wwii la powdered f'Tit to the wax base. Radiation of PCS or PCT particle size prior to mixing may be desired, losses of dust to the environment by air routes froa both sias seductiai and mixing operations would be ejected. -127- MONS 209107 3.3.4 Pecuniei ilaticns The information presented herein represents the current knowledge of decachlorcbiphanyl and polychlorinated terphenyls usage as wax fillers in the investtnant casting industry. This knowledge should be used as a basis for the development of an accurate assessment of the importanoe of PCS and PCT waste fran the industry, and of the adequacy of available substitutes. Significant information gathering efforts would be required to establish a oajplete picture of the practiaes, processes and product of the investment casting foundries and wax manufacturers. Definition of the waste streams and emissions from the processes used would require smpling and analysis efforts in addition to the gathering of available process data and other information fran the industry. The objectives of sudi a plan would neaessarily include the following: (1) 'Verification of the magnitude of PCS and PCT wax filler production and use; (2) Development of detailed process descriptions, including waste streene, leading to a oenplete mass balance for the production and use processes (including significant variations); (3) Definition of quantities and aoncentratiois of waste stream, including waste form, abatement techniques, and ultimate disposal methods) and (4) Evaluation of all reasonable alternatives to the use of PCBe and PCTs in casting. A, study plan to aooB^lish the abow objectives was dsveloped for OTS under Task ill of this progri (Contract 68-01-3259). 3.4. Secondly Fiber Rsoovary (Paper Recycling) The secondary fiber recovery industry aoxverts wastepaper from indmtrial, oammrcial, and sources into reusable pulp, whi<di is mh--(jentVr used to prodme paper products, either as is or blended with virgin pulp. In the Uhited States, thsre are approximately 230 paper mills -128- MQNS 2091 produae pulp Dipletaly derived (n> waetspapar ate 550 m^n uttoM 9ntid pulp acritains secondary fiber (typically 10 to IS psroant). waetapapar stands third bahind pulpvpod ml waataa fran otter forwt products as a source of paper pulp in tte united Statas. In 1974, fibar reaovary mills moved almost 13 million tons of waetapapar Cron tte nature's solid waata street*. Tte affluent discharges from sens of tte secondary fibar mills has bam docunantad by Kleinert to oostain Aroclor 1242,an apparent incitental EOS oontminaitt occurring in tte pulp product!as process. Table 3.4-1 shows tte P3 (aa Aroclor 1242) oenamtrstiens and disdiarge rataa for sons paper reoovery within tte Stata of Wisosnain. Tteaa data ware collected in 1975 by tte wiscavain D^artsent of Natural teanurrea in an effvt to survey PC3 disdiaxge*. Tte follarlng subsections present a review of tte historical uaage of Aroclor 1242 in nartcnlaas ospy paper production and a brief description of a secondary fibar reawery process. 3.4.1 Historical Use of POs in tte Psnar Industry Aroclor 1242 (*4iich appears to be tte predoeinant P*3 fc*d in mill effluanta) ^ waa used in tte oenufactuxe of carbonless copy papsr sold by tte Appleton Papar Division of tte NOt Oorporstloi during tte period 1957 to 1971. Ttelee 3.4.1-1 thxou^i 3.4.1-3 provide data indicatingj (1) Tte mgni- tuda of Aroclor 1242 oensiaptien in tte aunufacture of NCR carbonless paper; (2) Prediction quantities of Nt* caxbonlaea paper; and (3) Tte Might percent of Arcelor 1242 in taper. Ptte tteee ttelae, several sbpiificant facts are derived con cerning tte mepiitude of P'3 use in tte oanufacture of carbonless paper products. Sosa of tteaa facte axes (U Jpprogdsnbely 44 pomda of Aroclor 1242 wve pMrrtiiail (fm Monsanto) for tte mmifacture of NCR carbonless paper} -129- HQNS 209109 TABLE 3.4-1 PCS ajCENTMTICNS IN WISCENSCJ PAPER RIANT EFFLUENTS Plant Average PCB PCB No. of Concentration Discharged Determinations (RFb) Us./day Badger Paper Mills Scott Paper Marinette Oocnto Falls Shawano Paper John strange Paper Bergstron Paper Kimberly Clark Thilmany Paper Fort Howard Paper Mill Effluent Deinking Deinking a Mill Effluent American Can Sulfite Sewer Paper Mill Lagoon Qiaanin Paper Ocean Bay Packaging 1 1 1 1 1 4 1 2 1 1 3 1 1 1 1 <.l <.l <.l <1 4.00 28.40 0.28 <.l 2.60 6.40 7.07 0.10 0.14 0.14 0.45 - .037 1.25 .010 0.158 0.586 1.060 0.002 .012 .019 0.006 Aroclor Type 1242 1242 1242 1242 1242 1242 1242 1242 1242 1242 Not*, Effluent fVf data for thee* naiyani** was determined at tin* of PO sailing. -130- HONS 209110 TABLE 3.4.1-1 HISTORY CF ARDCLOR 1242 CDNSUMPTCCN EJ tHE i-RNUFACTURE CF NCR CASHLESS PAPER FOR THE YEARS 1957 THROWS 1971U) YEAR 1957 1958 1959 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 TOTAL - 1957 through 1971 (THOUSANDS QF POINDS) 587 779 1019 1149 1643 1953 2281 2705 3489 4246 4355 5801 6278 6611 1266 44162 tl}Fan d*tjTccnpil*d d r*port*d by Appl*tcn Pap*r Division, Mot*: MCR Corporation. -131- HONS 209111 TABLE 3.4.L-2 HISTORY OF NCR CARBONLESS PAPER PRODUCTION FOR THE YEARS 1957 THROUSi 1971 YEAR 1957 1958 1959 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 TOTAL/1>1957 through 1970 ESTIMATED NCR CARBQJLESS PAPER PRODUCTION - TCNS 10010 13264 17434 20703 25504 29708 34583 41762 51855 60594 69512 83250 87336 91576 88977 726068 Notail[Iw tnrlivtos 1971 bicaiH us* of Aroclor 1242 was ^MinHmui in May, 1971 but astimtad prediction of HOI r-yK-ni-- paper is for full year. -132- HONS 209112 TABLE 3.4.1-3 RATIO CF AROCXCR 1242 CCNSUMTICN FOR CARBONLESS TO NCR CARBONLESS ESTORIED PRODUCTION Year 1957 1958 1959 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 (A) Aroclor 1242 Oonsoiption {1) Thousands of Pounds1* 587 779 1019 1149 1643 1953 2281 2705 3489 4246 4355 5801 6278 6611 1266 total{2) 1957 thru 1970 42896 (B) NCR Carbonless Estimated Production Thousands of Pounds 20020 26528 34868 41406 51008 59416 69166 83524 103710 121188 139024 166500 174672 183152 177954 1274182 PCS Oontent j|y* x 100 2.9 2.9 2.9 2.8 3,2 3.3 3.3 3.2 3.4 3.5 3.1 3.5 3.6 3.6 - Avg. 3.4% NotaaA* Tam data ornyllad and reported fay AR3l*tcn Papars Division, tOt Corporation. WtOtMl rrrlirlas 1971 h^Tp-- uaa of Arcelor 1242 was discontinued in May, 1971 but aatinated production of NCR carbonless paper is for full year. -133- NONS 209113 (2) Thi average weight percent of Aroclor 1242 in carbonless paper was 3.4 peroent? (3) Of the total PCTa sold in the United States during 1957-1971, 6.3 percent were sold for the NCR carbonless paper application; and (4) 28 peroent of the total Arodor 1242 sold by Monsanto for plasticiser application was purchased far the manufacture of NCR carbonless paper. Although NCR developed and sold the product, the actual manu facturing step whereby Aroclor 1242 was inoorporatsd into the paper was per formed by tte `lead Oozporatiai of Dayton, Ohio, who exclusively supplied carbonless paper to NCR. NCR, in turn, either used the sipplied paper to manu facture ledger (business) form or sold and distributed the carbonless paper to other form manufacturers. Aroclor 1242 is reported to be the only Aroclor type used in the production of carbonless paper. Specifically, Aroclor 1242 was used as a solvent for certain color reactants whi<h taxe encapsulated into miexospheres 10-20 microns in dietster ml applied to one side of the paper during the abating process. The walls of the ndcrospheres consisted of a gelatin-gun axcbic fcmulaticn which was haxdanad by treatment with an aldehyde (such as formaldehyde). Since 1971, alkyl biphenyl catpounda have been used in place of Aroclor 1242 as the dye carrier. Very little is laicun about other uses of PCTa in the paper industry. Past usage of PCBs in paper (ratings and adhesives appears likely, although the quantities used not have been near the magnitude of PG3 usage in the ^ttTssi copy paper. Almost certainly PCBs were used in scent of the inks, and possibly paper colorants, which can also be expected to ocaur in westspaper. According to Monsanto, the famred Aroclor type used in inks was 1254, which contains most of the sane isarers as 1242 but at different relative concentrations. -134- MONS 209114 In addition, PCSa can enter the pulping process through coitanination of intake water and in virgin pulp. Little is known about the magnitude of any of these sources, or even how much carbonless copy pj^w asntaining PCBs remains in files, etc. to enter the paper recycling processes in the future. 3.4.2 Fiber Recovery Mill Process The following is a generalized description of the mill proaess for recovering paper fiber. Portions of this description was provided by the Bergstrom Paper Ccnpany in Naanah, Wisconsin. Figure 3.4.2-1 depicts the general proaess, ip to the paper making section, in blodc form. The fiber reaovery process is a purification prooess wherein fibrous materials are dai nkeri and separated from non-fibrou* materials through controlled cleaning and medianical treataent, followed by washing and cleaning. The aolor is next renewed fraa the pulp by a multi-stage hleerhing system aooonpanied by intermittent washing and arnitzifugal dewatering. Pulging_and_ES^nWH* The fiber regeneration process starts with feeder craws loading the aortad paper otto e belt conveyer. The oonvayor feeds e bydropulpar, where wastep^er is pulped and dsinkad through the action of hot water, steam, caustic soda, and deinking chenicals. The breaking down of the paper stodc is aooaiplished through a onfcination of mechanical and chenieal treadent. At this point, larger metallic objects and other nen- paper materials mixed with the westspaper are collected into tr^e at the bottan of the pulper. The < stodc leaves the hydxqpulpar vie extrusion through perforated plates, and goes to blending dwets for additional retention tine and agitation, item the blending cheets the stodc passes over a vacant filter whidi is used for best and chenieal reamsxy. Mich of the filtrate is recycled to the hydropulper; excess filtrate goes to treatment. The stodc is ttwt and sent to oantrifflers where sell metallic particles such as pine and staples are moved. -135- MONS 209115 CAUSTIC SOOA, DRINKING CHEMICALS, HYPOCHLORITE, CAUSTIC SODA Ft*** MJ'I. MILL FIMH RECOVERY PROCESS AND WATER EFFLUENTS -136- MONS 209116 Pulpwashing; Accepted stock ran the centrifflers goes on to rjYe washing stage. Stock washing is sculii^jlished in a four-stage counter-flow washing system. The first stage consists of cylinder washing, the second and third stages consist of sidehill washers, and the fourth stage is another cylinder washer. The cleanest water is used for dilution at the fourth stage, and the filtrate is fed to the preceding stage, finally reaching the first stage fron whidi the filtrate is discharged for waste treatment. Bleaching: following washing, the stock goes to a three-stage b Leathery. At the first stage the stock is chlorinated by sodium hypochlorite solution in a tcMr. After chlorination, the stock is washed on a vacuum filter. In the next stage the stock is treated with caustic soda and sodium hypochlorite. After retention in a second tower the stock is diluted and again washed on a vaeuun filter. It is than treated again with sodium hypochlorite in a third tower. Screening and Cleaning: After retention in the third tower, the bleached stock is diluted for the next da*\ing process, which is a threestage pressure screen system. Accepted stock fron the first stage pressure screen goes to a five-stage centrifugal cleaner system for rancval of smallsized heavy aonteninants. Following this, the pulp is sent to a four-stage systma of centrifugal cleaners for removal of lightweight contaminants. After the cleaning, the stock goes to a final washing stage and is then dewatered (thickened) and stored in high density towers for paper malting. Flew Rates and Qapcsition of Discharges: At Bergstrcm the separate waterborne dischargee fron the paper and the paper making proaess are cabined with other facility waste streams and directed to a central waste treatment systma. Only the effluent fron the primary clarifier of the waste treatment systm is discharged to the anviromsnt. The atvera^ effluent flew rate for Bargs txaa during 1975 was 3.9 million gallons per day. This volume rata is bmfcm down as follows: -137- MONS 209117 Process Oeinking Paper Making water Plane Disposal Plant and Miscellaneous Volume Race to Waste Treatment Million Gallons/Day 2.5 .9 ,3 .2 Table 3.4.2-1 is a tabulation supplied by Sergstran of the 1974 averages for various parsnter* in their raw water source and waste clarifier effluent. The average Arcelor 1242 concentration in the effluent was reported to be less than. 8 ppb. aeoanandation (Paper Recycling) t The information presented herein with regard to PCBs in paper recycling processes is based on a very limited study effort on the secondary fiber recovery industry. It is recentmended that a more detailed study be performed of PCBe involvement in this industry. Important aspects which should be addressed includes (1) Definition of paper recycling processes and the PCBe materiel balance therein (PCBe input versus PCBe content in effluent and product); (2) Definition of pest PCBe usage in p^wr and routes into recycled paper; (3) Developoent of present distribution of PCBs originally used in p^er; (4) Determination of applicable effluent treatment methodology and associated cost estimates; and <S) Projecting future contribution of PCBe to the environment frna this industry. -138- HONS *09118 TABLE 3.4.2-1 awocrntv <7 ww want mb cuxs-st onuiwr <1974 CMJU (Ba^ua Pp*r 03.1 JUdriji, uq/1 Nitrapwi. mj/1 Arsanlc, -9/1 BBTlllA! 'j?/l vyllitn, it/iaron, W/l Cafeiui. wqA QUorlda. sq/l OtloriM. aq/l Oircnlua, vq/1 <Sfc*lt, uq/1 OBfftx. vq/1 Cymlda, nq/1 MaldriJl. u<j/l rc&I Col Ifota Qxitc/100 ml riuarldi, mj/1 bptactilor, 119/I , U9A Mnur> u9/l ifldfl, ii?A (dtraca wlerajwi, sq/1 Kltrtt* H1&Q9M1, q/l xitUtfil HlaefMt, /l Oil*, nu, Gram, aq/1 Phonol, u9/l moafticcua, nq/1 FOb, U9/1 S*laoiut, 119/I Sdlfba, ^/1 Sulflda, ^/1 Sulflta, q/l bapMldad SaliAi qA Wndliua, 119/1 lino, 119/I Oj. ^/1 Ra Uitar <0.1 0.11 <1 14 <0.3 33 <1* 10 <0.5 <4 <14 <5 <o.oos <0.03 4 0.44 <0.07 <42 10 0.7 <31 0.39 <0.009 0.02 <1 4 O.U <0.9 < 41 <0.09 <2 <1 <1 *7 1.1 atnflar EtfliMnt <0.4 1.72 <8 140 <3 235 <1* 442 <0.5 24 14 71 0.12 <0.03 <10 0.41 <0.5 IS 50 0.5 <33 1.32 0.43 19.0 24.4 24 0.S7 1-0 (1242) <1 74 <0.05 <2 445 <29 420 449 -139- MONS 209119 3.5 Industrial USe of PCBs as Hydraulic and Heat Transfer FI'"'** 3.5.1 General , The use of PCBs in hydraulic and heat transfer systans increased rapidly during the 1950s and 1960s until, in 1970, tie maxinun sales by Monsanto for these uses, plus lubricants, were about 11.3 million pounds, or over 15 percent of the total 1970 reported donestic sales. Since 1971, Monsanto has not marketed PCBs for these uses, and although it should be noted that such usage of PCBs in deep mining equipment is expressly allowed by the CECE agree ment to whidi the U.S. is party. Whan PCBs sales for heat transfer and hydraulic uses were eliminated by Monsanto in 1971, the affected indistries turned to substitutes or, in a very few cases, imported PCBs. Phosphate esters have found acceptance in many types of hydraulic systsns where PCBs vers formerly used. Glycols and other alcohols have replaced PCBs in sans heat transfer syitsne, and there are a renter of other substitutes used for this purpose (including other chlorinated hydrocarbons). It is surmised that tiers are industrial concerns still using PCBs in these seni-closed systsns. Hesse reported at the National Conference on PCBs in Novster, 1975 that a niter of such users had bean found in Michigan. Later contacts with these sane flans indicated that all had volun tarily replaced the PCBs in their systans with substitute fluids. Very little work has been done to ascertain the magnitude of current PCBs usage for hydraulic aid last transfer purposes. Of the total reported Msnsarrto donestic sales of PCBs over the period 1957-71 for heat transfer fluids, hydraulic fluids, and lubricants, 81 "WiUm pounds, it sasns,reasonable that at least 95 percent have bean replaced by substitutes or were in systare now obsolete, Ch this basis the anoint still in use would be on the order of four million pounds. A figure of two million pounds still in use is prcbably nors accurate. -140- HONS 209120 . 3.5.2 Use of Imported Pt3 by Joy Manufacture Uitil recently, Joy Manufacturing Co. (Pittsburgh, Pa.) manu factured mining equipment whiih utilized a P09 motor coolant. Joy inports pQs, as a mixture similar to Arcelor 1242, from France (Prodelee). Presently, tie P09 type motors are no longer manufactured and have been replaced on new units by an air-cooled motor. However, PCS coolant fluids purchased fran France are being used for servicing the old 1 iquid coolant motors. Currently, tiers are approximately 1100 of the old motors in the field, each of which contains an estimated 3-4 gallcns of PG3 type coolant fluid, the operating time of these rotors before carplet* overhaul is between 1 and 2 years. The major benefit derived fran using the PCS type coolant was its fire retardant characteristics. Fran the information reaeived by representatives of Joy Manu facturing Chnpany, and fran available physical properties, it is estimated that between 40,000 and 60,000 pounds of the inported PCB type coolant fluid would be necessary to replace and tep off" the fluids in the old motors each year. 3.6 ascent Use of P(3s in Predict Cevelcgnent Activities Since the voluntary limitation on the sale of PCS oaipands in the United states by ronsanto, nail quantities of PCS mrpands have bean imported for new predict development by at least one U.S. aoqpeny. Such a use appli cation, by E. . duFont da Nemours end ., Wilmington, Del., was fer develop ment work cn a new polymer which is derived from the reaction of decadiloxobiphenyl (delta) and Eisphanol A* According to duFont representatives, they have imported small quantities of <*ka fran Ceffazo (Italy) for eaperimantal purpossa with the intent to develop a new product called NR-140 polymer. Approximately 2000 ponds of <Wta were imported in 1974* however, duFont did not import ary delta in 1975. A dfiiicn wn rot to comerdaliza the now predict because of tie associated with the regulation of PCBs. It is estimated by duFont that, if the now product had been . the annual purchase of delta would be in the range of 5-10 min inn pounds. -141- MONS 209121 BXBLIOOaPK? 1. Addaci, V.J., Letter to Mr. Rjssell Train with attedrnent entitled, "Statenent of Electronic Industries Association to Environrental Protection Agency Concerning Proposed Toxic Pollutant Effluent Standards far Polydrdarinated Biphenyls (PCB)", June 2S, 1975. 2. Air-cnnrliticning and Refrigeration Institute, Letter to Or. C.H. Thompson, EPA, Maxtii 27, 1974. 3. AFML-TR-74-237, "Mfg. Methods for Production of Quality Superalloy &v?ine Parts", DOC Acquisition No. AO B0074 DCL. 4. Blatl, Philip S.O., (E.I. duPont da Norours mi Cdtpany, Wilmington, Delaware), Personal aonnunicatian, August 14, 1975. 5. Bolin, A.E., (Van Train Electric Carp.), Telephone cannunication, October 31, 1975. 6. Butner, J., (Satgano Electric 09.), Peracnal camunicatian, October 2, 1975. 7. Clark, R., (Universal Manufacturing Osip.), Telephone oannunicaticn, November 24, 1975. 8. Colder, A.W., (Joy Mamfactuzing 09., Pittsburgh, Pa.), Personal oanmniceteioi, Ssptnber 8, 1975. 9. rnmhuh, W., (MoGrs* Plisan's power Systee Oiv.), Personal ccmmication, Septasber 23, 1975. 10. Falk, Bernard H., (National Electrical Manufacturers Association), Letter to Dr. C. Hugh Thaqpeai, Q>A, Msrdi 25, 1974. 11. Farnsworth, Geergn B., presented General Electric Testimony, FWPCA(307) Dodcet No. 1. 12. Gabel, H.b., Jr., (Niagara Ttaisfosnsr Cccp.), Telephone acnrunication, Novenhar 3, 1975. 13. Gmn, R., (H.K. Porter Co., Inc.), Telephone ocnmnicaticn, Noveebar 3, 1975. 14. Hart, L.P., Jr.i Wriest, Gary* Marquis, R.; and MsRuixie, w.R., (General Electric Qd.) # Personal oonunicatian, October 22, 23, and Nowntsr 11, 25, 1973. 15. Haase, J., (MiAigan D^artnant of Natural Rssouraes), paper presented in Olixago, EPA sponsored synpoaiisa on P(Sa, Novenber 19, 1975. -142- MONS 209122 .16 ttibrd, H.L., Ehcyclr^jedia of Chemical Technology, 1965, vol. 5, jp 289-297. 17. Jard Qaipany, Inc., Letter to the Ganstrar Products Safety Oairussicn, 2, 1974. 18. Jchnsi, L.A., (Research-Oottrell Manufacturing Division), Perscral cattnunication, October 28, 1975. 19. Kleiner, S., Survey of Effluents in the State of wisoonsin in 1974 and 1975 by the Wisoonsin Department of Natural Resources, Data presented in Chicago, EPA sponsored sytiposum cn PCBs, Nowfcer 19, 1975. 20. Kingsolver, W.S., (MoGraw-Edison Co.) , Personal ouuiunication, Deaenber 15 & 26, 1975. 21. Leighton, I.w., "Derenstraticn Test Bum of DOrr in General Electric's r.-irpi-ih injection Incinerator", U.S. EPA Region I, 1974. 22. Leisy, A.E. a anull, Warren, (Monsanto Industrial Chmicals Co.) Personal aonramication, October 8, 1975. 23. Leisy, A.E., (Monsanto Industrial Cheer! rail Co.), Personal aormmicaticn, Novwber 6, 1975. 24. Lewis, W.H., (President, Signicast Qorp., 9000 North 55th Street, Milwaukee, Wise.), Stat--nta made during lecture of Immanent Casting Institute meeting, October 4, 1975, 25. Monsanto Industrial Oo., Testimony, f>JPO0(307) Dodcet No. 1, Presented by Mr. W.B. Fapegeorge. 26. National Industrial Pollution Control Council's Report, "The Use and Disposal of Electrical insulating Liquids", June, 1971, p. 10. 27. Nelson, J.S., (General Electric), letter to Dr. Martha Sa^r, with attadmnt mtitlsd The Ihoact of a "Ban" on the Use of PCB in Capacitors, Nowber 21, 1973. 28. Nelson, J.C., and Simon, E.L. (General Electric Ocrapeny), Personal uuummi ration, S^tanber 4, 1975. 29. Oliver, O.M., (Standard Trmsformer Co.), Telephone camunication, October 30, 1975. 30. Qrtsan, J., (Sprague Electric Co.) , Telephone conaunicatioi, Novntber 20, 1975. 31. Pyegeorge, W.P., (Monsanto Industrial Omnicals Qo.), Personal uuirajnlcation, August 27, 1975. 143- HONS 209123 32. Piarls, A. Midiasl, (Mcnaanto Industrial Onmicals Co.), Polyciilarinated Biphenyl Study, Personal oomunicatian, Novnnber 17, 1375. 33. Report cn Power Transformer Troubles, 1969, Edison Electric Institute Publication No. 71-20 (1971). 34. Bollards, D., (Jaxd Corporation), Personal camuucation, October 2, 6, 1975 6 January 15, 1976. 35. Rountree, William C., (Assistant General Coins#1 for Legislation, U.S. Dept, of Cannarce), latter to Dr. C. Hugh Thcnpecn, EPA, March 26, 1974. (See discussion of PCB beginning on fourth page of attachment). 36. Salazar, A., (National Electrical Cfeufacturexs Aasodatian (NH4A)) , Personal octniuvicatian, August 19, 1975. 37. Solaocn, P., (Yates Manufacturing Co., Chicago, Illinois) , Personal eanmxucaticn, S^tenber 9, 1975. 38. Stanger, R.A., "Malitaring of the General Electric Ccnpany*, U.S. EPA Region II, Surveillance Analysis Div., Edison, N.J. Septantoer 26, 1975. 39. Thallner, K.A., (Helena Qorporaticn), Telephone acnnuiicaticn, October 31, 1975. 40. Thayer, J.H., (Gnersl Electric Co.), Personal oommioaticn, October IS, 1975. 41. Tuttle, Co Teeple, p.l.j Hutzler, J.R.; 6 Buttarworth, N., (Aerovcx Industries, Inc.), Personal aenmsiicaticn, Septenher 25 , 26, 1975. 42. Uptegraff, R.E., (R.E. Uptagraff Mfg. CO.), Talephons ccwnsiication, Novenbar 3, 1975. 43. Vollmar, John R., (Louie T. KLnidnr and Associates), Letter to Dr. C. Hugh Hopson, EPA, Much 22, 1974. 44. Wblsky, S.P., (P.A. Mallory t Co., Inc.), Telephone oonunication, Novenber 21, 1975. 45. WUratsr, W., (General Mnegar, Ccnsolidated Casting Carp, 2425 Carolina St., Dalian, Tans), Mi under 5, 1975. -144- HONS 209124 SECTION VI WASTE TREATMENT 'IKSNOLOGIES 1.0 n/raxucncN This section includes descriptions and discussions of existing and proposed technologies for the treatment of various types of wastes generated at PCBproducing and PCB-using plants. Also included are discussions of the presently available control technologies and technologies to be available within three years, plus technologies that will not be available for five or more years. The treatment and ocntrol costs included here have been developed and presented in the Task II report "Assessment of Kastsweter Management, Treatment Technology, and Associated Costs for Abatement of POa Concentrations in Industrial Effluents", EPA Contract No. 68-01-3259, issued February 3, 1976. 1.1 Summary of Waste Management Problem Areas Based upon detailed plant inspections and anminatLans of the processes in the production of PCT* and their uee in capacitors and transfoxmars, it has ban determined that there are four major categories of wastes to be considered: waste liquid PCBs, POa in westsustar, PCS contaminated solid wastes, and airborne PCS emissions. It has also been determined that the characteristics of wests* in PO* producing and using operations are similar enough that the same kinds of control and treatment technologies can be used. 1.1.1 waste T.iau-M pcts and Contaminated Scrap Oil The users of dielectric materials have strict requirements for purity. Typical requirement* are: Inorganic chloridas Acidity, wq KH/q water content Rssistivity, 100*C, 500 v, 0.1 inch gap Dlelsctric strength, 25*C 100 ppb maximum 0.01 maximum 30 to 35 pin maximum 100 to 500 x 109 ohm-am, minisun 35 kv minimun - 145 - HONS 209125 Whan these or other properties cannot be met at the producer's facility, or by the user during transformer and capacitor filling operations, and it is found that the properties cannot be restored to askarel specifications by filtering and drying, disposal is required. The typee of PCB contaminated liquids requiring disposal are: 1. PCBe contaminated with mineral oil 2. Mineral oil oontsninated with POs 3. Monreclaimsble oontoninated transformer askarels - arced askarels, askarels from mnufacturing spills and sizp acaziulations, and askarels from holding basins, drip and drain pans, 'ashing*, saeple jars and containers 1.1.2 POs in Wastewaters The neat likely pattaoys by which PCBe wrber wastewater streams are operator wash-up after PCB handling and groundspills that mix into rainwater runoff. The significance of the first pattway can be illustrated by the realiza tion that sixteen operators (or 4 operators 4 time* a day) vashing 1 ounce per day of PCS fren their hands, account for one pond per day of PCS discharge. Other intenster categories discussed in the industrial character ization section of this report are: 1. Incinerator scrubber and quench water 2. Stan jet ejectors in vacuus distillation 3. Capacitor dstargmt vash solutions 1.1.3 FCB-Oonfninatsd Solid wastes bumable. Solid wastes can be divided into two categories, burnable and non1.1,3,1 Burnable Solid wests Materials Containing POs Burnable wastes can be of by high-taeperature incineration. Such wastes consist of cellulesic materials, rags, presboard, vnod, sawdust, fuller's earth in bulk or in cloth bags, blotter papers, nitrile or oork gaskets, and similar materials. HONS 209126 146 1.1.3.2 Nonburnable Solid waste Material* Containing, or Contaminated with PCS* Nonburnable Mutes nay consist of capacitor and trans former internal atrrponents; steel, copper and altminvm aatponerts? filter units of the steel mesh construction type; and askarel druns and cans, wastes of this type should be drained, with the liquid oollected in drip pans, before disposal. 1.1.4 Air Emissions of PCBs Although PCBs have very low vapor pressures they can be anitted to the atmosphere from the following operations and practices: 1. Aroclor scrubbing of air in PCBs manufacture 2. Vapor exhaust from steam jet ejectors 3. Evaporation from accidental spills 4. Evaporation Cron hot surfaces as part of flood filling, inspection or holding operations 5. Vacuus puip exhausts 6. Evaporation from plant wastewater 1.2 Sunaerv of Current POs Waste Control Practices 1.2.1 Control of wests Liquid POe and Oontoninated Scrap Pile Plant visits have shown the major control methods to be inciner ation and ; in sealed drune sent to sanitary Landfills. Both incineration and landfilling may be carried cut by the facility generating the vasts, or the facility may engage a contractor. Mxiaanto, the only U.S. producer of PCBe, has an incinerator (designed by John Zinc, Inc.) that vaporizes PC3 liquids and sustains than in a turbulent burning gas at men than 2200*7 for 2 seconds. Che transformer manu facturer usee a John Zink flesignsfl incinerator that vaporizes PCBs and burns them at 1600 9 1000*7 for 3 aaoonds or longer; this facility can also destroy PCBs soaked into transformer internal parts, but cannot routinely handle spent fuller's earth. - 147 - HONS 209127 A muter of PCS users send their solid wastes to the Rollins Environmental Services facility at Logan Township, N.J. Rollins uses a specially designed complex having a rotary kiln and a liquid turbulent burning chanter, both of which exhaust into an afterburner. Liquids can be burned in eitl-er the liquid chamber or the kiln? in the kiln Liquid wastes can help to incinerate solids. The afterburner is 40 feet long, providing good residence time, and it is followed by a hot duct of about equal length that allows further combustion. Rollins claims a residence time of 3 to 4 seconds at a minirun tetperature of about 2400*F at the aft end of the hot duct. The gases then go to a venturi scrubber and a tower scrubber for cooling and neutralization. For non-PCS incin eration, Rollins sometimes lowers ccntjustion tsiperature to 2200F and residence time to 2 to 3 seconds. These residence times and tenperatures were chosen experi mentally to get 99.999-percent PC3 destruction. This facility also handles all kinds of solids, as will be explained later, and it operates with CPA approval. Another facility that incinerates liquid PCBs, with New York State EPA approval, is the QvnfTOl Corp.'s facility at ttodel City, New York. T.igtHde going to Landfill are sealed in druse and added to land fills that have deep clay bases and irrpervious bulkheads to prevent leaching and seepage. However, incineration is the preferred disposal method for liquids. 1.2.2 Control of PCBs in Wbefmters Our plant investigations have revealed that there are no methods being practiced whereby dissolved or otherwise bound PCBs in water streams are being either extracted from those streams or destroyed in them. In the separation of PCBs from wastewaters, PCBs and sludges are mnavad froa the bottom of wetsr bodies, while oily phases are removed from the surfaces. However, notiling as yet is being done to treat the water layer itself; this is tiie eras of PCS wastes control and treatment most needing development. In gmral, wests strums contain between 1 ppb and 500 fpb of PCBs; most levels range between, 10 and 50 ppb. PCS concentration of less than 1 ppb are undetectable. - 148 - HONS 209128  Several plants use methods to keep ti quantity of PCS contaminated wastewaters as snail as possible. A few plants planned adsorp tion tests with carbons and other adsorbents, but there were no full-scale operations. 1.2.1 Control of Solid Wastes Contaninatad with pra* The two current methods of Hipni of solid or semi-solid PCBe wastes are incineration and landfill. Since we fourel only ore PCB- using manufacturing facility with partial incineration capability, and Monsanto's incinerator cannot handle solids, all facilities except ore must ship their solid wastes away from the plant site far either treatment. The one plant with partial capability can incinerate transformer internals to recover copper, and also can incinerate paper, rags, cardboard and the like. However, they do not as yet, incinerate fuller's earth, contaminated dirt, and similar materials. These are duinued and stored for later disposition. - Although there are a number of experimental facilities through out the U.S. that could unftoutadly incinerate all types of solid materials, ore ocnnercial venture has received the bulk of the work. Rollins Environmental Services can handle liquids incineration. For solids incineration of almost all types, the tmtola burner or rotary kiln is used. Whan K3 contaminated materials are to be destroyed, the kiln tampersture is brcwght up to 2200*F. All kinds of solids, in 47-gallan lined fiber druns and not posing unusual safety hazards are accepted. The currant (late 1975) fee is about 7-l/2/pound. fcJditionsl charges of $3/fiber-dmn handling, plus transporta tion charges, and r""4Wy other charges for unusual problem, might be made. Rollins will not accept impact sensitive, radioactive materials, or heavy metals concentrations of more than 25 ppm in the pcts wastes. Foot wastes peeked in steel druns, Rollins charges a 510/dmn handling charge* As a gnral rule, anything padud according to the latest ICC tariff for hazardous materials will be accepted. As with the liquids incineration, the gases from the kiln at 2200*? p-- to the afterburner at a temperature of about 2500*F. (Vises exit MOWS 209129 149 the afterburner to a long hot duct that cotpletes ocmbuation and maintains the tanperature at 2400*F until the gases enter the venturi scrutioer, and thence to the lever scrubber and then the stack. Rollins has experimented with lower temperatures of 2000 to 2200'F and has not found destruction of PCBs to be at the 99.999 percent level desired. The resideree time for gases at the 2400*F trust be 3 to 4 seconds in a turbulent regime. With regard to landfilling, one ojirercial venture has handled a large quantity of the PCS solid wastes under supervised conditions. The Qienrtrol Pollution Services Co. of .Model City, N.Y., operates a landfill located on the shore of lake Ontario, under New Fork State EPA supervision, in a geologic setting claimed to be ideal for complete containtent. This "scientific landfill" is located entirely above ground on a bed of 40-feet-thick clay. Constructed on this foundation axe cells for receipt of drumed solid wastes. The cells are lined with 30-mil chlorinated polyethylene film, and wtan loaded, are seeled, or oovered with 5-feet of clay. At the bottom of each cell there is a snip, so that all leachate is collected and moved. That laachata is pH controlled, settled, filtered, and treated by flow through a carbon bed. The ground and surface waters axe checked monthly for chonical content by an outside analytical laboratory. The facility has been approved for usage as a PCS disposal site by the New York State EPA, and thousands of druse have been landfilled aver the last five years. An inventory is kept of the contents of each cell. Qtaotrol has the capability of converting semisoLids and sludges to solids by using silicate cant powders and proprietary gelling agents. Our review and analysis of the industrial situation far PCBs 'solid fetes control shows there axe adequate options, at higher prices, for safe M T"*1 and destruction. There is no longer a justification for open draping to the grtwid or in lagoons. 1.2.4 Control of Air Emissions of PCBs Most air amissions from siblent tstperature P(3t are not asntrolled o'r collected for treatment in any way. PCB etvissiens generally are - ISO - HONS 209130 collected as part of ths overall plant air exhaust, which frequently is to roof esdiausts without treattnent. Several plants used exhaust chilling and/ or fibrous or granular filtration of air; these methods offer the potential for PC3 mission reduction. The hot flood-filling of capacitors is followed by a oool don period before the filling tank is opened to the plant atmosphere. How ever, the tenperatuze is still between 100 and 150*F; the area of the opening is several square meters, through which tank gases can reach the plant atmoshere. The tanks have individual eodwist ducts, bit they lead directly to a roof exhaust systsn. The PCB-covered capacitors are held in an even at 100 to 150*F to prevent any moisture condensation before seeling. Vapors from this storage are ducted to the roof and vented also. In sane cases, westa scrap oils containing FCBs are burned together with fuel oil in standard boiler systms. In these instances ituch of the PQ content is probably vaporized and exhausted to the air, rather than incinerated. 2.0 CANDIDATE PCBi VASTS THEMMHT TECHNOLOGIES CCNSHERH) As part of the anmination phase of this study of alternative methods, we have contacted a mnbar of aquipnent sippliers, developers, and researchers, in both the U.S. and elsewhere. Key infomation wee obtained on potential methods of FCBs removal from, and destruction in, waste atari, by cooperative testing between versar, Inc., and several materials suppliers and process developers. Their assistance is gratefully acknowledged. vie visited the U.S. producer, tonsanto, and several transformer and capac itor nwtufacturars to eeoertain the nature, characteristics and quantities of plant effluents that now oentain measureabla anoints of POs, or might contain PCBs following a ^ill or other incident. This has provided the background for weighing the advantages and disadvantages of all available technology for poten tial appi iraition to PCBs west--ater treatment. Ha discussed and evaluated the control methods now used, possible shortoonings, and ideas for more optimized systems. . - 151 - HONS 209131 In order to find the new technology and approaches that might be forth coming, we made a corputar search of Chsnical Abstracts firm 1972 to the present, and focused on degradation, decaipontion and waste treatment data. Searches were also made of the Lockheed Engineering Index, National Technical Information Service, and Predicasts for information on new developrents. The text reference used as a source of sutmarized data prior to 1972 was: The Chemistry of POs, by Hutzinger, Safe and zitte, published in 1974 by Press. Candidate treatment technologies have been divided into the same four categories listed in Section 1.1. Also, as wt evaluated technologies, they were placed into categories, as follows, indicating their level of developitent 1. Darenstratad Full-Scale Treatments 2. Pilot-Scale Methods 3. Research Approaches to PCTe Removal or Destruction Serna treatment methods were designed for disposal of cenpounds similar to the POs, e.g., chlorinated hydrocarbons and other refractory organics. The full-scale plant treatments are reedy for application to PO waste problene now. Tha pilot-scale methods are expected to take one to five years to be developed to the point where they will be determined suitable, or un suitable, far plant-scale PC3e applications. Methods currently under development are expected to take three years or more before being ready for plant-scale applications. Section 2.5 contains a discussion of the applicability of various treat ments to the zero discharge objective. 2.1 Treatnent of Masts Liquid PCTe and Contaminated Scrap Oils Only two kinds of treatment or dif"--1 methods are considered suit able far wests PQ5e and contaminated scrap oils, and they are new being used. However, there are inprovnants and design features needed to prevent PCB transfer into the water, air or land. - 152 HOMS 209132 2.1.1 Incineration The standard configuration, long cylindrical steel oanbustion charter, having a length to diameter ratio of between 4/1 and 8/1 and well insulated with high alunina refractory brick, is suitable as a primary chamber. TVc injectors should be provided: one for a high-BTO gas or fuel oil, and one for the PO waste liquid. Prinary air or steesn is provided to vaporize oils, and secondary air is added to complete octnbustion and provide excess air. These feeds should be made tangentially, or with adequate baff ling to assure turbulent flaw throughout, and to prevent hot or oold spots in the chamber. It is obvious that almost any residence time mey be allowed for a gas flowing through a cylindrical chamber. However, there is a maxiraun residence time above which turbulence is assured throughout the chamber. Turbulence throughout is assured whan well temperatures are uniform in all parts of the chamber. Most fuel flames provide adiabatic ocmbustion torperatures of about 3000*F. When the more endothermic PQe are being destroyed, the flame can be rapidly cooled to 2200 to 2500rF; for the very high destruc tion efficiences desired, 99.999 percent or higher, this is the minimm tem perature range required, for a residsnoa time of 3 to 4 saconde. After ocmbus tion there should be allowance for afterburning, which may be accomodated in insulated ducts. These can be of sufficient length to assure total residence time of 3 to 4 seconds. Following the combustion phase there nust be rapid cooling of the gases, usually by the injection of oold water fran a peripheral ring of sprays or jets. Also, the cooling water should be neutralized so that hot hydrochloric acid contact with further components is obviated. In --we systems a high energy wituri scrubber is used to control particulates, if they are eiqpected in the gas stxesn. In all systars the gas strwm is than washed counter currently with water, or rater plus neutralising agsct, in sane form of a packed tower. Usually a dsnister is the lest elraent contacted by the gas before it is exhausted through the stack. Qm stack gas suasions and the scrubber effluent liquid should be monitored periodically for POe levels, and the incinerator should 153 - HONS 209133 haw adequate autanatic controls to prevent PCS* fran being snitted urdiestroyed. The chief fail-safe control is a pyrenetar that causes burner shut down if the carbustion chamber or duct tenperature drops be lew about 2150*r. There are other controls that can warn if such an occurrence might take place. These flaw rate controls on the primary and secondary feeds can be monitored so that low fuel flow, or high POe-to-fuel flow ratio can indi cate a twperature drop. Inadequate air flow can also cause tetperature decreases. All such parameters should be monitored, and adequate operator v^mings provided. And, of course, to prevent destruction of the venturi scnfcber sections, shutdown should automatically take place if cold water flow is ever insufficient. 2.1.2 Sanitary or Scientific landfill Sanitary landfilling is an alternative to incineration for PO users who cannot justify incineration facilities just for PCBs, and who have no wests pidep service organization within reasonable distance. Land fills that will adequately contain PCTs should have all the features described in Section 1.3.3 above, plus there nust be assurance that the liquid containers will be sealed and leak proof, and have long life in the landfill. 2.2 Treatmant of Wastewaters Containing PQs Treatment of wastewaters containing PQs has received very little attention in practice thus far. Our survey has found a variety of methods for reduction, and even far achieving "2aro discharge", of pQs in wastewaters. 2.2.1 Carbon Adsorption Carbon adsorption is a well-know water purification and industrial product purification technique. The use of carbon adsorption is well-suitsd to removing FOa from wastewater since it is cost effective in meowing high mniam-iiair weight, non-polar, relatively insoluble oonpeurds from water. All these requizeeants are met by the PSCi. As will be 'Mr-iirsd later, Veraer has conducted tests, in co operation with carbon suppliers, datenstrating the relative effectiveness of - 154 - HONS 209134 various activated carton products. PQ concentrations on the order of 1 ppto war* taken aa a reasonable effluent objective. The disadvantage of carbon adsorption is that once used, the carbon may have to undergo destruction by high tetperature incineration rather than be regenerated, as is the usual practice. The great advantaoe of carbon treatment is that a wide spectrum of other toxic organics can simul taneously be effectively rwoved from water. Carbon adsorption is currently being used in large-scale nunicipal water purification systems. Thus capital costs, operating aosts and reliability factors an well-team. At the 68th Annual AIChE Meeting in November 1975, G. Strudgaon of 2um Industries described design features for a 3 0-million-gallon-per-day carton system to be built for nunicipal waste water treattnsnt at Garland, Texas. This system will oost $5 million, includ ing carbon regeneration. Operating costs an expected to be $6,000 per day. Although carbon adsorption is the only mechanist thus far proven effective in removing PCBs, three other carbon-based treatment tech niques an under study: biodegradation, whereby bacteria-ooateri carton particles break down pollutants in waste**tar; catalytic action, wherein a very active surface holds pollutant molecules while other degradation or axidaticn reactions taka placer and chenical reaction, in which carbon is actually depleted as part of a chemical reaction that troves pollutants. The techniques wen also at the 66th Annual AIChE Meeting. As an adjunct to this evaluation study, versar conducted co operative laboratory adsorption isotherm tests with Carborundum Company and ICT-UB. These teats have extended the ranges of carton adsorption data pub lished by Calgen aerp. into higher and lower concentrations. Laboratory adsorption isotherm testing is a reliable technique for determining the feas ibility of adsorption treatment for PCTs removal fran wastewaters and specifi cally indicates: 1. Tha effluent levels of PCBs concentration obtainable by adsorption treatment 2. Hie weight of PCBs adsorbed at the concentrations being studied - 155 HONS 209135 - On the other hand, the laboratory teat does rot determine the necessary contact time for granular carbon beds to effect the desired reduction. This determination is usually performed in small pilot carbon beds under hydraulic flow conditions. Laboratory and pilot plant tests involving PCBa mist be designed to prevent losses of PCBa. The root of the problem is the very low, parts per billion, solubility of PCBs in water. Samples of pathways of experimental loss are: 1. Evaporation to the air 2. Adsorption an a variety of solid surfKes and sediments 2.2.1.1 PCBs Adsorption Testing by Carborundum Ccnpany versar, Inc., together with Garborundisn Co., con ducted a preliminary study to determine the ability of an experimental, aoalbased activated carbon in removing POs from water. This study also provided an analytical check in that both conpaniea made electron-capture gas chromato graph analyses on the sane sartples, and there was close agresmsnt an results. The coal-based activated carbon had a surface area of 950 to 1050 square meters per gran. The iodine raster was approximately the same as the surface area, indicating that alsost all of the pores had a diameter greater than 10 to 15 Angstroms. Tbs control anl tast samples were filtered before extraction and gas cheatstographic analysis. Tbs ranoval of POs by solids, surfaces, filtsr madia, and the like, was known and expected prior to these tests, thus a high PS concentration in the filtered control and test sanples was the target. The Pa mixture used was Aroclor 1254. It mis solub ilised by methanol bo give a 1000 ppn stock solution. Ibis was diluted with water bo prepare XOOO-ppb test solutions. Thbls 2,2.1.1-1 presents the date. The filtered control level is considered the actual level the carbon tea adsorbing, rather - 156 - HONS 209136 TABI 2.2.1.1-1 CAfBORUtOJM CO. TESTS OF PCBa (AROCXOR 1254) REMOVAL FROM WVTER BY AN EXPEOOENIAL ACTIVATED CAPBCtJ Prepared PCBa Concentration (ppb) Control - 1000 TTst 1000 Test 1000 Carbon Dosage*1* (n*j/l) -- 1.0 2.0 PCBa Cone. Before Treatment [Control Cone. After Filtering) (ppb) 160 160 160 Effluent PCB Cone. After Carbon Treatment (PPb) -- 59 20.6(2) 22.0(3> Percent PCBs Removal -- 63.1 87.1 ee.2 Test 1000 10.0 160 2.6<2> 98.4 2.4(3> 98.5 NOTES: ^Experimental material, coal-based, 950-1050 square meters/gram. *2*Versar Inc.'s analysis. (3,Carbor\jndi Os.'s analysis. 157 HONS 209137 than the prepared level. The filter removed 34 percent of PCBa ^ t.'-ese test run*. . As shewn in Table 2.2.1.1-1, the percent Pds re moved fran a concentrated water solution (160 ppb) at low carbon dosages was quite good. During plant surveys we found PC2s concentrations in -wastewater destined for river discharge to range from 50 to 500 ppb, so the 160-ppb con centration treated in this study was an intermediate value; it was, however, also the highest value treated in the cooperative studies under this program. Carborundum Go. plans to aontinue this effort to determine the effects of other carbon dosage levels an various feed PCSs con centrations, The data given here are only considered preliminary. 2.2.1.2 PCBs Adsorption Testing by ICX-US In a cooperative program with Versar, ICI-U5 performed preliminary adsorption tests to determine the ability of powdered carbon in removing Aroclor 1254 from water. Versar conducted all analytical tests for this program. The Aroclor was solv*ilired with methanol so that a 1000-ppm concentration of Aroclor 1254 in water was achieved. Two types of granular activated carbon were tested: lignite base, and coal base. Both types were ground to a fine powder (90 percent through 325 mesh) before adsorp tion testing. Prior to grinding, the lignite-base and aoal-baee carbons had a surface area of about 650 square maters par gram and 1000 square meters per gram, respectively. The test solutions were made up fran distilled, de ionized water to a volute of 1 liter. Four levels of Aroclor concentrations were treated: 10 ppb, 100 ppb, 500 ppb and 1000 ppb. Both the control and treated solutions were filtered before analysis. The great affinity of P3 for all solid surfaces was not fully anticipated, during these tests. The fil tration wes uniform for all sanples through 2.4-os Peeve Angel fiberglass discs (Qade 934AH). As can be seen in Table 2.2.1.2-1, most of the PCls were - 158 - HONS 209138 TABLE 2.2.1.2-1 ICI-US TESTS OF PCBa (AROCLOR 1254) ISCWM. FTOM WATER BY TVO TYPES CF OOWCRCIAL CARBOtS Prepared PCBe Concentration (ppb) Oontrol, 10 Test, 10 Test, 10 Oontrol, 100 Test, 100 Test, 100 Oontrol, 500 Test, 500 Test, 500 Oontrol, 1000 Test, 1000 Test, 1000 Carbon T/pe Dosage (nq/l) __ Lignitefl) aoaim -- Lignite Goal -- Lignite Coal -- Lignite Goal -- 4 4 -- 30 30 -- 100 100 -- 100 100 PCBs Cone. Before Treatment (Control Core. After Filtering) 1.07 1.07 1.07 11.15 11.15 11.15 5.32 5.32 5.32 37.5 37.5 37.5 Effluent PCBs aonc. (After Carton Treatment) (ppb) 0.177 0.190 -- 0.213 0.111 -- 0.09 0.114 -- 0.32 0.24 Percent PCBs Fteroval -- 83,5 82.2 -- 98.1 99.0 -- 98.3 97.9 -- 99.2 99.4 NOTES: (1)Larger pore, 650 square meter* per gm. (2*anallr pore, 1000 square meters per gram. HONS 209139 rwed in filtration. Hc***ver, by using the filtered "control sanple" as an approximation of tha amount tha filter removes frcm all feed sotples, we can get a ^xid preliminary estimate of the PCBs removal ability of the two kinds of ocmnercial carbons at various wastewater pollutant levels, and at various carbon dosages. Tha results of these laboratory tests indicated that postered carbon was highly effective in removing KBs from water at four levels fron 1 to 40 ppb. There was not a great deal of difference between the effectiveness of tha two carbons. Tha lignite carbon has relatively large pores and snallar surface area than tha coal-based carbon. The lignite-based carbon simulates tha activity of the coal-based carbon after the latter has a nixrber of thermal regenerations. Thermal regeneration tends to increase tie pore size, and lower tha surfaoa area of any given carbon. These kinds of activated carbons, however, tend to stabilize at about 550 square meters per grant, even after many reganarations. Tha conclusion from thasa results is that carbonadsorption can be effective in removing KB fran wastewaters, even after many thermal regenerations. It is quite significant that in all these tests, the treated effluent KBs levels ranged frcm 90 to 320 parts per trillion, which are well below the target maxioun K3 level of 1 ppb. Further testing is needed to get confirmatory iso therm data and oolizm test data. In oolimn tests, the granular form cf carbon was usad, and, therefore, seme of the interior portions of tha carbon were not as accessible as they would have bean in the powdered form. Thus the tests with powdered carbon, given on a weight fraction basis (i.e., pounds POs removed per pound of carbon), yield the maxinun weight fraction of PCBs that that cm be removed in a scalad-up ocnmarcial systmn. 2.2.1.3 PCBa Adsorption Testing by Calgon Corp. Adsorption isotherms ware run on Aroclor 1242 and 1254. Stodc solutions of each carpound were prepared in acetone at 100 mg/1. - 160 - HONS 209140 (D) Filtraaorb 300 (FS-300) activated carbon was used throughout. Carbon was added from, a stock suspension of 1 g or 2 g of pulverized FS-300 per liter of distilled water. Isotherms of Aroclor 1242 and 1254 were prepared by the following method. Exactly 1 ml of PCB solution was added to seven flasks, each containing slightly less than 1 liter of distilled water. Measured volumes of the 2 g/1 carbon stock solution was added to each flask to give carbon concentrations of 0,2,5,10,25,50 and 100 mg/1. The total volume of each flask was 1000 ml. After four hours agitation on a wrist shaker, each solution was filtered through 0.45 micron millipore pads ar*i stored prior to analysis in a refrigerator in quart aster glass bottles having Teflon-lines caps. A nickel-63 electron capture gas chromatograph was used for analysis; all samples wen extracted and oonoantrated approximately 100 times before analysis. The method is described in the 1971 A report, "Methods for Organic Pesticide Analysis in water and Wastewater. * Table 2.2.1.3-1 shows the POs removal data, and gives cooperative data for Aldrin. It appears that the Aroclors axe rmoved as effectively as pesticides. Removal from the 50-ppb level to the 1-ppb level seems possible. Figure 2.2.1.3-1 showe the Galgon data plotted to give the weight percent of POs that Filtrasorb-300 carbon can adsorb, at levels down to 1 ppb. As can be seen, the curves take a downward break at about 2 to 3 ppb, indicating that the weight of activated carbon required to remove a unit weight of POs is rising rapidly. If this kind of data is con firmed with larger-scale oolum testing, it would mean that ranoval of PCSs Iran water in the perts per trillion range is far nsra difficult than removal in the parts per billion range. Also from the figure it can be seen that the initial concentrations (CoL) of the Aroclors were about 100 ppb. Hcwevar, filtration before testing removed PCSs so that the starting concentrations for the tests were 45 and 49 ppb. - 161 - HONS 209141 Carbon Dosaoe Cm/l) Control 1.0 2.0 2.5 5.0 10.0 12.5 25.0 50.0 TABLE 2.2.1.3-1 RESULTS OF CAL3CN CORP. LABORATORY ISOTHERM TESTS FOR CARBON FEMOVAL OF PCTs Aroclor 1242 45 -- 7.3 -- 1.6 1.1 -- -- -- Residual (ppb) Aroclor 1254 49 -- 37 -- 17 4.2 -- 1.6 1.2 Aldnn 48 -- 26 -- 15 12 -- 6.3 4.4 - 162 - HONS 209142 % WEIGHT PICKUP Figure 2.2.1 J-1. EQUILIBRIUM CARBON ADSORPTION OF FOB'S FROM WATER AT LOW CONCENTRATIONS (CALGON DATA) 163 HONS 209143 Hager and Rizzo of Calgon Gorp. have described the essential eletents of full-scale adsorption systons in a paper presented to the EPA Technology Transfer Session on Treatment of Toxic Chemicals held in Atlanta on March 13, 1974. Each systsn is comprised of three basic functional ccnponents: 1* The adsorption treaenent of the wastewater 2. The carbon reactivation equifjtwnt 3. The carbon/water transport arrangement For POs, the practicality of reactivation mist be determined. 2.2.1.3.1 Adsorption Treatment of wastewater The adsorbers hold the granular activated carbon beds through which the wastewater flows. They can be designed for pressure or gravity flow to achieve the desired contact time of the water with the carbon. Suspended solids and space limitations also must be considered in the adsorber configuration. Flow rates usually fall under 10 gpm per square foot of carbon bed surface area. Contact times for industrial wastewater mixtures usually are in excess of 60 minutes, which is about twice the time orployed for purification of demertic sewage, vtwn suspended solids are present they can be filtered out by the carbon bed; this dual purpose of carbon bads can be usefully erployed as long as the adsorbers are designed to accomodate periodic backwashing and bed-cleaning procedures such as air scour and surface wash. For PCBs service, minimum backwashing would be desirable since back washing would creats large quantities of ooncantratad wastewater needing incin eration or treatment. Sens settling and prefiltering would be required for optimum syster performance. A well designed water distribution systen or underdrain systnn would insure good backwashing performances, as well as even distribution of water flow. Well established filtration design practices can be effectively anployad in carbon bad system. Carbon bads trust be periodi cally mowed via water slurry and obstructions to the flow of carbon from the adsorber should be avoided in adsorber design. - 164 MOWS 209144 Carbon bads are normally in excess of 10 feet deep and usually fall into one of four basic configurations: 1. moving 2. bads in series 3. bads in parallel 4. expanded bads The type of configuration selected depends on a nutter of variables; principal among than are total water flow, suspended solids, and degree of contaminant reduction desired. 2.2.1,3.2 Raartivation of the Grap"i-n carbon Thermal oxidation, using either mltiple hearth furnaces or rotary kilns, is generally nployed to reactivate the exhausted carbon. The size of the thermal reactivation equipment is based on the carbon exhaustion rata, i.e., poinds of carbon exhausted per thousand gallons of wastewater treated, and the weight of contaminant on the carbon. Excess capacity is designed into the thermal reactivation unit to allow for variances in carbon use rate due to changes in the wastewater flow and organic loading. The axhauatad granular activated carbon is heated to 1600 to 1800*T to effect volatilization and oxidation of tha dis solved organic contaminants. Oxygen in the furnace is normally controlled at leaa than 1 percent to effect aelective oxidation of conteoinants over activa ted carbon. A 5 percent loss of activated carbon per reactivetion cycle is an acosptable bench mark upon which to baaa granular carbon ayatma eoanonics. Particularly tag the PCBs, which require an incineration taipexaeure in excess of about 2200*T plus several seconds residence time, the reactivation equipment nust include an afterburner. An air san&ber with HC1 neutralization would be the last alvent of tha reactivation train. Thus far, tha regeneration of car bon used for PC8e adsorption has not besn proved. 165 MQNS 209145 2.2.1.3.3 Carbon Transport Granular spent carbon is usually trans ported between the adsorbers and the reactivation equipnent by water slurry, various putting designs can be erployed ireiludirg centrifugal and diaphragm ptr^ss as '-ell as hydraulic or pneunatic pressure. The transport piping should include flush ports and wide radius bends. Typical loading is between 1 and 3 pounds of carbon per gallon of water, depending upon distance and elevation considerations. 2.2.1.3.4 Materials of Construction Special consideration should be giver, to the selection of materials of construction with regard to conus ion and erosion. 1. Galvanic Corrosion - Any tendency toward galvanic corrosion due to water characteristics, such as conductivity and pH, will be enhanced in granular carbon bads. Mild steal tanks or adsorb ra holding granular carbon under water should be lined* Tanka can also be oonstruetad of ceiant or rtinforoad synthetic resins or plastics. Caitaon-in-watar slurry piping, which experiences only periodic exposure, is usually exanptad frem special corrosion considerations. 2. Erosion - Periodic replacement of the carbon bads can cause lining failures at exit ports in carbon tanks and ad sorbers. Special grades of stainless steal are usually errployed for such wear points. 2.2.1.1 Carbon Regeneration Alternatives - Wat Catalytic Oxidation For Mil installations, it might prove feasible to 11 ipiss of spent carbon by incineration. Carbon simply cajpames also offer ^anfc carbon ranoval services and off-sits regeneration. However, there is a new wastewater treatment tech nique which might be applicable to carbon regeneration, namely wmt catalytic 166 HONS 209146 oxidation. Several laboratory studiaa in wet catalytic oxidation an des cribed in Appendix C. Lockheed Missiles and Space Co. {Vlasta Treatment Systems Section) of Sunnyvale, California, announced in January, 1976, that they have a process ready for pilot plant evaluation and conroercial scale-up. In a preliminary look at the Pa destruction poten tial of t catalytic oxidation, a wastewater sarple from an unnaned user of POs was subjected to treatment. The PC3 mixture approximated Aroclor 1221 most closely, and was very concentrated to 5 ppm in the wastewater sample. Since 5 ppm is nuch higher than that Arcelor's solubility in pure water, it is believed that solubilizing agents or particulates ware carrying most of the POs. Within 20 minutes of treatment time, however, about 90 percent of the POs had bean destroyed, and no large quantities of reaction products wars detected. However, this is just one data point and confirmation is needed. The test reactor was a continuously stirred batch systnn, with air continuously sparged in. The test conditions used warn reactor pressure, 1500 psig; tenperature, 550*7; catalyst concantration, 0.5 gran; and reactor volute, 1.5 liters. The proposed use of wet catalytic oxidation is for carbon reganeration while in spent weter slurry form. Since the capital and operating costs of ths catalytic systmn are tied to ths hydraulic load, it might be practical to trap POs with carbon in wastewater, and than treat the carbon slurry by catalytic oxidation to destroy ths FCEa. in this way, PCSs would be moved frem the wastewater by ths highly efficient carbon adsorption method, while ths volune handled by the catalytic systmn would be greatly reduced. feasibility tasting for regeneration of activated carbon by catalytic oxidation ia needed. The activated carbon industry has long auu0nt alternatives to thermal regansration of carbon, because of ths loss of csrfise by oxidation. With solvent regeneration, or acid or base treat ment* tbs first tag-ration only produces about 40 percent of the active sur face, which than usually decreases to 30 percent after several more treatments. 167 HONS 20914? Such degradation is unacceptable. Thus the questions to be msverad are: a) Can catalytic oxidation destroy adsorbed POs on carbon, converting than to COj, RjO and Hd? b> Will the regenerated carbon have, say, 90 to 95 per cent of its original activity? c) Can the process be operated ecorcmically? The last question rust take into account the necessary operation pressures (500 to 20C0 psi), operating tarperatures (300 to 650"F), source of oxygen (air, 0^ or ozone), type and lifetime of catalyst, residence time, and materials of construction, among other variables. 2.2.1.5 Further Applications Date Id-US provides an excellent booklet entitled "A Synpoaium on Activated Carbon", providing considerable detail on applications. Id also provides information cn special graphical procedures helpful in the scale-up frcm isotherm to oolutn testing, 2,2.2 lltraViolet-Assisted Ozonation Both UV radiation, and ozone, separately, have been used in water purification for some time. But only in the last five years or so has the synergies of the aaefcination bean appreciated in the destruction of organ ics in wetar. TVe r--ieii organizations, Houston Research, Inc., of Houston, taxis, and westgata hasearrti Oarp. of Marine Del Bay, California, are ngagsd in dauelopmt of UV-assistad (or catalyzed) ozone oxidation of refrac tory organics. Both organizations have cooperated in preliminary tests of PCBs destruction, and the method has shown greet premise as a large-scale, eooncmic water treatment method, the are working spstly with 253.7 nanometer, neer-W, radiation, but thsy plan to investigate far-W mercury radiation at 184.5 mu It is of particular significance that these methods premise destruction of hydrocarbon organics conplately to COj and vmtar. Thus they are Likely candidatae for zero discharge and total recycle systmaa. Belated to this is the wrk of Lawrence at Envirorsnant Canada (Burlington, Ontario), tto la studying the use of naar-W radiation (about 168 MONS 209148 36S ia), available fran sunlight, in conjunction with titania or alunina photocatalyata rather than tha caibination of UV and ozone. Tim ultraviolet region extends to 380 m, and than blends into visible violet. Studies using visible light are described further below. UV radiation is generally provided by aannarcially available tubes, which whai operated at low power (and low pressure in tie emitting tube) are quite efficient in transferring UV radiation to water. Tim range of effectiveness is quite short, probably of the order of a few inctes maxunm, because UV tranani ssibility in water is poor, and is degraded further by even sail aunts of particulate natter. Oaona is sparged into the reactor, and vigorous stirring is provided mtil increasing turbulence or mixing power input does not further inczaaee reaction rate. Various hinds of efficiency values are given to rats different systsns, flows, arrangmnsnts, etc. For overall efficiency, the units of measure are total organic carbon rsnovad par watt-saaond of UV input, or per gram off oaona introduced. Since oaona gmarmtion is expansive, work is directed toward optima use of the oaona introduced. The ooet is almost oonplately that of the electric power used in tha silent discharge tube method of making ozone from air. And, of course, UV gmaration is also an electric power ooet factor. The following subsections UV radiation and its mole cular interactions, the of Pda, and UV>aeeistad ozonation variaanta with FOi, 2.2.2.1 ttolacular to ultraviolet Energy having in the ultraviolet region (10 to electronic transitions within molecules. The principal charaeof an absorption band are its wavelength and intensity. The vave- abeorpticn (X nax) corresponds to the wavelength of radiation equal to that required for an electronic transition. A molar 169 HONS 209149 absorptivity at maxinun absorption (E max) of 10,000 j*r role or greater is regarded as high intensity absorption. Low intmsity absorption is considered an E max of less than 1,000 calories per mole; bipteryl in alcohol at 250 rm has an E max of 18,000, and in hexane at 246 m, an max of 20,000. this would seam to indicate that the basic structure of the PCTs would be readily activated by a mercury lanp generating 253.7-m radiation. However, this absorption will be modified by the roaitoar of chlor ine atans attached to the biphenyl groups. If at any point in the destruction of PCS* saturated hydrocarbons are farmed, they will be unresponsive to 253.7-m radiation. Saturated hydrocarbons contain si?na electrons exclus ively. Since the energy required to bring about ionization of the si?n bonds is of the order of 18S keel par mole it is only available in the far ultra violet, below 200 rm. Single carbon-carbon and carbon-chlorine have about the sane high bond energy, and are similarly resistant to rupture; how ever, there is a mercury emission at about 185 rm, vrtiich should be capable of activating thoee bonds, thus making them highly reactive in the presence of oxidizers such as ozone. Thus it appears possible to produce the excited states in P3 molecules necessary to make then highly receptive to oxidation. Since ozone is a powerful oxidizing agent, and it too is excited in the same regions making it even core effective, the possibilities for a wide range of oxidations are present. This would seam to make ccnpleta destruction of PCBs to CDj, water and ad feasible. 2.2.2.2 Photodagrariaticn of PCSa Hrr* of the strength of the C-d bond, it has her^ totee^Mewd that little photochemical cleavage occurs, further, in the ilium fieti aT breakdown of EOT and related aospounds, cleavage of the aromatic C-Cl bond is usually not involved. However, Safe and Kutzinger reported in Katun in 1971, that haxachlorobiphanyl photolyzad readily in organic solvents wten irradiated at 310 rm. The resultant products are formed by seapwise loss - 170 - HONS 209150 of chlorine, rearrangement, and condensation. Other reaearetars have found that certain pure chlorobiphanyls and PO mixtures can be decatposed by 'N oratory UV sources and by sunlight, over long time periods. The v*ve length of the UV radiation appears critical to photochmical deacrrpositicn. low-pressure mercury l*rps mitting 254 m seem to be several times as effective as the UV fran sunlight, which is greater than 295 ran. Studies have been carried out in organic solvents and water, and in both liquid and vapor states. ttjch of the past work has ban on organic solvent solutions of PCBs in order to have high working concentrations. Vapor phase studies have bean run to simulate treatment of atmospheric missions in environ mental studies. Reductive dechlorination, the mein photoreaction of . chlorcbiphsnyla, is faster in tydroxylic solvents such as methanol and iso propanol. Even chlordbmxsne loses chlorine rapidly on irradiation in iso propanol. Ocnplsta dechlorination of a PC3 mixture has bean observed in 15 minutes in an alkaline isopropanol solution, using a marcury Imp (Anon., Chemical Marketing Reporter, Nov. 6, 1972, page 22). Biphenyl and sodiun chloride were identified in the reaction mixture. Photosensitizers can increase the decorpositicn rates. Tryptophan, disthylaniline, banzophanone and triphanylene sensitized the photo reaction of dichlosobiphanyl. The reaction was quenched by n-baxyl mercaptan and di-n-butyl sulfide. Ebperimnts in water solution have bam Impend by adsorption of the PCTs on the wells of reaction containers, particularly ones made of glass. ' Attanpts have bean made to use surfactants to keep the PQHftn suspension. Adsorption on such solids as calciizn carbonate, silica, and soils, in wetsr suspension, has been tested as an aid to photolysis. How ever, UV radiation will not penetrate deeply into solids, so adsorbed PCS rust be kept close to the surface. - 171 - HONS 209151  2.2.2.3 Experimental Factors in UV-Assisted Ozone or pcbs -------------------------------- For several decades the advantages of ultraviolet radiation in the sterilization of aqueous and dry media have been known. Like wise' the powerful sterilizing, oxidizing effects of ozone have been known. Cnly with the relatively recent advent of requirements for removing refractory organics firm water, and the ability to detect these organics in parts per trillion and even lower concentrations, has the need for powerful oxidizing capability ben felt. It was quite natural to canbine the two effects into a single treatment or staged treatments, with the result being a strong synergisn in many cases. Enough data has now accunulated to show that UV/ozone wastewater treatment is a powerful method for meval of refractory organics. It hae the potential of moving organics to an effective zero discharge level. However, as the decrease in very snail concentrations beocmes exponential with time, the residence time required in UV/ozone treatment equipment beocmes a critical factor. The following variables have ban identified as affecting resldanoe tins: 1. Molecular structure of the organic 2. Concentration 3. UV transnissivity of the wastewater 4. UV intensity 5. UV wavelength 6. Ozone concentration 7. turbulence and gas-liquid contact (transfer coefficients) 8. pH 9. TVnparature The following subsections present e^jerimental find ings about the relative significance of thasa variables. - 172 - HONS 209152 2.2.2-4 Destruction of POs and Refractor/ Oroanic* Houston sesearcn, TKcI i-------------- ------ 2.2.2.4,1 PCB Destruction Data In preliminary experimentation on the feasibility of PCSs destruction, a high pressure 650-watt mercury tube gener ating 253.7-nm radiation was used in a 21-liter reactor. Figure 2.2.2.4.1-1 shows the arrangenent for a snaller reactor. Oxygen, with an ozorw concentra tion of 2 percent, was sparged in at 3 liters per minute. This was felt to be excess ozone usage, but a good starting point for tests. A 1000-pprt solution of Aroelor 1254 in methanol wu used to get a 514-ppb solution of Arcelor 1254 in tater. Otherwise the solubility of Arcelor 1254, which is about 50 peremt pentachlorcbiphenyl, is only 12 ppb in water. It was theorized that signifi cant destruction of this oorpound would forecast even greater destruction of the other Axcelors now produced, which are all less chlorinated and more soluble in water. Figure 2.2.2.4.1-2 is a plot of the normal ized residual concentration of Aroelor versus time of UV-assisted ozonation. It can be sen that in 1 hour about 2/3 of the POe had ban deoarposed; and in 3 hours, only about 7 percent of the original POe retained. 2.2,2.4.2 Operating Data Obtained fron Refractory organicsrests -. Houston nssearrh has ban studying ozon ation fbr water purification for more than four years. Carperieon tests have shown that the Edition of UV radiation enhances the reaction rate by 10 to 100 fold. Further it was ftutd that, fbr the most refractory oanpeund they had tested prior to the POe, Katie add, there was essentially no reaction without UV assistance. However, with UV radiation, the oxidation proceeds rapidly at room taperature. Figure 2.2.2.4.2-1 shows the effects of UV and tapareture on destruction. The ordinate is the fraction of total organic carbon retaining, showing that for the 30*C or 50*C tests, with - 173 - HONS 209153 variable speed MIXER AIR OXYGEN FimZ2J.4.M. LAB SCALE APPARATUS FOR REACTION ANO MASS TRANSFER STUDIES AT HOUSTON RESEARCH. INC. HONS 209154 174 TMATMInT Tint IMINUTU aaoclo*irMctrruucriowavuv-abutioozonation 175 HONS 209155 Figur* 2.2.2.4.21. OZONE OX 10AT ION OF ACETIC ACID. EFFECT OF UV ANO TEMPERATURE (INITIAL CH3COOH-106 mg/1,03d) -3.5 mg/1) HONS 209156 UV, there ia nearly ccrplete deatruction to 00^ and water within 4 to 5 hours The fact that the curves are displaced to the right of the mass transfer limit ing line shews that sane chanical reaction rate urprovment can be sought. Figure 2.2.2.4.2-2 shows the oxidation iirprovanent achieved by doubling the UV power input, with near aonstant taiperature. Further description may be found in: "Ozone/W Process Effective Wastewater Treatment", by Prengle, Mauk, Lagan and Hewes, in Hydrocarbon Processing, October, 1975. These are a sampling of the kinds of opti mization experiments that mist be run with the PCS oxidation systart to obtain good econcny of design and efficiency of operation. 2.2.2.5 Destruction of PCBs and Refractory Organics at westgata Research Oorp. 2.2.2.5.1 PCBs Destruction Pete Cooperative testing and research battesn Versar, Inc., and Westgate Research, Inc., determined the effectiveness of Westgate' s UV-assistsd ozonation process in destroying PCBs. The following experimental conditions were used in the treatment of synthetic wastewaters containing Azodors 1254 and 1016: nairtnr volure 3 liters Reaction time * 4 hours (asccess tins used to give best chance of destruction) UV Souses one 43-watt, low-pressure Hg ltp operating at 253.7 rm Reactor type vertical, cylindrical, 18 indi long, 3 indi diameter (UV path length * 2 inches) Pressure aorespheric TJengaramixe 23*C pH * 6.2 - 177 - HONS 209157 Figur* 2.2.2A21. OZONE/UV OXIOATION OF ACETIC ACIO; EFFECT OF INCREASED RADIATION INPUT HONS 20915S Ozone feed = 70 milligrams ozone/minute in 3.4 -- " liters per minute of oxygen; or about 1.4 percent by weight ozone in oxygen Reactant preparation = Pure Aroclor 1254 was mixed with an equal portion of methanol, which was then mixed with distilled water to get an apparent true solution. A Hamilton syringe, with vernier calibration giving microliter increments was used to prepare an estimated 200-ppb concentra tion in a beaker. This solu tion was added to the reactor (3 liters). Then a 200-ml sample was withdrawn to get the "before" sample. When preparing the Aroclor 1016 solution, a more concentrated PCBs solution of about S00 ppb was achieved. The before and after treatment concentrations of PCBs are shown in Table 2.2.2.5.1-1. The data show that the destruction was highly effective in these pioneering tests; more than 99 percent of the original PCBs were destroyed. In addition, the final concentration was at the desired level of about 1 ppb. Such an effluent would be expected to be a reasonable stream for recycle operations and intermediate term zero discharge potential. Of course the contact time and ozone ex penditure were overly large, but the goal of this preliminary testing was to demonstrate destruction of two key Aroclors in use today. A more comprehensive study of the UV- ozonolysis of Aroclor 1016 was run, with samples removed from the reactor every 15 or 30 minutes for up to 4 hours. As shewn in Table 2.2,2.5.1-2, the initial PCB concentration was 237 ppb. Within 45 minutes the PCS level had been de graded to 1 to 2 ppb, a 99+-percent decomposition. After 2 hours the PCB con centration was less than 100 ppt. The last colurm in the Table labeled - 179 - HONS 209159 Table 2. 2.2.5.1-1 UV Ozonolysis Teatruction of Typical Capacitor and Transformer PCBs at 'eataate Research Initial (influent) Concentration (ppb) final (effluent) Concentration lppb) Aroclor 1016 790 0.5 Aroclor 1254 200 1.5 Table 2.2.2.5.1-2 Destruction of Aroclor 1016 by UV-Ozcrvation at westgate Research UV-Ozonation Tine (minutes) 0 15 30 45 60 75 90 120 150 180 210 240 Aroclor 1016 Cone. (ppb) 237.0 14.7 7.76 1.73 1.73 0.52 5.2 < 0.1 <0.1 <0.1 < 0.1 < 0.1 Cilorinatad Products Car tPtf - 0.00 33.8 25.86 21.80 18.47 17.63 21.43 12.64 16.91 9.12 23.07 12.53 - 180 HONS 209160 "Qilorinatad Products Concentration" is of particular interest. This is td* first tin* quantitative data on the residual ccrpounds in the reaction mixture have been caipilad. These residual ccrpcunda reach a 33.8-ppto level within IS minutes fran the start of the test and then erratically and slowly drop to about 10 to 20 ppb over the 4 hour period. The only statanents that can be made about these residual acrpsunds is that they are non-PCBs, but chlorinated materials. Possibly a different LTV wavelength, or ozone concentration, or the use of a catalyst or other agent could degrade these other products to the rcn-detectable level. 2.2.2.5.2 Pilot-Scale Tests of Refractory Organics Dacorposition ' Zeff has described pilot-scale tests of UV-assistad ozonation using 253.7-nm radiation ("LTV-OX (TM) Process for tlw Effective Hwroval of Organics in Waste Haters", presented at the 68th Annual Meeting of the AIQiE, tovefoar 20, 1975). This work has grown from a patented invention for a household appliance used to purify tip water. The effectiveness of the method is demonstrated by the reduction in total organic carbon (TOC) of S00 ml of tap water fran 5 mg/1 to 1 mg/1 in 1 minute, using 0.07 mg of ozone and 0.1 watts of 253.7-nm UV. The bacteria plate count was also reduced by a significant amount. In these studies, batch reaction condi tions were optimized to get closest to aaipleta TOC destruction with least Oj and UV energy u^ut. Than continuous and ao-tage operation* were investigated. As shown in Figure 2.2.2.5.2-1, a 6-inch-path length of UV was cenpared with a 3-inch path. In a batdi test, the longer path condition took 3 to 4 times as lcng as the shorter path to achieve the sane TOC reduction, in approximate accord with the isnna square law. The laboratory-scale equipment arrangsrent is shown in Figure 2.2.2.5.2-2. Table 2.2.2.5.2-1 presents TOC reductions for a 5-part organic mixture under two experimental conditions, shewing ozone usage - 181 - HONS 209161 F*urt 2.2.2.5.21. THE EFFECT OF UV PATH LENGTH ON TOC DESTRUCTION MONS 209162 IMPURE water Supply flowmeter WATER LEVEL REACTOR UV LAMP QUARTZ SHEATH GAS VENT OZONE GENERATOR oxygen or AIR SUPPLY FLOWMETER PURIFIED WATER Figur* 2-2.2.5.2 2. SCHEMATIC OF BENCH REACTION SYSTEM AT WESTGATE RESEARCH CORP. 183 - MONS 209163 REACTOR l REACTOR 2 overall TABLE 2.2.2.5.2-1 SUuliUd Tuo-SUflt, CMtlnuous UV-OtfiMtlM f I S CaapoMiit Hli it Ufttgtt* lUMirch Carp. (41 Mtt UV Input iMCtar 1) (2t Mtt UV Input tonctpr 2) HONS 209164 efficiencies, and energy usage efficiencies, with a simulated two-stage con tinuous operation. Zeff has calculated the prune energy oosts for CV-assisted 02Cnation based on a scale-up of a pilot reactor, The pilot reactor handled 20 gph, so that 210 of these units in parallel would hardle 100,000 gpd. The plant area needed for this equipment would be only 13 feet square, with a height of 3 feet. Based cn pilot tests of this reactor, it might be assured that it could convert wastewater of 40 mg/1 TOC to less than 5 mg/1, using six 43-watt UV lanps. it is assured that a CV energy require ment of 5 watt-minutes per millgram of carbon oxidized will suffice. Also, the ozone requirenent will be 2 moles per gratr^atcm of carbon oxidized, but at a 75-oercent efficiency, or 2/.75 - 2.67 moles ozone per grsn-atcm of carbon. Assuring a power cost of 1.5C/KMH; the ozone generating power cost would be S53.40 and the UV pcver would be $18.93; or a total of $72.33 per 100,000 gal. of water treated. Zeff points out that the 210 reactor modules would require* 1260 43-wett Lanps (six per reactor). This appears to be a large nutter of lanps, but it is actually very practical. Such arrays of lanps are regularly used for roan illunination in factoriea and larga offices, and the low-pressure mercury, lanps used hare are nothing but fluorescent lanps without the phosphor coating. An extended array such as this is nuch more energy-efficient than fewer high-power high-pressure industrial W irradiators; and maintenance and raplacenant of lanps is nuch sinpler. The life of the lawpower lairpe is 7500 hours as oatpared to 1000 hours for the high-power lanps. 2.2.2.6 Laboratory Test Results from AlBesearch Corporation In the laboratory taste of the AiBeeearch Corporation, high-pressure 450-watt mercury laps were used. The test solutions ware very dilute mixtures of methanol, ethanol, isopropanol, and acetone in water. The ozone wee introduced into the 4-liter organic mixture in an oxygen stream in ft 2 liters per minute; ozone concentration in the oxygen was 33 ng/liter. With the expenditure of 7.9 grace of ozone, the mixture of alco hols and acetone was reduced from 115 mg/1 CCD to 10 mg/1 in 2 hours. 185 - MONS 209165 2.2.2.7 Cements on UV/Oaone Teats These highly encouraging tests by three different ccrpanies in the destruction of sene of the most refractory organics en countered in wastewater treatment, give confidence that scaled-up systans can adequately destroy PCBs in industrial wastewaters. The next step required is detailed cost effectiveness testing in pilot-scale equipnent. 2.2.3 Non-Carbon Adsorbents for POs A variety of non-cartoon materials, seme well-known for treat ing water and seme that seem to be quite specific for POs removal, have been found. Limited cooperative laboratory testing of PCBs removal has been con ducted in order to gain insight into potential effectiveness. Materials considered or examined were: 1) Sohm and Haas Airtoerlita XAD series resins - These were latooratory-tested for PCBs reauval 2) Polyvinyl chloride - Tested by Canadian investigators for rai rmmval 3) Clays and Hums - Testsd by Mansanto for PQJ removal 4) Polyurethane - Tested by Canadian, Svmdish and other investigators for POs ranoval 5) Sphagnua Peat - Used in oonnsrcial water purification, but has ndtTeen tried with P(3s 6) Polvelectrolytes as floocina agent - Not really jrtrir*Mvfcsr hit aouLd he aids to fancying finely divided adsorbents frtm treated wastewaters; have not basn tasted 7) Coal - Not tasted with POSa, but being experimentally used fin water treatment 8) Sieves - Not tried with PCBS, since they were judged-STBe of improper character; they vculd be to preferentially remove water frm PCBs, rather than POBs frao water 9) Miscellaneous Sorbents - A number of proprietary Oil Sorbets, such as tha^lM Brand* series, that were not tested with PCBs, might have some application - 186 MONS 209166 2.2.3.1 The Airberlite XAD Series of yiwroretic'^*-'- a^iM 2.2.3.1.1 PCBs Adsorption Testing Cooperative preliminary ejgjenmental work uu carried out between Versar and Itotm arel Haas to test tfw PCB-^sorption capacity of JOD-4 resins. The tests confirmed the effectiveness of this resin (see Appendix ). Since carbon adsorption is the more estab lished technology for rwoval of organics, it was felt that a side-by-side o=nparison of a carbon and an Airberlite resin would be useful. These tests shewed that resin and carbon are conparable in PCBs rwoval effectiveness. The resin method includes on site regeneration, with the concentrated waste PCBs treated by incineration. Details on the apparatus and materials used by Ratal and Haas and the results of their experiments are given in Appendix A. 2.2.3.1.2 Process Concept for Resin Adsorption of ------------------ pas----------------------------------------------------------- Based -pan the experiments described in Appendix A, the Ratal and Hass experience has led than to envision the following plant-scale process, subject to further experimentation. The wastsweter to be treated is passed through one or mors aolinns, each containing polymaric adsorbent. Once the resin is loaded to capacity with PCS, it ia taken off line for regeneration. A water miscible solvent is usually used for regeneration, and is in turn dis placed frem the adenrhent by water. The stream resulting ffran this operation is carefully fractionated to optimise solvent recovery. The final rinse usually contains a very low Level of solvent in wetter and this mist be collected as a PCBs wastewater. The distillation oolism permits solvent raoowey at high purity, leaving water and P<3 in the bottoms. To minimize - 187 - MOHS 209167 distillation costs, a patented variation of the process, n} l.^j "superloading", is used to maintain a high PCS concentration in the final toxic material to be disposed. Part of this process includes a separator from which the organic phase is PCB while the aqueous phase is recycled to the adsorbent. A completely enclosed systan can readily be designed to insure mininun opera tor exposure to PCB. A process ccncept flow sheet of such a PCBs removal system is shown in Figure 2.2.3.1.2-1. scale design is as follows: The experimental work necessary to plant- 1. More extensive leakage data should be gathered for XAD-4 and other Amberlite polymeric adsorb ents, encatpassinq several influent concentra tions of P&a; other Arodors should also be tested. 2. The ability of the Amberlite polymeric adsorb ents to be aolvent regenerated should be dmronstrated and the optima aolvent determined 3. The capacity of the Antoerlite polymeric adsorb ents should be determined over a mmbar of loading/regeneration cycles to see the effect, if any, of long-term operation an capacity. The description of XAD-4 resin and its comparison with other Bohn and Baas resins that might also have application to P<3a removal are given in Appendix B. Further descriptions of non-carbon adsorb ants are presented in the Appendix C. They contain relevant experimental work an POs and refractory organics, and are included to give a nose ocnplete pic ture of the options assessed under this program. Also included in Appendix c are aumsries of catalytic reduction, catalytic oxidation, microorganism studies, ultrafiltration, and reverse osnosis. For the removal of P<3s from waetewetsr, all are considered to be in the research stages. Several have potential for contributing to zero discharge technology. - 188 - HONS 209166 pcb* reMOVAL process concept flow sheet BY ROHM ANO HAAS COMPANY - 189 - HONS 209169 2.3 'ftsatment of PQis - Contaminated Solid May** . 2.3.1 Incineration Incineration has been described in Section 1,3.3. For the variety of solids ranging firm granular particulate, such as fuller's earth, tn large chunks of solids, such as transformer internals, the best destruction method is rotary kiln incinerator, followed with adequate afterburning to prevent PCB vaporization. 2.3.2 Sanitary landfill The best tedmslogy for segregation of the PCSs solid wastes so that spillage, leakage to watarwys, or emissions to the atmosphere win rot occur, is described under Section 1.3.3. 2.4 Treatment of Mr missions 2.4.1 Condensation Methods Our survey found one plant that was practicing chilling of exhaust gases from PQa processing areas. With the low vapor pressure of PQa even at room tarperatura, it might be expected that they could be effectively swept out of chilled air with the condensing water. Undoubtedly this does occur to seem extent; however, the high activity coefficients of P<3s tend to keep them vaporised at levels near their pure liquid vapor pressure at that low taparature. Previous work by Versar has shown that PQe in stack emissions from sludge incineration are not j.amoved by water scrubbing Contract 68-01-1587). 2.4.2 Granular Adsorption Methods Althou^i no information was uncovered an the collection of P<3s from air stremna by any fosn of granular filter, it would be expected that such treatment should be effective. In fact, it would ba expected that the same adsorbents *<------* under Sections 2.2.1 and 2.2.3 above would be the moot effective. Activated carbon removal of organic vapors has bean practiced in sudl widely divergent circustances and dsvicee as gas masks, kitchen range hood syetmne, and submarine air recycle systems. - 190 - HONS 209170 2.4.3 Catalytic Oxidation of Organics in Evaporated Studies of vapor phase oxidation show the potential for PCBs destruction in air exhausts at lower than incineration tsnperatures. Catalysts would have to be resistant to HC1 vapors, but fuel savings and insulation savings would be large. This procedure should be amenable to all proportions of water and organics in such air streams. BorkowsJci passed PCS vapors over a catalyst at elevated tstperatures ("The Catalytic Oxidation of Phenols and other Inpurities in Evaporated Effluents," Water Research (1); 367 (1967)). Copper oxide was the most active of a large roster of catalysts tested and oxidation to carbon dioxide and watar appeared to be ocnplete at tenperacures over 300*C and at residence times of about 0.08 seconds. Without the catalyst, 1000 to 1200*C was required to achieve the same degree of removal. Walsh and Katzer studied contaminated air-water vapor streams over supported copper oxide and showed that the rate was first order in phenol and relatively rapid between 150 and 270*C ("Catalytic Oxidation of Phenol in Dilute Concentration in Air", Ind. Eng. Own. Prooese Design Develop, (12): 477 (1973)). At 150"C and a span velocity of 4100 hr"1 the phenol conversion was 99.6 percent, and there was little evidence of any intermediate organics in the condensate. These methods of air purification are in the research stages, and actual testing of PCTe in air is required. 2.5 The Fotani-l for Zero Discharge The beet method of achieving zero discharge, in the face of the prac tical problem of defining what a zero concentration is, is to establish total recycle. This appears feasible for wastewater, but not for solids or air missions. Portmstsly, for solids, incineration tactaelogy premises very high efficiency of destruction sinply by setting the taqpezatura and residence times high moo^. - 191 - HONS 209171 Fbr air ni**ioru, altiwjgh vapor pressures are low for pcss, large surface* have the potential for giving off significant quantities of pcBa, Versar research has found powerful adsorption and destruction methods for organics in air. If destruction equivalent to that achieved by incineration can be achieved at lever tejperatures through catalyzed reactions, near zero missions are possible. FQr wastewater recycle, methods of adsorption and catalytic destruc tion premise POs reduction to levels low enough such that reuse is practical. Our survey has shown sene nunlcipal and fresh weters contain PCS concentra tions of 1 ppb or greater, and many river waters can oontain many times that. Thus the recycled water at 1 ppb of PCB would be very suitable for reuse. 3.0 RATICWJX NO SEXSCTICNS 0T CUSR&RLY RBCOtDCn) VASTS TS&A3HNT METHCOS Based upon our plant surveys of tha PCB-using capacitor and transformer manufacturers, the single C.S. PCS manufacturer, and waste treatment equipment suppliers, and upon the analysis and evaluation of all available technologies whether in tziimarrlal use, pilot plant, or ressarch stages, Versar has developed reaentnandationa for tha most practical treatnant msthods available now. w* have also mad* predictions of methods applicable over the ritort- and lcng-texm future. Our current remrnrnriafInna are based cn technology that is either currently in us* and doing an excellent job of PCB destruction or removal, or holds greet praaiae of doing that job based tpon success in similar but ron-PCB, applications. 3.1 Incineration BsoameuleJ for Liquid PCTs and Scrip Oils For KBs and contaminated ng oils, we determined only two candidate msthodst incineration and sanitary landfill. It is possible that acme rtamlral aathoda dl aniaaart under wastewater treatment might later beoesa applicable to aonoaneretad PCB liquids, but the prospect is not deer at tbls time. Sanitary landfill is not recommended for liquids whan incineration is available. The potential for liquids escaping in large quantities from nurtured 192 HONS 209172 containers, caused by any of a muter of circumstances, and then causing massive leaching and liquid oontrol problem! at the landfill, is felt to be too great, Incineration, on the other hand, offers a straight-forward and physically sinple method of final destruction. Incineration facilities that have successfully handled PCS liquids are available in Massachusetts, Mew York, Delaware, Illinois, 'Texas and louisiana. Pilot or experimental facil ities are available in other parts of the country. With the increase m requirements for disposing of many other liquid organics, it is expected that new facilities suitable for PGte destruction will be added. Versar therefore recommends incineration, particularly if there is a choioa of the kind of disposal facility to be constructed. 3.2 Carbon Adsorption and UV-Assisted Ozonation Peccrmerded for PCBs in Wastewater ---- Our survey of wastewater treatment technology was extensive and excell ent potential for current, near- and long-term methods was fotard. The longer teem pilot- or research-scale methods hold greet promise for achieving zero discharge. FOr wastewater treatment, Versar's raccmrendation is carbon adsorp tion. This technology has bean well proved in a wide variety of industrial adsorption problems. It is constantly being successfully applied to the re moval of new organics from water. Our cooperative laboratory verk with several suppliers has confined preliminary reports of success in removing PCBs. All of the aspects of ccnmercial carbon adsorption, fra favorable capital and operating aooncmios to reasonable operating methods, materials of construction, and lack of transport of pollution to air or land, have bean proven for PCS-like materials. Thera is vary reason to ai^sct cannarcial success with PCS removal frtm wastewater. Potential problems with carbon adsorption includes the collection of ***--* water and spent carbon for incineration or other treatment, with these limitations in mind, we studied the various alternatives and have determined - 193 - HONS 209173 that the UV/ozone method is the best. However, it nust be appreciated that this technology is still sanewhere in the pilot-plant and research stage, but our cooperative testing with two equipment suppliers stows the method to be effective in destroying POs. It offers the potential of degrading breakdown products all the way to CDj, water and HC1. Any leind of process that generates no solids or liquids for Later disposal nust be considered for application where no wastewater treatment facilities mw exist, and where facilities for incineration of carbon systan wastes are not convenient. The major factors yet to be detenined for the UV/ozone system are aosts and operating practicality. Separately, UV and ozone systems are being used in ocrmercial applications, and it is therefore anticipated that tto cartoination will be practical. Choices of the propei. UV-radiation wavelength and power levels still need to be made, as well as methods of improving ozoneuse efficiency. It appears that aertnercial UV and ozone generators are suit able. 3.3 Incineration and landfill Beceranended for Oontaminated Solids Although incineration is reoanrandad for PCS oontaminated solids, because of its final destruction capability and prevention of any long-teen problems, sanitary or scientifically-controlled landfilling trust be considered a cloee second choice. At present, the only incineration facilities for hand ling the full spectrmt of PCB-contaminatad solids are those of Hollins Environ mental Services in Delaware, Texas and Louisiana. This limitation on locations for treatment requires that the alternate, landfill, be considered. Landfill, as practiced by Owstrol Corp., appears perfectly suitable for containment of PO-Gontmninatad solids, at least over a mediim term. Our reservation with this method is that it might be relegating a problem to the future. Our concern is thst some decades in the future, when a landfill might be closed, no agency will be prepared to handle the stop emptying and maintenance necessary to prevent leaching. HS anticipate that sane time in the future, many will have to be mined, and final destruction or recovery carried cut for land use or hazard reasons. - 194 HONS 209174 3.4 Dry Carbon Filter Adsorption Reoamended for Control of Air amissions For nuch the sane reasons listed in Section 3.2, we reccrmend that current emissions of PCBs in plant air be trapped in carbon-containing filters. It is recognized that other and better adsorbents may emerge from research, as described in Section 2.2.3, but it is felt that such advances will be readily applicable to any kind of filter pack, screen or cartridge system alreafy in use. the long record of proven capability of carbon adsorption is the main factor in its choice. However, since aontaninated carbon must be either incinerated or regenerated, over the longer term we see the use of lwtenperature catalytic oxidation methods as described in Section 2.4.3. Catalytic oxidation methods hold premise for near zero discharge, with the generation of no solid wastes. - 19S - HONS 209175 BIBLIOGRAPHY 1. Hutzinger, 0., Safa, S. and Zitkc, V., The Chemistry of KSi; CRC Press, 1974. -------------------- *-------------- 2. Cam, B., "Upflow - Ccvnflow Carbon Adsorption", Paper #85C; Nov. 19, 1975. 3. "Methods for Organic Pesticide Analysis in Water and Wastewater", Federal Register, Volume 3a, #75, Part II, 1971. 4. Hagar, D.G.: and Ri2zo, J.L., "Ramoval of Tbxic Organics fran Wastewater by Adsorpticn by Qranular Activated Carbon", presented to CPA Technology Transfer Sessicn cn Treatment of Tbxic Chemicals; Atlanta, Ga., April 19, 1974. 5. "A Syirpoeitm cn Activated Carbon", Id-United States, Willmington, Delaware, Booklet #19997; 1988. 8. Kutzinger, 0., and Safe, S., Nature, 1971. 7. Prangle, H.W., Jr., muck, C.S., Lagan, R.W., and Hawes, C.G., III., "Ozone/ UV Process Effective waatswatar Treatment" in HurtrmrProoessing. October, 1975, p. 82-97. S. zeff, J.D., "UV-OBCCUO Pzooeea for the Effective Removal of Organics in Wastewater", Paper #101C, presetted at the 88th Annual Meeting of the AKHE, Novnfcer 20, 1975. 9. Brice, C.A., at al., "Final Raport cn MET ffestewatar Treatment Systen", under Contract BABA 17-71-C-1090; July 15, 1973. 10. Borkcwiki, B., "The Catalytic CacLdaticn of Sfcanols and Other Inpurities in Evaporated Effluents", in water Raessrrh 1 387 (1987). 11. Walsh, N.A., and Katzer, J.R., "Catalytic Oxidation of Phenol in Dilute Concentration in Air", in Ind. Ehc. din. Prooesi r**ign U 477 (1973). 12. Misty, P., and Niddee, G., J. Chrtmat., 89:185 (1974). 13. Lawrence, J. and TobIm, MJ1., "The Adsorption of PCSa from Aqueous Solutions ani Swage", Progress R^ort (undated), 1975; Water Chemistry section of Center for Inland wastes, Burlington, Ontario, L7R4A8. 14. OMMr, HD.; in Analytical Letters, 12:983 (1971). 15. TudBer, E.S., at al. (Monsanto), in Bulletin of Ehviromental Oontaminatien and Ibid.oology 13(i) :86 (1975). - 198 - HONS 209176 16. Hague, R., et al., Er.vrrcmental Sciaioe Todirclngv, 8:139 (1974). 17. Berg, et al., Bulletin of Divirarmental Oontanination Tcsticolcejv, 7,-338 (1972): ' 18. Sa-rai, T., Genahiryohu Kogyo, 18(12):43--7 (1972). 19. Stuart, J.D., et al. (Uniwraity of Osnnecticut, Dept, of Qvenistry) , preprint paper: fiat. Meet. Div. Air, Water waste Chemistry, ?cs 1972, 12(2, 804). 20. anith, G., and Chen, J.w. (Southern Illinois Uhiversity), presented paper 101E at 68th Annual AIO Maething, Novwber, 1975. 197 - HONS 209177 SECTION VTI PRODUCTION AND DISTRIBUTION 1.0 PRODUCTION AND CURRENT USE 1.1 Oanestic Production of PG3a and PCTs Currently there is only cne taown ajimercial scale PCS production installation in the U.S., the william G. Kmrmridi plant of the Monsanto Ourucal Ooopany in Sauget, Illinois. This facility is specifically designed for dilorobiphenyls production and has a design capacity of 48 million pourds per year. Until 1971 PQJs were also manufactured at Monsanto's Anniston, Alabama plant which had a design capacity approximately equal to tl* Sauget plant. The Alabama operation was discontinued and the plant dismantled in 1971. PCBa manufactured by Monsanto are marketed under trecte name "Arcelor". Tables 1.1-1 and 1.1-2 present data fra Monsanto related to production and sale* of PCBe frua 1957-1974 and production of polychlorinated terptwnyls (PCTs) fran 1959-1972. The production of PCTs were terminated in 1972. Lhtil then in addition to PCBa (Aroclor series 12) Monsanto manufactured Aroclors 2565, 4485, 5442 and 5480. Aroclors 2585 and 4485 were blends of PCS* and PCTs and Aroclors 5442 and 5480 were two different grades of PCTs. Also given in these Tables are breakdowns of drastic sales psr uss category and by PCS grade. Detailed information and breakdown cn PCS/PCT blends and PCI grades is not available. However, Monsanto reports that the predaninant material produced was Aroclor 5480. vtisn prodioed and maxksted these materials were used in plasticizer applications. Figures 1.1-1 through 1.1-3 are graphical represen tations of these data. As can be sen fra Figure 1.1-1, the majority of the PCSs produced in the Chited Stsbas wae instated danestically. Production and sales of PCBa in 1974 were less then half of those for 1970, where production and sales of PCSs were at their maximum The difference between production and sales cn -198- MONS 209176 -6 6 T - TABLE 1.1-1 pcb t pct twnmciuic wo pct sales mxsamto oosniM, chemicals cm>my 1957 thru 1964 (Htxaanda of Fomk) 1957 1951 1959 1960 1961 1962 1963 u.s. PKXucncH cr fob mesne sales cr pa U.S. EXPORT SUES or PA u.s. pfccxcncN or pct* (11 32299 (21 m ooesne sales cr pa by cannon Heat Tranafer Hydraulica/Lubricarte Hiac. Indatrial Tranafooner Capacitor P lastidler Application! Petroleua Additivm - 1612 704 12955 1702B (1) - (1) 26061 (2) - 154* 755 571* 1409* 1*19 - (11 31110 (2) 2996 37919 352 14 (2) 3850 36515 37538 (2) 2322 38 3 53 38043 (2) 4468 - 2685 1569 5984 16499 4573 - .- 2521 1559 7921 16967 6244 " . 4110 2114 6281 15935 9098 * 157 3915 1681 7984 15312 8924 " 44734 38132 36 4 7 4920 582 394 5 1528 7290 15606 9181 " DOCSnC SALES BY PCB GRACE Arcelor 1221 Arnelor 1232 Aroclor 1242 Aioclor 1248 Aroclor 1254 Aroclor 1260 Aroclor 1262 Aroclor 12(8 Aroclor 1016 21 194 16222 177* 4461 7517 11 - - ' 16 111 10444 2559 6691 5982 184 72 - 254 240 11598 1388 6754 6619 359 102 101 155 18196 2827 6088 7310 326 189 - 94 241 19827 4021 6294 6540 361 158 * 140 224 20654 3463 6325 6595 432 210 361 13 18510 5013 5911 7626 414 2S4 - (1) Production figures ml PLartidler Application* figure* irvavai Labie during year indicated. (2) u.S. export Salas figures unavailable during >ear indicated. 1964 50 8 33 44869 4096 5288 929 4374 1692 7997 - 19540 10337 596 13 23571 5238 6280 8535 446 190 * HONS 209179 1965 1966 u.s. PRXucncN or pcx* H4 DOMESTIC SALES CF PCX* 517)6 U.S. EXPCPT SALES CT PCX* 4214 u.s. pKxtzncN <r pci* 6470 6584) 59076 6852 8190 dopcstic sales or pcx* by ooBoonr Hut Tr*n*f*r Hyciraulica/Lubriant* Kic. Irrtuatnd Trans foo>r CApacitor Pla*ticis*r Application* Patiol*u* AttitiW* 1237 4616 1841 8657 23749 116)6 - 1766 4256 1779 8)10 28004 13461 - OOCSTlC SALES SY PCS OWE Arodor 1221 Aroclor 1212 Arodor 1242 Aroclor 1248 Arodor 1254 Aroclor 1260 Arodor 1262 Aroclor 1268 Aroclor 1016 36) 7 31333 5565 7737 5831 558 196 0 526 16 39557 5015 7035 5875 768 284 0 owe 1.1-2 pcs t pct Nwmciuie mo pcx sales MMSAMIO nCUSnUAL OtMCUS OMMff 1945 thru 1974 nhOOanM Of Poinis) 1967 I960 1969 1970 1971 75309 62466 8124 9450 82854 65116 11231 8870 76389 67194 10624 11600 85054 73061 13651 17768 34994 34301 - 20212 2262 4643 1426 11071 29703 13361 - 2529 5765 1283 11S65 29SSO 14404 - 3050 8039 1079 12105 25022 16460 1419 3958 7403 1627 13828 26708 19537 T 3060 1552 1155 11134 i 14141 1 3259 * 442 25 43055 4704 6696 6417 840 287 0 136 90 44153 4694 8691 5252 720 280 0 507 273 45491 5650 9822 4439 712 300 0 1476 260 48588 4073 12421 4890 1023 310 0 2215 171 21981 213 4661 1725 1 n 33 34 1972 38600 26408 6388 8134 752 0 0 25656 0 0 171 0 721 807 349 5 305 0 0 20902 1373 42178 37742 8346 - 1974 40466 34406 5395 * 37742 31406 35 0 6200 0 7976 0 0 0 23531 57 0 6207 0 6185 0 0 0 21955 HONS 209X80 5 SO TS 70 5 0 58 2 so 48 o 5 40 98 90 2 28 20 18 10 8 OIFEERENCE between production SALES REELECTS INVENTORY CHANGES 1*89 1888 1887 1888 TEAK 1871 I8T9 1878 *+flgm 1.1-1 - U.S. Production of i and PCTi and CalM ul Phi mna -201- M0NS 209181 US DOMESTIC SALES IN MILLION LBS ripn 1.1*2 - U.s. rawiln Salas of K2U by DM uaa Applications -202- HONS 209162 tot*). OOHCJTIC 34LC3- PCBa IN MILLION LBS YEAR rlqm 1.1-3 - U.3. Donaotic Saltt of PCB by Tyjj* -203- MONS 209163 this graph reflects inventory changes of PCBs. Figure l.l-l also indicates that the production of PCTs increased steadily through 1971 when their pro duction was at the maximum. The production of PCTs was terminated in 1972. Table 1.1-3 shews production, sales and export of PCBs for the first quarter of 1975. Monsanto reports that sales for Aroclar are expected to increase at an average annual rate of 6-7 peraent aver the next few years. Additionally, exports of Aroclor are expected to maintain the sane ratio to the U.S. production as in the past. Figure 1.1-2 indicates that prior to Monsanto's voluntary restriction of sales to all applications with the exception of "closed electric system", approximately 13 peraent of the PCTs in the U.S. was used in "naninally closed" applications (heat transfer, hydraulic fluids and lubricants) and 26 peraent was used in "open End" applications (plasticizers, surface coating, ink, adhesives, pesticide extenders, and microencapsulation of dyes for carbonless duplicating paper) there entries of PCTs to the environment are more probable and PCT miss ions axe uneexttroliable. At present, almost all dermatic produc tion is being used in "closed electric systame" (transformer and capacitor applications) where PCT amissions axe more controllable. Between 1957 and 1971 there were twelve different types of Aroclor manufactured by Monsanto with dilorine contents ranging from 21 bo 68 peraent. Aroclor 1242 and grades lower than 42 percent chlorine made about 48 peraent of the production consunsd. U.S. Sale of Aroclor 1242 has dropped drastically since 1971 and has been replaced by Aroclor 1016. Sales of Aroclor 1254 re mind *out the swm for the period 1957 - 1974. currently, tnare are four different types of Aroclor manufactured by the Monsanto Ccnpany-Aroclcrs 1221 and 1016 tor caparitor applications and Aroclars 1242 and 1254 for transformer application*. Past and current id-us* of PCTs by types axe presented in Table 1.1-4. to the years parlor to 1971 the largest "open-end" use of PCTs and PCTs Km bem in pi applications. According to Monsanto, a large percent age of the pwrinr** nfi of Aroclor 1242 and lower chlorine content grades and the entire PCT production were used for this application. Following Monsanto's -204- MONS 209184 TABLE 1.1-3 PCS MWWFACTOTE AND SALES tCNSwrro industrial cmacxLS company First Quarter - 1975 U.S. PJODOCriCN DCtCSTIC SALES U.S. EXPORT SALES DOMESTIC SALES Transformer and Capacitor Dorcsnc saies by pcs gfnz Arodcc 1221 Aroclor 1242 Aroclor 1254 Aroclor 1016 picnarntfr umizAmy or akxlcrs Aroclor 1221 f Aroclor 1016 { Aroclor 1242 } Arcelor 1254 1 (Thousands of Pounds) 3532 7996 1538 7986 10 2201 2115 3660 Capacitors Trans footers -205* HONS 209185 EhfHJu ExiJtina Sales Capacitor* Tranafonaar* Salas Ptwsed'Oit 1016 TABLE 1.1-4 END-USES OF PCTl VC PCBe BY TYPE 1221 1232 1242 1248 1254 1260 1262 1268 XX X xc thIQU?! 1971 X X xc X through 1971 PCTa Hast transfer Hydraulics/ i liJancants X . hydraulic fluids . vacuun pn< . yi-twmnion turbine* Plasticizers X XXX X XX XX . ntbers . aynthetic raeina . carbonless paper XX XX X X X XX XXX XX xc Mtarallanaoua Inckjatrial . adiesiues XX XX X X . wax axtander* XX X . deducing agents XX . inks X . cutting oils X . pesticicte axtandars X aaalants a caulking at XX X XX xc xc Notaai (l)x danotas uh of * qi\an Arcelor in a (pacific and-uaa, Miila XX danotas principal vaa (2) PCT* denote serial 25.44 i. 54 ArocLora Sourcei Hiaaini InAstrlal Oiaial A. HONS 209166 voluntary restrictions in 1972 , Aroclar sales for plasticizer applications dropped to snail percentage to that of the previous years. Historically, capacitors have always been the single largest PCS use category except for the years 1969-1971 when Azoclar usage far plasticizer applications was higher. The major uses of PCTs prior to 1969 in order of voluna of material used is listed below: . Capacitors . Plasticizers . Transformers . Hydraulic fluids and lubricants . Heat transfer fluids 1.2 Foreign Production and Distribution of PCBs Known current foreign producers of PCTs are the United Kingdom, Czechoslovakia, France, Gennany, Italy, Spain and the U.S.S.R. Detailed infor mation an total production of PCBs outside the U.S. is not available. However, total foreign production of PCBs was roughly estimated by the Interdepartmental Task Force to be 80-85 mil Urn ponds annually prior to 1971. This value included 26 mill ion ponds produced by Jap. Farsi?! prediction of PCBs has, however, decreased primarily due to Japanese action ai banning the danestic production of PCTs. In 1973 foreign production of PCBs was estimated to be 43 million pounds, aooonting for a 50% reduction. Production, trade and use of PCBs by CECD timber countries for the year 1973 is givan in Table 1.2-1. The acmbinad PCS output of three major European producers, France, Italy and (hited Kingdan wee about 36 million pounds in 1973. World cameras in PCSs is ejected to decrease further, due to OBCD umber aotntries' activities, and to be essentially confined to rapedtor and transformer applications. 1.3 Sibitty of Regent PCBs and PCTs Inporta X sutnaxy of estimated iirports of PCBs since 1971 is presented in Table 1.3-1. Tnportstion of PCBs appears to be steady or increasing, and currently is in the range of one percent of the danestic sales reported by Monsanto. -207- HONS 209187 Tnhl* 1.3-1 - Production, Trada and I'm of PC3* OBOJ tabar CoimtriM (1973) (1) all miHltlM MW IB MUt-- (It ad--MlM la M --`l^la (*> 'MB' Ma a fOi M aa a IlmurW la plantloa 01 til* fl+a laaima Msut a pmt Cm piwnow'r iapenad (U) Ww( naartad aa la^an ana wwW'tla* auotad la uaaja * n (ill with naaaai a an nan aa m la uantann and rmiriiiri iMaial daUnltlvn elaM (111 Ma (lam IrrliaM 0.11 Mills pana ad 1a^ntad ntarial HONS 209188 208- Table 1.3-1 Preliminary Stannary of PCS* Inport Data for 1971-75 Versus Monsanto Production and Sales Data Estimated iaporta (lb) Monsanto Carnatic Salea (lb) Ispcrta aa Percentage of Cooestic Salea Monsanto Exports (lb) Atlo of Bqports to I^orts ` 1971 550,000 34,301,000 1.6 - Year or Portion of Year 1973 1973 1974 700,000 480,000 450.000 36,408,000 37,743,000 34,406,000 3.7 1.3 1.3 6,388,000 8,346,000 5,395,000 9.1 17.3 13.5 1975 450,000 16 moa) 7,986,000 (3 mas) - 1,538,000 (3 mas) HONS 209189 Qiring 1971 and 1972 moat of the PCTs imported into the united Start** originated in Japan, ostensibly corresponding to sales of stodcs un salable in Japan due to pending or established regulatory action. There apparently has been little or no U.S. deportation of PCTs from Japan since 1972. The major importer was Marubeni America Corp., West Caldwell, tf.J. Since 1972, most of the iaported PCTs originated in Italy, with a anall amount imported from Franae (manufactured by Prodelec) . This French material is similar to Aroclor 1242 and is used (40,000-60,000 lb. per year) as a coolant in mining machinery by Joy Mfg. Co., Franklin, Pa. Decachlorobiphenyl (Fanclor OK) is imported fran Italy by Yates Mfg. Co., Chicago, 111., for use in the manufacture of investment casting waxes. Estimated current usage is about 400,000 lb/year. Polydhlorotriphsnyls, also used in pattern wax formulations, appear to be imported at an increasing rate. Estimated Mounts are: 1973 160,000 lb. 1974 330,000 lb. 1975 (6 nos.) 200,000 lb. Major importers of PCTs are Progil, Inc. (formerly Prochimia) and Intsel Co., both in the New York City area. Most of the imported PCTs originate in Ftance (Prodelec). OH of PCBs aid PCTc in casting waxes appears to be generally stable or increasing slowly, id inter conditions of lade of regulatory control in the future, such use would be to aentinue at least at the current rate, cn tt* other hand, Joy Mfg. Oo. no longer manufacture* mining equipment using PCT* as coolant; th* amounts imported by Jay axe used to service existing equipment. However, aina* Jay import* only 10 to 20 percent of th* total, the overall import* will not b* affactad greatly by future decrease* in imports by Joy. 2.0 tlTIMII YEAR. BffRWCEJIffICNS FOR PCB PRXOC3ION Jtt USE IN EUCTKLCH, The evteject data base we --from domestic sales figures far Aroclar* reported by Mansto - rapedtor and tran*fonner sale* being sunned -210- MONS 209190 to obtain totals. For certain years (1972-1973), sales data were reportal in aggregate, and in sudi cases, the reported figures were taken as totals, and usage breakdown was acooiplished by assigning total amounts of Arodor 1221 and 1016 to capacitors and total amounts of Aroclor 1242, 1246, 1254, and 1260 to transformers. All 1975 totals wre obtained by quadrupling the reported first-quarter sales figures - a prooees which very likely yields an approximate lowr-bound to the actual yearly totals - and, ultimately. Table 2-1 was acnstxucted. Manifestly, the available data base is far too limited to fcem the basis for any rational statistical analysis. The strong partifcatianal decrement in the 1971-1972 interval precludes the application of incremental regression even if a fifteen-year extrapolation were not required. In short, then, trsid analysis becomes a generally risky proposition, and the optimum analytical approach seams to be limited to unbiased extrapolations of least-square linear fits to grouped subsets of the available date points. Given this, three date base subsets inr premising: (i.) ttw full base - using all reported and 1975-estiraated data, unwei^rted and unbiased; (ii.) (iii.) a singly-daletad base - using all reported data, but eliminating the 1975 estimates. This tends to wei^it tlw extrapolations (however weakly) with regard to recant (laat-dacada) performance only, but the resulting curves can thai be inspected without the bias of the estimated 1975 totads and triply-elated base - farmed by extracting the depressed 1971 end 1972 totals from the singly-deleted base. This Te* jwMi-w alimtnatad the bias of the 1975 estimates, and itiwMH tim effects of tt interval decrements caused by regulatory effects. (A r*T*l*r" noz* realistic picture might be obtained by placing a dacmsntal wight on 1975 totals -- itvWt the asmapticn that sane of the roll-back is react!vely -211- MONS 209191 Year 1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 (eet.) Table 2-1 Total PCS Breakdown by Use 1966 - 1975 Total (10` lbs.) 37.794 40.774 41.135 37.127 40.536 25.275 25.656 37.742 34.40* 31.944 Capacitors (10 ` lbs.) 28.884 29.703 29.550 25.022 26 .708 14.141 20.321 23.566 22.000 20.644 Trar-sforrers (10 * lbs.) 8.910 11.071 11.585 12.105 13.828 11.134 5.335 14.176 12.000 11.300 -212- HONS 209192 ' indioad by the strong depression in the 1971-1972 totals. Thia would result, hever, in externally biased extrapolations, and justifying a long-tean lag of such effects with the avail able data appears difficult.) These data bases, and the unbiased, least-square 1 inrt-r extrapolaticns derived from than, are graphed in Figure 2-1. Inspection of the curves shews that the 1975 estimate has little effect on the aggregate total; an event readily accounted for by noting that the singly-deleted base has tha effect of depressing tha capacitor total only slightly mote than it elevates tha trans former total, the triply-deleted baae, however, provides almost no perturbation to the transformer total derived fran the full baae. inspection of the curves for the aggregate total and the oyeeitor total indicate that this arises fran the fact that the ratio of their time-derivatives (slopes) for the triplydeleted base is almost equal to its value with the full base. Generally, the developed extrapolations disagree with mid-1975 industry estimates for the near-term future. Apparently, Monsanto and capacitor manu facturers tend to e^ect 1975 totals to raamible 1974 totals, followed by a five to tan percant increase in 1976, and a general four to five percent increase over the preceding year for 1977 an. Cbviously, increases by. a fixed percentage over preceding years yields exponentially increasing totals - an event un doubtedly straigly desired, but probably wholly utopian. Transformer manu facturers appear to tand torard a more conservative view; General Electric for exaple, expecting the &mand for power transformers to riss and tha demand far distribution transformers to fall -- probably yielding e general saturation of tha salaa figures when integrated over all types. Taking tha available information into consideration, tha ispreesion remains that the triply-deleted date bases probably provide the most likely picture of %het mbit be expected over a 25-year term. Naturally, midi scenarios assure the external statue quo as constant; tedmological, eoaxxnic, and regulatory factors being enable of producing strong (and unassessable) variations in usage patterns. As a matter of fact, very recently, Monsanto has publicly announced that they would support a cassation of the PQi produc tion when suitable alternative materials beaane available. -213- MONS 209193 rlgut* 2-1. Uhbi^aad Exbi^oLatians of Laaat-Squw* T ina>r Curvaa for pa Pza&icticn and Um In Electrical ftpnpnent HONS 209194 3.0 OVBALL MOERXAL BALANCE Three separate approaches have been taken to obtaining overall data on total PCBa production, historical usage, and current distribution in the enviroiment. Most of the uncertainty lies in the period 1930-1960, for which Monsanto data are ladting. Use of PCBs in transformers, particularly in electrical distribution systems, apparently began almost simultaneously with utiwercial production. Extensive use in capacitors can be traoed to the intensive development and use of electrical hone appliances, starting in the mid to late 1940's. Use in adhesives, paper, lubricants, etc., prcbably began in the early 1950's, and use of PCBs as a heat transfer fluid began early but increased rapidly between 1950 and 1970. Using the Monswto production data for 1960 to 1975, and assuming a i inmr increase in total PCSs production between 1930 and 1960, we obtain: Production 1960 Production 1930 Total - 75 - 60(30 yr * 19 * 10* lb/yr ave) 850 * 10* lb 570 * 10* lb 1,420 * 10* lb Estimates of total PCBs usage by U.S. industries for the period 1930 1975 axe given below: PCBe by use category Capacitor 6 transformers Heat traaftr Hydraulicm/lubricants Misc. industrial Carbonises aopying paper Other plasticizer uses Petrols** additives Total from Monsanto Estiaefeed total U.S. imports of PCBs Qrant total PCBs usage 965 * 10* lb 20 * 10* lb 80 * 10* lb 27 * 10* lb 45 * 10* lb 115 * 10* lb 1 * 10* lb 1,253 * 10* lb 3 x io* lb 1,256 * 10* lb -215- MONS 209195 Alternatively, we have fitted least square asrrelatioia to ee* of the sets of Monsanto sales data for various uses, and to the danestic <mls set frtxn 1357 to 1974, projected eadi plot back to 1930, and integrated. These operation, plus the addition of several other well established data points, produoe the following results: Total Danestic Sales, 1930 - 1970 Danestic Seles, 1971 - 1975 Total Exports, 1963 - 1974 Estimated Escorts-, 1930 - 1963; 1975 Monsanto In-House Use (unreported as sales) 767 * 10* lb 166 * 10* lb 82 * 10* lb 70 * 10* lb 25 * 10* lb Total 1,112 * 10* lb As a comparison with the above, the 1973 Foster D. Snell study of PCBs concluded that the upper bound of U.S. usage of PCBs over 1934-72 was 1.175 x lrf lb. Adding usage figures for 1973-75 (about 105 x 10* lb), plus 150 x io* estimated total exports, one obtains: Estimated Total U.S. Production to Date Estimated Total U.S. Usage to Date 1.43 * l(f lb 1.26 * Ilf lb Dus, it that the approadws taken to obtaining overall pro duction and use quantities frcm various types of estimates yields: U.S. Production Maxiiw MiniauB 1.4 x lrf lb 1.1 * lrf lb U.S. Usage Iteins Minimus 1.25 * lrf lb 1.0 * lrf lb 216- MONS 209196 Sufficient data have been generated to allow an approach to the usage quantity through estimated quantities now in use or in the enviraretent: Trstffonners - 135,000 in serviae x 2,250 lb/unit average content 300 * 10 * lb Power Capacitors - 5 x 10* in service x 36 lb/unit 180 * 10` lb average content Industrial Capacitors - 790 * 10* in 0.35 lb/unit servioe average * content. 270 ,, 10* lb Total in Electrical Serviae 750 * 10* lb Total Other Than Electrical 8 * 10* lb Grand Total 758 * 10* lb Estimated "free* PCBs in the enviromant (sea section IX) 150 * 10* to 175 x 10* lb Estimated amount degraded or incinerated (20 x 10* lb. by contract incineration; 5 x io* lb incinerated with swage sludge and other solid wastes; and 30 * 10* lb degraded mono and dichloro barelogs) - 55 x 10* lb Estimated anoints to landfill or dtxrpi Ten percent of capacitor and transferrer usage as production wastes - 1.06 * U/'* 0.10 m 110 x 10* lb Obsolete electrical equiprent (capacitors mainly) - 80 x 10f lb Other sources (paper, plastic*, etc.) - 100 * 10* lb Estimated total 290 x 10* lb In stannary i Amount in use Amount in landfills Amount "fine" in sail, water, air, sediment Amount degraded or incinerated Total 758 x 1<f lb 290 x ltf lb 150 x 1(3* lb 55 x l(f lb 1,253 x l(f lb 217- MONS 209197 Thus, using estimates, we can account far the maximum usage of 1.25 * 10lb. calculated previously. Ms believe that the ranges of production and usage are well-defined by the maxinun and mininun values presented above, and that the aacuracy of the maxinun values are sufficient for use in gross calculations pertaining to the PCS# problem. -218- HONS 209198 bibliography L. Colder, A.W., (Joy Manufacturing Co., Pittsburgh, Pa.), Personal Gamunication, September 8, 1875. 2. Er.vironnental, Directorate, Organization for Eoanonic Cooperative and Develcpnent, General Information an PCS Monitoring and Qontrol, Paris, September 11, 1974. 3. Poster D. Snell. Inc., Maidcat Input/Output Profile, Proaess Technology Assessnent and Entry Into the Bwircnnant of Polychlorinated Biphenyls, EPA Gontract 68-01-2106, Deoacber, 1973. 4. leisy, A.E. and 2mll, W. (Monsanto Indutzial Clinical CO.), Personal Gcrtmunication, October 8, 1975. 5. Papajeorga, W.P. (Monsanto Industrial Chemical Co.), Personal Ormunication, August 22, 1975. 6. Polychlorinated Biptanyls and the awironnent, Interdepartnent Task Force on PCBs, Washingtai, 0. C., May, 1972. 7. Solanon, P. (Yates Manufacturing Co., Chicago, Illinois), Personal Qmunicatian, August 8, 1975. -219- MONS 209199 section vi n ` 1.0 INnCOUCTICN SUBSTITUTES FCR PCBs In 1970/ the Monsanto Company announced a voluntary restriction an sales of PCBs for all tut closed electrical applications. As a result of this action, since 1972 the use of domestically produasd PCBs has been limited to the manufacture of electrical capacitors and the manufacture and maintenanae of electrical transformers. Satisfactory substitutes have been developed for all of the other previ ous usee of PCBs except in the manufacture of investment casting wax. Inparted PCBs have been the sole souros of msterial for this application. There are no complete data available on imports; however current aggregate information indicates that PCS imports are about one percent of danastic production. A raster of materials are currently being developed as substitutes for POe. The replaoamt of PCBs by any of these materials will depend cr> the specific technological, eanoadc, and institutional requirements whidi govern each specific ^plication. The evaluation of tha subatitutaa muat be based an careful of *n of these factors aa they apply to each specific application where PCBa are currently being used. 2.0 EXECTRiaa, CAPACITORS An electrical rupee!tor is a device which stores electrical energy whan a voltage differential is applied across the device. This stared energy reappears in the circuit as the voltage is deczeesed. The capacitor therefore performs an electrical function equivalent to that of a spring in a mechanical system. The amount of electric charge (q) whidi a specific capacitor can store -220- MONS 209200 is a function of its size, or capacitance (c), and the voltage (v) q - cv (i) and the energy stored in the capacitor (w) is a function of the cap*:itance and the square of the voltage: w !jcv2 (2) This energy is stored in the capacitor in the form of an electric field and in the dielectric material which is exposed to that field. 2.1 FXaicticn of the Dielectric Material then a material is placed within an electric field there is a ten dency for the chargee associated with the constituent molecules of the material to move in the direction of the field (the positive charge neve in the direction of the applied field, the negative charges in the opposite direc tion) . If the material is a conductor, the mobile charges, usually electrons, will move freely under the influsnee of the field and a current is said to flow. However, if the material is a ncn-ocnductor, the applied electric field will reuse a spatial displacement of tha charge aaitars of tha constituent molecules, with ths result that surface charges will be induced on the material. Tha charge on opposite faces of ths material will be opposite in sign and will generate an electric field within the material opposing ths applied field. Such a material is known as a dielectric and is characterized by a paraefisr defined as tha ratio of the electric field that would exist in that space if tha mdiisn were replaced by vaoiin to that actually found within ths dielectric - this parasater is referred to as tha dielectric constant. The dielectric aonetant of most materials, at least at low frequencies, is greater than unity. Since tha effect of an ^plisd electric field cn a dielectric median is the j--w* of a surface charge, it is clear that work oust be dene in the separation of these chargee. Clearly, the larger the applied electric field, the larger ths surface charge, and conversely, when the electric field is named, tha surface diarge is zero. The energy that is required to es tablish the necessary surfaoe charge is stored within tha dielectric and can in meet cases be recovered without loss by ramming tha external electric field. -221- MONS 209201 In practice, tha external electric field is estAlislwd by applying electrical charges to a pair of metal plates placed cn the opposite surfaces of the dielectric. Although the geometry of the oanfcxrtor-dielectxic sand wich can talcs a wide variety of forme, the specific gecnetry that is of nest interest is that in whidi conductors are parallel plates separated by the dielectric. In this case the capacitance of the device is given as r _ eA C * ~S (3) where e is the dielectric constant, a the area of eadi plate and d the spacing (the thidmess of the dielectric). As is stated above, the magnitude of the surface charges that are formed cn the dielectric increases as ths applied electric field increases. Eventually, tha external electric field may Leans sufficiently strong to rup ture the bends that hold together the chargee cn the individual constituent molecules with ths result that ths dielectric breaks down; i.e., conducts cur rant. the critical voltage (V^) for a specific capacitor is vc " Ecd <4> where Ec is the dielectric rgngth, i.e. ths nsadjiun potential gradient (voltage) that the dielectric can sustain without rupture. Clearly, ths dielectric aonstant and tha critical voltage, or dielectric strength, are essentially unrelated. the critical voltage of the dielectric material can inpose severe Limitations on the maximal voltage at whiedt a capacitor can operate. The electric field strength in a capacitor is strongest at sharp edges and points causad by surfaca roughness and ths edges of ths conductive plates. If ths electeic field at thaaa points axossds tha critical voltage of ths dielectric, a oozens discharge can occur t4iicdi results in currant leakage and heating of ths c^adtor and ciuass dwical degradation of tha dielectric material This critical voltage for corona discharge dapands on both the gecMtzy of the capadtor and the properties of the dielectric, and is Sown as the corona voltage. Air has a rathv low dielectric strength; the pres ice of air bttfelee in tie dielectric will result in corona discharges if the capacitor ia operated at applied voltages above about 270 volts. -222- MONS 209202 ttwn several capacitors, say Cj_ and Cj, ara aonnactad in parallel, than'the voltage across eadi is the same, V, while the charge on the cap*:itors is C^V and Qj * C^V? hence the capacitanae of the parallel oartoination is given as (5) Cn the other hand, if the capacitors were connected in series, then the charge, Q, wwld be the sane for each. In this case, the respective poten tials wcwld be given as * Q/C^ and V2 - q/C2 , with the result that the total capacitance is given as 1/Ct - l/(\ * VC2 (6) Fran the above considerations it can be seen that the effect of a snail hole through the dielectric will be to produoe a very snail reduction in the overall capacitance, since the resulting structure may be considered as two capacitors, cne with the normal dielectric, the other with air dielectric, in parallel. Cn the other hand, the breakdown strength of air is considerably less than that of most practical dielectric materials, so that the effect of such a discontinuity in the dielectric will primarily be in reducing the critical voltage of the resulting structure. On the other hand, the effect of a gap between the dielectric and the plates is more serious since the resulting structure will act as if it were made up of several apadtors in sarias. Fran Eq. ($), it can be seen that the snallast capacitor in a series circuit will determine the total capacitate of the structure. Thus, a gap betwean the plates and the dielectric will have the effect of reducing the capacitance without a reduction in the dielectric strength. In moat practical deviaas, the assumption that the sole effect of the dielectric is ths reduction of the internal electric field by the induction of surface chargee is not entirely correct. In all such practical cases, than is a leakage currant that flows through the dielectric. This leakage currant produces heat within the dielectric, nils leakage is vary aell in useful dielectrics, but ths heating effect is not always -223- MONS 209203 negligible.. An additional dissipative procwi results whan the dipole intent induced within the nclecules of the dielectric is rot exactly in p^iase with the inducing electric field. In those cases where in the ocnstituant rolecules have a permanent dipole nunent, i.e. water, the inability of the orientatiro processes to follow the Ganges in the applied field becanes the daninant energy dissipation process; this is the basis of dielectric heating. The oritiination of the mechanism by whidi energy is dissipated within the dielectric is call ad the loss-tangent; the snaller the loes-tangent, the smaller the energy loss within the dielectric and hence the better the capacitor. 2.2 Practical Capacitors In its simplest form, a capacitor is a pair of metal platas separated by a dielectric material. Depending an the application, a great variety of structures have ben used ranging frem parallel plate mica or glass dielectrics far very snail capacitors, through tantalun-tarvtalun oxide-tarrtalim structures whidi have very large capacitances with very low operating voltage ratings. The capacitors ttiidi use PCBe as the dielectric material have capacitance values in the range of a few tenths to tans of microfarads and are usually spiral would of two thin alutinus foils and two paper spacers. To illustrate the utility of spiral winding, a 0.5 md capacitor made of two layers of alu minum foil 2.5 Inrtws wide by 0.0005 indies thide and alternate layers of paper (dielectric constant 2) 0.001 inches thidc, trould have a diameter of only 0.9 inches, whereas, in the plane parallel configuration, the structure would be 2.5 inrhae by 220 inches Inddntelly, talcing the dielectric strength of the paper to be of the order of 500 lev/an, the tnltege rating of the above exanple a^adtes would be about 1250 volts. The manufacturer of spiral would metal/papar capacitors nust avoid the presence of nail imperfections in ths paper dielectric and must insure oaiplete and reliable matching of ths metal foils to the surfaces of the paper. As A alternative to the requirement of very high quality control of the p^er and of the Conning prooees, it has bean found to be cost effective to evacuate the speoee within the wound capacitor and to subsequently fill -224- MONS 209204 the voids with a suitable liquid dielectric material prior to sealii^ the consisted unit. This liquid displaces any air which may be left in tie capacitor, thereby raising both the dielectric constant and the critical corona inception voltage. 2.3 Required Properties of Dielectric Liquid The properties that are essential for the liquid dielectric can be described in terns of the functions that the liquid must fulfill: . Electrical Properties - Should have a dielectric constant at least as lazgs as that of the solid dielectric spacer, and a dielectric strength at least as high as that of the solid dielectric. The liquid must have a low loss factor to assure electrical efficiency and a high resistance to the formation of corona disdiarges. . Physical Properties - Mist be liquid at a suitable tetperature to allow processing of the capacitor. Further, it should be liquid over the operating tonperature ratge of the resulting capacitor with a sufficiently small coefficient of thermal expansion so as to fulfill its function over tha entire tanperstore range. Mist have a boiling point sufficiently elevated to enure that the vapor pressure at the maodnus operating tsncera^ure of tha capacitor doas not causa rupture of the container. . Properties - Mist be dwnically cccpatible with ths "H* dielectric material, and with tha metal plates. Specifically, tha dielectric liquid oust wet both the plates and tha solid dielectric without altering either material dmicaUy or physically over tha entire operating tnpsrabure range. Tha dielectric liquid oust also be chmically stable at elevated tanperstores and in the presence of intense electric fields so that its properties do not change over time. -225- MONS 209205 ' Flamvability - Should ba ncn-flannabla and prodioe ro flawnable breateixm products if electrical arcing occurs within the capacitor. ' Cost and Availability - Should be ine^ensive and readily available with well defined and standardized properties. ' Tbxia.ty - Should ba ncn-todc and its possible break down products should be non-toxic. ' Ebvironaantal Persistence - Should be ervirormentally degradable and ncn-bioacomilating. ' Legislative Acceptability - Must ba acceptable under the Ian of the U.S. and of all other aountries to whidi creators are exported. Should ba acceptable under the relevant electrical codes which govern the use of capacitors. 2.4 The Use of PCBi in Capacitors PCBs have been the standard dielectric liquid used in almost all liquid-filled capacitors since 1929. Prior to 1952 the liquid used in capacitors was Aroclor 1254 (54 percent dilorine); it was than replaced by Aroclor 1242 (42 percent chlorine), which has better electrical preparties. In Septenbar 1971, Monsanto intro&aad a new capacitor liquid, Arcelor MS1016 , which is a merimert Aroclor 1242. This material is the steidard against which the properties of any other proposed capacitor dielectric fluid must ba coopered. 2.4.1 ProearH-- of ora Capacitor Dielectric Liquid^ Ua properties of Aroclor 1016 are as follows t Electrical Properties dielectric constant (ASH* D-150-47T) 5.85 (25C) dielectric strength (ASTM D-149-44) resistivity (ASTM D-257-46) >35 KV >500 x 109 loss-tangent (Dissipation factor-ASTM D-150-47T) 0.0025 -226- HONS 209206 Physical Pggparti.es melting point (pour point) viscosity at iaoF boiling point specific gravity (25C) coefficient of theanal expansion -19C U-81 SUS 32S-366C 1.362 .00068 cc/ccC Qandcal Properties corrosiveness > liquid - nonooricaiva breakdown products - oorrosive solvency: high, but satisfactory materials have been developed stability (max. service tanp.) 95C Flaansbility liquid (Cleveland open exp flash point): 141C breakdown products: nonflannable (prinarily Hd and carbon) Cot and Availability oot availability - no prebit S 5.14/gallen -227- HONS 209207 . Persistence envirormental - very persistent % biodegradation (48 hour activated sludge) 33 - fc loaccurulating - very . Tegislative Acaeptability banned in Japan, essentially banned in Sweden 2.4.2 Advantages and Disadvantages of PC3a in capacitors Aroclor 1016 has a relatively high dielectric constant of 5.85 which is well matched to the dielectric aenstant of 6.10 of the paper used in capacitors. This mixture of PCBs is chanically very stable, even in the preaence of high teiperatures and intense electrical fields. It is prob able that seme slight dechlorination of the PCB occurs during the leng tesn operation of capacitors. The resulting HCl would lower the dielectric strength of the PC3. However, the Aroclor 1016 used in capacitors usually contains a few tenths of an* percent of a chanical scavenger (usually an organic epoxide) which reacts with any HC1 which is found, and thereby extends the life of the capacitor. The only major problems associated with the use of PCBs are their ectiee anvirormntal persistence and chronic toxic properties which are made more severe by the high degree of bioaoasiulat i m vhich occurs in the environment. Ttw reant restrictions inposed by the govsummits of Japan and Sweden on the use of PCBs in those aoentries will require that a suitable sub stance be drveloped far use in electrical equipnant which will be exported. 2.4.3 Usage of PCBs in fhpariters The Genre! Electric Oo. reports that approcimately 100 million PCS type capacitors are produced annually in the U.S. with a value of 140 MtiHrw dollars, most of than for first-tins use. ^ Total annual P'33 Wfili--il c^adtor msufacturing is 21 million poinds, about 50 perwnt of which is used in large power factor correction capacitors. -228- MONS 209208 Capacitors used in lighting and air canditiaiing ^plications certain 0.005 to 0.09 gals. (0.05 to 1.0 lbs.) of PCBs. The largest power capacitors contain about 6.7 gals. (77 lbs.) of PCBs. The met papular site oontains about 3.1 (36 lbs.). The National Electrical Code requires that any installation of capacitors in which any single unit aentains more than 3 gallons of ccntiustible lirruid shall be in a vault like that required for tranafosnrs. (4) The life expectancy of capacitors exceeds 10 years for lighting applications and more than 20 years in electric utility power trans mission application. Althcwgh capacitors are ccnsidered long-lived products, they could fail due to poor process control, materials quality and mis application. According to G.E., existing PCS capacitors have been developed to the point that failures are considered essentially negligible. In ea<di application, the first-year failure rates are less than 0.2 percent. This level of life and reliability had not been achieved prior to the introduction of PCBs. Furthermore, the relative ncn-flaranatoility of askarels significantly redress the fire hazard that might otherwise armrpany thoee failures that result in nature of the case. Capacitors are not rabuilt and returned to service after failure. They are dispoeed of and replaced by new capacitors. 2.5 Alternatives to the Use of PCBs in Capacitors There are two main approaches that might be adopted in the developnent of subetitutae fer the PCBs in capacitor applications, (a) a straight forward leplacnant of PCBs that would require minimal alternation of the preasnt production techniques; and (b) the introduction of new production techniques designed to eliminate the need for a liquid dielectric. In either case, the alternative solution oust be significantly less envirorrentally dis tressing than the currently used PCBs. 2.5.1 Substitutes for PCTs So leng as ths present method of axu(auction of cqwcitors is used, (die dielectelc ll'jdd is required and must necessarily satisfy the physical, chemical, and taddty requirsients at least as veil as do PCBs. These raquimsnts can be relaxed only in conjunction with a more or less severe restriction cn the lwnrlmm operating teiperature of the capacitor, cn the other hand, sen* sacrifice in the dielectric aonstant and dielectric -229- HONS 209209 strength muld be possible by increasing the dimensions of the capacitors. In many applications this increased size would be troublesaw, but rt so serious as to be impractical. Further, there are some applications in which the nanflaimability of the dielectric liquid and of its possible breakdown products could be somewhat sacrificed. Finally, the cost factor aould be consi&rably relaxed. A mxsber of canpomds are being developed as replacements far PCBs in capacitors. The following list of ourpounds mist all be con sidered as possible substitutes for PCBs in at least limirari applications. 2.5.1.1 Phthalate Esters; 2.5.1.1.1 Dioctyl Phthalate; (POP) Current status: Used in caper! tors in Japan. Used by Gneral Electric Os. under the trade nea "Eoonol" in ca pacitors manufactured for export to Japan. Advantages . Price: one-half that of P<3. Availability: Widely ueed as a plasticizer for FVC. Dielectric Oanstant: 5.3; similar to PCB. Disadvantages: Owical stability: capacitors are 1 invited to 35C max. vs 95C max. for PCS. Oceana inaction voltage: lower than P<3.^ Flammability: Flash point is relatively high (220C) but men floanable than PCBs. Toxicity: Suspected carcinogen. tional testing is required. Extensive addi 2.5.1.1.2 Diisenatyl Phthlate: Current statue: . currently being tested by Exxon Chemical aider the trade name "Enjay 2065". -230- HONS 209210 Advantages: Dielectric Constant: Similar to DOP. Availability: Can be made by a modification of the OOP manufacturing process. Chemical stability: Better than OOF. Disadvantages: ' Availability: Not currently available in large quaitities. Flaanahtlity: Better than OOP, but more flannvable than PCS. Toxicity: should be similar to DOF. 2.5.1.2 Alkylated PCS 2.5.1.2.1 Isopropyl Dichldcobiphenyl Current statust Being test marketed in Europe by Pxodslec under the trade nans "OilaraUcylane". ^ Advantages: Electrical properties: Can be uaed as a direct substitute fcr PCSe. Bioaanomitraticn: Lass oonosntrmted in food chain than PO. aMore degrad^le than PCS. Disadwitagea: Cost: Twos that of PS, resulting in a 5% to 10% increase in the cost of capacitors. FImmobility: More flmmable than PCS. Tonricity: Acute toxicity % that of trlddorobiphenyl, eiunnic tadcity has not yet been fully investigated. 231MONS 209211 2.5.1.3 Alkylated QUorodiphenyl Oxide 2.5.1.3.1 Mondbutyl Stonochlorodiphenyl Current status; Being marketed by Clew Chemical Co. under the tr*Je name ")5S-4169L". ^ undergoing long tern servioe teats in capacitors by McGrav-Ediscn Co. Advantages; Electrical Properties: loss-tangent lower than PCB.1'3' Ooroia inoepticn voltage higher than PCS.*3* Biodagraciafinm Three times as degradable as PCS. Bioconaentration.* Less than one-tenth that of PCSa. One-twenty seaond that of PCS in 90-day rat feeding test. Acute tod.city; LD^g " 10 gn/kg vs 1.6 gn/kg for PCB. Does not irritats rabbit skin or cause chlor- Disadvantaqes; Electrical properties! Dielectric constant is senewhat lower than that of PCS (4.5 vs 5.85) which will require a larger plate area for a given capacitance. Availability; Currently not available in large quantities. Two to three years would be required to build sufficient manufacturing edacity to supply the capacitor industry. Costi Likely to be higher thn pa. FLannsbilityi Sanewhat more floanable than PCSj flMh point - 104C.C9) Chronic toxicity: Reported to be not tcutagenic in the Anas test. Long term tests of the tcodcity of biodegradatioi products hove not ban resorted. It is suspected that highly tcocic dioxins may be formed as a degradation product, *7* sp axtmely careful long testing will be required to prove the environmsntal safety of this oonpound. -232- HONS 209212 2.5,1.4 Silii Current status: Developmental work is being dene in the U.S. by Da# Coming Co, Mo information is currently avail able, but Da# Coming has indicated that a fonnal armourcement will be made late in 1976. 2.5.1,5 Diaryl Sulfone Current status; The Mmsanto carpany has been conducting extensive tests with a proprietary dielectric 1 iquid trade named "MS-1238".<2) Detailed dienical information is not currently available an this material; hOMver, an example cited in German and U.S. patent dis closures is a mixture of tolybcylyl sulfone, isopropyl biphenyl, and minor ingredients whidi may be antioxidants. Conplete information has been premised by Monsanto for the lata first quarter of 1976. Advantages: (MS-1238) Dielectric constant: 6.0 Corona inception voltage: similar to PCS. Biodegradation (48 hour activated sludge): 70% + 10%. Bioaociimlationt does not concentrate in food chain. Toxicity; Rat oral LDjg 3.8 g/kg. Rabbit dermal U>50 - 5 to 8 g/hg. Otsadyitanesi (ICS-1238) FLeaubillty: more flarmable th*l PC2e. Chronic toadcity: lade of data. 2.5.2 <"rinfcjgn_ofJ)islectric Liquids in Oiperltaa Bhhm of the and strongly interacting requirements cn a liquid dielectric meterial, there is considerable interest in the developMBt of capacitor ileelijns which do not require a liquid dielectric. Tl rather advanced tedrology involved in the production of very thin plastic films of very hl^i physical integrity, such ae is required in many food packaging applications, has opened the way for the production of plastic -233- MONS 209213 films of suitable dielectric assistant aid dielectric strength far capacitor applications. The parallel development of methods for the deposition of thin, carefully controlled metallic films on ncn-aorvducting surfaaes, such as is widely practiced in the ssniconductor industry, suggests that the use of a liquid dielectric material ajuld be cirasnvented by metallic films deposited onto suitable plastic substrates. The resulting metallized film can be spirally wound into useful capacitors. The essential problems associated with this approach, aside frcm the development of suitable high spaed processing equipment, lie in the selection of a plastic substrate that is tractable but also stable at sufficiently high operating temperatures, and in the ootplete elimination of air firm the capacitor. An aridi timeI problan with this approach lies in the nature of the polymers that hove been studied; nearly all of the suitable materials are themselves flennabl* and so are their probable breakdown products. A renter of different plastic films are used in low voltage DC capacitors, ttsst of these materials exhibit a relatively high loss-tangent (dissipation factor) which results in over-heating then subjected to an alter nating electric fisld. Only polypropylene has a loss-tangent sufficiently law so that it can be used in PC capacitors, and the dielectric constant of this material is about 2.2 tvs 5.85 for PCB). The polypropylene film that is used in capacitors is con siderably thinner than that used for packaging and decorative applications. There is no current source of satisfactory capacitor grade polypropylene film in the U.S. The technology for metallized polypropylene film capacitors comes frcm Pye TJC of Bigland which is partially owned by Philips. Represen tatives of this carpsny have approached moat major U.S. manufacturers. Currently, this tednology has been purchased by one U.S. manufacturer at a oost of four percent of their capacitor sales far the life of the technology usage. The failure rate of the dry film c^acitors is reported to be 20 times that of PCT filled capacitors, primarily due to aorona disdiasgee into air that is trapped in the dielectric layers. Present efforts an dry film type c^eeitars are directed toward the development of a suitable capacitor design. Polypropylene capacitors are widely used in Eur^e at voltages up to 250 volts. Capacitors suitable for U.S. aiplications are not ejected for 3 to 5 years. -234- MONS 209214 2.6 The use of PCS Capacitors in Electrical Equipment Each of the specific usee of PCS capacitors imposes special requirements an the performance of the c^acitor and on the properties of the dielectric liquid. The evaluation of the various substitute liquid dielectrics and of the dry capacitor designs nust be based an the suitability of the resulting capacitors for each of these uses. 2.6.1 Power Factor Correction The largest use of PG5 filled capacitors is to increase the efficiency of electrical poher distribution by correcting for the power factor of inductive nadiinery such as industrial motors, induction furnaces, and fluorescent light transformers. In general, the load iiqpcead cn a poter line by these electrical devices is not purely resistive, but is also partly inductive. The voltage drop (V) across surti an inductor is proportional to the rate of change of current through the device; hence (7) wtwre the negative sign eigpresses the reaction of the inductance (L) to a dwge in current (i) through the inductance. If the curmt is expressed in the form jut i - i0.' (8) wtwre j * T , e*1* - (ooe ut - j sin ut), u - 2irf, f * frequmcy. Than VL - jut i - Zj, i whose 2^ is the inductive react anna given by jut . (10) -235- MONS 209215 diff On the other hand, for a capacitanoe (c), tha potential 1 j'-c (11) where Q is tha electric charge on tha plates of the capacitor. Hence, the capacitive reactance Z is given by Zc 1 ]3c (12) If a series circuit containing inductive (L) , capacitive (cl. and resistive (10 elements has a potential difference v v a^6 across it, the relation between current and applied potential difference is given by /*di +L + 1 i dt - Voe,jwt A solution of this aquation, is in tha form (13) i-t + > (14) where 6 is tha phase difference hetnaan tha applied potential difference and tha r*eulting series circuit current. On substitution of tha assured solution into tha differential aquation (13), ana finds {juL + R - j-i ) i - V (15) which la, in tha general (Ohm's Lar) form, Zi - V where -z (16) (16') where 1*1 (16 ) -236- MQNS 209216 and Can-1 and, in order to satisfy Eq. (16) 9- rii (16 ) (17) where T la the period = y which, on integration, yields 09) where 4 is the phase angle given by Bq. 06*'') The laportsnce of the phase angle is bast ilesi i lleil by noting that electrical power is gmrated in such a mmar that the voltage and cur rent are in phase, i.e. (oos a) .... ^ 5 0. Power generated - power acnsunsd Power loeeee in trenenieeim VoIo - VoIo aoe 9 VoIo (1 - ace 9) power loee due to unfavorable phaee angle (20) Since the voltage is fixed and aoe 9 < 1, the tranniseion line currant nuat be inriaaaert in order to supply the Iced vtai there is a legging phase mgis. However, the resistive losses in the trsismission lines ere to the square of the cumnt tnramitted. Therefore, -237- MONS 209217 efficient trananission of electrical energy requires that the net ahase araie. or pc*mr factor, of the load be as close to unity as possible. This power factor correction is aciiievad by the introduction of a capacitor in series with the inductive load at the load end of the line. The finction of a capacitor in such a circuit can perhaoe be better understood by examining the interchange of electrical energy ancng the varicws aorponants of the circuit. In an inductive device, such as a motor or a fluorescent light, whidi is subjected to an alternating current, a consider able amount of energy is stored in the form of a magnetic field arei then returned to the circuit in the form of current vfaen the voltage decreases. In a purely inductive circuit, this current is transmitted bade to the generator and is lost in the form of heat in the trsraniseicn lines. The energy required to form the magnetic field diring the next cycle icust then be supplied by the generator. If a capacitor is placed in the circuit near the inductive load, the energy fxon the collapee of the magnetic field is stored in the capacitor in the form of an electric field than the voltage decreases, and than is transferred back fran the rapedtor to the inductive device to reform the magnetic field during the next cycle. Since the energy to form the magnetic field is transferred between the capacitor and the inductive device, it does not in the >rilfM,ri*4'w lines. This degreases both the heat losses 1.1 the transmission lima and the anount of mergy required from the generator. The capacitor used for power factor correction functions as a toiporary storage device for electrical energy. It is important that the siargy losses be minimised, implying a low Loss-tangent for the c^acitor and a mipinmi *1 tt hannei the --and the indictive device. The other physical and electrical properties of the capacitor are a function of the particular application. There are three general types of power factor aorrectifn capacitors > high voltage power, low voltes paer, and lighting ballast 238- MONS 209218 2.6,1.1 High TA3ltage Poor Factor ^p^itara Poer factor correction can be fumisted by the electric utility by installing capacitors at substation locations. These capacitors are designed to operate at high voltages of 4800 to 13800 volts, and are manufactured in a sire range fran IS kvar to 200 kvar, Eadi capacitor contains about 2 to 2*j gallons of PC3s, moat of whidi is trapped in the porosity of the paper dielectric. These capacitors are generally installed in banks in a substation or moulted in groups on utility poles. The failure rate of high voltage power factor capacitors is approximately .3% per year. These capacitors are usually protected by fuses so that the failure of one capacitor in a bank will not cause failure of other c^acitors. Picturing of these capacitors on failure is relatively unusual, and even when the case does rupture, loss of PC3 is generally less than Italian as meet of the liquid is absorbed by the paper in the capacitor. The high voltage power factor capacitors are usually installed outdoors in nan-hazardous locations. Fire resistance is therefore of minor importance. The dielectric must hava a high dielectric amstant and a high resistance to oorona formation in order to operate successfully at high voltages. 2.6.1.2 Iam Voltage Power Factor Capacitcrsi Electrical utilities structure their rates so that there is an aaonanic advantage to the industrial user to supply the power factor correction for major inductive loads such as motors, induction furnaces, and welding madiines. The capacitors for thest applications are designed to operate at 250 to 575 volts. The PCS/^aper aembinatien used as the dielectric in spiral wound capacitors eperatas most efficiently at a voltage of 400 volts per au. Tednolnglcal limits ai paper manufacturing limit this dielectric to a i h 1 liman of about m mil, so the full efficiency of these capacitors la not arfvieved at voltages below 400 volts. Haaever, -239- MONS 209219 capacitors of this typo are used far power factor correction far voltage applications down to 220 volts with the motors in heavy duty whole-house air conditioners. Low voltage capacitors are usually built into the equipment or located close to the inductive madiinery in manufacturing plants. Irrportant requirements of the dielectric and low flaimability, low toxicity of the liquid and its degradation products, are chemical stability to achieve long service life of the capacitors. Dry film capacitors could find consider able use in 220 volt applications where space is not a severe limiting factor, as in air conditioners. 2.6.1,3 Lighting Ballast Capacitors Normal fluorescent light fixtures an designed to operate on 110 volt power circuits. The fluorescent bulbs, however, require about 300 volts to operate. This high wltage is sillied by a transformer which is built into the fixture. A snail percentage of fluorescent lights are built with a coil-and-oore transformer and no poar factor correction. These units are sold for household use on the basis of low initial price. The power factor of these lights is about 0.7. The fluorescent lights which are mamfactured far comerdal and industrial applications all have the high wltaga supplied by a ballast. This ballast aonsists of an auto trsnafonner aonnected in series with a 4uf capacitor. The capacitor is of fioil-PCB-psper construction and is sealed into an aluninw can. The transformer and capacitor are padcaged in a steel can which is filled with a mixture of asphalt and sand as a potting impound. This finished ballast is about 1" x 2*j* x 12", and has a life -expectancy of 10 to 15 years in normal service. The lighting fixtures using this arrangeewt have a power factor of about 0.9. The capacitor in a fluoresflMt li^tt ballast is usually installed very close to the tailbs, and deputing on the design of the fixtures, the ballast operates at taeperatures of IS to 90C. -240- MONS 209220 High efficiency merairy arc and sodiun arc lights are widely used for highway lighting and other high-intensity applications. The bellast units whidi supply the high voltage for these lights are similar to these used in fluorescent lighting, except they supply rare power at a higher voltage. It should be remembered that the stount of energy that can be stored in a capacitor is proportional to the square of the voltage, so that a 110 volt capacitor would require 8 times the plate area of a capacitor operating at 300 volts. The major requirements for ballast capacitors are: snail sire, implying a high dielectric constant; ability to operate at 300 volts, whicdi implies a aarplete exclusion of air so as to avoid oorcna dis4iarge problems; chatiical 1 < +y when exposed to 90C for long periods of time; and non-flannability because of the use of the ballasts in houses and other flatmeble, hazardous Locations. Mrovtnc reports that they are developing a dry type metallized polypropylene capacitor whidi could be used in fluorescent ballast ^plications and that this design would be good for industrial applications up to 370 volts. Application of these units uo to 440 volts is ccna.v^red a possibility. This substitute, whan available, would be suitable for 50 percent of the current capacitor applications. It would increase the cost of low voltage power factor capacitor* by 20 percent as copared to a PCS unit but would double the aost of ballasts (separata units would be required for purposea of start and storage). The film and metallizing equipment used in these capacitors are manufactured in Europe and currently nuat be imported. The use of this technology will require major redesign of the parent products, particularly *ban used in fluorescent light ball acts and roan size air conditioners, nereiee of spaas and tstpsraturs Limitaticne, the dry film capacitors could not generally be used to replace failed capacitors in existing electrical equipment. -241- MONS 209221 It should be noted that the general use of dry film capacitors in European fluccesaant lights is not amparable with U.S. practice. The European line voltage is normally 250 volts, whidi is below the corona discharge voltage into air, but whito allows a decrease in size of the c^aritor by a factor of 6 oonpored to 110 volt applications. In addition, the European fixtures are usually single bulb, rather than the dual bulb fixtures used in the U.S., and the auto transformer is mudi less reactive as it weds only to increase the voltage fron 250 to 300 volts. As a result, mich less capacitance is required for power factor correction in European fixtures, and the c^acitor, can operate efficiently at normal line voltages. Finally, the capacitors in European fluoresoant fixtures are installed as discrete components to allow for their replawnent; this is necessary henenee of the higher failure rate of dry film capacitors aatpared to U.S. capacitors. In spite of the relative severity of the technical requirenents for U.S. ballast capacitors, industry sources indicate that there is probably a 50 percent chance that a usable dry film capacitor will be available in the U.S. by the id of 1976. 2.6.2 Motor Starting Circuits Electric motors for residential use are designed to operate an single phase current. A number of different methods axe used to develop the rotating magnetic field that is required to start the rotor, and these methods differ in the mount of torque that is developed at low speeds. Certain applications, particularly compressors in air conditioning units, require a very high starting torque. This is addeved in a single phase rotor through the use of a capacitive starting circuit. shewn belowi In a capacitor run rotor, stator windings axe connected as 242- MONS 209222 The starting field is connected to the power supply through * capacitor; the result is a starting winding currant which. the applied voltage. Hence, at standstill, the rotor sees fields nearly 90 apart in tine as **11 as 90 apart in space. The resulting, effectively rotating, field results in high starting torque and a high power factor (important during the period when the hade etnf due to rotor notion is low so that the starting current is significantly higher than the naming current). Because of the inductive effect of the starting winding, the capacitor is subjected to a voltage substantially higher than the line voltage. Meet 110 volt appliance motors are designed so that the capao-tor operates at an effective voltage of 370 volts, thus making optimum use of the characteristics of foil-PCB-paper capacitors. The capacitor not only performs the neoessary function of generating the starting field, but also provides significant power factor correction. In larger motors -- primarily 220 volt air finr^ motors - the PCS motor rtn is sized for cptimra power factor correction and aiWHmai capacitance is provided taxing the first few seoends of start-up by an electrolytic raped tor 1 parallel with the PCB capacitor. The electrolytic capacitors provide very high capacitance in a snail package, but they have a fHwipat-inn factor of about 7 percent whidi causes rapid tenperatuxe inrrmaas The electrolytic capacitor is disconnected by a centrifugal switch wtmn the rotor reaches running speed. This prevents failure frem overheating and results in a configuration with good operating character istics and satisfactory power factor. The motor run capacitor is normally built into the motor. This results in a rsquirsnsnt for snail size, long life, and fire safety for the capacitor, it is possible that dry film capacitors oould be used in this application. However, the hi^i voltages suggest that a liquid dielectric capacitor would be more suitable if a satisfactory substitute were developed far F3e. -243- HONS 209223 In sane a^Iicatiana, DC motors can be used m pi^e of single phase PC motors. Such DC motors are used in sate European electrical appliances where the electronic speed oontrol that can be achieved with the DC motor results in a savings ocrpared to the more complex speed control mechanisms required with an PC motor. In these European appliances, the DC power is sillied by a siliaon rectifier. However, the output from the rectifier oust be filtered to eliminate the PC oaiponents, and this filter drauit normally uses a liquid filled capadtar. In addition, the X speed oontrol circuit requires an additional capacitor. while these circuits could be redesigned to eliminate the use of capacitors, the resulting DC motor would not appear to be econaiucally competitive with the capacitor run motor except in a limited number of special applications. 2.6.3 Electronic Filter Capacitors Rectifier drcuits are used to stpply DC current to electronic oaiponents. For instance, the circuitry of most U.S. television sets operates at 300 volts DC. The output of the rectifier must be filtered to achieve a stable DC current. Most television sets use a PCS capacitor operating at 300 volts to pass the PC cmponsnts of the current. This achieves the required 300 volt DC power required by the other conpcnsnts. negul rensnti for this an long life at 300 volts, snail size, and good fire resistance. Either a dry film capacitor or a suitable t igiiid dielectric capacitor oould be substituted for the PCS capacitor in this application, alttwugh the larger size of the dry film capacitor may Limit its use in repairing existing television sets. 2.7 instltu^inial Barriers to Substitutes for FCBs in Capacitors The final chelae of an acceptable substitute for PCBs will be made by the apadbor omifacturezs baser! an the performance characteristics and fire Mftty at altasukts dielectric materials. This <hoioa will be affected by parfozawca vsra&iee that are emmon in this industry and by evaluations of safety ae reflected in the codes and regulations vhi<h govern the use of capacitors. The traditional industry practiaes and the formal regulations both inpoee institutional barriers to ths acceptance of a substitute for ?CBs. -244- HONS 209224 Th*M barriers an a major factor in the rapid replaaenent of pCBs, ard should be canfully acnsidered in the fonnulatian of goverrrant regulations ard m the industrial marketing of alternate dielectric materials. 2.7,1 Performanoe Aouptabi Lity Capacitors are sold with stringent performance warantees which cover both the capacitanoe and the ejected life or maximm failure rate of the capacitors- These warantees are based on various capacitor standards which are established by industry groups. The wide usage of a particular type of capacitor will depend cn the existence of relevant standards whit*. allows the user to dvxae equivalent capacitors fran different manufacturers. Currently, no industry standard exists for dry film capacitors for PC applications. However, sudi a standard is being developed by a acnmittee of the E.I.A. and should be formalized by the end of 1976. This standard will establish mirdrun performanoe criteria for any dry film PC capacitors whidi nay be nsnufacturad. Sales of caparitors to perfbananos specifications irpliss the acceptance of ocnsidsrable liability by the c^ucitor manufacturer. Because of the a^ansa of repairs to lighting fixtures and appliances whidi have been sold to oonsuaexs, the liability due to early failures oould easily wirnewri the coat of the capacitors. A situation of this type occurred during the 1960's when many fluoresant ballast capacitors failed pransturely. This group of failures occurred when the voltage stress cn the PCBs was increased, resulting in a slightly increased rats of degradation by dedilorinatian caused by corona discharges. The increased failure rate was not apparent cn short tenn testa; the replaoarent of the failed ballasts was very expansive to the capacitor manufacturer. This probles was solved by the addition of a chemical scavenger to the PCS- Parana of the oocuamoe of past performance failures and the hhtfi potential cost of future failures, A capacitor industry can be expected to be very omservative in the introdictim of substitutes far PCSs. Substitutes will be only after the accwulaticn of substantial lcng term (3 to 5 years) service testing data. Sinos the greater blodeqradabl lity of the -245- MONS 209225 substitutes irplies that they will exhibit lower ctwiical stability than PC3s, considerable testing at servioe aonditicns will be required to support the general use of any of these materials. This requirerent of extensive service testing would be expected to delay the general acoeptanoe of p substitutes by 3 to 5 years. 2.7.2 Fire Safety The use of capacitors is governed by several industry standards whidi artoody the general servioe e^erienae and risk factors as perceived by industry representatives and fire insurance underwriters. 'These codes and regulations are specific for various applications of capacitors. The major applications must therefore be considered separately. 2.7.2.1 Utility Use of Power Factor Correction - Most of these capacitors are installed in substations or ars moulted on poles. In general, the locations of these capacitors are ncnhazardous, and there is little risk that fire dosage or personal injury will result fron the failure of a utility capacitor. The failure of existing utility capacitors may result in uncontrolled loss of P3s into the enviroraent. The frequency of /--pfHfrnr rupture is reportedly quite low (estimated to be .02%/year) and the amount of PCS lost to the environment probably does not ucead 2 to 3 pounds per rvpserH-jg- rupture. However, because of the large number of capacitors in servioe d the lade of men for containing any leakage, the total environnantal load fron this source may total several thousand pounds per year. rurrifc standards far the disposal of failed c^acitors containing more tturn 2 pcuids of PCS requires that they be buried in sqpervised dry land fills that meat state rsquirenents. d) in addition, the standards require that these capacitors be labeled with a warning as to their eatfirannRtal hazards. `Otis label trust also aontain detailed disposal pro cedures. The major apparent lade in these standard! is in the area of control and disposal of leakage fron failed creators. The necessity for such awtrol may offset the aocnonic penalties associated with the replaoeient of PCT capacitors by units whidi are anvironnsntally less objectionable. -246- HONS 209226 2.7.2.2 Industrial Use of Power Factor Qarrection Capacitor Th* use of pmer factor capacitors in industrial plants is gwarred by state fire regulations and by the National Electrical Code (4) whidi has been formally incorporated into CSKA regulations. The National Electrical Code requires that capacitors that contain .Tore than three gallons of flaimabie liquid be enclosed in a vault or installed in a outdoors fenced enclosure. The definition of flaimable t is not explidt, but the effect of the code is to give large PCS capacitors a significant economic advantage oaiparad to those containing other liquids. Proposals are currently being considered to define a class of transformer and caparifcr liquids whicii are self extinguishing. This may eventually lead to a change in the code so that vaults will not be required fcr large capacitors in industrial applications. This coda change is unlikely to be made prior to i ssuano* of the 1981 code. 2.7.2.3 Limiting and Appliance These small capacitors axe usually built into th* ballast or ^pliancs. Failure of ths capacitor prior to the cbsolescerce of the light or appliance is infrequent, and ths capacitor is scrapped as part of ths entire asamdly, Currently, most of this material ends in irunicipal landfills. with growing popularity of reclaiming metal value* from irunicipal waste, there will be on increasing anoint of PCB whidi appears as contaminants of scrap steel and is v^arizsd ar burned off in the steel furnace. The major drawbadt to the us* of substitute materials is the firs safety of ths appliance. Ocnpleted ballasts or appliances trust meet rauunn safety standards as by tests rorwiictert by Underwriters Laboratories, necmee the anoint of 1 Iguid contained in these capacitors is small, there is probably little increase in fire hazard if a flennabla liquid is used, especially if the capacitor is fused to prevent rupture of the case. However, acceptance of flannsbl* in casedtors will have to arait action by Underwriters Laboratories, and reosnt conversations indicate that they have not yet established either specifications or test procedures for electrical equipment containing flarmabl* liquid caper!tors. ^ -247- MONS 209227 3.0 EUCmoVL TRANSFCFMERS Polychlorinated biphenyls are used as liquid aooiants in electrical trans formers which are located in enclosed or hazardous locations, pfag have an advantage over the other major liquid transformer coolant (mineral oil) in that they are nonf lanmable. Gaseous aooiants are also ncnflsimable, but gas cooled transformers have disadvantages which are considered below. Alternative liquid aooiants are probably available, but to data svana have been found whidr have all the advantages of PCSs. The following analysis includes a suimary of the purposes of transformers in electrical circuits, heat generation in trans forms, currently-used cooling tedmiqueg, materials being investigate! as substitutes for P<3s, and institutional barriers to the use of substitute materials in place of PCSs. 3.1 Heat Generation in Electrical Circuits In direct current electrical circuits, the power, P, delivered at a load consisting of pure resistance (s.g., a light bulb) is the product of the electrical current, i, moving through the load and the voltage, v, acrosa the load, P - CV) (i) (21) But since currant is proportional to voltage for a given resistance, V - (i) (R) (22) wtwxe R, the resistaice, is the constant of proportionality. It follows that power delivered to the loed resistance is the product of voltage, V, and the square of the current P - i^ (23) Since the wires that carry electrical power Cron the sits of gsnsraticn (be it a battery or an electrical generator) to the load resistance ti nt+mr resistance to the flew of electrical current, a portion of the power is lost -hr-,Th heating of the wires oainecting the load to the poser source. Far a given wire diameter, electrical resistance is pH to the length of the wire. In many circuits (s.g., an autonobils electrical systmn), the power lost in the tranmnitting wires is small in -248' HONS 209228 ccnparison to the power delivered at the load (such as the headlights). How ever, in transmitting electrical power over lcrg distances, the raistance of the wires could cause the dissipation of a significant portion of the erergy intended for the load. In alternating current circuits, the power dissipated in a resistance (either in the load or in the wires carrying the power to the loai) is given by P i2R. (The relation, P (VI (i), always applies to power dissipated in DC circuits, but in AC circuits the egression only applies when the voltage and current are in phase with each other, whiA isn't always the case. In meet practical instances involving purely resistive loads it is a fairly accurate mans by whidi to calculate the power dissipated.) The expression, P i2R, is not influenced by the phase relation between voltage and current and thus apD i ee to both alternating and direct current circuits. It is apparent from this expression that the energy dissipated in a transmission wire having resistance R is proport ional to the second power of the current; thus, if the current being delivered to the load were to be doubled, the energy lessee in the trsismission wire would be quadrupled. n iiww-ij>i electrical power is often generated many miles fron where it is to be used. There are hundreds of thousands of miles of power trans mission lines in this aountry, and it is not unusual for the electrical power gamerated in one place to be used hundreds of miles away, whi<di means that a considerable mount of electrical resistance must be overcome in transmitting electrical energy to the user. The method used to minjjnize energy losses in transmission lines is to reduos the current, i, and thus minimize the i^R losses (also tawwn as Joule tsatlng losses) in the transmission wire. In order to deliver maxinun power to the lead, the transmission voltage, V, crust be increased since the power delivered is (as with DC circuits) effectively given by P (V) (i). Thus, if the tmasitted current, i, is reduced by a factor of 2 - which reduces the Joule heating losses of the transmission line by a factor of 4 the voltage of the transmitted power must be increased by a factor of 2. -249- HONS 209229 In practice, the electricity which is used in hemes at 110 volts is trananitted at voltages ranging up to more than 700,000 volts - roughly 6500 times greater than ostmon wall-sodwt voltage. As a result, the Joule heating losses are (6500) 2, or more than 40 million, times less than if the power were transnitted at 110 volts. 1.2 the Nature and Purpose of Transformers The purpose of a transformer in an electrical circuit is to trans form electrical power fran its high-current law-voltage characteristics at the gaiarating farility to the low-current high-voltage characteristics needed for efficient trananissicn; and then, at or near the site of use, transformers perform the opposite fmotion, bringing the power bade into its low-vsltage (typically 11Ov or 220v) high-current form. A transformer consists of t&e windings vhidi are joined by a magnetic yoke. An alternating current applied to cne winding (the primary winding) creates an alternating magnetic field in the yoke. This magnetic field indunss an electric current in the other, or secondary, winding, in a ample transformer,- as shown in the following sketch, the ratio of voltages in the primary and secondary windings is equal to the ratio of turns in the windings, or CONE '(NON) There are two types of transformers used in the electrical pc**r industry! power tmformers (used for "stepping the voltage at the plant) and distribution transformers (used for "stepping down" the voltage at or near the site of prefer use). Power and distribution transformers operate an the ssm principle - they differ only in whether the primary or secondary winding has the greeter lufeer of turns, if the transformer is being used for -250- HONS 209230 sopping tp voltage, then the primary side is the cne having fewer turns: for stepping dam, the primary aide is the one having most turns. Hie lengths of wire in the windings offer resistance to the flow of electricity, the result being the production of heat in the windings. Heat is also produoed by electrical currents induced in the transformer aore by sare medianisn that induces currents in the secondary windings. Since the electrical resistanoa of most conducting materials increases with tarperature, the efficiency of the transformer (i.e,, the ratio of the output power to the input power) is maximized if the transformer is kept at a low operating taperature. Therefore, all transformers used in the electrical industry have provision for cooling, based on either gaseous or liquid coolant. The coolants in cannon use today are: mineral oil | | liquid cooled transformers air | | .dry type transformers 3.3 Desired Properties for Transformer Heat Transfer Fluids The purpose of the best transfer fluid in a transformer is to absorb the heat produced in tits windings and ooze, to transfer the heat to cooling fins, and to pmids electrical insulation within the transformer. The ideal fluid should have the following properties: Heat transfer: Be a liquid with a low viscosity, high heat capacity, and hi^i boiling point. (The use of lew boiling point or gaeee would require that the transformer be enclosed in a pressure vessel.) Chemical sfAinty. Not degraded by prolonged exposure to high tenperatures. Non-flamnabla in the event of an electric arc within the transformer and subsequent case rupture. Mcnooiiceive, with non-corrosive products resulting fraa ixpfflpwe to an electrical arc. lew solvency toward other materials used to construct ths transformer. -251- HONS 209231 Electrical properties: High dielectric stmgth. Law loss-tangent (minimized dielectric heating of the fluid}. High resistance to aorona formation. Toxicity; Non-toxic and biodegradable. By-products fran exposure to arc should also be non-toxic. Cost: Low cast- Availability: Readily available with reliable properties. 3.4 CIse of PCTs in Electrical Transformers PC33 cooled transformers amount for about 5 percent of all trans formers in servioe. The PCS coolant in these transformers is a mixture of 60 to 70 percent ?CBs and 40 to 30 percent tridilordaenzsna. The PCSs currently used in these mixtures are sold by Monsanto under the trade news of Aroclor 1242 and Aroclac 1254. The mixtures of PCBe and tridhlarcbenzne are caraenly taown by the generic term Askarsl. Askarsl is defined by the National Electrical Code as "a generic term far a group of ncn-flamable synthetic chlorinated hydro carbons used as electrical insulating madia. Askars!s of various oonpositicnal types are used. Under arcing conditions the gases produced, while consisting predominantly of non-oorbustible hydrogen chloride, can include varying anouits of oembustible gasea depending on the askarsl type". The meet cormcnly used askarsl ccRpoaitions are Inertaen (Westlnghouss trade name far 60 percent PCB mixture) and Pyranol (General Electric trade name for 70 percent mixture). Tim exact ax^oeiticn of both Pyranol and Inertaen have bean changed fran time to time, but they have almost always bean mixtures of PCBs and trichlorbbenzene. Prior to tits mid-19501 s, tits insulating liquid used in many trans formers (Gttttral Electric fanoulaticn) was a 50-50 mixture of Aroclor 1260 (60 chlorine) anl trichlarcbenzene. in the late fifties the benzene ^ was ^x> * mixture of tri- and tetraehlardbenzanea. in S^itmtmr, 1971, at ttosanto's suggestion, the Aroclor oaipcnent was changed to Aroclor 1254 (54 penmnt chlorin). The currant Vtestinghouse fcrmulaticn (Inertaen,) utilizes Aroclor 1242. -252- HONS 209232 . Ths volune of askarel used in various transfomers ranges frcn 40 to 1500 gallons (440 to 16,500 lbs), with an average of about 230 gallons (2500 Lbs). Cne ttwafoaer manufacturer, General Electric, estimates the total nurber or askarel filled transformers put in service in the U.S. since 1932 to be 135,000; virtually all are still in serviae. Typical lifetime of a transformer is often greater than 30 years, and units that do fail are usually rdouilt and returned to serviae. The current production rate for askarel filled units is about 5,000 per year, requiring same 10-15 millien pounds of PCBs. Liquid coolants in transformers have better heat transfer and heat capacity characteristics than gaseous coolants. Askarel has the further advantage of being ncn-flanrable. The other advantages of askarels are their high dielectric strength, their outstanding chemical stability, and their relatively lew viscosity. Disadvantages , in addition to the envirornental threat, are the highly corrosive HC1 they produce whan arcing takes slaae and their cost, which is about eight times as much as mineral oil an a volune basis. Mast aslcaxel-fillad distribution transformer* are located inside public, cannerdal, or industrial buildings, or on ths roof tops of such buildings. No special enclosures or vaults are required except as are neces sary to prevent accidental electrical or mechanical contact of persons with the equipment. However, the Nsticnsl Electrical Code does specify vaults for the indoor installation of PCB-fllled transformers rated mors than 35,000 volts. Askaxel-fillad transformers are limited by ths dielectric strength of the ito ratings below 69,000 volts. Mast power transformers are situttsd in moots locations where fire or explosions are not a threat to property. Mineral oils are cormonly used in power transformers in these safe locations. However, sans utilities use askarel-filled power transfonrers at generating stations. Step transformers used to supply ths high voltage electricity to electrostatic precipitators are usually mounted on or very near the stack. This ths problems associated with the in-plant distribution of high voltage power. These transformers are usually askaral filled units to minimize fire hazard in the usually crowded area of the stack. 253- HONS 209233 ' Railroad looonotives whidi operate cn high volt^e PC power from overhead catenaries are used in the U.S. Northeast Corridor. Askarel-filled transformers are counted in the engines or under the self-powered passeiger cars, and reduce the catenary voltage to that required by the traction rotors. These electric locomotives are mostly limited to passenger service cn the Northeast AMTRAK routes and on the cownuter lines around Philadelphia arri New York. Large askarel-filled transformers are used in the old GG-I locenotives, under the Metro Liner cars, in various cornuter cars, and in the new E-60 looonotives. (TVaenty-six E-60 looonotives are currently being delivered to AKTRAK by General Electric; eadi locomotive contains 710 gallons of askarel) . Penn-Central Railroad operating rules require the use of askarels in all locomotives using the towels and stations in Nw York. This rule has teen in force as a fire safety measure ever since an early GG-I locomotive con taining a mineral oil-filled transformer was involved in a fire inside a tunnel early in the 1940'a. 3.5 Present Alternates to the Use of PCBe in Transformers Askarel-filled transformers axe oily used where considerations of fire safety, reliability, availability, and cost make such a unit preferable to an oil-filled transformer or to a dry type transformer. These alternative types of transformsxs axe currently used in 95 percent of all applications, and could, with piopei. engineering design, be used to replace most of the remaining askaral-filled units. Consideration would have to be given to the specific limitations of these designs that presently make aakarel-filled transformers preferable far pertain applications. 3.5.1 Mineral oil^illed Transformers If safety were not a consideration, there is no reascn why oil-filled transformers could not be used in all applications. Askarel-filled transfcaasrs coet about 1.3 times as nudi as oil filled units of the sane capacity, and thus most users prefer the oil-type where passible. The oilfilled transformers are tire sans size as the askarel units, and axe considerably lighter in weight. In additiro, mineral oil has somewhat better heat transfer characteristics than does askarel, and an electrical arc in mineral oil results In breakdown products that are ncn-corrcsive. -254- HONS 209234 Ths major disadvantage to mineral oil is its flaroabiliey. Transformer mineral oil has a flash point of 145C, and if an arc occurs within the transformer, the breakdown products will be hydrogen and methane which are also flatrable. Detailed records of such failures are maintaimd by the . (13} electrical industry. Tire Underwriters da not approve of the use of oils and other flarmable liquids for indoor applications; where oil-filled trans formers are not specifically prohibited as on-site replacements for askarel- filled units, the National Electrical Oode inposes certain restrictions upon their mode of installation. Oil-filled transformers are used in almost all power trans former applications aid for most substation distribution applications where the high voltage fran the transnission lines is reduced to 12.8 lev for local distribution. Most rural pole moulted transformers which reduce the voltage to 220 volts are also oil-filled. Hie issue of flannability only becomes important where the distribution transformer mist be buried, as in many urban . applications, or located close to, within or cn the roof of the building whidi it serves. Askarel-filled transformers are used far most of these hazardous areas. Oil-filled transformers can be used in these applications cnly if they are suitably isolated from floatable structures or if these structures are suitably safeguarded against fires. when transformers are located outside of the building they service, however, the low-voltage power oust be brought into the building vis cables or Insulated buses, incurring energy loeses due to Joule heating in the additional low voltage transmission lines. 3.5.2 Own Air Pooled Transformers Trsnsfomsrs can be built without the use of a \ iquid cooling rrsdiwu One type of dry trans fcmer which is quits successful under limited oasUticns is the open air cooled transformer. In this design, the required is provided by air whiA passes through the transformer due either to -255- HONS 209235 thermal ocnvection or forced fan circulaticn. In those sizes where air cooled transformers are available, they are about equal in price to askarel-filled transformers of the same kva rating. However, the following limitations govern the successful use of open air acoled transformers, and prevent them from being considered for many applications using askarel-filled transformers. Heat capacity; Wie power drawn fron a transformer usually varies over a fairly wide range. The rating of a transformer is basically governed by the power whidi it can handle continuously without over heating. If a liquid filled transformer is operated at overload conditions for a short period of time, the liquid will vt as a heat sink, absorbing the excess heat produced in the transformer without a rapid increase in tenparature. The result of this thermal inertia is that liquid-filled transformers can operate at outputs of up to 200 peront of rated capacity for a period of one to tsto hours with out being damaged. An air cooled dry type transformer does not have this heat sink available, and is limited to operating at a maxinun service rating near its continuous rating, where the current drawn on the trans former does not vary greatly during the day, this limitation is no problem. However, in meet cases the variation in load would require that a dry transformer be sized 20 peromit to 30 peraent greater in capacity than a liquid-filled transformer for the sane application. Dielectric strsrerths The 1 {quid coolant in a liquid-filled trans former also provides a significant level of electrial insulation between the various currant carrying coipcnants within the trans former. Air has a oudi lewer dielectric strength, and open air transformers are limited to a maodnun voltage of 25 to 40 kv. The problma of electrical insulation is even more severe if the open air cooled transformer only operates intermittently. When the trans- fomer is operating, the heat generated within the windings keeps their insulation dry, and maintains a high dielectric strength of __ this insulating material. However, when the transformer is not operating, the ooils oool to anbient tenperatures and the -256- HQNS 209236 insulati.cn can absorb moisture fton the air which reduces its dielectric strength. Therefore, an open air aled transformer rust be carefully dried before being put into service after each tine it has been allowed to cool. One final problem with dry air cooled transformers is due to the tendency of dust to be attracted fran the air to the coils by electro static attraction. This dust can build up in the coils which blocks the flow of air and causes overheatinc, or the dust can form conductive paths which short circuit the transformer. Dry open air cooled transformers are generally limited to dry, clean locations where the load requirements are fairly even and acnstant, and where the irexirun voltage does not exceed 30 kv. This type of transformer is being successfully used in large office buildings, particularly tall buildings where the trans formers are located every few floors. Even in this application, there are situations which are beyond the capabilities of the open air cooled transformer? far instance, in the Sears Building in Chicago, which is over 1400 feet tall, the electric power is brought into the building and up to the distribution transformers at 123 kv, which is beyond the voltage limitations of open air nryVlsri transformers. 3,5.3 dosed Gas "llled Transformers Transformers can be built which use a dry inert gas (usually at an elevated pressure) as a heat transfer median. These transformers avoid the maintenance problems caused by moisture and dust in cpen air cooled trans formers. However, they are similarly limited in overload capacity because of their reduced thermal inertia compared to liquid filled transformers. Closed gas filled transformers must be installed in pressure tight containers due to the changes in gas pressure caused by changes in torperatura. However, the maxima voltage ratings of these gas filled trans formers on be equal to that of liquid-filled units. -257- HONS 209237 A muter of different gases have been successfully 'isaj. as hetransfer media in closed gas filled transformers. Tt rcat cairon gas used in the (J.S. in this application is the fluorocarbon hexafluoroethane (CjFg). Nitrogen and sulfur hexafluoride have also been used successfully in certain applications. Helium has not been found to be a satisfactory gas for this application because its low dielectric strength results in corona discharges within the transformer. Hydrogen gas is unsatisfactory as any leak in the transformer would result in a severe fire hazard. Because of the necessity for the pressure vessel container, gas cooled transformers are 30 to 40 percent heavier than askarel-filled trans formers, and cost two-thirds more th*i askarel transformers (ani twice as midi as oil-filled transformers). In addition, the gas filled transfosners must often be specified in a larger size than the liquid-filled transformers to allow for the expected heavy load peaks of power ocnsmption, 3.6 Current Alternatives to the Use of PCB Pooled Transformers The National Electrical code has dstailed specifications for trans formers which assure that transformer installations meet both fire and shock safety requimerits. These safety requirenants are atoieved by the use of either ncn-flamable transformers (askarel or dry type) or vaults, or both. Tiw final choice of the type of transformer to be used in each application will be a function of the code requirenants and thair eomcmic consequences. 3.6.1 Vault usage Beouirenents for Transformers The National Electxial Code 1975^ considers three types of transformers in connection with indoor vaults: dry type, askarel insulated, and oil insulated. i insulated transformers installed indoors and rated at more than 35,000 volts oust be ancloeed in vaults, acaarding to Section 450 23. This sene specified that askarel transformers installed indoors and sated onr 25 kva aust .have pressure-relief vents whito rust either be mated to the outside of the building, or same other provision must be made for "absorbing any gases generated by arcing inaide the case". -258- MONS 209238 ' n* 35,000-volt criterion a3n applies to dry type trarsformers; they mist be contained in vaults when in indoer installations. The Code also specifies that dry-type transformers rated at more than 112h leva must "be installed in a transformer roan of fire-resistant construction". Thus, if space is not a consideration, dry-type transformers - which, generally occupy a larger volume than equivalent-capacity asJtarel insulated units - can directly replace asJcarel-insulated transformers. In f'ape* where space is not available for the larger-voluned dry-type transformers to replace the asJcarel-insulated units, or there the drytype units might emit too nudi noise for a given location within a building, oil-insulated transformers would be required as replacements for askarel units. Section 450-24 speciflee that oil-insulated units nust be installed in vaults, but the following exceptions are made: 1. if the total capacity of the transfeemer does not exceed 112)] leva, vault walls need only be 4 inches thidc instead of 6 inches as specified in Section 450-42. 2. Vtore voltage does not exceed $00, a vault shall not be required if suitable arrangements are made to prevent a transformer oil fire from igniting other metarials. 3.6.2 Vault Oonstructicn fleguirecents fu Transformers Section 450-42 of the 1975 National Electrical Coda specifies the catstzuctiai requirseents of vwlt wells, roof, and floor. "The walls and roofs of wilts shall be cnetructad of materials whidi have adequate structural strength far the partitions with a minimis fire resistance of 3 hours." (Sixinch thidc reinforced oncsete is stated in the Code as being typical 3-hour ccnetxQCtian.) "The floors of wilts in contact with the earth shall be of concrete neb lees than 4 inches thidc, but when the wilt is constructed with a space or other stories below it, the floor shall have adequate structural strength t<x the Iced inpesed thereon and a minimum fire resistance of 3-houre." 259M0NS 209239 . Vault doors are specified in Section 450-43. "Eadi doorway leading into a vault fran the building interior shall be provictad with a tightfitting door having a minimum fire rating of 3-hours" (as defined by the NFPA) . "A door sill or cud: of sufficient height to confine within the vault the oil from the largest transformer shall be provicted, and in r case shall the height be less than 4 inches." Locks are required for vault doors, and "doors shall be kept lodced, access being allowed only to qualified persons". The Lodes shall be arranged so that vault doors can be easily opened fran inside the vault. the following: With regard to ventilation openings. Section 450-45 specifies Location: "Ventilation openings shall be located as far away as possible fran doors, windows, fire escapes, and aombustibla materials." Arrangement: "A vault ventilated by natural circulation of air shall be permitted to have roughly half of the total area of openings required fear ventilation in one car more openings near the floor and the reminder in one or more openings in the roof or in the sidewalls near the roof; car all of the area required for ventilation shall be permitted in one or more openings in or near the roof." Size: "For a vault ventilated by natural circulation of air to an outdoor area, the amfcined net area of all ventilating openings after deleting the area occupied by sanane, gratings, cr louvers shall not be less than 3 square inebee per leva of transformer capacity in service, and in no case shall the net area be less than one square foot for any capacity under 50 kva." Covering: "Ventilation openings shall be aovered with durable gratings, sexasns, or louvers, according to the treafinmt required in order to avoid unsafe conditions." "All ventilation openings to the indoors shall be provided with closing danpers of not less than No. 10 (G steel that in rarpmss to a vault fire." Ducts: "Ventilating ducts shall be obstructed of fireresistant material." -260- HONS 209240 Section 450-46 specifies the drainage requirements for vaults: "Where practicable, vaults containing more than 100-kva transfonw capacity shall, be provided with a drain or other means that will carry off any aacumilatiai of oil or water in the vault unless local conditions make this impracticable. The floor shall be pitched to the drain where provided." Section 450-47 requires that pipes or duct systems "foreign to the electrical installation shall not enter or pass through a trans former vault". Piping or other facilities provided for fire protection or for water aooled transformers shall not be considered foreign to the electrical installation. 3.6.3 Transformer Vault Construction Costs In an effort to determine the cost factors in the construction of transformer vaults, various construction ccnp-nies in the Washington, D. C. area were contacted. It was discovered that the incidence of vault construction in existing buildings is virtually zero; apparently all vaults existing in Riding* built in the last twenty-five years were constructed as integral parts of the the same aa any other room or enclosure in the building. Thus the cost of constructing a vault cannot be easily broken out fran the oast of the entire building structure, especially since the prime contractors in the construction industry oftsn subcontract the various facets of the construction work (e.g., concrete fasns, concrete pouring, plaiting, ventilation duct work) and the portion of the work required by the vault is included in the oost of construction of the entire building. The construction ccnpanies were reluctant to make cost estimates far installing vaults in existing buildings unless detailed drawings were submitted as a basis for estimation, aid of the half dozen largest contractors contacted, none had any readily available data fran previous such installations, and all claimed such installations were extremely rare. The National Electrical Code allows the installation of oilinsulated tzansfoDoers in outdoor locations adjacent to the site of power use. In the Washington area, aa in many urban areas, "manholes" are used to house transformers in outdoor locations. -261- HONS 209241 Useful oost infonraticn cn manhole installations was obtained through the Potomac Electric Pcwsr Canpany of Washington, D, C. Manholes are precast concrete structures whidi are conronly installed in public space directly adjacent to the building receiving electric service. (The steel gratings seen in the sidewalks of downtown areas frequently cover manholes containing transformers.) Manholes are supplied usually by precast concrete product manufacturers. Cbsta quoted by one manufacturer range iron $875 for a 6* x 6* x 6' (inside dimensions) model to $1700 for an 8' x 10* x 7* model. These costs include delivery to the job site and installation into the excavation. According to Pepco, manholes are usually installed flush against the property line of the building being served. In sane cities, the local gowmnent pays fee the manhole and its installation, but in Paco's customer service area* the customer pays the aoet. (Pepco custaners also pay the aoet far vault construction then transformers must be installed cn private property.) Pepco used to install more than one tmsfcaar par manhole, but experience with fires has lad then to put only one vxiit in each hole. According to Pepco, there are no specific codas relating to mantola obstruction, but it is likely that local oodae influnoa specific installations. Papou provides the final 18 or so indies of each manhole installation in order to bld the entire inetallatiai into the surface grade; in such cases, arri whan Pepco has occasion to cast its own manholes, the local building code must be fOlloMd. -ft* average cost cf installing a 5V x 17' manhole is $10,000; no cost-range data were available film Pepco. Iha Tahoe re^iirecent is typically 800 to 700 man-hours, and total time is about one *ak. Cost factors includes 1. Marking day restrictions - fee n?le, rush hours in sane parts of the city restrict *ric hours to 9:30 to 3:30, but the laborers must be paid for a full days work. -262- MONS 209242 2. Rain time - the laborers do not writ in the rain, but they nust be paid. 3, ftocky soil - hand digging (i.e., with pneunatic drills and homers) be required in lieu of power shovels. In such cases labor costs - whicdi account for 70 to 75 percent of installed cost - can more than dotbla. The only other aoet for manhole installation is the "public space permit fee", a one-time fee to the lorel government whicdi is about $20 in the Washington, . C. area regardless of sire of the rtenhole. Because they are lighter and easier to handle, dry-type trans formers are used very often by Pepco, especially in roof-top explications where noise is not a consideration and ventilation is not a prcblen. This lightness and ease of handling, in conjunction with tha lade of vault requirements for dry-type transformers of less than 35,000 wits, might make roof-mounted drytype transfozmere tha most ooet effective replaarant fer askar*1-insulated units in areas where the sir is relatively free of corrosive gases and dusts which could affect the transformer. 3.7 Substitutes for PCTa in Ttansfonnars Because of the evidence that PCS* are damaging the anvironnent, con siderable work is being conducted to find a satisfactory substitute for PCBs in askaral-fillad transformers. These efforts by various mamfactuxers are attracting considerable interest in the business and technical press.15J The goals of these efforts is tl developnant of a heat transfer liquid whidi will hsve satisfactory heat transfer properties, be anviroimentally acceptable, and be nen-ftamable. These requiranants are basically contradictory; the drenical stability required for aonpleta non-flamability ing>lies that the i igiM say be nen 'biodegradable and may acctsculata in the environment. There fore, h of the Hyide that here bean developed sacrifices a certain degree -263- HOHS 2092^3 of firs resistance to adiieve envircnnantal acceptability, The following liquids hsvs been preposed as substitutes for PCBs in transformers installed in hazardous locations. CAA' . ` *. 3.7.1 Fluorocarbons Certain fluorocarbon ocnyuunds have properties similar to the POs, and seme study is being carried out in this area.However, fluorocarixzis are highly volatile in oatpariscn to PCBs, and they are about six times as expensive at this time - though, of course, higher production volumes would lower their cost. 3.7.2 Silicones Low viscosity silicons fluids (on the order of 50 centistcites) are also possible replaovents for P<3e. Silirones are currently produced by four caipanies: General Electric, Dow Coming, Union Carbide and Stauffer. The silioone fluid ieojimended by one producer is polyiiirethyl silCKane, which has this moleaular structure! H3C -- SSii------Ot-- Si -- 0 -- I s 3 Trsnefer; Silicone fluids have the special advantage of a relatively tiysraUae-Independent visoosity. The silicone fluids have scmewtaat poorer heat transfer characteristic than askaxel, but can be substituted directly for aekarel in adating transformers, resulting in only a snail ismaaes in the transfaoner rating. Electrical Properties! (18) Dielectric Gsnstant Dielectric Strength BMistlvity rrlssiperira rector 2.72 400 volt/nil 7.1 x 1014 ohtt-ca 1.8 x 10*5 at 100 hz, 23C -264- HONS 209244 _ Flmability: Polydimethyl siloxan* has a higher flash point thfl^OOMBtlctud, ncn-fCB transforner coolants: 280C mtsuj H6C for mineral ail (SCBs have no true flash point). The hsat of ombustion of 50-oentistoke polydimethyl silcscam is Iomt than that of minsral oil - 7.67 kcal/^n versus 11.0 kcal/gm - and since ths siloaonea bum mare slowly, they are considered poor fuel. (18) Ctt the ttidsiwriters Laboratories fine-hasard classification (in whidi water is rated as 0 and ether as 100) polydimethyl siloxaiw is classified aa 4 to 5, whidi is slightly higher than the 2 to 3 rating given to ECBsf but is considerably less than ths mineral oil rating of 10 to 20. Ecological Persistence: These compounds do not biodegrade, ae meaeured by sewage sludge breakdown to COj. However, there is evidence that they partly depolymerlae to low molecular Might ccnpomds upcn cmtact with soil and water. Since ultra-violet light 3scuyeses methyl silicones, sunlight exposure mey be the medunin for enviramental degradation. Binemmiletion: No tendncy for or bio- aanoantratim has occurred in experiments. In ths mannals ths ccrtycmd is not through the gastrointestinal tract or the akin. Tcsd.city: Da PC3 substitute developed by Dear Coming for transfoomrs is called 02-1090. This is a mixture of polylinethyl siloxanes of various duin l*igths diidi have a visaoeity of 50 C5. The literature cn environmental and health characteristice of silicones(20> refers to at least six fluids, moat of diidi are probably similar to the 02-1090 but sane of wtiidi could bo other mixtures with aerbain additives. By necessity, the usefulness of p>i~>)idled tnrtonlngical data depends ai the validity of the assumption that all of these anyoisids have identical pexsistanoe, bioaccuniLatian, ad todcity ptepartiee. -265- MONS 209245 . A revlar of toxicological studies of silieenM reports! the miaHaq results:(20) 5v. / Dietary Toxicityi LDS0 Cists) >28 gra/kg Extended Feeding 'Teste: Guinea pigs - 47 gnyTcg/day for extended period no toxic effect. Mallard ducklings and bobuhite quail - 5000 ppm for 5 days - no affect. Rats - 20 <yn/kg/day for 28 days - no effect. Rats - 190 mg/kg/day for 90 days - no effect level. Beagle dogs - 300 mg/kg/day for 120 days - no effect. Mice - 3% in diet for 80 weeks - no effset. Man - TOA allows siliaonss as food addlti^ws at to 10 ppn. The major deficiency in our lauvlsdge of the siliacnee to be in their fate in the mvircmant and the toxicity of their breakdam products. Post: The silicone transformer fluids currently cast up to twios as nuch as PO* on a vol-une basis. Avi^ WviHty: Dow Coming is curxmtly completing evaluation of polydimethyl sUonme ae a high voltage insulating fluid. They report, thou^t, that a rmat teas 100 pexosnt rsplscront of FOe in trsnsfonnsrs by tills fluid is not possible. If a transformer market were to develop for -266- MONS 209246 polyjtfjsrtbyl aHacm* tha praamt dnnsstic opacity could only ba aiaquata to ply naw transfanoars. Tha tin lag far a 100 paraant raplscanant of PCS* in trarafonnais by polydimathyl sllcxana would ba on tha ordar of 5 to 10 yaars. 3.7.3 High Flaah Point Minaral Oila Tha flaah point of minaral oil is a fvncticn of its nolacular wight. Cruda patroletm can ba rafinad to hava *y raquirad nr>i^tir waight war a wida ranga. This makas it poaaibla to tpadfy any particular flash point that is dasirad for tha minaral oil transfasnsr liquid. This approach has basn takan by RIE Corporation in tha davalopnsnt of thair propriatary tranafoanar liquid whidi has tha trada njraa RIEff. tOSt9 is a highly rafinad paraffinic minaral oil whidi has a flaah point of 29C, appnmcLmstaly tha sans as tha SOCS siliocna liquid propoaad by Dow Coming. To achiava this hi^mr flaah point, tha oil is rafinad to hsw a highar mnlamlar waight md oonaaquantly a hi^ar viscosity whidi raduoas its affactivmaaa in oanvactivn cooling. It may ba poaaibla to adiiawa a lout viaaoaity without sacrificing tha fira raalstsnoa of tha liquid, but this modification has not yat basn dsnonatrmtad. Ths major currant advantaga of tha hii flth point minaral oils is thair low prica ralstiva to silioaia and aakaral, and thair inharent biodagradshiUty md low traririty. 3.7.4 High Flash Faint Synthatic Hydrocaifeona aixturaa of synthatic hydrocarbons may rasult in a having tha high flaah point charmctarlstics of RON or ailiaona aoBhlnd with a ralatiwly Low viaooaity and satisfactory hast trarafar disractacLstics. Tha Manaanto Oo. is nportadly tasting such a mixtura -267- MONS 209247 tfcidl has the trad* rune MCS-1866. No technical details are avail*l* on tha saco^t that it is claimed to hm flamsability and heat trmafsr pcopvtiM equivalent to si I icon* at a nudi lower coat, and to bs awirawitally acceptable. Menaanto haa stated that tha technical details will ba mada public early in 1976. 3.8 Institutional Barriers to tha Use of Substitutes for PTfla Tha National Electrical Ooda recognizes only three classes of transfanners: aakarel, mineral oil, and dry. The Code requinrents for askarsl and mineral oil transformers differ only in the vault requirements: far transformers located inside buildings or in hazardous locations, vailts are required for all mineral oil transformers, but only for those aakarel trans formers rated at over 35,000 volts. Aakarel transformers are econanically attractive for many applications bacaiae the savings in vault costs ncce than offset their higher price relative to mineral oil transformers, and their reliability is better than that of opm air cooled transformers. In all cases, technically acceptable alternatives axe available to raplaoe aakarel trans fanners} the only Llirdtatlens are eocnaidc. All of the substitute liquids that ham been davelopad are acre flenehle than Mkarels, but lees flsonabla than mineral oil. These liquids cto rot acme within the ***"<of aakarsl in the National Electrical Ooda, and their use is gemmed by the rules that apply to oil filled tmafoaners. Thus, ttere is ro or tsdswlogical incantive to use these altsmata under prawnt ends regulations. If the Cbds is to be chmgod to offer an emnrmic incantive to the use of these liquids, the relative safety of sash liquid oust bo assessed, and a >*---4 < oust bo sods as to "how safe is safe ku^` . In particular, test -268- MONS 209248 HONS 2 0 9 2 4 9 TABLE 3.8-1 PFCPEKTIES OF TFANSFOFMER LIQUIDS *r TESTED BY RTE CCHPORATlaJ* FLU 1 0 *0eeTi ts : TRANSFORMER OIL RTEMF SILICONE OC * 200 AS KAREL 0 I elect* tc 0 i e1ee tr i e Strength (astn 0*877) kV (25C-fluidi n received from vender) Jl 37 3* (o Oitltctric Contsinc pQMr Factor 50C 100 c 1 soac 2-2.5 <01 1.0 2.5 2.2 0.6 2.2 <0.5 2.7* 0.6 0.9 i .5 *$ ._ dm'pation Factor {ASTm 0-150) volume Retiitivity (ASTN 0-1169) Ohm-cm .0006 1.0 . I0,J <05 1.1 . I013 .0002 5.6 * I0U 03 5.0 I0,J thcrml Flash Point e Fire Feint C Four Foin t C Theme 1 Conductivity 2SC cet/tiec-^-FO/eie Specific Meet (cal/gn/C) 2SC Coefficient of Expantlon(cc/cc-C) so 162 <*S7 .000118 296 121 -21 .000297 39) .0006) .*50 .0008 306 360 -55 .000)60 3*0 .00106 -- 37 .000262 .266 .00067 physical Specific Grevlty (ASTM 0*1810) 25C Interfeclel Tent Ion (dyne/ca) Neutralization Nuafcer (gKOH/gran) Vltcotlty (centticokei) 25C 5<C IOOC 150*0 .88) 69.6 <02 16 8 ) .88) 25.5 .011 800 '50 26 8 961 20.8 <01 So 30 16 12 1-5*5 50.0 <01 18 10 6 <3 * Reproduced Crcm report: "Orvirannentally Acceptable Insulating Fluids May Replace AaJtarsls", by D.A. Dudostt, RTE Corporation; May 8, 1975. -270- MONS 209250 a flfiMfeility problem dus to the breakdown products of ttw transformer oil. If tflfcwsrs the case, neither siliccne oil nor high flash point mineral oil would be significantly better than the present transformer oils. Because of the limited test data that is available, it appears unlikely that the proposals will be approved for inclusion into the 1978 Coete. Since the deadline far submission of proposals for this PMs revision has passed, the most likely date for any Cbde revisions is the 1981 Qode. The general acceptance of alternate liquids in piece of askarels will only oacur after the performance of these liquids has bean demonstrated by prolonged service tests under realistic conditions. The effect of the Gode is to prevent the testing of alternate liquids in transformers which, under the rules, must be filled with askarels. The inclusion of the Code into the regulations of the Occupation Safety and Health Administration is an additional institutional barrier to the acoimlaticn of adequate performance eager ienoe. 3.9 Smlative Merits of Alternatives to Mew Aekarel Transformers The relative merits of the various alternatives that have been pLTjpneerl are sutmarized in Table 3.9-1. Special consideration most be given to the suitability of eadi of the alternatives to the major types of trans formers which curmtly use askarels. 3.9.1 Distribution Transformers Very few transformers presently use askarels. These transformers are generally installed at the site of major generating plants, and there would be little difficulty in designing these plants so that mineral oil cooled transformer* could be used safely. 3.9.2 Power Transformers Askszel erat+a transformers are used in buildings and industrial plants without vailts where the naadaise voltage is less than 35,000 volts* Currently available alternates in new construction are: -271- MONS 209251 good Uae d ^ iw r ii cn Qoda ra g u la tic n a b a in g d u n g a d to a llo w s e lf M ineral o il transfotanar in v a u lt : fHt eW 1 liil l Is ft s fR Mi &S h gE E i a Ttoidcity 1 1 1 1 Bp* TABLE 3 .9 -1 s I | sp 1mo Ml Ml t-oo tfot Fire Risk ! $5000 to $50,000 mora H Ben utsr (<a -trt Goat/ i? i? Do o t rans former ftT(loo Oo relative to askarel Xo transformer . z to Reliability I good u1 s u a lly i sH 1 vs PCB ro o < M (no tn ro 8| 8| ConverLability 1| -ft of present & 11 ons turners K4* *< if < ; . Mineral oil transformer instill*! in a vault Opm air ax;lad transformers - limit*! to dean dry environments with even pou*r reauiranants. Satisfactory far most office buildings and shopping centers. Mineral oil transformers at a site aay from the building. This will be satisfactory far meet trailer parks and industrial plants except for those locations where space is extremely scarce. A possible, future, alternative may be to use a "self extin guishing" transformer fluid in those applications where askarels are now required. This alternative requires that major changes be made to the National Electrical Code. 3.9.3 Precipitator Transforoers These are high voltage step-up transformers vhidi are irounted on or near industrial stacks. It should be possible to use mineral oil cooled transformers in all such applications. 3.9.< p-i1wrarl TranlfbgIBIS These transformers use askarel die to PmnKbntral Railroad regulations. However, foreign esqarianoe indicates that there is no significant fire risk fraa the use of mere flammable liquids in these transformers! European practice has traditionally bean to use mineral oil in looonotive transformers. Jfcout ten years ago m. experimental transformer wee built in France whidi used m enclosed gas pooled (sulfur hexafluoride aoolant) trans former. (22> Although senauhat limited in peak power output (overload conditions) ccrparad to oil-filled traiafonners, it perfomad satisfactorily during extensive tests. Howavsr, this typs of transformer did not gain wide acceptance because it wa more es^eneive than oil-filled transformers, and there was not felt to be any significant safety problem associated with the use of the oilfilled units. Qeraral ttotars Corporation raoaitly supplied a danonstration electric freight looomcrtive to the Pam-Central Railroad far test. This -273- MONS 209253 lagsaotive is designated a type GM-6. The transformers in this locatetive i sreffryllad by a wiish manufacturer, and an filled with mineral oil as DffilK regulations would not allow the use of PCBs aval for test purposes. As a result of this material choice, this denonstrator locenotive is not alland into the tunnels into Nev York. Japanese practice over the past four years has beoi to use silicone oils in new railroad transfomars. No service problems have been reported. AMISAfC is presently negotiating the lease of several new electric Locomotives fran France. Preliminary specifications call for the transformers to be able to operate satisfactorily with mineral oil, askarel, or silicone oil ae the coolant. 3.10 Replacement of Aslcarels in Existing Transformers There are currently about 135,000 aekerel-filled transformers in service in the United States. These transformers aontain an average of 2000 to 2500 pounds of PCBs mi. far a total in serviae inventory of about 300 million pounds of PCBs. Accidental loaaee of askarel may oacur due to failure of these transformers and accidental spills during servicing. It has bean suggested that ttwae lessee may be a significant source of PCBs into the arvlrorroant, and that this source of pollution could be minimized by refilling these transformers with an approved "self extinguishing" transformer liquid. 3.1C.1 Pt3 Losses Pus To Transformer Failures The irddanoe at failure of askarel-filled transformers has bean estimated to be 0.2 percent par year. No more thah 1 percent of these failures result in a rupture of the transformer case and spillage of liquid. The usual failure involves only a venting of gasas fran the transformer safety valve, foLlnwel by operation of the circuit breakers to remove the power from the transformer. Thus the expected incidence of spillage is pmdmhly on the order of 3 transfosnsrs par year containing perhaps 6000 lb of PCS. Tinner, nset askarel transformers are installed in buildings or in vaults where there is e provision fer containing any leakage, it is probably -274- MONS 209254 neeanabl* to .iwra chat the claanvp activities following a tranafonimr nnBK, art 90 to 99 pcent effective in recovering the spilled askarel, whidi linq|irthe total uncontrolled loss of askacels from trztnsfonwr natures total of 60 to 600 lb per year. If it is assured that the venting of vapors during a transformer failure results in the loss of an average of two lb of PCB due to evaporation, the total losses frem this source will be about 540 lb per year. Thus, the total annual entry of PCS into the envirorront due to transformer losses is on the order of 4 lb per million lb of PQJ in service. 3.10.2 aiyironmental Effects of tn Askarel Feplacnrent Program The proposal to drain the existing askarel transformers and refill them with an environmentally acceptable heat transfer liquid pre supposes the availability of sufficient quantities of a liquid having satis factory fire resistant properties and heat transfer properties equal to askarel. No such material is currently available. The use of either silicone oil or a high flash point hydrocarbon material would require a change in the National Electrical Cods regulations whi<h govern the installation of transfonners. in addition, all of these materials have poorer heat transfer characteristics than aakarela, whidi may require tha derating of all the transfoarers. Assuming that a satisfactory substitute liquid were available, the retrofitting of the existing transformers still faces a lumber of practical prcblmns. The asst difficult problem is the achiewent of thorough draining of aakarela fran the existing transfonners. Much of tha liquid Is held in the insulation of the transformers by capillary action; staple draining of a trans former only moves 80 psraant to 90 parent of the liquid. Therefore, it will be neaassary to flush eadi transformer 2 or 3 times with a 1 iquid whi<h will dissolve the rmoaining askarel, and whidi is < > .npstihls with the liquid used to refill the trarafionner. This raquirsmmt of ocnpatibility could ba a major problem; for instance, *v--1 an intdscibls in silicons foils. It en reasonably be expected that the draining and flushing of *i Mkanl-fillad trrnisfamar will result in an average of 800 gallons of askarel mid PCB oentmninatad liquid. This liquid oust be shipped to an incinerator and burned under controlled conditions. Disposal of the liquid -275- H0NS 209255 The result of this draining, flushing, and refilling pro cedure will be a transformer which is filled with 300 gallons of an environ mentally acceptable liquid that is contaminated with 10 to 20 lb of PCB. This reduction in the amount of PCBs in service will reduce the severity of potential transformer failures, but will not eliminate the need for careful handling or eventual disposal of the contaminated liquid. A more serious concern would be the amount of accidental spillage whidi would occur when the scrap askarel and flushing liquid is shipped to the incinerator for disposal. The current lade of sufficient incineration facilities would require that much of this liquid be stored in drums or tanks for an extended period of time. In addition, the accidental leakage from broken drums and other accidents whidi can be expected to occur during transportation can be expected to release PCBs and flashing solvent to the environment. 3.10.3 Effect of Leaving Askarel Transformers in Setviae The alternative of leaving the askarel in the transformers until they became obsolete or fail is probably to be preferred to retrofitting these transformers with a less toxic liquid. The existing askarel should last the life of the transfanners; only infrequently is it neaessery to filter the i irpiid to remove the degradation products of minor internal arcing, and askarel loeeee during this filter cycle should not a:nosed 1 percent of the total liquid in ttv transformer. Askarel for makeup of these lcsies will not be available cnoe it is no longer used in new transformers; Monsanto has announced its intention at dosing the only U.S. PCS manufacturing plant as soon as satisfactory substitutes are avsilable far PCSs in electrical equipment. This should not prove to be e major problem in the maintenance of askarel trans formers, as lossss of can be replaced with pure tricdilorcbenzene. The menllinq mixture will be suitable as long as the concentration of the PCBs is above 50 percent; below this concentration of PCBs, solvent attadt on -276- MONS 209256 tha solid insulation may occur, Omelets replaamnnt of the transferer by lade of askarel should ba infrequent and should not inpoea a Leant eccnanic burdsn an tha alaCtrlcal industry. Tha dacislon to leave existing askarel transformers in service also gains time for the sclutiai of the problem of scrapping failed or obsolete transformers. Current specifications require that transfomers be drained and flushed before being scrapped. This, however, cannot be expected to move more than 95 to 99 percent of the P<3 fran the trans former internals. It is currently very unusual for transformers to be scrapped, but when they are scrapped the value of the metal is sufficient to mate recycling attractive. There is currently no acceptable facility for the recovery of metal from failed transformers. Special procedures would have to be used to prevent K3 residues fran being carried throu^i into the scr^> furnaces. This will eventually be a significant problem. Better solutions to the problem can be expected if the problem is delayed by leaving existing transfosners in service. 4.0 BMssawr casting The Invent casting pro ness is a lost^noc casting process in whidi a pattern is molded from wax and than invested or surroisided by a slurry con taining a refractory ouedc. After the aermnic mold is dried to an appropriate strength, tha wax pattern is melted or burned out leaving a molded cavity. Molten metal is than poured into the cavity, and solidified by cooling to form a cluster of metal castings. Meintsnanoe of close diamioial tolerances requires that tha shrinkage of the wax be carefully controlled during the initial pattern step. This ocntrol requiraa either slow cooling of the pattern vbile thi wax is solidifying or the use of a wax material whidi shrinks very little i^cn solidification. 4.1 rmctlm of the Filler tetarial One matted of modifying the wax to achieve minimal shrinkage is to n the war with a finely powdered material that is insoluble in the wax and remains at the tanpexature at whidi the wax is cast into the molds. -277- HONS 209257 this filler does not chan?* JUU (Cron a Liquid to a solid) on cooling, Its very low shrinhage, and the resulting slurry of wax ani filler will more dimensionally stable than will be the pure wax. The second step in tha casting process is to bum tha wax residues out of the ceramic mold so that the mold will be carpletely etpty when Tetal is cast into it. This requires that the filler be volatile at the temperatures used to fire the molds, and that the vapors be ran-toxic. 4.2 Use of PCTs in Investment Casting Sane of the pettem vexes, especially those used in the casting of metal parts requiring tight dimensional tolerances, contain decacdiioiobiphenyl (deha) as the wax filler. Decachlorobiphenyl waxes contain approximately 10 percent (perhapa up to 40 percent) of tha decarftlorobiphenyl filler Pattern waxes are recovered and reused several times to form the sprues and gates of the patterns, wax is apparently used an average of 2.5 times. During the dawaxing process the virgin wax (used to form the pattern) and the old wax (used to form the gates and sprues) are collected as one mixture. Little of the wax is destroyed in the prooess; therefore, it is probable that the investment casting foundries store or dispoee of relatively large snounts of used PQ-oantaining wax. It is estimated that approximately ans to 1.5 million pounds of deca- dilorobiphanyl-fillad wax is purchased yearly by U.S. investment casters. The oost of the EQ-finert wax is in tha range of $0.70 per pound. (24) Imported polychlorinated terphenyls, whidi exhibit preparties very similar to deca- dilorcbiphenyl, is used as a pattern wax filler. There is only ona U.5. producer of deha-filled wax, and this anpany also produces PCT-filled pattern wax. 4.2 Ah infejae and PI fyhanh^ges of tha Use of Paha ECBs in Investment Casting' ~ "' " The deka PCBs have nearly ideal properties for fillers in investment <-tig waxes. These materials are only slightly soluble in the wax, retain ii 1<4 at the wex casting terperatures, and volitilize carpletely at the firing teiparatuxes without charring or burning. 278- HONS 209258 The oily disadvantage to the um of daks PCS ia its suspected nviiviuaiilal persistence and, by analogy to the other pqj*, its ' :io direct evidence of environmental damage fron this compound found to date. 4.4 Alternatives to the use of Deka PCBs Potentially acceptah le process alternatives for the deka PCBs <-r.ii^ utilize either a replacement filler material or an unfilled wax. 4.4.1 Replacement Filler Materials Properties required for a filler are: high, itelting poinv (over 300C) , high heat transfer coefficient, low thermal coefficient of linear expansion, and minixiun ("zero'*) ash. The following materials have bean suggested as possible replacements for deka PCB. 4.4.1.1 Isophthalic -Acid Isophthalic add has been used as a filler material to a limited extent, but the grade of material that was previously available left an ash reside on firing. A new grade of isophthalic acid, only recently by MOQO Chidcals Carp., exhibits nudi lower ash and metal contents. The various grades of material available fron MGCO are as Grads IPA 85 IPA 99 Cost in Bulk $0.24/lb SO.27/lb Garments High ash Previous use history IPA 110 IPA 220 $0.31/lb SO.35/lb Being phased out New - low aah Althou^i there is a considerable body of literature on phthalic acids and phthalsta esters, their anviromental fates are not tncun. Degradation mites of degradation products, etc., which are of greet importance to an aesesnant of anviromental acceptability have not been studied in d^th. It am be * that this will be the case far most filler substitutes. -279- HQNS 209259 4.4.1.2 Polystyrene Polystyrene plastic is available fran a nutbar of suppliers including Dew Chemical Co., Monsanto, and Foater-Qrant. If this plastic were reduced to a sufficiently fine powder, it would have physical properties equivalent to delta PCB and should perform satisfactorily as a wax filler. The huUt ooet of polystyrene pellets is $.40/lb, and the sire reduction should cost an 5.08/lb of filler. Upcn fixing, the polystyrene could be expected to depolyrerire to styrene which would be volitilized. styrene vapor has known toxic properties. This potential problem may limit the serious consideration of polystyrene as a wax filler. 4.4.2 unfilled Waxes Prior to the use of PCBs or PCTs as fillars, unfilled waxes were used. Industry sources claim that reverting to the use of unfilled waxes would increase production costs by about 10 percent. However, new types of infilled waxes have recently bean introduced to the market, and it is claimed that their properties are equivalent to the filled wex and their ooet is slightly lower ($0.80 to $0.65/lb) f27) Although the exact formulation at these waxes is not known, thay reportedly contain no Alorinated additives. 4.5 Conclusions - Substitutes for PCB in Inveatmait Casting Technically adequate substitutes for dscachlorcbiphsnyl filler in pattern waxes to be available. Maxima increases in costs would be about 10 percent. The only producer of wax containing PCBa aculd prcbably change to other types with very little technical diffiailty or eomanic impact. -280- MO NS 209260 Capacitor! SUfMUGf SUBSTITUTES FOR PCBs PCBs are used as the dielectric liquid in almost all fC capacitors by the electrical utilities for pwer factor correction and in various industrial applications including appliance motors, fluorescent light ballasts, and pocr supply cixoiits in television receivers. P<3s are miquely suited for capacitor applications because of their high dielectric constant, chemical stability, and ncn-flannability. A neuter of different (hardcals are being developed as replacements for FCB capacitor fluid. There is not yet sufficient data available cn the electrical perfosmnoe, chronic toxicity, or cRvircnnental effects of any of these liquids. Dry film fC capacitors are also being developed. These capacitors axe significantly larger thi liquid-filled capacitors and axe limited to a maxima of 280 volts. Satisfactory dry film c^adtoxs will not be available until there axe two asperate technological breakthroughs: 1) the development of a plastic film that oembinas a high dielectric constant with s lew lasstangent; 2} the developnant of winding techniques that exclude all air fron the winding of the c^xrrltor. Although it is probable that satisfactory substitutes for FCB* will be developed within the next 5 years, no such material is presently available and nudi arirtiHcnal rasasrti mains to be done. Tranafognsrsi FCBs are used as a major cqtpciwnt of the ncn-flmmnable transformer lignin tacun as aakaxel. Only about 5 percent of all transformers are ooolad with Mkaxel. These are the transformers which, are located in buildings and other hasardous locations where firs resistance is of greet importanns. Mast transferrers ace oonlad with mineral oil. This 1 lqnid is flamable and the National Electrial Coda requires that oil-filled transformers be -281- HONS 209261 installed in fire proof vaults when they are used in buildings. Vaults ere not required for askarel-filled transformers that are rated at less than 35,000 volts. Although the askarel-filled transfonrers .ire 20 percent to 30 percent more expensive than oil cooled wits, the saving* cn vault construction oosts more than offsets the difference. Other currently available substitutes for askarel-filled transfarmers are open air oooled transformer*, whidi are limited to lower voltage applications in clean, dry environrents, and cicesi gas cooled transformers v*iidi are more expensive than aslearel wits. Both of these dry transformers have lower overload capacity than do aakarel and oil-filled units. Technically satisfactory alternatives are available to the use of trans former* ocntaining PCBs. The present choice of PCS units is based cn the relative costs of the alternatives. Several substitute liquids haw bean suggested which are leas flacmable than the currently used mineral oil, but whidi are more floanable than vkarel. Theea liquids are characterised as being self extinguishing - i.e., they do not continue to burn after being ignited by a manantary electrical are. Proposals have bean sutaLtted to the National Electrical Code to allow the use of these self extinguishing materials under those auditions where askarels are presently specified. Because of die relative lade of service experience with these liquids, it is unlikely that these proposals will be accepted. The next Code revision (1978) will probably continue to recognize only aakarel end "oil fined" transformer*. It is likely that ths "self extinguishing" liquids will prove to be setisfsetory alternatives to PCS*. Substantial eigeriano* cn the performance of the liquids will be required before the Code raquiments will be changed to fHair UM. Qe restrictive Electrical Code, whidi has bean incorpor ated i"*" tbs 068k Regulations, may act to inhibit ths accumulation of this ad thereby act to pvtp* ths gier*1 aconitines of these substitutes for PCS*. It has also been suggested that PCS* be drained from existing tzansfamers and replaced with a less toxic material. Analysis of this alternative suggests that it may have a wane effect ai die snvircraent than valid the continued use of PCB in die transfoxmsrs. -282- MONS 209262 SMART DIVESTMENT CASTING Dekachlorobipheny1 is used by one manufacturer in the fonmlation of investtnent casting waxes. The delta PO acts as an inert filler which reduces the shrinkage whid occurs when the wax solidifies. Other manufacturers use polydilorinated terphenyls (PCTs) far the same purpose. All of the deka PO and PCTs used in investment casting waxes are irrportad. Several substitutes are available for deka PO waxes. These include the replaamsnt of the PO with isophthalic add, or the use of new low shrinkage non-filled waxes. Oanplete elimination of deka POs frcn this application should be possible without causing significant problane. -283- MONS 209263 HEFEfSNCES 1. Quids Lines far Handling and Disposal of Capacitor-ard Transformr-o-^AakareU Containing PolydMcrinatad Biphenyls, ANSI cld7.1~ 137*. Natiaial Standards Institute. Inc.. N.Y.. N.Y. f .TanmiTy a, 1TT3-- 2. wood, David/ Chlorinated Biphenyl Dielectrics - Their Utility and Potential Substitutes, (Presented at the National Conference cn Polychlorinated---------Biphenyls, Chicago, II., Novarber 19-21, 1975), Mansantto, 1975. 3. Nelson, J.D., (General Electric Caipany), "Effluent Limitations for Iters on Toxic Substances List; Economic Impact of a Bar in PCS," Contained in CCmnunication to Dr. Martha Sager, Chairnan, Effluent Quality Information Advisory Oannittae, Novwnber 21, 1973. 4. National Electrical Code - 1975, National Fire Protection Association, Boston, MA, (NFPA No. TO-1.97$7 NASI Cl-1975) , 1974. 5. Personal acnnunieatiaa with taowledgable individuals in the electrical equipment industry. 6. Indiank, E.J., (Bonn Chemical Oo.), Uarioal Presentation, National conference on Folydilorinated Biphanyls, Chicago, II., Nowfaar, 1975. 7. Bey-Coquais, Bruno, (ProdsLee, S.A.), Verbal Presentation, National Conference on Polychlorinated Biphanyls, Chicago, II., Novenber, 1975. 8. Branson, D.R., Health and Bwironaental Properties of Daw XTS-4169L Capacitor Fluid, (Oral Pr--entatien to the U.S. E.P.A., WastungtcnT D. C., October 16, 1975), Dow Orenical Oo., October, 1975. 9. Branson, D.R., (Dow Chemical Oo.), uazfeal Presentation, National Oonfeianoe an Polydilarinated Biphanyls, Chicago, 11., Nwenber, 1975. 10. Ntontganery, Riduxd, (Dow Ooming Oorp.), Verbal Presentation, National Oonfeianoa on Polydilorinated Biphanyls, Chicago, 11., Nowfeer, 1975. 11. Tuttle, clifften, (Aerovooc Qo.), Personal COmunicaticn, septertssr, 1975. 12. McAllister, John F., (General Electric Oo.), "Benefits of PCS Use". Letter to Dr. Shnzd J. Burger, Jr., Executive Office of the Preeidnt, Office of Science and Technology, Decanter 30, 1971, 36 13. Pt--'t on Power Transformer Troubles, 1969, Edison Electric Institute, ji-aylnn MO- Ti-?nr l5W- -------- 14. "The Riah to Maricet for PCS Substitutes", Business Haalt, January 19, 1976, pp 3GE-31E. -284- MONS 209264 15. Bloanquist, W.c., "What is the Future for AaJcarel", Power, vtol. 120 FAruacy, 1976, pp 68-70. --------- ' ? 16. Interd^artmental Task Forae cn PCBs, Poly<*larinated Bioteiyl* aixl the Ertviroment, Washington, D. C., Hay, 1377! ------------------- 17. Burrow, R.F. 6 Ozbadt, T. (Do# Coming Corporation, Midlani, Midiigan) SHrgone Fluid Filled Transformer - An Alternative to Aakarel are! DryTypei. Transformer?, (Presented at the Doble Engineering ALlit Boston, >*., Azarin 9-13, 1973), Do# Coming Coro., 1973. 18. Burrow, R.F., & Vincent, G.A., Silicone Fluids vs ffydrocaihan Oils:, a Caipariacn of Thermal and Electrical Perfonaanoa f'mtiili.rjM, at the 1974 Winter Meeting, IEEE Power Engineering Society, M.T., n.Y. , January 31, 1974), HIE Paper No. C 74-258-0. 19. Report an Dielectric Medina Older the Classification Progran - File 1*0466, underwriters Laboratories inc., May 26, 1972. " 20. Rowe, V.K.; Spenoer, H.C.; Bass, S.L; "Tcocioological Studies on Certain Coimerdal Silicones", The Journal of Industrial Hygiene and Taxiooloov. Vol. 30, No. 6, pp 332-15T 21. Dudoett, D.A., Environrentally Reputable Insulating Fi^ i%y Replace Aakaial (PrsaentB at the General frosting, Edison Electric institute Tranmssion and Distribution Camittee, Minneapolis, Mim., May 8, 1975), HJS Corporation, May, 1975. 22. "TTansfannataur dais le gas", Chapins ds Far, No,246, 1964-3, p 96. 23. Solemn, P. (Yatas Mamfacturing Co., Oiicago, Illinois), Personal Canaxiication, SepLwter 9, 1975. 24. Lewis, W.H. (President, Signicest Corp., 9000 North 55 St., Milwaukee, Wise.), Statamtts during Lecture of Investanant casting Institute Meeting, October 4, 1975. 25. Edwards, Dan (Oiicego laboratory - Standard Oil Oo., Amoco Chemical Corporation, Joliet, 111.), Personal Ccmuiiceticn, October, 1975. 26. Connailay, J. (New Yack Office, Standard Oil Co., Mood Owlcal Corporation, Joliet, 111.), Personal Canuiieation, Octriaer 1975. 27. Davidson, R. (Freemen ttaufacturing Oczppty, me., 1315 itelne An., Cleveland, Ctiio), Personal Cenasiicaticn, Nowber 1975. -285- HONS 209265 SEEnai DC PCS* PLEASE AND CUMULATIVE ENVUOMOTAL LOADS 1.0 ESTTMOES CF FEEZ PCBs Dt THE ENVUOMUT 1.1 PCS* Losses to the Envirormant Slnoe 1930, by Use arri by chlorine Content of Molecule `-------------------`----------------- This sectiai includes an analysis of ths estimated anounts of PCSs whi<h have escaped to ths environnant, by molecular chlorine content. The approach and results axe sarmarized below. Loss factors, which include spillage losses during manufacture or use of the end products and losses due to inadequate disposal methods, are estimated on the following basis: Use Category t of Yearly PCS Use Lost to Ehviroment Closed electrical systans (transformer* and capacitors } 5% Hydraulic and heat exchange fluids 60t Plasticizers 251 Miscellaneous industrial application 90* Eadi of the assigned loss percantage factors can be ths subject of aonsiderable controversy. Suffice it to say that ths choice* made appear to be reasonable based on the widely varying infbroeticn considered. The foliating date hews been aenpubad an ths basis of the production and sales date released by Mxisanto on ths PCSs. since by far the largest production hae bean in ths fbsa of Arcelor* 1242, 1248, 1254, and 1260, these data are based only on thoee four mixtures. tfee Factors fee POs" were nggputed from ths Monsanto PCS manufacturing and salsa data utilizing ths donastic sales by category Influent Tin Since the detailed breakdown far the period 1930-1957 was not available, it wae aaimad that the pattern for this period followed the average 286- MQNS 209266 for the period 1957-1959. Estimates were then prepared of the actual produc tion and use of the individual Aroclors listed above. Table 1.1-1 is a tabulation of the estimated mounts of Aroclors that have escaped into the enyirorenent, assmung that 51 of the KBs used in cap*:itors aM transformers escaped; 604 of that used for hydraulic media, and heat exchange Tredia escaped; 254 of tnat usea tor plasticizers escaped; and, finally that 90% of that used in miscellaneous industrial uses has escaped. These data may be expressed in terms of chlorine aontent, based on published Monsanto data on the isansrs typically present, by chlorine content in eadi Aroclor type. The results fran such an exercise are presented in Table 1.1-2. The totals in the right-hand oolmn represent the emulative totals of all escaped PG3s by the year listed at the left. The ccrputed speetrmi of chlorine contents based on the emulative data on Table 1.1-2 is presented, fer selected yeaxe, cn Table 1.1-3. The average chlorine content for the set termed "average values* is 4.38 chlorine state per molecule, tampered to: Chlorine Cbptsnt (ators/imlecula) 3.67 4.22 5.35 Thus, the distribution as is cam closest to Aroclor 1248. Hcwever, if it is ----* that all mono- and di-<hlaro biphenyl were biodegraded or otherwise destroyed, that the average chlorine ocnteit of the "wild" PCBs would be 4.67, intermediate betwen 1248 and 1254. If the tridilcro isarers were also subtracted out, than the omposite average chlorine oontent would be 5.0, which begins to unbare fawrsbly with 12S4. 1.2 `Patel K3e Acomulstion and Current Rates As a rough estimate of the total PCBs currently available to the biota (is active transport, in biological systens, etc.) in the Unitad States the total of 172,800,000 lb. from Table 1.1-1 may be reduced by a factor -287- MQNS 209267 1930-56 1957 1958 1959 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 1242 18709 1991 1431 2298 2955 4082 3992 3648 4597 5928 7010 7442 7789 9182 10072 3232 48 310 310 TAH 1.1-1 PCB EyVIBOlMElfEAL LOAD By Apnrrnu, TYPE [In Thousands of Pounds] 1248 5395 704 1065 1597 1226 1745 1452 2062 2160 2260 1932 1794 1881 2190 1536 112 - - Aroclor Type 1254 1260 5003 676 917 1142 989 1295 1222 1166 1224 1456 1247 1158 1615 2172 2575 717 229 399 309 3559 932 783 1118 1191 1341 1258 1503 1664 1096 1041 1111 954 997 1044 266 20 - 1016 167 1045 1177 1098 Total PCBe 32466 4303 4196 6155 6361 8469 7924 8379 9645 10740 11230 11505 12239 14541 15227 4494 1342 1886 1717 Grarxl Tbtal - 172.8 * 10*lbs. 288- HONS 209268 1956 1957 1958 1959 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 TABLE 1. 1-2 CUMJLATIVE OWIFOWENIM, PCB liOAD __________ BY CHLORINE CCNTBJT [In Thousands of Pounds] Sil --2 561 2540 621 2813 664 3020 733 3351 822 3760 944 4326 1064 4874 1173 5389 1311 6030 1489 6846 1699 7796 1922 8799 2156 9850 2431 11088 2733 12428 2837 12880 2881 13073 2938 13324 2992 13561 --3 6210 6894 7487 8417 9465 10922 12301 13693 15369 17436 19747 22154 24674 27639 30735 31723 32131 32663 33165 di 8221 9174 10130 11584 13070 15135 17048 19095 21473 24315 27328 30406 33673 37543 41462 42624 43086 43700 44272 a* 8936 10070 11311 13086 14805 17128 19279 21575 34160 27123 30097 33080 36376 40368 44523 45657 45782 46046 46265 Si6 4017 4709 5419 6388 7344 8529 9640 10835 12153 13391 14568 15754 17053 18625 20362 20840 20928 21076 21193 a? 1759 2182 2558 3085 3632 4162 4751 5437 6192 6728 7230 7755 8243 8782 9365 9517 9539 9563 9582 8 285 360 423 512 607 715 816 936 1069 1157 1240 1329 1405 1485 1569 1590 1592 1592 1592 a. Total 36 32,365 45 36,363 53 41,064 64 47,219 89 33, 580 39 62,049 102 69,973 117 78,352 134 87,997 145 98,735 155 109,966 166 121,471 176 133,710 186 148,251 196 163,478 199 167,972 199 169,314 199 171,204 199 172,821 -289- HONS 209269 1956 1960 1965 1970 1974 Average Value* TABLE 1.1-3 computed spectrum of chlorine ccweent FOR WILD PCTa ______________________ [In Peraent] weight Percentage of laorers Containing Cl IPP 2 --3 ^4 5 S* --7 9 1.7 7.8 19.1 25.2 27.4 12.3 5.4 0.9 0.1 1.5 7.0 17.7 24.4 27.6 13.7 6.3 1.1 0.1 1.5 6.9 17.7 24.6 27.5 13.6 6.8 1.2 0.1 1.7 7.6 18.8 25.4 27.2 12.5 5.7 1.0 0.1 1.7 7.8 19.2 25.6 26.8 12.3 5.5 0.9 0.1 1.6 7.4 18.5 25.0 27.3 12.9 6.0 1.0 0.1 -290- MONS 209270 accnurting for envircimental degradation of less chlorinated isawrs and other destruction processes. Based cn Table 1.1-2, this should be ^out 20 to 30 million pounds, resulting in a total of free PCBs of about ISO million pounds. Estimates by Nisbat and Sarofim^ in 1972 for total P<3a available through air and water dissipation mount to 180,000,000 lb. since 1932. This value is within four peront of the above estimate of about 173millian pounds based cn the Loss factors specified. Application of the five percent loss factor to the 1974 ttonsanto danestic sales yields an estimate of 1,720,000 lb. lost to the enviimnent during 1974, to which should be added a maxima of 50,000 lb. lost froa imported materials. The 1974 total of 1,770,000 lb. altering the envirarment in available focus represents about 1.5 percent of the total mount estimated above to be available to the biota in the U.S. The 1,770,000 lb. per year mount may be acnpared with estimates for 1974 by Peakall121 as follows: Industrial leaks and disposal - 890,000 to 1,100,000 lb. Disposal in Amps and landfills - 15,000,000 lb. Total - 16,000,000 lb. The figure of about 10 percent loss froa the above required to match the 1,770,000 lb. per year loss rate doss hot appear unreasonable. However, it should be pointed cut that the 16,000,000 lb. per year figure for leaks and froa ?nhill represents almost half of Monsanto's reported 1974 domestic sales, and mist be questioned. 1.3 Current PCBa Disposal in Landfills and Dw The mast important currant sources of land-disposed PCTs are: (1) Solid wastes from the manufacture of PCSs and electrical equipment (including reject capacitors and transformer internals) -291- HONS 209271 (2) Failed capacitors; (3) Capacitors in obsolete equipment; and (4) Municipal solid wastes other than electrical (obsolete equipment, sewage sludge, paper, plastics, etc.) Cne relatively minor souroe is the transfonrer service industry. This industry handles about 2 x 10 lb. of PCBs annually (roughly half new PC3s) ^ssuning that 5 percent of the Ps handled ands up as solid wastes (from ^iltraticn, etc.\ results in 0.1 x 10 lb./yr. of solid material enterino the landfills. The major sources are treated below. Land-destined solid wastes from production of EOa, capacitors, and transformers are estimated to con tain about 1.2 x 10 lb./yr. of PCTs. Reject capacitors and transformer internals add about 0.7 x 10 lb./yr. to landfills. Since most PCBs used in inveetsent casting are eventually land disposed, this adds 0.4 x 10 lb./yr. Aiding in 0.1 x 10 lb./yr. for transport and other losses brings the total of land lisposad PCBs firaa production and first tier use to 2.4 x 10 lb./yr. The failure rate for PCB-impregnated capacitors is estimated at one parent par year. On this basis, and asstrung that the failed equipment enters a landfill or imp, than about one percent of the approximately 450 x 10 lb. of PCBs estimated to be in service in capacitors, or 4.5 x 10 lb./yr., can be expected to be landfilled. Capacitors whidt haw not failed but are contained in obsolete equipment (TV sets, light fixtures, etc.) also end up in land disposal sites. This ppHyt to aaall capacitors only, and it is estimated that one percent of the total an discarded in this manner each year. The anount of PCBs in volved' is- (0.01 x 270 x 10), or 2.7 x 10 lb./yr. The aemiiL erf PCBs currently contained in Land-disposed rrunicipal and wastes other than that aaaignable to transformers and capacitors -292- HONS 209272 is difficult to estimate. Approximately 160 million pounds of pCBs have been used in plasticizer and other "open end" applications or in applications such as hydraulic or heat transfer system. Mxt of this usage occurred between 1960 and 1972, and it is likely that vp to 80 percent of the total is either free in the envirorment or already in Land disposal sites. The rest of this material, estimated to be an the order of 30 million pounds can be thought of as being literally "in service'' or used and awaiting dis posal. A prime example of the latter is used carbonless copy paper currently residing in files and awaiting disposal or recycling. It is estimated that about seven percent of this 30 million pound reservoir, or 2.1 million pounds, enters land disposal sitss eadi year. In addition, it is estimated that 0.3 millim pounds of free PC3s in the environment are added to land disposal sites each year from a variety of sources (sewage sludge, dirt, garbage, etc.). This brings the total for nunidpal and non-electrical wastes to 2.4 x 10 lb./yr. Souras PCTs Added to Landfills and Duces, Wastes frm Production and First Tier Ose Failed or Obsolete Capacitors C^edtors in Obsolete Electrical Bguipnent Other Municipal and Industrial Mkstae wastes fros Transformer Service industry 2.4 x 106 4.5 x io6 2.7 x 10 2.4 x 10 0.1 x 10 Total 12.1 x 106 Peekall's^ estlaats of 16 x 10 lb. of PQJe far leaks and disposal in 1974 is about 30 peroatit hl^sur than the above total. Peakall ^ also estimated a total d 50 x 10 lb* for leaks and disposal during 1970, whidi is war two-thirds of ttXMRto's 1970 rsportad donastic sales of about 73 x 10 lb. Hr the abaanoa of no other amparabla data, wa estimate a current land disposal nee of batman 10 X 10 and 15 X 10 lb./yr. -29> HONS 209273 It should be noted that several large first-tier users of FCBs are not currently land-filling their solid wastes, hut are storing the dnnrad wastes on-site in anticipation of potential regulations on disposal of such wastes. The wastes being stared are estimated to contain at least O.S x 106 lb. per year of PQs? this is included in the above analysis as being finally disposed of in landfills. 1.4 Release of PCTs via Industrial Effluents (Waterborne) Based an data obtained fra industry, the following average PCSs waste loads for water effluents were estimated: PCBe Production Capacitors Transformers Total 1117 Ib./yr. 2139 Ib./yr. 62 lb./vr. 3318 Ib./Vr. This nuafcer is very snail in caparison to the estimated 10 x 10fi to IS x 106 lh. par year of FCTa going to landfills. The above values for industrial disAargss do not include PCBe dis charged to nunidpal systans for those plants having discharges to rivers (tan plants). In the production category, all discharge is to a nunidpal system. It should ba rated that the above waste loads represent current Industrial practice, it mey be assured that, prior to knowledge of tha adverse enviroomtal effects of PCSs, ouch of the types of material currently land filled was rat iHapnsel of properly end thus entered the anvironaant directly. 1.5 Spills of pqa During Transport Tha most caplets set of transportation spill data for PCBe avail- abla to us are far tha 6/74 to 6/75. The spills during transport and the quantities inmlsad are as follows: -294- MONS 209274 location iricn, Ga. I^rfrenoe, Ala Erie, Pa. UnJcwwn Total Gallons Spilled 117 600 120 -100* 937 (10,213 lb.) In addition, during this priori, three railroad capacitors failed ha New York City area, spilling on tha order of 50 lb. each, or a total of lb. Sinat this occurred during transit, we chose to add this anount to above total, for a grand total of 10,363 lb* spilled in tha transportationralatad incidents. This probably represents a minima figure, since transport of defective product units (capacitors and transformers) and of ?CBa containing wastes can be expected to release PCBs. On the basis of the above, a tentative nmfcer of 10,000 lb. par year of transportation-related spills of PCBs is advncad. g? Capacitor diipeant via truck cwerturnsd; leading wits and soaked dirt revved fine albs for ntear ant incineration. -295- HONS 209275 FEFEBQJCES (1) Nlabet and Sarofim; Envirm. Health Perspect., 1, 21, (1972). (2) Peakall, D.B., "PCS* and Their Qivirotmantal Effects", CPC Review, Issue 4, 1975. -296- HONS 209276 SECTION X HONS 2 0 9 2 7 7 P edsral Phosphorus Os. ashed to supply biphenyl in q u a n titie s fo r use as a haat tra n s fe r f lu id in th e r e fin in g o f lu b e o i l s . He s e t up a p ilo t p la n t fo r th is purpose. one of the bottom from the benzene plant, has a fuel value of 1 to 2/pour*i. Hcuwer, a 97 mol S pure biphenyl can sell for about 6 per pound. By product streams of this type are rich in biphenyl (typically 15-20* by v*ight) It can be seen that wastauaters from a process like this oould be source of methyl biphenyls found in water supplies. Coal tar amounts to about 3% by weight of coal processed. Biphenyl is part of the heavy oil fraction, along with substituted naphthalenes, accounting for about 10% of the tar. Thus biphenyl generation could amount to one pound for every ten of ooal processed for liquid fuels. As more enphasis is placed on coal conversion, the potential contribution to the environmental load of biphenyl may increase. Cne degradation route to biphenyl wes found. It is possibly of importance since it indicates a pathway from chlorinated terpharyla to PCBs. Vlwn vapors of tarphanyls are mixed with hydrogen and heated to 650-850*C., benzene and biphenyl are formed. Best results are obtained whm 4 to 6 mols of hydrogen per mol of terphenyl are used (based on a Monsanto Patent). Typical tarphanyls are Dow's "Tarophen" and Monsanto's "Santowax". The above indicates that PCBs oould be produced by the incoiplete incineration of chlorinated terpharyls, or possibly front terphenyls themselves in the preavtoa of deccnpoaing PTC or other source of chlorine. There is no recorded production data for biphenyl for any period of time. Oats for biphenyl is included in the "other non-fuel" uses of benzene, which includes BBC, anthraquinene, and several other caipounds, in addition to biphenyl. This %4tole category has amounted to between 50 and 100 million gallona of bmeane equivalent per year aver the last 30 years. Cne industry source estimate for the early 1970's was 5 million gallons of beiem equivalent going to biphenyl. Allowing for the recent burgeoning interest in dye carriers by doubling that value, there oould be as much as 80 iw411 >. pounds of biphenyl old annually in the U.S. This does not aeon too unreasonable since one localized area of Georgia acoomts for 22 million pounds 3er year. -299- MONS 209279 . On balance, a "best estimate" of SO million pounds per year current biphenyl use would seen appropriate. 2.3 Properties and Characteristics of Biphenyl Biphenyl is a rather stable organic ocnpcund, and it is resistant to thermal and radiation degradation. Sane of its properties are given in Table 2.3-1. TABLE 2.3-1 PHYSICAL OCNSTWTS OF BIPHENYL Solubility in weter at 20*C., mg/1 7.5 Malting point, *C 69.2 Freezing or congealing point of umuercial product. "C Soiling point at 700 os, *C Flash point, *C Fire point, *C Ignition tKperature of dust clcwi, C 68.5-69.4 255.2* 0.2 113 123 650 _________ TeeneraLure, *C 100 200 300 Vapor pressure, ata Liquid dansity, g/as3 0.970 0.251 0.889 2.436 0.801 Hsat opacity, csl/g 9aat of vaporization, cal/g 0.427 95 0.509 82 0.590 68 350 5.509 0.751 0.631 60 -300- MONS 209280 3.0 PBCWEN BIPHENYL REACTIONS YIEU3ING PCBs The ttwc categories of biphenyl reactions examined in this section are the direct chlorination of biphenyl and the joining of two chlorinated phenyl groups into the biphenyl configuration. 3.1 Chlorination of Biphenyl Although conflicting statarenta can be found in the literature, it is accepted that biphenyl is more easily chlorinated than ben2ene due to less resonance stability in the biphenyl. The behavior of biphenyl is ocnpiicatad by the non-coplanarity of the two rings. Because of repulsion between the 2 and 2' hydrogen atoms, the rings of biphenyl itself have an angle of about 45* between their planes. This non-coplanarity greatly diminishes the resonance interaction betveen the rings, and is believed to make biphenyl more prone to reaction than benzene. Since benzene can be brcnlnatad with branine at 0 *C in the presence of iron, and also chlorinated with chlorine in the presence of icon at 50*c, we can expect significant reaction of biphenyl with chlorine in the presence of iron below.50*C. Also, solid biphenyl reacts with branine vapor to give first 4-bronnhiphenyl, and than 4, 4'-dibronobiphenyl. Biphenyl malts at about 70*C. The <:umen.ial production of PC3e by chlorination of biphenyl in the presence of an iron catalyst is conducted above 70*C in order to obtain and maintain the molten state for ease of transport and for better mixing with the added chlorine. The higher terperaturs conditions may also be important in the formation of the higher chlorinated homologs, but this is also dependent on contact tins. The chlorination is exothermic. The ease with which biphnyl may be chlorinated to two isomeric mcnochlostbiphanyls is bast illustrated by an early description of a pilot plant synthesis by Jenkins, McCullough and Booth, of the Federal Phosphorus Cocpany, in 1929.^ They used a tarperatura just high enough to malt the biphenyl, and achieved iron catalysis by using iron filings. Schmidt and Schultz and Kramers had shown that antimony pantachlnrida was a catalyst for the reaction. 301- MONS 209281 Hi* method used by Jenkins and cowerkers led to the formation of 2-chlarobiphenyl and 4-chlorobiphenyl. In this reaction sane dichlorobiphsnyl is always produced, with the amount depending an the tsiperature of chlorination and on the quantity of chlorine added. Higher tstperatures during the chlorination produce higher percentages of dichlorobipheryl. When the theoretical amount of chlorine for monochlorobipheryl is aided, consider able dichlorobiphenyl is formed. the general conclusion derived front this synthesis evaluation is that it is quite reasonable to expect that chlorine contact with biphenyl at ambient temperatures will yield PCBs at a measurable rate. The effects of tenperature, dilution by air or water, lade of iron catalyst, presence of other catalytic impounds, presence of UV radiation, and other reaction conditiona present in the environment are not known. 3.2 RrwrHma Cmfeining Phenyls to Produce Biphenyls TWo aromatic nuclei can be joined to farm a biphenyl by interaction of a diazcniiza salt and a hydrocarbon (benzene) ixdar the catalytic influence of metallic oopper or zinc (Gattennan procedure). In the method developed by uiLmarm, many biphenyl derivatives are mode by the treatment of aryl halides with copper powder. The halogen atm must be reactive. N02 is an exaiple of an activating groip. These two procedures are of special interest because reactants similar to the above reactants, or their progenitors, have bean found in public weter supplies. Ebcanples are mono-, di-, and trichlorobenzene and chlorinated nitrobenzene. Hutxinger, Safe and Zitko synthesized teentythree chlorobiphenyls using a nuzber of different routes. ^ His impounds ranged from mono- to decachlorobiphsnyl. Hi* gmeral procedure used involved the us* of diazo empounda. Hi* specific chloraniline, selected to give the desired PCB, is heated in aonoentrated hydrochloric acid to about 50*C, than cooled to -5'C and dlesotizad with a solution of *" nitrite in water. Hie mixture is stored for 30 minute* at this low terperature, then filtered. The filtrate is added to aol4 vigorously stirred benzene, and a solution of sodiim acetate (or -302- MONS 209282 90da.ua hydroxide) in vater. The mixture is stirred for 12 hours at 25C., and then the PCS is recovered fran the benzene layer. As an ample, by this method, starting with 2, 3, 4, 5 - tetrachloroaniline, they synthesized 2, 3, 4, 5 tetrachlorobiphenyl. They also prepared decachlorobiphenyl by the exhaustive chlorination of Aroclor 1268. The Axoclar was mixed with twice its weight of antUrony pentachloride, and heated for four hours at 150*C. Wolf and Kharasch shared that irradiation of orthoiodophenol in benzene gave 2-hydroxybiphanyl with a 651 yield. The conclusion drawn fran this review of the reactions of a nuttier of aryls is that there are a nutter of lew taiperature reactions (0-50c.) that are capable of yielding biphenyls. In addition, sane of the reactants have already been identified as present in water supplies. 4.0 BIPHENYL USACE 331 HEAT TRANSFER FLUIDS, DYES MO PAOOGING Although the prime usage far biphsnyl is the production of PCBs, it also . has important use in heat transfer fluids, as a dye carrier, and as a paper or paperboard irpxegnant. 4.1 Heat Transfer Fluids In heat transfer fluids, for the bnperature range 250-360*0, biphenyl is used alone, or in ozrbination with other expounds. Dcwthenn "A", or Diphyl in Europe, is the ocebination of biphaiyl with diphanylosdde. A mixture of biand terphanyls was used as a coolant-moderator in the ABC prototype organicliquid cooled nuclear reactor at Piqua, Ohio. 4.2 Dye Carriers for Polyesters and Polyolefine Disperse dyes (dye and carrier oarbinatiers) are the most widely used dye type for umndified polyesters. Dye uptake is rather slm, and frequently pressure dyeing above 100*c is used. Also, carriers or acoelerants like biptmyl are used to cause the fiber to swell and allow mare rapid penetration of the dye into the fiber. -303- H0NS 209283 Polyolefin fibers are also difficult to dye. Their non-polar nature and impermeability are the problem properties. However, dye carriers such as biphenyl penetrate these fibers and leave the insoluble dye residue within the fiber. Of course, most of the carrier would be ejected to leave the fabric in dye-setting and washing processes. Disperse-dyed polypropylene fibers generally lade the bright colors sought in apparel, but they are used in tufted carpets and upholstery fabrics. 4.3 Biphenyl as a Mold Preventative in Packaging Biphenyl itself has been used for many years as a mild fungicide un citrus fruit wrappers and packaging, the 2-hydroxybiphenyl sodiwt salt has also been used as a preservative, germicide and fungicide. the use of biphenyl as cne ingredient in impregnated tissue for wrapping citrus fruit began in the Middle East, then grew in the U.S. An odor control agent was added since biphenyl has such a pronounced odor. Practically all of the biphenyl containing coating is now applied to the inside of the oacrugated cardboard cartons used for shipping citrus fruit; or the biphenyl is to a pad of sheets placed inside the carton. It would be impossible to ship citrus fruit across the G.S. in cartons, without a blue mold preventative like biphenyl. Years ago, "orange crates" of open lattice wood were used to let air circulate through and reduce nold formation. However, this exposed the fruit to the drying effects of air, external molds, water, dirt, etc. He new sealed cartons prevent all these preplans, but absolutely require a mold retardant. The ooating an cardboard or in tissue consists of a petroleua jelly or similar base with about 15-201 of biphenyl. During the raid-1950's, the FDA investigated the toxicity of biphenyl, and some of the results of this investigation emerged as a threat to the future of the $40 million/yr. segrant of the kraft paper industry devoted to making the ^ cartons, linen, wrappers etc. for citrus fruit shipping, the Institute of Paper Gienistry (UC) was chosen to determine methods of analysis, -304- MONS 209284 and to referee an investigation of the potential prohian. As a result of the work by IPC, biphenyl was given a clean "bill-of-health" by the eta aM has continued in use. 4.4 General Siphenyl Occurrence in the Environment The above descriptions of biphenyl usage indicate a potential for its widespread occurrence. Of particular interest here is the occurrence of biphenyl in industrial usages where water treatment by chlorination is practiced, as in paper recycling and dyeing operations. 5.0 PCBs GENERAnCN AND WASTB4AIER SCPEPIflTS IN A MAJOR U.S. BIPHENYL USACE LOCALITY For the past three years. Dr. Peter Gaffney of the Biology Department of Georgia State University has been investigating the problem of biphenyl and PCBs contamination of a watershed in northwest Georgia. He has also conducted experiments on the conversion of biphenyl to PCBs. Support was provided by the Georgia Envirormental Protection Division. He estimates that this locality uses about 22 million oounds per year of biphenyl as a dye carrier in carpet dyeing. This relatively sell geographical area accomodates 250 to 300 mills representing 651 of the world's carpet and rug industry. Also, w. C. Tincher of the Ehvirorrnantal Resources Center of Georgia Institute of Technology has bean studying the problmn of biphenyl effluents frcm polyester carpet manufacturing in Georgia. Other workers have been concerned with the residual odor of biphenyl in carpets. In New England, R. A. Hites of MIT has bean analyzing river water for biphenyl wastes from dyeing processes. Dr. Gaffney originally interested in the problem of biphenyl and PCBs in water whan he was celled to investigate a BCD problen at a nunicipal waste treatment plant. TWothixds of the flow to that plant (4 million gpd out of a total of 6 million gpd) came frcm a carpet dyeing mill. Mien looking for agents that might affect the bianass in the activated sludge portion of the plane, two queetione arose: -305- MONS 209285 1. Qould the biphenyl (used as a dye carrier) discharged firm the mill be affecting the biota, since biphenyl is a krown nold suppressant? 2. Could the biphenyl be converted to PCBs during waste treatrwnt chlorination, and oould the PCBs exert a harmful affect an the biota, as well as contribute toxic organics to downstream water supplies? Although these studies are still underway, preliminary data indicate that PCBs can be formed in the suspected manner. The original report of Gaffney's work told of finding 18 ppm of PCBs ithe scrapings frtm the surfaces of trickling filter rocks in the nunicipal treattnent plant. ^ At the time, no PCBs nn detected in the influent. This seemed a strong indication of PCBs formation within a nuiicipal treatment plant. The plant was using about 350 pounds per day of chlorine for influent odor control and effluent disinfection. When it was later discovered that there wea an upstream transformer plant using PCBs, further testing indicated there we detectable PCBs in the intake water to the mill and the tom. Dr. Gaffney continued hie previous work on chlorination of organics as they pass through rm^jclpsl treatnant plants. ^ The tests and data are consid ered preliminary at this tima, and furthar reaction and analytical data are highly desirable. In laboratory tests, detectable levels of PCBs we fanned when 10 mg/1 of biphenyl were aided to deknirert water, held at 20*c, and then 1 rrg/1 of chlorine was arri tt* reactants kept in contact far cne hour. Fiftesn peaks were formed in the electron capture chromatogran (a haxane in vnter control gave four peels with the sane treatment). Man iron was included in the reaction mix, flour more peaks were formed (total of 19). It is believed that tbaea peaks are largely chlccobiphenyls. Addition of an Aroclor to the pure wateg resulted in the growth, by SO fold, of the peak height for dichloro- biptanyl <ia to chlorination. -306- MONS 209286 Wien tmicipal wastewater was analyzed before and after Laboratory chlorination, as described above, the dichlorobiphenyl peaks increased in height by ten-fold. Although the tentative conclusion from this work was that PCBs can be formed through chlorination of biphenyl in wastewater under laboratory con ditions, extrapolation of the results to actual wastewaters Cron industrial sources is probably pranature. Even noire tenuous, but of equal interest, is the possibility of further chlorination of PCB molecules via chlorination. Howvar, it should be noted again that the use of biphenyl as a dye carrier leads less to its dissipation in products than to its eventual des truction or discharge as waste. Assisting that half of the biphenyl so used appears as waste, a biphenyl to PCS conversion of even 0,01 percent during chlorination treatment for the 22 million pounds per year of biphenyl in northeast Georgia corresponds to the generation of over 1,000 lb/year of Alorinated biphenyls in that area. 6.0 POTENTIAL CBGRAMTICN At SUBSEQUENT REACTION OF EOT AM) FELA1H) OOMPOUC6 IN THE ENVUWMNT TO P0BM PCBs It appears possible that there are a nmtosr of oonpeunis in the environ ment that could be partially la i mu mil and than reacted with their cen de- ccxrpoeition products, or with other reactants, to produce POa. As early as 1969, Plimner and Klingabial reported that CCMJ, dichlorobenropherons, and dichlorobiphenyl, were all products of the photolysis of COT or COE in methanol at 260 rm ultraviolet radiation. (8) This conversion may be sensitive to reaction conditions. In the sane year, Hosier, Quenzi and Miller did not observe fonnetion of PCB* or CCKJ when they subjected solid COT or XT in hexane to UV Irradiation at 254 mu Since that time, moat lasesri-hrs publishing on this topic have suggested the possibility of conversion of COT to PCBs. Paakall and T.inrer stated that the possibility that PCBi could be derived fron COT should be considered.'101 They did cot believe this oould occur in metabolic processes in tissues. How ever, they felt that UV catalyzed free radical reactions to form dichlorobiphenyl from COT oould be expected in the atmosphere. -307- MONS 209287 Although they could envision tautaneric shifts leading to various lsaters of dichlozobiphenyl, they could not theorize a route to more highly chlorin ated biphenyls by these DOT reactions. They also pointed out that PCBs extract ed frat biological materials matched well with the PCTs found in Aroclors like 1254 ;or.e-hal5 pentachlorobipheryl, and about one-quarter each of the tetrachicro and hexachlorc harologs). Thus, if DCT degrafation to dichlorobiphenyl were taking place, further chlorination would also have to take place, by sane other reaction, to lead to the material found in biological specimens. Peakall and Lincer also point out that the ethane catpcnent between the two rings in DOT is the weakest part of the structure and is the site at which most transforma tions of COT take place. The PCBs, not having that weak point between the two benzene rings, thus are expected to be more stable than DOT, which is the case. Maugh again reported an the COT conversion potential, apparently unaware of the Pliraner and Klingebiel report, and shewed the potential for vapor phase p.hoto,lys.is. (11) Peakall, in his recent conprehensive review, "PCBs and Their Environmental Effects', does not cite other references for other machanisns of COT conver- oil However, Kothny, in a letter to the editor of Ownical and Engineering News, states a case far the formation of gaseous chlorine fron particulate chlorides under the influences of ozone and solar radiation/^ He states that the chloride loss fron particulates, formed by the evaporation of water from sea spray, "has bean Ison for some time". Kothny then goes on to attribute PCBs formation to the reection betwean a wide range of aroratics that could be present in the atmosphere, and chlorine, formed as described above. He also suggests potential PCBs formation from all manner of waterborne aromatics by action of nunidpel and industrial chlorination of pure and wastewater. 7.0 OCtCARISCN Of POTENTIAL INAWETOEOT AMHENT REACTIOS Of the types of nations cited in this section as holding potential for inadwtant ambient production of PCBs, the possible chlorination of biphenyl during industrial and nuncipal water and waste treatment appears to the authors to have the most significance. In general, the other reactions cited would -308- MONS 209288 require tw steps (chlorination plus condensation of aryls or decanposition of EOT followed by recaifcination of selected fragments); they also would be ejected to involve ocrpounds present in relatively low concentrations canpared with potential biphenyl concentrations in sane industrial waste streams. Fbr all of these reactions, however, rono- al dichlorobiphenyls would be the expected products. Although these are believed by rrany researct*rs to be significant (especially in an aquatic envirorment), it is generally accepted that they are more easily biodegraded and less bioaccunulative in comparison to the more highly chlorinated PCB hanologs. The possible forma tion of more highly chlorinated PCBe from mono- and dichlorobiphenyls is thus also of interest to the envirormsntal PCBe croblan. 3.0 PCBe FOUND IN THE OTLLejTS OF THE MACHINEMf AND MECHANICAL PRODUCTS (^NUFACTURING INDCJSTRf For same time it hee been suspected that PCBe could be found in the effluents of other industrial categories which are not recognised as being sources of PCBe entry into the environment. A review of data presented in the draft Development Document For Effluent Limitations Guidelines for the Madiinery and Mechanical Products Manufacturing taint Source Category (FT5A Oontract No. 8-01-2914, volute 3, June, 1975) indicates high concentrations of PC3s, in the order of 2 to 28 mg/1, in the effluent of the plants groined in this category. This grot^ of industries encompasses 173 different product group segments manufacturing over 4000 different products in over 100,000 separate plants. These products include such varied goods as wire, tractors, x-ray equipment, sporting goods, automobiles, television picture tubes, and jewlry. Because of the variations in manufacturing operations frem plant to plant, categorization of this industry was based on the manufacturing processes utilized, thereby a specific plant was defined by the applicable process sub categories which dssrrlbs its overall aparatian. Rationale used in subcate gorizing this group of industries was that the manufacturing processes, not the product, generate the effluent discharge. -309- MONS 209289 Based on the above, this group of industries was divided into the following twelve general manufacturing subeategories: Subcategory 1 Subcategory 2 Sibcategory 3 Subcategory 4 Sibcategory 5 Sibcategory 6 Sibcategory 7 Sibcategory 9 Subcategory 10 Subcategory 11 Subcategory 12 Casting and elding - Metals Mechanical Material Removal Material Forming - All Materials Except Plastics Physical Property Modification Assoobly Operations Chsptical-Fl octree! ismical Operations Material Coating Molding and Forming - Plastics Film Sensitizing Dockside Ship Building Activities Lead Acid Battery Manufacture The PCBs concentrations in the raw waste fmn the overall machinery and mschanical products manufacturing point source subcategories, as abstracted froa the abovmantionad draft Effluent Guidelines Cocunent, are presented in Table 8-1. This table shows the minimus, maximum and mean PCBs oncentrations as found froa saepling and analysis work conducted by the con tractor on 240 raw waste itrsens in the point source category. As reported in this document, all ssples wars taken downstream of tha manufacturing processes, but prior to any treabnant. It can be sear froa Table 8-1 that PCBs concentrations in tha effluent froa this groip of industries are nuch higher than those reported for the major PCBa user industries (capacitor and transformer industries). Within tha machinery and manufacturing industries PCBs could be used in paints, inks and plastics, as wex fillers in casting operations, as hydraulic and heat transfer fluids, and in lubricants. It be mentioned, however, that there are questions as to the valid ity o the analytical techniques used during this study. Subsequent studies anluctsd by Versar Inc, on Sibcategory 12 (lead acid battery manufacture) under ETA Oxitract 88-01-3273 have indicated no detectable levels of PCBs in tha -310- MONS 209290 TABLE 3-1 PCBs Concentration in the Effluents of the Machinery & Mechanical Predicts Manufacturing Subcate^ary - 1 2 3 4 5 6 7 8 9 10 11 12 Manufacturing Operations Casting 4 Maiding of Nonferrous Metals Mechanical Material Ramval Material Forming - All Materials Except Plastics Physical Property Modification Assembly Operations Owaical-Electrochenical Operations Material Coating Smelting and Refining of Nan- ferrous Metals (biding and Forming - Plastics Film Sensitizing DocksIda Ship Building Activities (2) Lead Add Battery Manufacture PCBs Concentration ________rrg/1 (I) Min, Max. Avq. 0.2 5.1 0.2 63.3 2.1 6.997 0.2 63.3 0.2 100.0 0.2 104.4 9.367 12.342 15.553 0.5 2.8 0.2 224.8 1.65 18.241 0.2 18.0 - None 0.3 123.9 9.1 - 28.136 - Nona 7.5 30.0 18.75 Nate: (1) Information obtained fron the Development Docunent for Effluent Limitations Guidelines for the Machinery i Mechanical Products Mamfacturing EPA Oontoact No. 68-01-2914, Vol. 3, June 1375. (2) (to water effluent; all solid wastes. -311- MONS 209291 effluents; hwever, evidence of the preswice of chlorinated hydrocarbons was found. Effluent Guidelines study on Subcategory 10, Film Sensitizing Industry, is currently underway. According to the information presented in Table 3-1, this subcategory was demonstrated as having the highest levels of PCSs concentration in the outfalls. Verification sampling work to be conducted on these effluents will provide a further test of the validity of the data in Table 3-1. It is considered quite likely that effluents frexn industries other than those directly involved with the production and process usage of PCBs ray exhibit significant mounts of PCB contamination. Much of this contamination, if found, could be attributed to past usage of PCBs and products containing PCBs, although, as stated elsewhere in this report, current usage must also be considered a possibility. % our knowledge, no significant effort to determine the extent of PCBs contamination fmn such sources has been made. -312- MONS 209292 REFERENCES 1. Jenkins, R.G., McCullough, R., and Booth, C.F. (Federal Ptospheris Carpany), Ind. and Eng. Q., 22, 31 (January, 1930). 2. Schmidt, H., and Schultz, G., Ann. Chan., 207, 338 (1881). 3. Kramers, K., Ibid, 189, 142 (1877). 4. Hutzingar, o., Safe, S., and Zitto, V., Bull, of Env. Contamination and Toxicology, 6, 209 (1971). 5. Hblf, M., and Kharasch, N.; J. Ctg. Q., 26, 283, (1961), 6. Gaffney, P.E., Science, pg. 367, February, 1974. 7. Ingols, R.S., Gaffney, P.E., and Stevenson, P.C., J. Water Pollut. Control Fed., 38, 629, (1966). 8. Pliraner, J.R., and Klingebiel, U.I., Chanical Camunications, 1969, p. 648. 9. Moeier, A.R., Guenzi, W.D., and Miller, L.L., Science, 164, 1083 (1969). 10. Peakall, O.B., and Linear, J.L., Bioeciance, 20, 9S8, (1970). 11. Maugh, J.M., Science, Mey 11, 1973, p. 578. 12. Peekall, O.B., "PCBe and Their Environmental Effects", CRC Reviews, 5, Issue 4, 1975. " 13. Kothny, E.L., letter to the Editor of Chemical and Engineering News, January 19, 1976, p. 5. -313- HQNS 209293 SECTICN XI ^DVmEJT OF PCBs IN THE ENVIRCNMEJET __ GENERAL DISTRIBUTION MDCEL 1.0 rNTRODUCTICN Thus far in this report, ths history and current status of PCBs production and usage, treatment and disposal aspects, and gross estimates of current environmental distribution have been presented and discussed. Transport of K3s within the environment is extremely important in the assessnent of future environmental distribution of PCBs. In turn, knowledge of future PCBe distribution will allow the assessnent of potential regulation of PCBs production and usage. Projection of future biological effects also depends upon the distribution of the substance of interest. Transport of PCBa hetrnwan soil, water, sediments, the biota, and the atmosphere is of obvious local environmental inportanae. Measurable anounts of PCBa have bean found in Antarctic iae, showing that atmospheric transport over long distances does occur. Transport phenomena at the various phase interfaces are of obvious importance to the mobility of any environ mental acntaninant, but in most cases, and this is particularly true of PCBs, such transport properties are not known and have not bean treated success fully in a theoretical manner; On the other hand, analysis of the transport and distribution of a given acntaninant requires sufficient knowledge of basic transport prooeasas on which to base reasonable estimates; ths estimates can then be evaluated using an internally consistent model and available experi mental data. A ainpla, first-order mass halanns model has been constructed to treat the overall PCBs eoonony of an artificially bounded region of the lithoephese. In order to test ths validity of the model, it was applied to Lake Michigan and the associated drainage basin. Lake Michigan was selected tot this application of the existence of a considerable body of -314- HONS 209294 r*ctt data cn PCBa concentrations, because of the anvirurewital and ocrawr- dal significance of PCBa oontwunaticn in Lake Michigmi, and thia lake, in spit* of its sirs, represents a relatively closad syatan (estimated water retention time of 90 years). the total envircmantal load of PCBa, and its variation with tin*, represents a very important input to the mass balance rocWl. An analysis of available data was performed to provide this input, one important result of which was an estimate of the variation of atmospheric fallout rate with tire. Atmospheric fallout appears to be the most iitportant source of PCBa entering Lake Miehigsi, although this may not be the case for other areas (the lower Hudson River is one possible exception). For exetple, in 1974, atmos pheric fallout onto the lake and its drainage basin accounted for approximately 85 percent of the PCBs input to the lake. The rationale for the model is described in Section 2.0 below. Sub sequent sections dserrlhs the application to Lake Michlgw and the results and conclusions thertfraa. The development of the model is presented, in full, in Appendix D to this report, d the supporting date used are tabulated in Appen dix E. 2.0 RATICNALE FOR MCCB, DeVELGMSn The first order model drives basically frem the assertion that the total of PCBs entering a bounded region of the lithosphere nust be fully *caotntsd far by: (1) Incorporation into specific phases of the bovndsd region; (2) loss from the region vie mass transport; and (3) Degradation by process-- operating within the region. In ^plicatim, the region under study is selected to be sufficiently large and well defined that adequate averaging can be aooooplished. The Lake Michigan ana, Olid* masts the above criterion, was selected as a suitable region Cor study. Bis region included the nominal drainage basin of the lake -315- MONS 209295 in order to provide an estimate of the PCBe entering the lake frcri ruoff. After suitable boundaries were defined, an overall mass was constructed. The source function was constructed so as to account for all point and non-point sources. The distribution over the various internal phases of the syatari (aqueous solution, biota, and sediment) was then estijnated. Additional terns were introduced to account for POSs loss frcra the region due to mass outflow and surface evaporation. There was ap parently no need to introduce a teon to account for degradation since such processes are thought to be of small Importance for PCBe. The form of the mass balance was then as follows: B(t) it At^ + AMg + AMS + AMq + AMg (2-1) where: B(t) is the sourae or driving function whidi describee the input rate for PCBe; is the dungs in the mesa of PCBe dissolved in the aqueous phase of the region? AMg is the dungs in the mass of PCBe contained within the biota of the region; AM# is the dunge in the ness of PCBe ocntained within the sedi ment of the region; AN is the mess of PCBe carried out of the region by (water) o mass transport; and AMg is the ness of PCBe carried out of the region by evaporation (oodistillation). 2.1 Tine of the PCT Input Rate [B(t)] The distribution of PCBe between phases within the region is governed by processes ldlidl are to act independently of the actual ocnaentrations involved, the tin depedeva of equation 2-1 is therefore ocntained in the driving function, [B (t) ]. -316- HONS 209296 Sensitive analytical methods for PCBe have been available only for a few years; consequently a sufficiently reliable and detailed data base to allow the direct determination of B(t) is not available, in view of this, it was necessary to construct a model which aould be fitted to a direct esti mate of B(t) for a specific time, in order to approximate the appropriate time dependence of B(t). the details of the ccnputatian by which B(t) was determined are contained in Appendix D (Section 2). For the purposes of this stannary, it is sufficient to state that the major input of FCBs to the region selected (Lake Michigan) was from atmospheric fallout; thus the time dependence of B(t) was estimated from knowledge of the time dependence of the fallout. Table 2.1-1 is a summary of the input PC3 from all sources during the period 1973-1974 and is a summary of the detailed data which are presented, along with suitable citations to the sources of these data, in Appendix E of this report. Table 2.1-1 Sunnary of PQS Input Sources (1973-1974) to lake Michigan Point Sources Lake fallout Basin fallout* 1.6 x 103 lbs/yr 6.4 x 103 lbe/yr 5.4 x 103 lbs/yr Then B(t> - B(1973-1974) - 13.4 x 103 lbs/yr * It is that 50 percent of the basin fallout actually enters the lake as inputd) 3.0 AFFLXOttXCN Of TS MCDB, TO LAKE MICHICMI results of si analysis of PCBe distribution within lake Michigan an sunriasd In T^sla 3.0-1 (The details of the amputation are given in Section 3 of Appendix D). -317- MONS 209297 &ble 3.0-1 Overall PCBs Balance for Lake Michigan Area During the Period 1930-1975 TOtal Input Total in Solution (Water) Tbtal in Biota Total in Sedinent Total in Outflow Tbtal Evaporated 1.49 x 105 lbs. 1 x 10S lbs. 3.64 x 103 lbs. 1.7 x 104 lbs. 9.07 x 103 lbs. 1.93 x 104 lbs. The last entry in Table 3.0-1 indicates that sane 13 peroent of the total input to the lake has ben lost by evaporation (oodisfiliation) from the surface. The concentration of PCBs in the aqueous phase and the (average) concentration in the biota ware calmlateri; the results are displayed in Table 3.0-2. Table 3.0-2 Derived PO Concentrations in Lake Mldiigan water and Biota CXsnr the Period 1930-1975 Date 1930 1935 1940 1945 1950 1955 1940 1945 1970 1975 '"water <ppt> 0 4.9 x 10~4 1.34 x 10"2 7.12 X 10"2 0.28 0.68 1.60 2.92 5.35 9.10 '"biota* (ppt) 0 1.97 5.36 x 102 2.84 x 103 1.12 x 104 2.72 x 104 6.4 x 104 1.17 x 105 2.14 x 103 3.64 x 10 -318- MONS 209298 "Ow values presented in Table 3.0-2 are Late-witei averages so that considerable variations fron these values an to be expected from point to point within the late; for instance between the rcrthem portions and the heavily acntardnated regions on the southR^stam shore, in addition, because of the considerable spread in species-specific concentration factors (ard the wide variation in intra-species concentration factors) it can be surmised that FCB concentrations in higher predators could easily have exceeded the ppm level by 1960. 4.0 RESULTS AMD CCNCIJJSICNS 4.1 Results Even thou^i the model used is only first order, it is apparently able to describe the relative significance of the natural processes whidi control the distribution of PQJs. The strong focus an fallout as the primary input source of PCB to Late Midiigan suggests the need for further study of the nature of the processes by whidi PCBs beams airborne and thus beams part of the available atmospheric reservoir. The attaint to model the atmospheric reservoir of POs, discussed in Appendix o (section 2), yields results that indicate significantly greater curur Lative atmospheric loads thai the preliminary estimate, made by Nisbet and Sarofim, of a emulative atmospheric reservoir of 3 x 10*' tons 19 to 1970. The estimate of Nisbet and Sarofim leads to a half-Lifa, front the model, for FCSs in the atmospheric reservoir an the order of ei^it years. This value is considerably in romnsi of the reported lifetime measurements, an the order of 20 to 40 days, far atmospheric PCBs. However, the obeervation that signifi cant levels of PCTa are fiorad in piasant snowfalls and in packed anew in the Antarctic(4} suggest that the vplicable half-life may indeed be considerably longer than 20 to 40 days. bution It is suggested that further refinement of the anvirerasntal distri [ii aemtal in Appmdix D (Section 2) will lead to a resolution of -319- HONS 209299 this appareit discrepancy, This refineient will focus attention on the nature of the physical processes inwlved in atmospheric transport of PCBs and may sixyjest methods of reducing PCB fallout in the future. The observation that evaporation and/or oodistillation sens to be a significant prooess by which PCBs are returned to the atmosphere is of im portance. It should be noted that the magnitude of the evaporation rate con stant necessary to achieve mass balance in lake Midiigan is in excellent agree ment with that computed from the simple kinetic theory of gases and with that catpjted from the theory of oodistillation discussed by Madcay and wblkoff (see Section 4 of Appendix 0 for a detailed treatment of this subject). The observation that the PCB input bo lake Midiigan from point sources seams to be a rather small part of the total input suggests that re* duction of point source PCB effluents may only slowly correct the present problem. 4.2 Cbnclusicns The first order trees balance model described herein seams useful in describing the historical situation as it explicitly addresses the question, "Bow did we get tMze?" The model requires refinement before it can be used to allow a reasonable estimate of future conditions. Significantly more detailed data are required aa to the teiporal variation of inputs and concentrations as well as an the internal transport processes by which localized concentrations are smoothed and distributed over the whole body, vtiila the present model seams to very well with the situation that obtains during an interval of rising abacus oanooitrations, there seams to- be little experimental or theoretical guidance as to what will happen if, in the future, aqueous ocn- uaitrations begin to fall, it is not known whether the biota and the sediments will act as reservoirs to return their PCB loads to the system. The processes, if any exist, whidi will eventually remove or inactivate the PCBs already in the lithosphere are not known. -320- HONS 209300 Th application of this modal to the situation in Lake Midiigan scans successful, it will be of interest to apply it to regions which are more cmplex or of larger scale. 5.0 BIBLIOGRAPHY 1. ftjttner, F., Fundamentals of Limnology, Uhiv. of Toronto Press (1952). ---------------------------------------------- 2. Nisbet, C. T. and A. F. Sarofim, Environmental Health Pro spect!ves, Exp. 1:21-38 (1972). 3. a. Sodezgxen, A., Mature 236:295-397 (1972). b. Risebrough, R, w., et al; Nature (12/14), 1098-1102 (1968). c. Harvey, G. R., et al; J. Marine research 32 (2): 103-118 (1974). d. Harvey, G. R. and w. G. Steinhauer, Atmospheric Bnwircnnent, 8(8):777-782 (1974). 4. Peel, D. A., Mature 254 (3/27):324-325 (1975). 5. Mackey, D. and A. w. HbDcoff, Btv. Sd. a Tedi. 7(7):611-614 (1973). -321- HONS 209301 SECTION XII RBGUIATOKf ACTIONS CN PCBs 1.0 introoucticn The risk of increased aconulatian of PCBs in the envirorrant as well as appreciation of the difficulties inrolved in imposing workable environmental controls in most end-use manufacturing operations have led some nanufacturers and a nurber of govemnent agencies to take steps to regulate PCBs or to restrict son uses of PCBs where mission risks axe obviously quite uncon trollable. 1.1 Measures Taken by the ttoufacturers In 1971, Monsanto Company, the major producer of PCBs, instituted a piogian *iich led to voluntary restriction an sales by the Msnaanto of PCBs for all usee except the manufacture of sealed electrical equipment (transformer and capacitor applications). Sales for hast transfer applications were phased out in 1972 dill* sales far other non-electric applications were discontinued in 1971. As a result, current production related to point source discharges of PCBs axe more controllable than in years prior to 1971 whan PCBs were widely used in thousands of 'Cpsn-Ehd* and "nominally closed* operations. Furthermore, fay 1971, at Mnsanto's suggestion, the capacitor and transfoxmer industries famed a standards ooranittes. The members of the oonmittee include representatives from the three affected industries, EPA, Department of the Anny, Dspartanmit of Agriculture, the TSmesses Valley Author ity, the National Bureau of Standards, and the Geraral Services Mtoiniatratlon. Also i girsisnral wees the Certified Ballasts Manufacturers Association, the Electronic Industries Association, the Institute of Electrical and Electronic Engineers, and the Mtionel Electrical Manufacturers Association. In the fall of 1972, wlmr the of the American National Standards, this ccnnittas published fd handling and t guidelines (M5Z-C107-1-1974). This docu ment establishes pcooeduxes for labelling, shipping, general handling and i'T'Ttr disposal of and m*T-ijil containing PCBs. 'Avis standard -322- HONS 209302 has been pixpoeal also by NEJA and is currently being used voluntarily by the transformer and capacitor industries. The above measures taken by the ranufacturers could be effective in PCB control if they ware supported, urplsnented and enforced by the Federal Govexrment. 1.2 Measures Taken by the CJ.S. Government The Government of the United States has taken a number of steps with the objective to reduce the PCBs aontsnt in foodstuffs and reduce snissions from all sources. The following Federal laws are relevant for the regulation of PCBs. 1,2,1 Food, Drug and Pontic Act (21 CJ.S.C. 301 et seq.) The Food and Drug Administration has set tolerances for PCBs contamination of animal feeds, foods, and food packaging in its final rule making dominant published an July 6, 1973 (Federal Register, itol. 38, No. 129). These tolerances, (pressed as parts per million are as folia*: (1) Milk (fat basis) 2.5 (2) Dairy products (fat basis) 2.5 (3) Poultry (fat basis) 5.0 (4) Eggs 0.5 (5) Complete and finished animalfeeds far food producing minis 0.2 (6) Animal facd caeponants 2.0 (7) Fish and shellfish (edibleportion) 5.0 (8) Infant and Junior food 0.2 (9) P^er food - packaging material 10.0 The FOod and Dn^ Administration provides, upon request, the analytical inetfnle used for enforcing these tolerances. The FDA enforces the FDC Act by various mains, including inspection of food eel alii 1 ilneiif i to determine whether the provisions of tha Act axe being violated. These inspections include the col lection and analysis of food ssqplas. figTM of the smplaa are taken by FDA cn a routine surveillance -323- HONS 209303 basil to determine tbs presence of specific aontaoinanta. However, the actual r.'jrber of FDA conducted routine saiple and analyses is few and this agncy relies heavily an information an the known or suspected existence of specific instances of food contaninatian. 1.2.2 The Egg, Meat and Poultry Acts The Consumer and Marketing Service of the u.s. Department of Agriculture {USD*) administers three acts relevant to the PCS problem; tha Egg Products Inspection Act (P.L. 91-597) % the Wholesome Poultry Products Act (P.L. 90-492); and Vholeeane Meat Act {P.L. 90-201). These authorities apply to meat, egg or poultry products from the time they reach the processing plant until they are purchased by the aonsumer. Cnee they leave the plant, they are also under the FDC Act. The Department of Agriculture uses FDA guidelines for its Egg, Meat and Poultry Acts. 1.2.3 The dean Air Act {42 U.S.C. 1857 at sag.) Mr. David Young of the Southern California Coastal water friaerrh Project in a report prepared as pert of an Q8D (Bwiroruental Research Center - Corvallis) contract acknowledges that the air contributes about onethird of the total POS loading of the ocean. His conclusion that air is a sig nificant route of P9 transport is based on afflumrt and aerial fallout measuremanta mada in the aoaetal areas of Southern California. The current understanding is that air transport of PCBa is a contributor to the P3 loading of othar madia. However, the conclusion reached by the pollutant strategist board of the Strategies and Air Standard Division is that the air act of 1970 is not an effective legislative measure for control of PCBai but that far PCBa should be considered for control. The i miiiiht<fn neda at that time was to control PCBa fay regulating the produc tion, use and aiyi-i of PCB-uuitaining products. The gsneral authorities contained in the clean air act ara not applicable to the majority of P<3 dischargee since PCBa from most PQ applications. -324- HONS 209304 such as for clogad electric systms, are not emitted into the air by the opera tion of industrial and nimicipal facilities. In these applications. pa missions are aseociated with accidental losses and waste disposal in landfills. Additionally, PCBa enter the air via the burning of refuse containing PCS waste products. These types of air missions can be controlled oily by preventing PQ products from being incorporated into the refuse. Control of missions fran landfills may require specifications on how waste is cowed and, in sane cases, the application of plastic materials to prewant sublimation. However, in the case of PCS applications for the investment casting category, FQi can enter directly into the envircrmant from the operation of furnaces which are used for purposes of setting the sold and removing the wax from the mold, in this latter application, the air act can be used as an important tool for the regulation of PCS entry into the environment. 1.2.4 Federal Whter Pollution Control Act (33 U.S.C. 466 et sag.) Section 304(a) of h*g Section 304(a) of the Federal Meter Pollution control Act (EWPOU authorizes the AtaLnistxator of ERA to enforce state water quality standards established by the States and approved by the Federal Gowtrrrasnt, if the Stabs is not adequately enforcing the standards. In 1973, water quality criteria were proposed to limit POs to 2 ppe in mfeient waters. The 1973 j.n.upused level has bean mors reoantly reduced to 1 ppt due to evergrowing gannem on the health and ecological effect of PC3s and on the basis of further review of available data. Section 307 (a) Wfl A national effluent standard for POs has bean proposed under Section 307(a) of !WO. Section 311 of FWPa In 1974, the Office of Air and Mater Programs acted to minimize accidental spills of PCS through the enforcement of Hazardous Substances Section of the Hater Pollution Control Act. Currently, pursuant to Section 311 of this -323- MONS 209305 act, proposed guidelines on the levels of haaaful quantities of PCBs accident ally released into navigable waters and rates of penalties for such spills are being developed. Section 304(d) of FWPCA Section 304(d) of the effluent guidelines pranolgated for several industrial categories certain limitations on PCBs. For exaiple, effluent guidelines praiulgated for the steam electric power generating cate gory aontain limitations of "NO Discharge" for PCBs. Furthermore, epa reports that NPDES permits limiting PCS discharges have already bean issxmd for several facilities. 1.2.5 The Refuse Act of 1899 ( 33 U.S. C.407) Section 13 of the 1899 Refuse Act forbids tha discharge of any wastes, other than municipal wastes, into navigahls waters without a permit. This act would be an effective tool in the control of PCS discharges into tha watarvmys if the permit program required the reporting of POs as a separate itam. Presently this is not a raquircmnt. 1.2.6 The Operational Safety and Health Act (29 U.S.C. 651-678) Chemical hazards in the workplace are regulated under the Occupational Safety and Health Act (CSHA). Tha Secretary of Labor, in coopera tion with the Secretary of Health, Education and Welfare, is authorized to set and enforce operational safety and health standards applicable to businesses affecting interstate oonmarce. In title 29, Section 1910.93, the limits set for chlorodiphenyl caipoudi as an air contaminant are 1 mg per cubic meter for Aroclor 1242 and 0.5 mg per r*+A* meter for Aroclor 1254, based cn 8 hours average exposure. The D^arOent of Labor could enforce these limits on PCBs. 1.2.7 Act to Regulate Transportation of Bylosives and other Dangerous Articles (18 U.S.C. 831-33*) The Deperonent of Transportation (DOT) regulates the transport of hazardous subetanoas under the Act to regulate transportation of explosives -326- MONS 209306 and othsr dangerous article*. Under CFR Title 49, Subpart G F^ruary 27, 1973, DOT claeaifiee poisonous substanoes into three categories: Class A - highly poisonous material Class B - moderately poisonous material Class C - irritating material The responsibility for insuring that this standard is met remains with the manufacturer and the shipper, vxz;1,2,8 Federal Insecticide, Fungicide, and ftadanticide Act (FIFPA) ---------H I55=I33Kr----------------------------------------------------- On October 29, 1970, the Pesticides Regulation Division, admin istered then by the Department of Agriculture, issued a notice (PR Natioe 70-25) to all pesticide manufacturers and distributors to eliminate the use of poly chlorinated biphenyls and polychlorinated terpheryls frcm their fontulation and products. Presently, then should be no pesticides on the market or in use containing POs. Ihder the FBRA act, ell rsstlcidee shipped in interstate ummeioe sust be registered with the EPA. Presently, ERA can refuse to register a product if it will cause injury to hunans or the anvironoent if used ae direc ted. A product already registered with SA can be cancelled if it is found that it no longer meets the criteria of registration. Congress is currently considering bills to renew the FORA act. Kara than 20 ananAnants to FSRR are pending in tha Bouse and Senate. Ons of these amsndtawita, if adopted, will give the Secretary of Agriculture the power of veto ouar ERA by requiring USER concurrence in procedures leading to pesti cide cancellation or changes in classification or regulation. This ansndnent will loosen ERA'S controls on dangerous pesticides. 1.2.9 Needs for Federal Oontrol It can be sumrized that curmtly four govemnsnt agencies, tha ttnaantao Oaiqeny and ISA emprise the regulatory forces restricting the use ani distribution of POs. ERA, OSHA, FDA and USDA have authorities to regulate 327' HONS 209307 and monitor food levels, disposal into waterways and housekeeping and safety practice* in the work place. EPA forbids the use of POe in pesticides and regulates their discharges into the waterway. OSHA can regulate PCS hazards in the work place. FDA forbids PCS use in food processing machinery and limits PCS levels in food, feeds and paper food-packaging material. USDA follows FDA guidelines in egg, meat and poultry products. Monsanto manufactures more degradable PCBs and sells then only for selective uses, and NEMA recommends standards and guidelines for handling and disposal of PCT containing materials. Each of these available authorities has a Limited focus and is inadequate to prevent sore PCBe from entering tha environment. Both Knsanto's and NEMA's actions are volimtary and have no lew behind them far enforcement. The government has no power bo control and restrict iaports of PCBe and if it desires to restrict the use of PCBs in selected applications, it has no authority to irposs this restriction cn any manufacturer. the above actions can only be implemented through the proposed Ttncic Substances Oontrol Act (T9QU. TS would give &A the needed authority for formal banning of certain PCS uses and sanctioning National Standards and Guidelines for handling and dliposal of PCS containing products. Thus EPA could with the PCS problems in a far mere orderly and effective manner. Addition ally, the TSOk would enable D>A to require testing for health and ecological effects of near chemicals which are being proposed as substitutes for PCBs. Thus, this measure could prevent new chemicals from cresting health and ecologi cal problems similar to those from POe. This preventive approach of controlling chemicals is a sere reasonable and oo*t effective method than the current approach of corrective measures after the denege has bean dene. Therefore, the passage of the Toxic Substances Act by Congress is an important step in dealing with problems such as POs. 1.3 latsmaticnal Decisions and Aqreensnt There are currwrtly no regulations to restrict the importation of PQJa as a chasLoal for use in applications banned by the Mansanto Conpany. As a 328- HONS 209308 result, PCS is being iapcctad by a far aatpanies for use in several "opw-end" or "nominally-closed" applications. In 1972, with hopes to bring about a culti-national urderstarxling on PCS uses, the United States asked the Organization for Eaonaisic cooperation and Development (OECD) through its Environment Ccranittee to review national policies on PCBs and also identify products moving in international trade which contained PCBs. In October, 1972, OECD, whose rwmbers include all major western industrialized oountries plus Japan and Australia, met to discuss the U.S. proposal to control manufacturing and trade of PCBs. In the October meeting the CECD Council decided that for adequate protection of health and anvixcnnant, PCBs should be controlled by the actions of individual mender oountries. It was agreed that in order to insure that heme production was not substituted by imports, control action by governments through licensing or other means was essential. It was further recognized that means to injure proper collection of used materials, safety in transport of raw POs and asaeseient of sistitute* for POa ware of utmost importance. Details on the council's decisions were issued on February 14, 1973. 'foe major thrust of tha decision vest A. PCBa should be used for industrial or cannarcial purposes in the following applications t - As dielectric fluids in transformers and capacitors - in haat transfer applications (othar than that for applications in foods, drugs, feeds and veterinary products) - As hydraulic fluid in mining equipment with "tsprt to the above uses, the CECD Qxmcil raaotmndad that PCBa stmld only be ueed if adequate environmental controls **re exercised and when the requimrt for non-inflmmability outweighed the needs. B. Mnufacture, use, recovery, disposal, inport and export of POa should be controlled and regulated. Special labelling for bulk PCTs and PCB-ocntaining products should be instituted 329- MGNS 209309 HONS 209310 this restrictive measure to include the heat-transfer ard hydraulic-fluids industries. 1.4.2 Measures Taken by Sane Goverrments 1.4.2.1 PQi Producing Countries Actions taken by governments differ widely, ranging from acceptance of the measures taken by the manufacturers to a more strict regulation. ^ance The government has taken no active legislative action and has accepted the local manufacturers decisions. These include: - Complete cessation of sales for heat transfer purposes, in pharmaceutical and food industries, paper production of carbonless copying paper, marine paints and cutting oils. - Providing information to manufacturers about the dangers of PCB, with a view to cancelling their use in or on products in contact with foodstuffs. Germany The government is taking the approach of supporting the manufacturers1 decision to stop selling KB and is pursuing the 'voluntary signing of bilateral agreements to restrict the amount of imports. Additionally, tolerances of P<S in foodstuffs are being established. Japan PCBe have bean under governmental control since 1972. There have bean practically no production, import or export of PCBe in this country since 1972. The two aoxspaniea, Kanegafuchi Chemical and MitsubishiMxisantOr which had ban producing PCBa in Japan ceased their operation and sus pended their sales in 1972. Cne exception has ban the production of PCBe for railroad transformers which was discontinued in September, 1973. The use of -331- MONS 209311 existing stocks in railroad transformers is permitted, subject to the condi tions that there be no discharge to the environment. Beginning in 1976, pp*r plants will be prohibited fran accepting PO contaminated paper for recycling purposes and they will be required to build treatment facilities to met the general discharge standards. Inports of equipment using PCSs have been decreased drastically since 1972. For these products importers must cooperate with the users to ensure that the ocnponents containing PCBs are properly disposed. Manufacturing of PCBs are rigidly controlled by the Ministry of International Trade and Industry (MITI). Any catpany who desires to manufacture PCSs trust apply to MTTI for a permit. The Japanese government anticipates a total ban on PCSs in 6 to 10 years. These efforts have had markable results, and the envixonnantal lewis of PCB in Japan have subsided and are pected to continue diminishing. ifrltad Kingdom The government is taking no official action and is accepting the decisions of the manufacturers. Additionally, there is a high duty on imported PCSs (about 23%). 1.4.2.2 ttoff-Producing Qountriae Canada Initial activities are under way to collect necessary data far restricting PCBs pursuant to a new Envimrantal Contaminants Act which should be enacted by 1976. Finland ' The use of carbonless copying paper is totally banned and Legislation is being proposed to require prior authorization for the use of PCBs by the Ministry of Social Affairs and Health. Furthastore, ccnpulsory labelling and diipneal instructions are being introduced. -332- MOMS 209312 Netherlands A gmtlaoan's agreansnt is in effect that PCBs will no longer be used in the manufacture of paints, inks, lacquers, adtesives, resins, wire and cable ooatings, lubricating oils, hydraulic fluids arri copy ing paper. Norway . Since October 1971, only the Ministry of Social Affairs can authorize the use of PO*. Sweden Since June 1, 1972, only the environmental protection board can authorize the use of PC3> or ccnpounds containing PCBs. Furthermore, caipulsory labelling and identification of PCB content an the wrappings have bean introduced. Switzerland Since October 1972, PCBs or products containing PO> may not be sold to the public or to light industry. Heavy industrial use is subject to prior authorization, 1.5 U.S. Custtonm Bsgulaticns Pursuant to Cartons Bureau Directive CDS 36-72, July 4, 1975, the field offices of the Customs Bureau have bean specifically monitoring the inflow of PCBs and this infaansticn is forwerdsd to &A. The information is not public. -333- HONS 209313 BIBLIOGRAPHY 1. Baaman, R.D., ESA's Pollutant Strategies Branch, Polychlorinated Biphenyls. Private Oammication to Mr. Lindsey, A.W,; Office of Solid waste Manage ment Program, Ncvernfcer 20, 1973. 2. Colsnan, J.H., Acting Director Duty Assessment Division, Polychlorinated Biphenyls. Private Cotimnication to Mr. Barden, J.D., Versar Inc., October 15, 1976. 3. Qivircnnent Directorate, Organization for Eocnamic cooperative and Develop ment, "Polychlorinated Biphenyls, Their Use arri control", Paris, 1973. 4. Op, CLt., Septsiber 11, 1976. 5. Op. CLt., February 7, 1975. 6. Environmental Regulation Handbook EIC-Enviromient Infocnaticn Center, Inc., New York, New York. 7. Polychlorinated Biphenyls and The Environment, Interdepartmental Task Porte on PCSs, Washington, . C., May (1972), 9. Steigezwald, B.J., Director, EPA'i Office at Air Quality Planning and Standards, "Air Traneport of Polychlorinated Biphenyls (POSa)Private Ccntamication to Mr. Stralrv, r., Asaistant Administrator for Air and Water Msnagwent, September 29, 1975. 9. Stottlanyar, J.N., Department of Traneportat ion, "Transportation Regulatione for Toxic Subetanoae". Private Oanaaiiestion with Contoa, G., Versar Inc., Septanber 10, 1975. -334- HQNS 209314 APPENDIX A P<3 ADSORPTION TESTING BY XAD-4 RESIN Experiments and Results The apparatus and materials used by Beta aid Haas were: Two glass colums - 1/2 inch in diameter Adsorbent wlune - SO ml in each colum Adsorbent bed height XAD-4 Anberlite polymeric adsorbent - 16.5 indies ^rtivated carbon (Filtrasorb 100) - 15 inches PCS material used - Aroclor 1254 (manufactured by Monsanto) A feed solution representing a PCS contaminated waste stream was prepared containing approximately 160 ppb of PCS. Because Aroclor 1254 is very viscous, it was solubilized in methanol prior to dispersion in water. Metharcl increases the solifeility of PCBe in water. In order to maintain a constant flow through out the experimental run, two batches of fesd solution had to be prepared. The imposition of each solution is prssantsd in Tfeble Ar-1. Table A-l Opposition of Feed Solutions Feed Solution A - 13.25 liters 0,0022 ga of PCB or 166 ppb 2 ml of methanol or 119 ppm Feed Solution B - 13.25 liters 0.0029 ga of PCS or 218 ppb 2 ml of methanol or 119 ppm The influent solution was passed simultaneously through the column of Mberlita polymeric and the colum of activated carbon at a flo/ rate of 2 bed-voiunes per hour (0.25 gpm/ft3 resin). Smples ware collected iron each daily, so that each ample ncminelly represented 48 bad wlunes of A- 1 HONS 209315 effluent. Liquid passed through both oolunns for five days, or until 240 bed volutes of effluent (12 liter total volume) were collected fran each col-jm. Prior to analysis, the P<3 in each effluent sample was extracted into a volume of hexane equal to one-tenth the volume of the origiial sarple. The influent material, which was sailed four times during the run, was likewise extracted into the same proportion of henne. This single stage extraction ranovad more than 95 percent of the PCS* present in the aqueous sauries. The extracted effluent sanples were then evaporated to 5 mis, further concentrat ing the PCS* present. These evaporated sanples were then sent to Versar Inc., for analysis. The results are given in Table A-2. Table A-2 Reductions of PCB (Aroclor 1254) Concentrations Through Use Of Antoerlite Polymeric Adsorbents and Activated Carbon Nominal DS Throughput (BV) Influent Concentration (ppb) Effluent Concentration (ppb) Atberlite Adsorbent Carbon 1 1-48 2 49-96 3 97-144 4 145-192 5 193-240 25 (Feed A) norie detected 21.1 (Feed B) 0.69 0.69 0.246 0.031 0.023 none detected 3.478 0.050 0.055 0.025 none detected 0.045 A significant amount of PCS was adsorbed onto the wells of the influent container, as can be seen with Feed A, vtdxti originally was prepared with 166 ppb of PCBs. This loss by adsorption an equipment surfaces also has been detected in other tests, end trust be taken into account. Both the Anfeerlita polymeric adeorbent and the activated carbon reduced the aonoantxation of POa in water to lase than 0.05 ppb. The higher concen tration of PQi for the first day's tt of effluent through the realn beds oould be due to so incenplete conditioning of the beds, resulting in seme material I*--*-<7 out of the resin. The high concentration of PCSs in the last sarpla from the polymeric adeorbent mist be viewed with seme suspicion, A-2 HONS 209316 particularly sine* it indicates an effluent having a oorcantxatian higter then that in the influent. Anberlite polymeric adsorbents can usually be solvent regenerated, because the energy of adsorption is Rich lower for resins than it is for carbon. Hence, adsorbed solute can be removed ainply by passing an appropriats solvent through the resin, work performed by Musty and Nickles (J. Oiromet., 89:185 (1974)) with PCSt and a solution of 10 percent diethyl ether in hexane as a regenerant indicates that 78 percent of the POs on an Anberlite polymaric adsorbent can be recovered using this mixed solvent. In addition, Rohm and Haas have found that simple alcohols or ketones are effective solvents for these resins. Undoubtedly, a more efficient solvent could be found that would quantitatively move PCBa Cron polymeric adsorbents. Activated carbon, which has a nucb higher energy of adsorption than do these reelns, requires a more energy intensive process of regeneration, such as thermal rejuvenation. The ability to solvent regenerate Artierlit* polymeric adsorbents in situ would provide the advantage of generating only the Buce-iaadllyhandied-by incineration liquid phase POs westes. A- 3 MONS 209317 APPENDIX S MACHDREITCLTAR RESINS FHCM R0H4 AND HAAS 03. Description Ion exchange resins have the capacity to selectively recover ionic constituents, both inorganic and organic, fran water through an ion exchange mechanism. Organic coipounds are often exchanged or adsorbed irreversibly onto an ion exchange resin. This may cause a decrease in capacity so that the operating life of the resin is diminished. The more recently develop^ macroreticular type of ion exchange resins are polymeric adsorbents used specifically for adsorbing aztmatic and aliphatic n-iyinmrU from water. Structures The mecroteticular structures are characterized by having unusually Large surface areas as ccnpared with those of conventional gel structures. Using the newer macroreticular polymerization technique, it is possible to widely vary the particle pore size, pore size distribution, and surface area. Polymars with very anell pores (5 m or less) and high surface areas (in the range of 900 square meters per gram) can be prepared. At the other end of the spectzun, pore sizes an the order of 30 micrometers, visible under modest magnification, are possible. The macroreticular polymerization technique is applicable to a wide variety of manners. It is possible to introduce functional groups onto the surface of the preformed macroreticular polymers. Thus, a great range of surface types is possible, limited cnly by the availability of manners or the applicability of reactions to introduce functionality. The full line of macroreticular adsorbent constitutes a epactnas of surfaces fran the least polar to the most polar. For POe novel, the nonpolar and intermediate polarity adsorbents should be used. The deedcal structure of Artberlite XAD-2 and Artterlits XAD-4 (see Figure B-l) is representative of the nonpolar adsorbent series. Figure B-2 shows the acrylic-ester imposition of Asterlite XAD-7 and Asterlits XAD-8, the iitternediata polarity adsorbents. The physical properties of these Ambarlite XAD adsorbents are sunnarized in Table ^1 B-l HONS 209318 r Figun B-l B-2 MQNS 209319 Figun B-2 B- 3 MQNS 209320 Table B-l Typical Properties Of Antoerlite Polymeric Adsorbents Qtonical Mature Heliun Porosity Surface Area Uolune 1 cc/gram mVgram Nonpolar Average Pore Dia. Angstrom Skelatal Density grams/cc Nominal Mesh Sizes XAD-1 Polystyrene 37 0.69 100 200 XAD-2 Polystyrene 42 0.69 330 90 XAD-4 Polystyrene 51 0.99 750 50 Intermediate Polarity r xad-7 Acrylic Ester 55 1.08 450 80 XAD-a Acrylic Ester 52 0.82 140 250 1.06 1.08 1.09 20 to 50 20 to 50 20 to 50 1.25 1.26 20 to 50 25 to 50 HONS 209321 An important aspect of the Anberlit* adsorbents is the nature of the different surfaces. Hie pheranenon of adsorption on solids involves van der Waals' forces which bind the adsorbate cn to the solid surface. Many types of interactions, such as hydrophobic bonding, dipole-dipols interaction aai hydrogen bonding, are important. It is not possible to predict accurately which materials will be adsorbed well by a given adsorbent; however, from a practical point of view, a useful concept is that hydrophobic or nonpolar mole cules or portions of such molecules are attracted to hydrophobic surfaces, while hydrophilic or polar materials are attracted to hydrophilic or polar surfaces. Examples of these interactions are presented in Figure B-3. if each organic molecule is thou^it of as having both a hydrophobic and a hydrophilic end, then the hydrophobic end will be attracted to hydrophobic adsorbents such as Anberlite XAD-2 and Arcberlit* XAD-4, while the hydrophilic end will be attracted to hydrophilic adsorbents. This type of reaction is particularly true when the adsorption takes place from aqueous solution. For PCSs, it would be ejected that the biphenyl portion would be typically aromatic and hydrophobic, and thus attracted to an aromatic resin. Increasing the chlorination of a blphanyl would reduce its water solubility and this reduce what little polar character the PCS might ham. thus, the PCS would not have a "polar end" and would be strongly repelled by the weter phase and strongly attracted by the resin. A recent study by Janes Fritz, et al, of Iowa State university, ported a resin method for exLlacting trace organic oontmninants from water. He also dmisualed the feasibility of selective desorption of these contaminants, using appropriate eluants, so that the contaminants aauld be identified. He also established the performance or retention efficiency of ths resin in isolating these oonpocnds. A sizonsry of theee results is given hare: B- S MONS 209322 onimmoN ahowatic sohpO.-is mo:j polar solutions SORPTION ON ALIPHATIC SONHEMTS FNOU POLAfl SOLUTIONS Nun 'Pl.VtNT mK SONTTION ON ALIPHATIC SOnOMT3 mOU NON POCAI1 SOLVENTS Figur* B-3 B- 6 HONS 209323 fcisorbert: Particle Sire: Flow Rata; Amberlite XAD-2 unless otherwise indicated 100 to 150 mesh 10 BV/hr. (1.25 gjat/ft* of adsorbent} Test Conpounds Benzene Benzene sulfonic acid Phenol Phenol (Anberlite XAIK7) Aniline (Anberlite XACH7) Naphthalene Influent 100 3.0 0.4 0.4 4.0 0.05 Effluent 0 2.1 0.22 0.06 0 0 Retention Efficiency 1 100 31 45 36 100 100 It can be seen that Anberlite XAD-2 and Araberlite XAD-7 were 100 percent efficient in recovering the nonicnic organic expounds. These results predict good success with PCB adsorption. Cn the other hand, ionic solutes as well as strongly ionized expounds, such as benzene sulfonic acids and ^toluene sul fonic acids, were not retained with the sane high efficiency. It was noted that retention efficiency of a contaminant increases with increasing molecular weight in a hxologous series, indicating that the higher chlorinated PCBa would be the best adsorbed. B-7 HONS 209324 APPENDIX C MON-CAEBCN ADSORBTION AND OTHER RESEARCH STAffi PCB THEADENT TECHNOLOGIES 1.0 POLYVINYL CHLORIDE (PVC) AND POLYURETHANE POWE John Lawrence and ao-workers of Environment oanari* have reported prelim inary teats using PVC, polyurethane foams, carton, and the XAD resins for removal of PCBs from both synthetic wastewater solutions and actual raw sewage. H. D. Gesser (in Analytical Letters 12:383 (1971)), reported that a poly urethane foan colum quantitatively adsorbed POs from water. Lawrence founi that carbons, polyurethane foame and XA^2 strongly adsorbed PCBs frtm aqi^ous solutions, but ter* nuch less effective with raw sewage. He found that pvc, however, was very effective in removing POs from raw sewage. Dr. Lawrence is the only investigator taown bo have worked with PVC for adsorbing PCBs. Following is a sunnary of his test procedures and results. I.1 Experimental Method for PCBs Adsorption Tests, by Environment Canada TWo stock solutions of Aroclor 1242 and 1254 vere prepared by vigor ously mixing an excess of each Aroclor with water for 8 hours, allowing the solutions bo stand overnight and carefully decanting off the true aqueous phase. The water used was double distilled, the second distillation being from an all glass systan. The concentration of these solutions, determined by gas chroma tography, was 45 * 10 ppto, v*iich is consistent with the published solubility for Aroclor 1254 of 56 ppb. All solvents used were glass distilled pesticide grade (Caledcn laboratories, Inc.). The activated carbons ecployod were lignite-based hydxodarco 400 (ICMJhited States) and anthracite-based Filtrasorb 400 (Calgcn Corporation). These were prvtraated by heating to 300*C far 12 hours, cooling, and twice extracting aach 500 <gn with 2 liters of hexane. The extracted carbon was than filtered and air dried. The polyurethane foams used we DiSPo plugs (Canlab Stppliee Ltd.) and Fbame 1115 and 2328 (B.F. Goodrich Ltd.). (The first C- 1 MONS 209325 two digits in the Goodrich products relate to the density, i.e,, l.i ard 2.3 lb/ft3 and the second two digits to the hardness). The foams were shreddwi and successively washed with n-hexane (several times), acetone aid distilled water. They were then air dried. This pretrMbnant was developed to rarove trace organic ccntaninants fern the surface of the foams. The rracrcreticular polystyrene resins Antoerlite XA^2 and XAD-4 (Rbtm aid !!aaa caipany) were pretreatad by successively washing each 500 gm of resin with 1-liter batches of water, methanol, and water. The cleaned resins were stored in sealed glass containers under methanol to prevent than from drying. Polyvinyl chloride chips (tonsanto Ocnpany) were washed several times with n-hexane and air dried. TO determine the adsorption characteristics, 100-ml aliquots of stock Aroclor solutions were stirred rapidly for 30 minutes with weighed amounts of adsorbent and than the adsorbent wee removed by filtration through a Millipcra prefilter pad. Five milliliters of n-hexane were than vigorously stirred with the filtrate for 45 minutes and the organic extract withdrawn. These extracts were analyzed with a gas chraaatograph (Varian series) equipped with an election capture detector (NiS3). The gas ooltmn (l.ftat x 1.5 urn i.d.) was SO packed with 4 percent OV-101 and 6 percent CV-210 an Oizanoeorb w HP mesh. Nitrogen was used as a carrier gas at 50 ml/tain. The injection port, colum and detector twrperatores were 250*C, 200*C, and 300*C, respectively. Extraction and analysis of water mpi-- spiked with known amounts of Aroclor indicated that greater than 98 perosnt of the PCBe were detected by this method. Kastweter wee collected from the Hanilton Sewage Treatment plant at ti raw seuejs inlet pipe. Sanpling was carried out using all-glass containers to insure against adsorption of PCBs onto container walls. The samples were stored at a constant tparmture of 3*C and in all cases were treated and/or extracted within 24 hours of collection. In the evaluation of PCS adsorption from sewage, the procedure described above for pure Aroclor solutions was followed, except that 100-tnl senples of raw sewage were stirred vigorously with the adsorbent for 1 hour, and than the adsorbent wee separated by filtration through a 60 mesh, stainless-steel screen. After washing, the screen did not retain any raw swage and, with the exception of activated carbon, 100 percent C-2 MQNS 209326 separation of adsorbent was achieved. The filtrates were then twice extracted with 50 ml of n-hexane in 500-ml separatory funnels. The aqueous portion was discharged and the organic phase, after being dried through 15 g of .n^SO^, was reduced in a rotary evaporator to approximately 3 ml. The sample was purified by liquid-solid chromatography on a florisil support colism using petroleum ether to elute the PCB fraction and then the eluate was evaporated to 3 ml. Prior to injecting the sample into the gas chromatograph, it was shaken with 0.2 ml of mercury to remove residual sulfur compounds. The PCBs in the sanples were identified by caiparison of their chromatograms with chromatograms of standard Aroclors. The total concentrations of PCB in raw sewage usually averaged 9.8 * 4 ppb. 1.2 Experimental Results of PCBs Adsorption from Sewage and Synthetic Wastewater ' Adsorption data for Aroclor 1254 and 1242 on PVC, activated lignite carbon, anthracite carbon, two polyurethane foama, and Anberlite XAD-2 and XAD-4 resins are shown in log-log form in Figure C-l. The weight of PCB adsorbed per unit weight of adsorbent is expressed as a function of the equil ibrium concentration of PCB remaining in solution. The sets of data do not follow any of the tuuiui isotherm expressions (e.g., Langmuir, Freundlich, BET), and consequently a theoretical interpretation of the results has not been attempted. It is evident that the two carbons and XAD-2 have the greatest adsorptive capacities; however, a residual concentration of less than 3 ppb could not be obtained with lignite carbon. Both polyurethane foams appear to be good adsorbers, with relatively high adsorptive capacities and low residual levels. DiSPo polyurethane fan plugs are also evaluated but these have identi cal adsorptive properties too the Goodrich Foam 1115. The lower efficiency of XAD-4 is surprising in view of the similarity between it and XAD-2 (they differ only in pare diameters; 9 nm for XAIV2 and 5 nn for XAI>4). The lower efficiency of me, whldi hae no uauxueLiailar structure, can be explained by its lever surface area. The surface area per unit weight is reported as 500 to 2000 m2/<p for carbon, 750 a2/gn for XAD-4, and 330 m2/gs for XAD-2, but only 2 x 10 3 m2/gm for WC '-Hps - there being no macxoreticular structure in PVC. This gives an area ratio for XAD-2/PVC of approximately 10^. C- 3 HONS 209327 i PVC e lignite cmbqn OXORICH 1115 FOAM GOCCRICH 2328 FOAM XAD -4 XAD-2 ANTHRACITE CARBON * 1000 PCS REMAINING (ppb) Figure 0-1. Adsorption of Aroclor 1254 on P.V.C., Lignite Carbon, Anthracite Carbon, Polyurethane Foods and Jttberlite !D-2 and XAD-4. * Indicates adsorption of Aroclor 1242 rathsr than 1254 C- 4 MONS 209328 Than as* two ootplicating conditions associated with adsorbing PCS* Cm raw sewage rather than fron synthetic aqueous solution: (a) sewage contains other hydrophobic organic matter thich ccnpetes for the active sites on the adsorbent, and (b) roach of the PCB has already adsorbed onto ti sus pended solids by the time the sewage reaches the treatment plant. Corriition <b) can be dononstrated easily by filtering raw sewage and monitoring tie change in PCB concentration. With typical raw sewage containing 10 ppb PCB, vacuus filtration through a Millipore prefilter pad results in tie removal of about 75 percent of the PCBs. It is therefore necessary to find an adsorbent which is not only relatively specific to PCBs, but which also has sufficient affinity for the PCBs to reverse the PCS-suspended-solid equilibrium. Table C-l shows the percentage of PCS (including both Aroelor 1254 and 1260) **~TM+>~* from raw sewage by five different media. With the exception of the PVT, approximately 1 911 of each media was stirred with 200 ml of raw sewage for 45 minutes; approtimataly 10 911 of PVT were used to acnpensate for its lower surface are*. Tb minimize th* inconsistency of raw sewage, th* data have been averaged over several determinations an different days and with different sewage sanplee. The data indicat* that PVT and XAD-4 ax* more effective than caxfeon or polyurethane foams in tens of pemntage of PCB removed from raw sewage. This is surprising sines the graphs far PCB adsorp tion for pure Aroelor solutions (Figure C-l) predict the opposite. Lawrence believes the reasons for this apparent anomaly area (a) th* active sites on carbon are preferentially ocagied by hydrophobic species other than PCBs in the sewage, and (b) p--solids adhere to the surface of carbon and foam Ktlng as a barrier to further adsorption. These results indicate that PUT is superior to the other media for moving PCBs fron sewage. Lawrence's work is continuing, with studies of methods of scale-up and continaous or nultletage operations with PVT. Optimal retention time, and methods foe continuous addition of fresh PVT and rwoval of spent PVT are under study. The strong oarpetition between organic solids and nan-organic media is 4 further in the following discussion. C- 5 HONS 209329 ADSORBENT Lignite Carton Polyurethane Foam Antoerlite XAD-2 Anberlita XAD-4 PVC 46 35 23 60 73 * Include* both Arodars 1254 and 1260. Data are avenged over several determinations to minimize the variations in raw sewage. C- 6 HONS 209330 1.3 PCB Adsorption on Clays and Organica in the Soil E. S. Tucker and oo-vcrkers at Monsanto reported on studies of migration of PGBe {Arodor 1016) through various soils as induced by perco lating water (Bulletin of Environmental Contamination and Toxicology 13 Cl)s 86 (1975)). The results were to be used for estimating PCS* leached fran landfills. Their tests first led than to believe that the higher the clay content of a soil, the better its retention of PCB*. The experimental procedure stployed consisted of percolating water through a colum packed with soil coated with Arcelor 1016 and then monitoring the effluent water for PGBe. The soil coloms enployed wen approximately 3 inches in disaster by 12 inches high, and wan dry packed in layers. Each soil layer was 3 inches thick, with the first layer being unooatad soil, followed by a layer coated with 2.5 percent (w/w) of Arodor 1016, and then another layer of unooatad soil. An acetone solution of Arodor 1016 wes used to coat the air-dried soil, followed by novel of the acetone in a rotary evaporator. Three different types of soils vwn used in this study. The charac teristics of each an show in Table 02. The intent was to simulate the various soil types which could be enooisitarad at different landfill sites. The soil types and the procedure aeploysd have been used previously to evaluate the soil nobility of agricultural chenieals. Distilled water was fed from a reservoir at a oonstant pressure to each soil colum. The effluent flaw rates wen observed to increase the first few days, than decrease, anl finally level out. Apparently, after the wetting phase sane channeling oocun until the soil beuimas aatpnseed in the oolixen. This effect was most pconomoad with the silty soils. The average flw rates for Norfolk Sandy lorn, Ray Silty Loan and Drunnar Silty day loan wan 0.26, 0.53 and 0.32 liters per day, respectively. The effluents than wan quantita tively aiaorbad on polyurethane oolirms, than extracted and analyzed by electron capture gee Uimuatngi'^ihy. C- 7 HONS 209331 Table 02 Soil 1 Sand Silt Clay % Organic Carbon MorfoUt Sandy Loan 82.5 11.0 5.5 1.0 Hay Silty loan 6.2 83.2 9.6 1.0 Drum Silty Cli 2.8 55.4 35.8 6.0 C- 8 HONS 209332 1.3.1 PCBs Adsorption Results PCBs adsorption results are given in Table C-3. TTese results indicate that clay was a strong adsorbent for PCBs, This would be in hjiu_ rant with the work of R. Hague and co-workers (Qnvironnantal Science Tfechrclogy, 8:139 (1974), in which clay was found to have a high affinity for PCBs. So^ ever, in later work with pure clays, the retention was found not to be as good as expected. Attention was then directed to the organic portion of ti* soils, and Tucker, et al, have tentatively decided that the organic fraction is rare important to the adsorption of PCBst it can be seen from the data that tte high-clay-content soil wes also the high-organic-oontent soil. Further investigation of sane clays might be warranted. S. Pearson of Hercules, Inc., in a personal ooRcunication, stated that bentonite clay was vary effectiva in moving other pesticide wastes from water. The finely divided clay was then rapidly moved from the water with "Hereofloc". 1.4 Spahgrasn Peat (Lignin-Celluloee) as an Adsorbent The above work by Tucker, and the general finding that in sewage sludge the solid phase contains many times the mount of PCBs the waiter phase contains, leads to the conclusion that natural organic matarials from the earth might make good adsorbents for PCBs. Although it has not yet bean tested far moving PCBs, there is a ccmnarcial method of continuous wastewater treatment, called the Hussong/Couplan ffetar Treatment Systan, that usee sphagram peat. The peat is formed into a continuous met an e mash belt through which wastewater is sprayed. The systan has shown high effectiveness in moving certain organics and metals from waste waters. Capital costs for this systm average about 600 per gallon of daily capacity. Operating oosts, when treating a dye house affluent, were 70 to 140 per 1000 gallons. 2.0 GKNX1XC mOCTSJN In the literature review, two approaches were found for modifying the ohmlea! structure of PCBs in order to aid in vests control. One approach was the C- 9 HONS 209333 Tabla C-3 PCBS POUND IN PERCOLATING WATER Norfolk Sandy loam Total Effluent UoIum (1) ppb PCBe 1.3-8.1 10.1 13.5 25.5 48.1 ND ND 23 63 63 Bay Silty Loam Total Effluent Volute CD ppb PCBe 2.7-16.4 20.7 27.6 51.9 98.1 M3 65 92 153 136 Drummer Silty Clay Loam Total Effluent Volume (1) FPb PCBe 1.6-9.9 12.5 16.6 31.4 59.2 ND ND ND ND ND .-O - Nbne detected, < 1 ppb C - 10 HONS 209334 caplets chlorination of PCBs, to give decachlorobiphenyl, the rationale being that the carplately chlorinated biphenyl wsuld have the least solubility in water of any PCS, and thus would be much easier to adsorb ard rerove. fcwwer, decachlorobiphenyls are also the most refractory PCBa. A better approach is the dechlorination of PCBa to give biphenyl or bi cyclohexyl. 3erg, et al (in the Bulletin of Bwirormantal Contatination Toxicology 7:338 (3372) state that POs can be dechlarinated quantitatively with hydrogen over platinw or palladium catalysts to give bicyclohexyl. T. Sami of Japan (in Genshiryohu Kocyo 18(121:43-7 (1972)) reported ti* degradation of PCBa using the cobalt 60 isotope. Ganna irradiation at a level of 10 18 ev/gism produced chain dechlorination in an alkaline propanol solution saturated with nitrogen. Alkaline concentrations of 0.01 molar gave about 40 times the dechlorination that a neutral solution gave. A process of reductive dechlorination, more amenable to lot^cost operation and caansrcial sealsup, is being developed by a wary, Saltonstall and co-workers at Bivirogenics Systmns CD. of El Hants, California. 2.1 Reductive Dechlorination of PCBa at Envlroqsnlc* Systems Oarp. Ehviroganics, originally working in chlorinated pesticides, has devel oped catalyzed reduction process methods for the following ccnpoundst DDT CCD Ralthans Perthane Methoxychlor Lindane aldrin Oilordan* dleldrin endrin hsptschlar taxephsns Aroclar 1221 Arodor 1242 Aroclar 1254 Aroclar 1232 Aroclar 1248 Aroclar 1260 Hit reductive dechlorination reaction has ben run at ambient tanpera- ture and pressure, by flowing the liquid chlorinated hydrocarbon through a oolum containing wwinr iron granules coated with a 1 <<* copper and blended with said. The copper enerts a catalytic action. pH is maintained at nearly neutral, since with low pH, say 2.0, the iron conversion rate to ferrous chloride increeees 10 tine, but the dechlorination reaction is not such faster. The chlorinated hydrocarbon is converted to a hydrocarbon. PCBa, in this process, aeon to lose chlorines stepwise, leaving unidentified PQ horologe. C - 11 HONS 209335 Qivirogenics is new under EPA contract (68-03-2364) to develop and demonstrate an effective bench-scale (1-3 gpm) low-cost process for the treat ment of dilute (ppto to 1 ppm) aqueous manufacturing and processing wastes containing PCBs. Specific objectives and guidelines include: 1. Reduction of PCBs to 5 ppb or less, with levels of < 1 ppb desirable 2. Sufficiently lew projected treatment cost to be econenucally attractive 3. low expected toxicity of all effluent products, incluiing both degraded PCBs and any added reagents 4. Use of readily available materials, both in construction and as reagents The process entails sijiply puiping the liquid to be treated through the catalytic colum. Process characteristics that might be proposed far the scaled-vp PQ5 operation, based on what has been learned about the other pesti- cides thus far, are: catalyst: 100-meeh metallic iron granules coated with 0.1 railliequivalants of copper per gran of iron support: 60 to 100 mesh (approx.) sand timber of beds: 4, operable in series or parallel bad opposition: 500 pounds of iron catalyst, plus 3500 pounds of sand flow rates: 2 to 10 gpa. /ft1 pressure drop: about 10 pel pH: kept neutral, through caustic addition piping; 304 ss, with teflon tape seals tanka: Steel with epoxy ooating inside pcstiaatmnt: wastes are assured to be free of undissolved solids ird oils aM are fabric filtered before entering process The expectations for westowetsz PQJ reductions with suen a pilot plant are beaad on --u - to 2-inch-diametsr oolum lab casts that gave reductions of PCBs froa 50 ppb to *ess than 0.1 ppb. 0 - 12 HONS 209336 Tt capital coat of the equijnent to process 100 gpa is estimtad at $65,000, plus tank storage and consmartion ooats. Operatic coats, including amortisation of capital, is estimated at 720 pec 1000 gallons of effluent. 3.0 CATALYTIC CKZDKTTCN AMD MTSTFTJAMBms ABACTIONS The catalytic oxidation of PCS* include* oxidation by: air, oxygen, ozone, hydrogen peroxide and chlorine dioxide. The reaction is usually assisted by catalysts or reaction sensitizers. PCBe are very resistant to cimical attack. Msnaanfco states that they are not affected by boiling sodium hydroxide, or by long contact, say 10 days, with oonoentrated sulfuric acid at esbient tsrperaturs. There is no apparent reaction in a bcnb of oxygen at 250 pel and 140*C. 3.1 Strong Acid* ftaasian worker* have reported nitric acid deoaepositicn of PCB*. they used nitric acid at a specific gravity of 1.4, and refluxed two PCS*, a pentschloro and a haptachlcro hnmalng, tor periods ranging to 100 hour*. Ihcy found ii- and trichiambenaoic adds from the tenser, and tri- and tetra chlarobansoic acids fra the letter. Leas concentrated nitric add would not oxidize thee* azpcwds, nor would potaaeim permanganate or chronic acid. Ibnewr, mono-, di- and trlchloroblphenyls can be oxidised to the aorresponding chlorobensoic add* with chronic anhydride and acetic add. The less rigorous conditions can ales proton* a large mixture of nitrated chlorobiphenyls. 3.2 BjaeUdch--jeal Qddetian Notwithstanding theea axeiplaa of oxidative resistance, J. D. Stuart and oo workere at the Oapt. of Oanistzy of university of Connecticut have con ducted laboratory elec&ai--dcel oxidations of PCB* at ambient taiperatuia and pceewre. ttey PCBe having one to ten chlorine atone, using very high anodic potentials in e dry swthylcyanide advent, they hypothesise a series of react iina starting with hydrolysis from trace* of water present and ending with oxidation. C - 13 HONS 209337 A nuiim of other catalytic oxidation investigations of refractory organics are being conducted in the U.S., with sane being sponsored by EPA. Although PCBs have yet to be tested in these investigations, the netted* have sufficient power and flexibility to indicate PCBs could be destroyed. In addition, these methods have the potential for zero discharge of pollutants since they have converted refractory organics to ODj and water. 3.3 Catalytic Oaonation and ultrasound Oeccrposition of Organics Gerard anith and J. w. Chen of Southern Illinois University have presented results (68th annual AIChE Meeting in NOwfcer, 1975) of catalytic ozonations of non PCB organics in aqueous system, They have tested catalysis with oxygen, and ozonation without catalyst, and neither method had the effectiveness of catalytic ozonation. An Fe^O^ catalyst was used, and phenol and ethyl acetoacetats ware used as model compounds in water. The liquid re tention time in their flow reactor system wee 25 minutes, and ths gas flow (using 30 mq/liter aonoantration of ozone) wes 0.1 liter per minute, under theee conditions, TOC wes decreased 95 percent for an initial TOC of 100 mg/1, and 85 percent for an initial TOC of 400 mg/1. The packed reactor had the aqueous solution flowing down, and the ozone flowing 19. In axperimants preparing the effectiveness against refractory organics of ozone plus Haney nickel and ozone plus ultraaomd, anith found that ths reactions ware similar. Also, he found that ultrasound and oxygen gave similar reactions. Ultrasound was led at 800 KHz, and 4 to 5 watts par an^. It appeared, however, diet these effects wars not additive? for axaiple, adding ultrasound to an ozone catalytic react1m did not materially change the re activity of the ozone and catalyst alona. Ha also found that at these ambient immature* and praasurae, phanol * rapidly, but other organics, including oxygenated aromatics, resulted rather than impounds expected from nature of the aromatic ring. 3.4 Catalytic (addition of PCBa L. It. Rose at Dmivar research Institute has studied the wet catalytic caddation of strong wastewaters having CCD values of 3,000 to 15,000. Tests C - 14 HONS 209338 stand tint reacting Fe2 (S04>3, Cu S04, and HjOj at a pH of 5.0, and Fenton catalyst at a pH of 2.5 reduced 000 concentrations by 95.4 and 96.0 percent respectively after 2 hours at 400*F. Platinun cotide as a solid catalyst i<*i gave good results. Most of the organics were oellubiosics. 3.5 Wet Catalytic Oxidation and Catalyst Durability J. F. Katzer and co-workers at University of Delaware have been studying elevated pressure and Carperacure catalytic air-oxidation of refrac tory organics. They are currently being supported by EPA in a study of the durability of catalysts in wastewater environments. In a paper soon to be published in the Journal of the Water Pollution Cbntzol Federation, Katzer reports on studies of the oonplete oxidation of phenol to 0D2 and water in an aqueous mediun using a supported copper oxide catalyst. Rapid degradation rates were found, and the rata data were used to run preliminary design and costs for cccmercial-scale wests treatment plants. His conclusion is that catalytic oxi dation of wastewaters is ooet oatpetitive with other physics! chemical treebrent techniques. Katzer found that pressures of 10 to 20 atmospheres, and tenperatures of 100 to 200*C, were required to get adequate reaction rates yielding bp to 99 percent conversion of organics to 002 and water. It was found that ambient tapereture and pressure generally caused more adsorption an a variety of catalysts than did any reaction. 3.6 Dye-Sensitized visible Light Photo-CXidaticn of Organics R. L. Sanks and ao-woxkar* at the Civil Engineering Dipt, of Montana State University are working on the dye-sensitized, aerobic, photo-waririation of refractory organics. They were able to rapidly break apart the benzene ring of creaol using such dyes as methylene blue and bengal rose. The key to the process is that in the preserve of suiligftt and air, methylene blue can produce singlet oxygon from tt 02 in air. There are two forma of this singlet axygan, with a half n of only a ndllisecord, but with the ability to easily shatter benzene rings. Sanks visualizes a process wtaraby a lagoon containing wastewater with refractory organics, aould have the dye molecules attached to a long chain alkyl C - 15 HONS 209339 or a- floe of sat* kind to keep then at the surface. The sun would provide the photolysis, and little dye vould be aansuned as it is a catalyst in tlw reaction. Such a process, if it can be developed, suggests a route to a very low-cost method of obtaining zero discharge, and water recycle systens. 3.7 Chlorine Dioxide Qfirtfition International Dioxide, Inc., of New York City is offering a stabilized chlorine dioxide, which is being used by nunicipalities far taste and odor con trol of water. It is used as an adjunct to chlorination and can decoipose chloramines. It oxidizes and destroys phenol and does not chlorinata. Un stabilized CIOj is a dangerous explosive, this stabilization offers a very powerful oxidizing agent for potential degradation of organics. 4.0 Ltai'HJCnCW OF PCBs by mtocorgmjisb The (3--tlstry of PCBa by Hutzinger reports only on pure cultures of microorganise shewing metabolic activity on individual dilorobiptwyls. one culture, Rh<*rT*1M japonlcue only converted the mono- or dichlorobiphaiyls to chlorotydroxybiph--yls or possibly nulti-hydroacybiphanyls. Mare premising results were obtained with two Trias of achrerebacter, isolated from --age effluent. Under aerobic auditions, 4-chlatobiphmiyl wes converted to 4-chlarQbansoie acid. The arganiea was apparently able to attack the nonchlorlnated bmuana ring, met of these degradations talcs a ranter of hours to occur, mra raoantly, chlorinated biphenyls tp through pentachloro- biphanyl have bean a by adunmbactar. mnsanto vets able to denonstrate a significant reduction in the mono-, dl, and trichlorobiphaiyls of Aroclor 1242 after 72 hours of tiesttaant with activated sludge. The higher chlorinated hemplogs did not se-- to be affected. The of PCBs by microbial action fra aluigae and fra pare nil uies of bacteria seated to give results similar to animal matabolian studies. Urn loser qpacias, again up through tha trichloro hamlog, vere de- acepoesd to phenols, catechols and related impounds. C - 16 HONS 209340 The importance of oxidative conditions was demonstrated in tests with silage containing PCBa. After several tenths of storage of Aroclor 1242 with silage that had undergone fermentation reactions under anercbic conditions, no change in any of the PC3e had taken place. The use of DOT degradation as a model for PCB degradation conditions may not be helpful. Results of a study by Johnsen (PCB Newsletter, January, 1973) showed that when di- to hexachlorobiphenyls were incubated far one month with soil and with soil containing cattle manure, no indication of PCS metabolism was found. Under these conditions, p, p' DOT degrades almost completely. It has also been found that biphenyl itself is more easily degraded or hydroxylated than any of the chlorinated biphenyls. 5.0 REVERSE OSMOSIS AND ULTRAFILIBATICN No tests for PCBe removal by reverse osnosis or ultrafiltration were found in our literature survey. Generally, these methods have found most success in moving dissolved salts fran water. However, E.I. DuPont reports, in a private ocnnuiication, that they have achieved 90 percent removal (rejection) or organics in watsr at tha 1000 to 2000 ppm level, they accomplished this through the development and use of a hollwfiber permeator syston having fibers of aronetic polyamides, the systmn is repartad to work well on organics having molecular weights greater than 100. this would indicate probable success with the PCBe, all of which have molecular weights in the range of 200 to 400. Based on their experimental work with wound polyamide mortoranes operating on chlorinated hydrocarbons in watsr, U.O.P.'s Fluid System Division predicts a 95 to 97 percent removal of aqueous PCBe at 50 ppb concentrations, they point out however, that the reject water stream of concentrated PCTe would contain 10 to 20 percent of the original volume of wastewater so that a certain amount of recycle would have to be built into the system to reduce the generation of con centrated wastewater. Reverse ostosis systans cannot tolerate suspended solids in the feed wastewater: under optinun conditions they can operate for six month to one year before any maintenance or cleaning is required. C - 17 HONS 209341 W. L. Short of the Chanical Engineering Dept, of the University of Mass. reports thet with ultrafiltration, 50 percent rejections of phenols and chlorinated phenols has been achieved. He believes that rejection of a given ouqpound can be improved by attaching some of that oarpound, or a similar material, to the irafcrane to act as an electronic barrier. C - 18 APPQJDIX D MASS BAIANffi MXE, TOR PCS DISTRIBUTION 1.0 rtJTROXCTICN AND MASS BALANCE EQUATION In order to disoover the effect of various possible regulatory efforts on the distribution of refractory organics in the gemral envixonnent, an attaspt has been node to determine the manner by vhidi a specific group of such com pounds, PCBs, has beosma so widely dispersed, to datazmir* the dynamics of the distribution process and to determine the changes in specific distribution that may be ejected to result from several regulatory alternatives. Specifically, the effect of the wluntary ben introduced by Monsanto in 1970-71 can be demonstrated. It would be meet useful to construct a mathenatical representation of a suitable serpent of the environrent based at the existence of large quantities of valid analytical data taken over a sufficiently long time interval so as to allow the reliable extrapolation of the important tins effects. Unfortunately, the necessary data are not available. The recognition that PCBa were an anvironnantal hazard cere after their prolonged and widespread use in industry. In addition, tha ability to analyse anviranental saplee far very low lewis of PCBs is also s recant dewlopoant. There has bean too little tin sires the development of thasa sophisticated and exceedingly sensitive analytical techniques to have illrnwl anything lite a ocnplets spatial and taaporal study of the levels of PCBs in any given region. In view of the serious lade of a truly adequate data base, and because of the need to have at least a first order vnderstanding of the physical processes involved in the transport and distribution of PCBs, i attwpt has bean mads to construct s methmatical nodal which should contain at least a gam of the true situation, specifically, the model serves to indicate something of tha nature of tha problem, aid of tha types of msasurensnts that will be required to con struct a truly satisfactory endei to guide future regulatory activities. TO sake what follows pacific, the derived nodal is applied to a study of Lake Michigan vhere a considerable body of information, of Late origin, is available. D-l MONS 209343 1.1 Maas Balance Model In order to construct a mass balance model to be applied to a body of water such as lake Michigan, it is appropriate to decemii* the manner in which an increnental increase in PCB content is distributed within the various processes available. In what follows, it is explicitly assured that; (a) there are no effective mechanism for the degradation of PCBa which are operative over the time scale involved. (b) The PCBa that remain in the body of water are distributed be&wen that portion in solution in the aqueous phase, that in "solution" in the biota and that contained within the sediments. (c) The essential loss mechanise* are evaporation from the lake surface and carry off due to the outflowing waters (in this case - through the Strait of Mackinac). In terms of these assurptiens, a differential equation can be developed that describee the time rate of diange of the coneantratiai in the various phases in tem of the irput rata of PCBa. This equation may be integrated under various aseurptians as to the time d^andanoe of the irput rate to yield alternate expres sions for the concentration of PCB within the separate phases as a function of time. 1.1.1 Model Development let B(t) be the rate of injection (lb/yr) of the PCBa from all sources at a reference time t [where t (years) * 0 in 1930]. Then, within the interval t to t + At, an incremental amount of PCBa equal to B(t)At will be injected into the syetam. This quantity of PCBa will be partially partitioned Into the various phases, with the balance removed by evaporation and/or outflow. If Q(lbe) is taken to represent the total water mass in the lake (assuned to be constant) and C^t) the concentration of PCBa in the water D-2 MONS 209344 at tin t, than cw(t it) cw(t) 1Cw it it which, in terms of the definition of concentration, causes an increase in soluted PCB of magnitude CC ^w-Q-- At* (1-1) In a wide variety of environmental situations(1) there appears to exist a rather definite relationship betn--1 the concentration of PCBa within the sediment and/or the "average" member of the biota and that of the water in vhidi they are inmersad. These relationships are herein defined as and are assured to be indapandnt of CMtac end of time. Using the relationahipe expressed by Bq. (1-2), the incremental increase in the mass of PCB stored in the biota is giren as awa-^sr at' d-3> Oreze it is assured that the concentration of PCB within the biota waa in equilib ria with that in the water at tin t and that G(lhe), the total mass of the exposed biota, is constant over the period of interest. Sladlarily, if the rate of deposition of sediments is taken to be Ddhe/^/yr) and the area of the lake to be A(m2), then, assuming that the principal processes between water and sedinanc occur within tha aqueous phaaa the tattling out process, the incremental PCB pixdcv^ by the sediments is glrere as* dmsea. - ADqCw (t)t (1-4) D-3 HONS 209345 AC [whar* the additional tarn 0/2) ^ at is considered snail, especially as at * o]. , If the rate of outflow from the Lake (through the Strait of Mackinac) is taken as s (lbe/yr), then the loss of PCB due to this outflow rtwy be taken as: tion is given as "`"outflow SCw(t) it (1-5) Finally, the mass of PCB carried cut of the system by evapora ^ev^ * U-6) there K is the evaporation rata constant which will be discussed below. NOW, the principle of conservation of mass requires that all the injected PCB be accounted for, (note thet no effective degradation processes are considered to be operative) from which it follows that B (t) it * ^ * *We + + ^outflow + *evsp : * Introducing tha definitions of eadi of tha incr--ital mass loads, and proceeding to the limit At + o and dropping tha subscript w since the only oonoantretion appearing ia that of tha PO in water, the operative diffarsntiel equation beocmes (Q + (*) d*o + (S + K +.*>0)C - B(t) (1-7) thich, for oonvenience in what follows, any be rewritten using the substitutions, Y 5 OTTST 3 + K + AOp Xs '4 V ' (1-8) g|+ XC - YB(t) (1-8l) D--4 MONS 209346 Tha general solution of Equation (1-81) takas the form r<fC(t) - a VB (t) eXtdt U-9) where C(t) la tha conoantraticn of PCS in water at the reference tire t (tf - 0, 1930). Tb solus Equation (1-9), it is necessary to evaluate the various constants [Equation (1-8) ] and to disaover an appropriate form for the driving function B(t). 2.0 PCB PBCDUCnCN, SALES MO ENVHOMNIM. LOAD In tha following section, an attarpt is made to evaluate the production and sales of PCSa during tha pariod 1930-1975. Data published by Monsanto^2* haw ban presented alaawhare in this report. From the derived erpirical expres sion for tha total salaa as a ftnction of tins, as wall as front tha enpirical evpraaaima for transformer, capacitor and othar uaa categories, it will bs poasibla to estimate tha total nviromntal load of PCBs as s ftnction of tins. Fran this analysis, it will ba poasibla to astimata that portion of tha total environnsntal load that is, in fact, frea and which tharafore is responsible for the widespread distribution of thaaa refractory oospounda. Aa a final at^>, it will ba r------to aatinata tha time d^endsnoe of tha free (wild) PCB input to a closed systan aueh as Lake Michigan. 2.1 ^irlcal BKcesantation of PCB Salaa, General and in Specific IfaaCabaaarias'------------------------ :--------------- ------------------------------- 2.1.1 Pariod 1930-1970 tha Monsanto sales data for PCBa, it is possible to fit for each category which, to a satisfactory degree, rep- of that parameter- In eadi case, it is assured that form) lnQ(t) * a + n In t (2-1) D-5 HONS 209347 (a) Tbtal Production U* derived pi-rical expression for the yearly pro duction takas tha foot, for the pariod 1930-1970, Qprod(t) - 2.94 * lOV**1 ltoe/yr (2-2) Tha ^propriata pirical expression far tha yearly sales, for tha 1930-1970, takas tha torn (2-3) Tha corresponding expression* for capacitor salaa and for tmafomar salaa are (far tha pariod 1930-1970) Capacitor aalasi Q ,,L(t) " 2.03 x 10* t,'1M lhs/yr 'TMlr Ttansfoxasr salsst 0^XJ(t) 2.02 x 10* t1'17 lhs/yr (2-4) (2-41) In tha about egressions, it q>licitly Manned that ba noted that it is (a) tha gi%en Monsanto data are accurate and c^maant tha great preponderance of PO pirytirticn and salaa within tha U.S. (b) tha tranda noted in tha interval 1954-1970 are aii^tle aontinuaticna of aarliar txsnda, so that tha curves *#dch fit tha pariod 1954-1970 can, in fact, ba uaad to omv tha aotira interval, 1930-1970. Xhfbnstion rsportad elsewhere in this xspart suggests that tha aaanfassiavtion above mi$t result in low estimates for total U.S. salaa; theredEniv tha raaults derived free this aialysis nuat ba considered aa a lower bcw*~enr tte actual situstian. D-6 MONS 209348  In any case, mmerical evaluation of expressions (2-3) anl (2-4). suggest that a weighted average for the proportion of PQ that were erployed in electrical a^licaticns is of the order of 3 0.62 (i.e., 62%) (2-S) The remainder of the sales during the period 1930-1970 was for non-electrical applications. 2.1.2 Period 1971-1975 In 1970, Monsanto instituted a vcluntary ban on the sales of PCBs restricting their use to electrical applications. As a result of this ban, the empirical relationship appropriate for sales in the post 1970 period is Q'sales(t) * 3,31 51 1QT (2-6) In addition, during this period essentially loo percent of PCS production wes used for electrical applications; i.e. 8 - 1.00 (1970-1975) (2-7) Tb detamins the total sales and total electrical system usage for the period 1930-1975, Equation (2-3) my be cabined with Equation (2-6). Integration over the appropriate tins frane yields -9-33 - M` " and for total electrical system usage. Equations (2-4) and (2-6) with (2-7) may be oonbined and, cn integration, yield, 7-u -101 " The^alsnoa, 2.21 x 10* lbs, were used in non-electrical applications. D-7 HONS 209349 2.2 BwironBental Load of PCSs 2.2.1 introduction PCS*, or for that matter any other refractory chemical com pound, may exist in the envirorment in two distinct states: (a) that material which is in a form such as to remain localized and thus is rot actually available to enter the sensitive portion of the enviroment, i.e., the biota; and (b) that material which is not so constrained and is thus free to enter the sensitive portion of the enviroraent. this latter portion of the environmental load will be referred to as "free" or "wild" PC2s. The significance of the first category lies in the fact that the ccrtairsnsnt is not of infinite life and thus material in category (a) can and will eventually beocre a oarporent of category (b). For those rnrpunrli for viiich there exists relatively high rates of degradation with in the environment, the category (a) is of somewhat lesser importance than for those refractory fnrpoinde for which the only inactivation mechanist is the enLi^peiit with non-available fom, for example, in deep ocean sediments. In order to estimate the rata of accinulation of PCBs in category (b), it is first necessary to determine the rata of entry of PQs into the category (a). This will be followed by an analysis of the processes by v^iich this total envircmaRtal load eventually because wild PCBs. It is -- --* that, in any time interval t to t t At, a fraction a < 1 of the total sales during that interval was directly lost to the environmt. It is further --a that a fraction B < 1 of the total sales was used in the nnufactura of long lived electrical ocnparwits. If the average lifetime of these electrical oonpcnants (time of service prior to their being discarded as obsolete) is y, years, then during the time interval t to t + it, (2-8) D-8 HONS 209350 will enter the environment as part of category (a). In addition, the direct entry is given as ^ Qg(t) At (2-9) The remaining sales (l-o--3) Q(t) was used in the production of relatively short-lived products, such as carbonless paper, hydraulic fluids, etc., which are assured to have an average lifetime Yj years. Thus, the entry of this material into the total environmental pool is given by (l-a-8) Qg(t-Y,) at (2-10) If the three aonpcrents of the total environmental load, Me^(t) are sunned, the resulting differwvtial equation for Mey(t) becares, in the limit as at - o dM^tt) 3t~ a Qg(t) + (l-a-8) Qg(t-Y,) + B Q^tt-Yi) (2-11) or Mev^ (2-11*) In order to obtain a numerical evaluation of Equation (2-11') it is appropriate to note thet 6, the fraction of initial sales utilized for electrical applications, is grwn by Equation (2-5) for the period 1930-1970, and by Equation (2-7) for the poet 1970 period. An eatimete of the factor a, the fraction of direct losses, can be obtained by noting thet (a) approximately 104 of the electrical material wee Lost during transport, production and processing. (3) (b) approximately 304 of the non-electrical material wee Lost during transport, producticn, processing, and use.^ >9 MONS 209351 Hence, ' 3 - (0.1) (0.62) + (0.30) (.38) 3 - 0.17 It is further assumed that ?! 20 years Y, 4 years(6) (2-12) (2-12 ') If the expression of Q#(t) given by Equation (2-3), aotpLed with the estimated values of a, 3, y, and yj( is introduced in Equation (2-11), the total envitonmntal load (t) may be cccputed. The integrated foot of Equation (2-11) is: jMev(t> * 71.07 ^0.17tl` *31 + (0.21) (t-4)"*31 + (0.62) (t-20) *-1 * (2-13) The nuariol results axe svnmorized in Table 2.2.2-1. It should be rotsd that, in contradistinction to equations such os Equation (2-3), which represent the yearly sales, Equation (2-13) represents the cusulatiw load in pounds. 2.2.3 Effect of ttonsanto's Voluntary Ban at PCB Sales In ths actual situation, as a result of the voluntary Monsanto ban on PCB solas, the expression H^tt) gitwi by Equation (2-13) oust ba nrrtfled to account for post 1970 levels. Thus, far ths period 1971 and later. t-- 4 t--+Y, t^(t) - M#v(40) + 0.11 Q' (t)dt + (1-0-6)J Q(t"Yj)dt fo (2-14) D-10 MO NS 209352 Data 1930 1935 1940 1945 1950 1955 1960 1965 1970 1975* 1980* t(yrs) 0 5 10 15 20 25 30 35 40 45 so TABLE 2.2.2-1 Mey(t> - Environmental PCS Loai Without Partial Ban [Fran Equation (2-13)] Mey(t)(Iba) With Partial Ban [Fran Equation (2-13/2-15)] Mev(t)(lbs) 0 1.42 x 104 3.35 x 10S 2.32 x 106 9.1 x 10* 2.62 x 107 6.23 x 107 1.31 x 10 2.54 x 10 4.58 x 10 7.79 x 10 0 1.42 x 104 3.35 x 10S 2.32 x 106 9.1 x IQ6 2.62 x 107 6.23 x 107 1.31 x 10 2.54 x 10 3.76 x 10 4.66 x 10 *Squation (2-13) is not actually valid for tha poat 1970 period, but if the voluntary ban had not ban inyoasd, the aatimatad (L(1975) would have been as raootdad in Tabla 2.2.2-1. D-U MONS 209353 Sihetitution of the appropriate forma of Qg(t) and Q '(t) and integration results in Mev,t>44> - (l-a-3) a (t-Yj)4' 11 + a'51 (t-40) + 5731 + 4.35' (2-141 o which, on introduction of tha appropriate ntmrical values [note a' - 0.1, i.e., after 1970, tha only use of PCBs was in tha manufacture of electrical equiprent from which sene 10 percent of the material used is discarded as scrap]; becaies Mev(t>44) - 2.99 x 10* + 3.31 x 10* (t-40). + 44.1 (t-20)',, (2-15) this Latter Equation (2-13) has bean used to oenpute tha 1975, 1980 entries in tha fourth ooltim of Table 2.2.2-1. By oaipariaan of the last two entries in Table 2.2.2-1, the direct effect of the voluntary ban in 1970 beocmes obvious. 2.3 Mobile or Free Qr/Lrornantal PC3e, (t) 2.3.1 Ganeral Considerations on Mobile PCTs tb consider the processes by which the general envirorrental load of POe heenmae free, i.a., tha proeeaaae by which is generated, it ia naceaaary to oensidar that sane fraction of tha direct losses are in a form such that the lost material umadiately hsccmaa mobile; i.e., spills and/or evaporation losses. Further, tha non-mobile material is usually encased or enclosed in scraa sort of container which will eventually be degraded thus i the stheequent escape of tha aonpenant PCB. H fraction of tha total sales that is waste occuring in all production uses of P<3e is aQg(t) of which sore fraction c is directly mobile. S>12 MONS 209354 Hus, -in the tii interval t to t + it, this cenponent introduces an anount EaQs(t)it (2-16) into the free environmental pool. The renwirrier (I-e)oQ (t) which enters the environmental reservoir is oontained in a state steh that the PCB content is gradually released with a time oonstant r2 s l/'2. Thus, within the reference interval t to t * it, an amount > z (l-c)3Qs(t)it (2-17) enters the nobile pool. Further, a fraction S of the yearly sales was used to manu facture long Lived electrical opponents, assured to ha*m a useful life of y, years, after which the aonpcnants are scrapped. Thus, the contribution of this source to the general environmental pool is 6 QjCt-y^it (2-18) The electrical containers in which the PCB is arcloeed will eventually decay, with a half life tl 1/X1. The additional ccrrpcnent entering the mobile res ervoir will be \8Q#(t-y1)it (2-19) Finally, the remainder (l-a-6)Q#(t) was used in the construction of products assumed to have e useful life of y2 years, after which they are discarded, thus contributing a uiijjueiL to the general anvirorasntal pool: (1-0-8) Q#(t-yI)4t (2-20) If it is further reamed that these products have a lifetime t1 1/X2 against decay, den the oenulhirt-irrt to the mnfaile environmental pool will be X2(l-a-8) Qs(t-Yj)4t (2-21) 0-13 MONS 209355 On carbining Equations (2-16), (2-17), (2-15) and (2-21), the liadt it - o, the differential equation for mav(t) beocnes dmev(t) - saOs(t) + *,(l-c)oQs(t) + \3Qs(t-Y,) A, (l^s-fl)Qs (t-Y,1)' * [ea + *,(l-e)aj (t) * AJa-a-3)Q>(t-YI) * Al3Qs(t-Y1) (2-22) but, fra# Equation (2-3), Qs - 311t3'3* at3*3* If the parametric values given in Table 2.3.1-1 axe substituted into Equation (2-22), the equation beuonee f f fn^(t) - 24.32 tJ*3*dt*6.53 (t-4)3*3* dt + 1.93 (t-i Jo Jo Jo 24.32 - nn? 6 6.53 + 07 i% n . 1*33 4 j* * 07 (t 20) Thus, m^t) - 5.54t`"M + 1.49(t-4)**3* + 0.44(t-20)` (2-23) Table 2.3.1*2 Hie results corputed from Equation (2-23) are tabulated in 2.3.2 Effect of 1970 Ban on Mobile PCBs It is nof appropriate to discover the effect that the partial him established in 1970 can be ejected to have an the ncbile PCB load, mav(t). D-14 MONS 209356 TABLE 2.3.1-1 Parameter Values fcr Equation (2-22) and Equation (2-24) u = 0.17 i = 0.62 a - 0.21 0.40 1-: = 0.60 S * 0>1' T:-i/i = 6.9 years Ai 31 '01' Ti-i/i 69 years Y; * 4 years y t * 20 years i- = 0.1 ; - 311 i* = 3.31 D-15 HONS 209357 The operative change occurs as a result of the substitution of Equation (2-6) for Equation (2-3) in the time interval after 1970. Tte resulting expression for mfiv(t *40) is given as (recalling that the ban also stopped sales for non electrical applications): which, on integration and evaluation of the ooefficisits, becomes, using the parametric values listed in Table 2.3.1-1, n^v(ta 45) - 7.59 x 107 + (0.44) (t-20) * *17 + 1.32 x 10* (t-40). (2-241) Nunerical values derived fran Equation (2-241) are listed in colum 4 of Table 2.3.2-1. Again, the effect of the' voluntary partial ban of 1970-71 is apparent. It will be useful in what follows to express the numerical relationship given by Equation (2-241) in the approximate empirical form (ti 40) - 4.ait* m (t > 40) - 1.69 x 10*t *01 ev (2-25) 2.4 AtDoepheric Rseervoir of PSs, ma(t) Suppoee that sens fraction 9 of the instantaneous addition to the mobile environmental ** is vaporized. Then within the interval t to t * it 0-16 HONS 209358 TABLE 2.3.2-1 Estimated Total Environmental PCB Load [Me\j (t) ] and Mabile Environmental PCB Load [m (t) ] S'* Get* 1930 1935 1940 1945 1950 1955 1960 1965 1970 1975 1930 1990 (years) 0 5 10 15 20 25 30 35 40 45 50 60 m (t) ev (lbs) 0 6.49 x IQ3 1.40 x 10S 8.62 x 105 3.14 x 106 8.54 x 106 1.89 x 107 3.86 x 107 7.01 x 107 1.19 x 108 1.90 X 108 4.30 x 108 Notaat U> (2) (3) From Equation (2-23) Fran Equation (2-241) From Equation (2-15) m (t) oorr*2) ev (lbs) 0 7.01 X 107 8.31 x 107 9.04 x 107 1.07 x 108 M (t) aarr^1 ev (lbs) 0 1.42 x 10J 3.35 x 103 2.32 x 10 9.1 x 106 2.62 x 107 6.23 x 107 1.31 x 108 2.54 x 108 3.76 x 108 4.66 x 108 8.41 x 10S 0-17 MONS 209359 Further, suppose that the material contained within the mobile pool is vaporized with a tune constant * l/\Jf then the additional oorponent of the atrosphenc reservoir is given by r dm (t) a dt V ! mev (t) Finally, suppose that the lifetime, r. * l/\k, of the atmospheric reservoir results in a decay of md (t) given as r dma (tj ~ar- -A % md. (t). L JC The total change in ma (t) with tine is then given as <na(t) ["dta\a(t) 1 ~] j" dma(t) 1 "dt"" L-aE"J.+ L^t-4+ L-dt~^ (2-26) which on sifcstitutian of the appropriate expressions yields the differential equation for mey (t) as follows: da (t) dm (t) St" * *- ma(t) - 3 -^T + \ mev(t) '2-27) for which the general solution is na(t) - e" j[S dm (t) --It----- + A, m (t) dt 3 ev dt (2-28) rt After substitution from Equation (2-25a) and integrating by parts, the interim result is 1 (3.5) (2.5) ti.s _ (3.5) (2.5) (1.5) D-18 dt (2-29) M0N5 209360 9 Zt i It now becomes important to evaluats ths paraneters, Aj, ^ j which afpear in (2-29). First, it is notad that tht emulative total of material entering the envixonrant fran 1930 to sore time t is given by the sun (2-30) since the two tests in the integral are simply source terms. Cn substitution for n^v(t) fran Equation (2-25) and carrying out the integration. Equation (2-30) becomes, after simplification, mjt) - 4.83t"s [e+^-t] tot L *J (lbs) (2-31) It is important at this point to indieats ths essential difference hetisen Equation (2-29) and (2-31). Be latter. Equation (2-31), represents cuailatir* FO load to the atmosphere in the time fran 1930 to the time 1930. On the other hand. Equation (2-29), which contains the time constant. decs/ of the atmospheric PCB load, nprsaants ths instantaneous KB load in atmosphere at time t. lb return to aquation (2-30). Niabat and Sarofla^ have estimated that ths emulative load of vaporized PCB in the period 1930 through 1970 was 3 x 10* tons or 6 x 107 lbs. If it is assured that e, the fraction of free PCB directly vaporized, is 0.1, then Equation (2-31) rosy ba used to evaluate \j follows it# r 40x, m.(t) - 6 x 10' - 4.83(40)'"* 0.1 + -y-y ii#* L* X, 0.0918 yrs and (TJ)t^I 7.55 yrs. (2-311) D-1'3 MONS 209361 In view of the results displayed in Equation (2-311) arel with the additional assumptions that \t >> >,, X,, > 1, Equation (2-29) may be approxi mated as ma(t) * js* + 4*59[ (2-32) By definition of a(t), the fallout, a(t)A - \,,ma(t) - 4.83t1,5 j A + 4.50 J where A " 8.66 + 1011 ft1 as the area of continental (Mited States. Solving for o(t), 3(t) |xjt+4.Se| (2-33) where ipon, in 1974, a(t) 1.06 x 10 * lbs/ft2/sec, (2-33) yields a value of o(t - 1974) - 1.3 x io'T lhe/fftVyr., a result clearly not consistent with the taiown value. 'Dm obvious suggestion to account for this discrepancy is that the Nisbst^ value of the emulative at mosphere load from 1930 through 1970 Is Incorrect. Howar, no conclusion as to ths reason for this can bs reached at present. 2.4.1 Tims Dependence of o(t) and of B(t) Frost Equation (2- 33) and the loom value of a (t) in 1974 (1.06 x 10- lbe/ftl/yr), it is apparent that Equation (2-33) yields the correct value if the term X tt 4.58, so that, it is appropriate to take, where 9 - o.i o (t) - a,, (t) t* ' * UM/ftVyr (2- 34) and, since fallout constitutes the predaoinant PCS input source to lake Michigan (see Section 3), the forcing function B(t) will be taken to be of the form B(t)-at*` (2-35) D-20 MONS 209362 coefficient a will be evaluated in terra of the specific app-nTM for which Equation (2--3S) is the driving function. 3.0 DERIVATION OF PHYSICAL CONSTANTS FDR LAKE MICHION 3.1 General Properties^8* Fran various atlas and other sources, for Lake Michigan A - 2.24 x 10* mi2 - 6.24 x lO1^ ft2 " area of lake. S 1.2 x 10^* ibs/yr [6 x 10* ft^/sec in average flow through Straits of Madcinac) Q - 1.1 x 1016 lbs - total water mass in lake. A* - 5 x 10* m2 " 1.29 x lO^2 ft2 (a\erage drainage area) 3.2 Proportioning Constants In order to determine the nest appropriate values far the propor tionality ocnetentSf o'and n, in the absence of a v*ll-foundad theoretical ex planation of the physical processes which determine thmn, it is necessary to rely an in-situ raasurwnents of acncentxatian or wide regions of the target water body to establish reasonable statistical reliability. Actually, such a body ofdata doss not exist for lake Michigan at this time. On the other hand, such data do exist far lake Ontario which should allow at least a reasonable estimate of the appropriate values far lake Michigan. 3.2.1 Gonetra+-<TMi Ratio of Biota to Water, n Seepling of Lake Ontario, omducted in 1972 at several near shore and mid-lake situ, indicated the following^9* a. FOB in fiah (alewivea, ezelt, sliny sculpin) 2 . 35 - 5.13 x 106 j^t b. FOB in water (total acre, dissolved +particulate) - 55 ppt c. Average FOB in sediments 1.2 x 105 ppt d. Average FOB in wet planktm - 7.2 x 106 ppt e. FOB in the banthoa - 4.7 x 10s ppt 021 MONS 209363 In view of these data, it appears that a realistic value for the oarutant i, considering the nature of the food chain, is [n - 4 x 10"] for lake Ontario v*u.di, inference, should also apply to Lake Michigan. It ^VDuld be noted that n is taken as an average concentration ratio over all ran kers of the biota; thus, there will be specific species stwing considerable variation from the assured value. Since the basic physical processes that aoootnt for this partitioning of PCS-like materials should be ind^endent of the actual concen tration of PCBa in the aqueous phase (so long as the aquaoua solution is less than saturated), it is rsamable to assure that n is independent of tine. 3.2.2 Concentration Ratio of Sediment to water, o Fran a muter of measurenents of sedlnent levels within lake Midiigan (24 sites), (1* an average PCB concentration of 38.2 ppb was calculated; this is ths preasncs of an average water concentration of 20 ppt. Sines thsss spscific points were taken from ths southern part of ths lake, where the contanination is known to be higher, an average value of o has been taken to be: 0 - 2 x 10* Us deposition rats for ths lake, D, D 5.7 x 10* lbs/mi2/yr 3.3 Biots Mass, G, for Lake Michigan A rspresKitative value for ths hi mess in Lake Michigan, recognizing ths relatively limitsd data that are available on specific species and the absenoe of a detailed ecological pyranid, may be obtained fren the estimates oontainsd in TSfeLe 3.3-1. In Edition, relatively polluted nature of the southemnost por tion of ths Lake results in large masses of benthic species, such as tubifex >22 HONS 209364 TABLE 3.3-1 Eatirata* of Biota Mass for Lika Michigan Eatiinataa for tha Fish Hui121 .4 Laka trout (fron Midiigan watars of the Laka) - u.2 x io lb (1972) b. whitafish (in ftartham Lika Michigan) c. Quba (thoaa availabla to botton trails) (nota: daclina in diuba fron 139 x 10 lb in 1943-45) - 33 x 10 lb (1972) - 15 x 10 lb (1973) d. Alawlvna (thoaa availabla to botton txwla + astimata of tha ndduatar individual!) - 2 x 109 Lb (1973) Cabo faatimata baaad on tha mnfear stockad) - 7.6 x 10 lb (19721 total - 2.i x io 9 Lb (1972-73) far t-ha plankton Bionaaa; a. *tr-- 300 kg plankton/hactara of laka b. Azaa of laka 22,400 ad2 5.1 x 10 hactaraa c. Pljnktm bicnaaa - (5.1 x 10) (X0 kg) - 1.74 x lO^g - 3.8 x 109 Lb 0-23 HONS 209365 worn*. In view of this, it is assured that the benthic bianass is of the order of 4 -x 10* lbs. Finally, in terms of the above, a representati^ value for the total biotic mass, G, appears to be of the order of 10Lbs which, in view of its approximate value, is taken to have been constant over the time interval of interest. 3.4 Input Rata [Bft)1 for the Period 1973-1974 The PCB inputs to Lake Midiigan consist of three parts: a. that due to fallout cn the lake; b. that due to fallout an the drainage area and subs^ quant extraction by ground waters; and c. that due to point sources, industrial and sewage treatment plants. 3.4.1 Point Source I^uts Data cn PCB concentrations are available only far eight of the tributary stxeane in Hldtigan. In addition, historical data collections extend bade beyond 1970-1972. These data, for the St. Joseph, Kalamazoo, Grand, Muskegon, Marristse, Broa&sn, Elk and Portage Rivers113* indicate that, during the recent period, the yearly lead of PCBs from these rivers *as about 1000 Ib/yr. Using these limited data cn stream ocncentraticn due to industrial and seiinige treatment plants, the following estimates of yearly load can be madet (14) Michigan - 217.2 lb/yr (1974, STPs) Wisocnain - 1,150.0 lb/yr (1974-75, paper plant effluents) Wisconsin - 130.3 lb/yr (1974-75, STPs) Wisconsin - 20.1 lb/yr (1974, raise, industry) Indians - 123.3 lb/yr (1972, STS*) Illinois - 3.1 lb/yr (1971, STPs) 1,644.0 lb/yr-1.6 x 103 lb/yr 0-24 MONS 209366 3-1-2 lout or Laks Michigan A variety of fallout rata measurements hawe bean reported1175 indicating rates as high as 0.5 lbe/iniVyr 97 ug/mVyr in the heavily indus trialized portion of Swaden^^ to tha other extra* of 17.5 ug/mVyr ctaerved in Iceland. In via# of tha rather heavy concentration of industry in the Lake Michigan area, it will be assigned that tha average fallout in the 1974 era was 50 ug/mVyr. thus, taking tha area of tha lake to be 5.8 x 10L m2, the annual fallout should be of tha order of Bfallout direct ' 6 4 x 111 1974 3.4.3 fallout onto Drainage Basin In order to ccnputa tha contribution of PCB input to the lake due to fallout on tha drainage basin, tha separata aontributicna fran each of tha sljouQiing states is ccoputad in Table 3.4.3-1. 3.4.4 Total Input to Lake (1974) Fran Table 3.4.3-1 and tha data in Sections 3.4.1 and 3.4.2, tha contributions to tha PCB input are taken to bet Point sources 1.8 x 103 lba/yr lake fallout 6.4 x 103 lba/yr Basin fallout 5.4 x 103 lba/yr (where it is assuaad that 50 percent of basin fallout actually altars tha lake)(12) B(1973-74) - 13.4 x 103 lba/yr From Equation (2-35), B(t) - at*"* D-23 HONS 209367 TABLE 3.4.3-1 PCBs Inputs to Lake Michigan - 1974 a. Tor the Michigan portion of the drainage basin: PCB load (50 ug/m2/yr) (6.0 x L010 m2) 3 x 1012 ug PCB/yr - 6.6 x 103 Lb PCB/yr b. For the Wisconsin portion of the drainage basin:(1' PCB load (50 ug/ra2/yr) (3.7 x 1010 m2) - 1.9 x 1012 ug PCB/yr - 4.1 x 103 Lb PCB/yr c. Por the Illinois portion of the drainage basin: *20* PCB load * (50 ugA2/yr) (8.0 x 108 m2) - 4.0 x 103,8 ug PCB/yr 88.1 lb PCB/yr d. Fbr the Indiana portion of the drainage basin; (211' PCB load (50 ug/ta2/yr) (1.85 x 108 a2 9.3 x 10 ug PCB/yr - 20.4 lb PCB/yr e. Itotal annual fallout from all four sectors of the basin: - 1.08 x 104 It PCB/yr D-26 HONS 209368 vAlldi for the reference year, 1974, mi estimated to be 13.4 x 101 - J (44)1 *5 a - .0237 so that, in what follow* B(t) - 0.0237tJ`1 (3-1) 4.0 APPLICATION CF THE MASS BALANCE DQUATICN TO LAKE MICHIN 4.1 Physical and Hydrologic Constants for La)ce Midiiqan The valuta used for the various physical and hydrologic constants for Lake Michigan are listed below; A S Q D n 0 B (1974) - PCB irput rata in 1974 - 1.34 x 104 lbs K - evaporation rate constant * 2.2 x 1014 Ibe/yr (this asswpticn will ba dlamssar) below] Than, from tbs data above, the various factors appearing in Equation (1-9 M may ba evaluated as follows; ADo - 2.23 x 10" Iba/yr Q + Gn - 1.14 x 10" (lbs), <Q + Gn)~* - 8.77 x 10~l? (lbs)*1 S + K + ADo 5.7 x 10" lbs "a-rs D-27 HONS 209369 4.2 Integration of the Maas Balance Equation In term of the parameters for the Lake and the assured form for B(t) fran Equation (3-1) the differential equation for C(t), Equation (1-9) beoanss: C(tf) 2.OB x 10 -0 e .0 Stf,J ftcS.S a 0. a st dt (4-1) where the PCS concentration is taken to be zero in 1930, i.e., at t - 0. Equation (4-1) cannot be directly integrated in terns of sinple algebraic functions so that recourse nuet be had to mnsrlcal integration to yield the results tabulated in Table 4.2-1. EOr convenience in what follows, the relationship between Cw(tf) and t will be assisted to bs of the form: where b, and n are determined by a least squares fit to the date in Table 4.2-1. Use results of this analysis may be sumerizad la the equation Cw{V " 4,56 x W*1*1/'41' (4-2) Fran Equation (4-2), the change in C^ft) over a one-year pariod is fcumd to be *w<t) dt 2.01 x 10-l,t,*'l` (4-21 > Thus, for the reference year, 1974, the amrage water oonoantraticn was about 8 x 10~11 and the dungs in concentration during the reference year was 0.80 x 10~li. Ftoa these data, it is possible to determine the material balance during 1974 as is shown below: D--28 HONS 209370 Total input Increase in solution Increase in biota Increase in sediment Increase in aitflow Net loss due to evaporation 1.34 x 104 Lbs 9.81 x 103 lbs 0.32 x 103 lbs 1.9 x 103 lbs 0.96 x 103 lbs 1.52 x 103 lbs Fran Equation (1-6), it is now possible to estimate the evaporation rats constant K, Am svje 1,52 ^ 8 x 10 - 2 x 10l* Lbs/yr Tb discover the material balance over the entire period, 1930 through 1975, the total PCB infwt to the Lake is given by i <w/ B(t)dt 7f/*)t1*1 0.0237 dt *n - 1.49 x 10s Ibe (4-3) (4-4) .-1 2 - 1.68 x 10 emulative 1in Lake Michigan in the various phases are stmmsriaad belowi Tbtal trput (1930-1973) Tbtal in water Total in biota Tbtal in sediments Tbtal in outflow - 1.49 x 103 Ibe - 1 x 105 Ibe 3.64 x 103 Ibe - 1.7 x 104 Ibe * 9.07 x 103 Ibe Net loea due to evaporation " 1.93 x 10 Ibe D-29 MONS 209371 Oat* 1930 1935 1940 1950 1960 1965 1970 1975 TABLE 4.2-1 Ccncwntxatim of PCS in Solution in Laic* Michigan* fcf Cw'V Cwct) (ppt) 00 0 5 4.94 x 10*16 4.94 x 10'14 10 1.34 x 10-14 1.34 x 10*2 20 2.79 X 10-13 0.28 30 1.60 x io'12 1.60 35 2.92 x 10_U 2.92 40 5.35 x 10-12 5.35 45 9.10 x 10-12 9.10 *Maa*umnt* in 1970 indieat* a rang* of aqu*ou* aoncantration of l to 7.S ppt(l31 D-30 HONS 209372 Fran the net loss of PCB due to evaporation from the above data, and the defining equation for the evaporation losses, Equation (1--6), the evap oration rate oanstant K may be evaluated. lm K - -S2E. ?w(t>At 1.93 x 10" 1.68 x IQ'12 x 45 2.56 x 101" lbs/yr (4-5) Hie several values of K, fxan Equation (4-5) and the mniw value determined from the 1974 situation, are averaged to yield a useful value K - 2.2 x 101" Ibe/yr (4-6) 4.3 TScporal Variation of Concentration of PCS in the vazious Phases of the Lake It is now pnsslhle to coofeine the relationship 'greeted by Equation (4-2) with the definition of the biotic concentration f^rtor n fron Equation (1-2), to determine the variation of biotic concentration with time. The data amnarated in Table 4.3-1 indicate the trends, than it is noted that the concentration data in Table 4.3-1 are given in parts-per-trillion, it is dear that the avenge biota concentration neared the one part-par-million level on as early as 1965. It is also evident, because of the considerable spread in specific biotic concentration factors for specific species, that the higher predictors could easily have ain-aartart the cne ppn level as early as 1960. 031 MONS 209373 1ABLE 4.3-1 Harporal Variation of Biotic Concentration Data Cw lKt> biota (jpt) 1930 1935 1940 1945 1950 1955 1960 1965 1970 1973 0 4.9 x io-4 1.34 x lO-2 7.12 x 10-2 0.28 0.66 1.60 2.92 5.35 9.10 0 1.97 5.36 x 10' 2.64 x 10 1.12 x 10` 2.72 x 10' 6.4 x 104 1.17 x 10! 2.14 x 101 3.64 x 10' >32 MONS 209374 4*4 Physical Interpretation of K. the Maas Evaporation Constant 4.4.1 Kinetic Theory Experimental data^2*^ on the evaporation rate of Aroclor L2S4 indicates that, at 100*0 (373aK), the evaporation rats is 1.47 x L0~* gn/anVsec and the vapor pressure is S x 10~! inn Hg. Fran elementary kinetic theory of gases, the relationship between evaporation rate and vapor pressure is given m(gVanVsec) - 6l/l p (4-7) where 6 " the measure of the probability that a collision with the surface does not result in the molecule sticking to the surface R the gas oenstant per mole (8.31 x 107 erg T * the abeoluta temperature m - the molecular weight P - the vapor pressure [*K] tgne] 2 [dynes/an ] Fran Equation (4-7) anS the known evaporation rate, the mmerical value of 5 may be onmput-ad as followa; 1.47 x 10- - 6 325 2it x 8.31 x 10' x 373 i/i 5 x 10~* ~760 x 10` or 5 5.47 x 10 (4-8) If it is --that 5 is not tmiperamre dependent at temperatures considerably removed from the normal boiling tetparamre, and that Equation (4-7) may be spiled to a solution as well as to the puce liquid, than at anfaiant temperature (298*K) where the vapor pressure of Aroclor 1254 is 7.7 x 10 as Hg, (24) i/1 mtgp'o^/sec) - 5.47 x 10 325 2ir x 8.3 x 107 x 298 -! 7.7 x 11 760 10* or as - 2.53 x 10""n gn/sec/an1 D-33 HONS 209375 tlw the area of the Iake is 5.8 x 101 u an1, tens* . m( lbs/year) - 2.08 x lO11* Obs/yr) (4_9) B value of m from Equation (4-9) is in excellent agreement with the valv* of K arpirically determined to be 2.2 x 1014 Ibs/yr. 4.4.2 Application of the Theory of MacKay and Wolkoff^2^ f2fi\ Following MacKey and Wblkoff, the rate of material loss for a slightly soluble solute from a water-air interface is given, for a systsn wherein the solute concentration is less than the saturation concentration, by: dCi at VvC:is (4-10) where: A E Pis i G' (3 area of the lake surface (6.24 x lO12- ft2) mess evaporation rate of water (1.38 x 1012 li/yr)*1^ equilibrlm vapor pressure of pure solute (7.7 x 10~S urn Hg) molecular weight of solute (325-Arodor 1254) mass of water from wtiich evaporation occurs mnlemlar weight of water (18) saturation concentration of solute (6 x 10-8) *272 equilihrim vapor preaeuze water (23.7 an Hg) acnoantration of solute in the evaporation layer density of water (62.5 lbs/ft2) Equation (4-10) mist be for the present situation to taka into account the effect of fallout on the solute concentration. Hue, for the case in point. _ a(t)A gisMi ,, dt G' G'Wii 1 (4-11) D-34 HONS 209376 . U* expression a(t) v*iich occurs in Equation (4-11) is taken to be of the fom (fcan Equation (2-34) ] o(t) - 1.67 x 10'l"t!-5 (4-12) Further substitution of G' - AoS, where C is the thickness of the layer frcm which evaporation is occuring, and E - Aol*, where 1 is the evaporation rate in ft/year, reduces Equation (4-12) to the fom ^i _ 1.67 x Kr'V-1 dt 5o Ci r-Wis (4-121J vftich is now applicable to a unit area of the lake. The solution of Equation (4-12`) is oonplicatad by the fact that , the layer thickness, is unknown. Tb obtain sane idee of the magnitude of 5, it is reasonable to assure that Ci(t) " *V(t) <4-13) vtere y may be a Auction of tine. Substitution of Equation (4-13) and the appropriate nanarical values with Equation (4-12) and evaluating for t - 44 years (1974), yields (after using Bqiation (4-2) for Cw(t) ] 8.22 x 10'" Y + 2.66 x 10-1' - L5L^X 10 (4-14) Ms#, m i-- y m tha definition of K. ttnoa, Cron this last relation, A Wil evaluated at t 44 years. X - 10.92 (4-15) Substitution of (4--IS) into (4-14) yields Y - 0.S7 5 - 0.052 ft (28) (4-16) D-35 HONS 209377 It is apparent, from Equations (4-16) and (4-13), that this analysis suggests that the average concentration in the layer is less than that in the bulk water, i.e., y < 1. The reason for this apparent ananaly can be seen by recognizing that Equation (4-12) is in the form !PiA xi 5 Imp?-- - 617 (4-17) is the effective decay constant for the surface layer concentration. In terms of the half-life (r.) -10 hours 1 t/z (4--171) Equation (4-17) may be integrated from a time t to t + 1/1 to yield, vtare the interval is sufficiently short that a (t) ray be assvxned to be aonstant; CL - 0.37 + 3.34 * 10 (4-18) If the relationship between CL and C^, given by Bqwtion (4-13) is introduced as (C^ - PCSe concentration at time t) Co-^io than Y(1 f 0.37) 3.34 x 10 S# Y - 0.74 (4-19) This shows good agreecant with the results expressed in Qquetion (4-16). D-36 HONS 209378 S.O KSULTS MO CONOU6ICNS 5.1 Results Even though the model used is only first-order, it is apparently able to describe the relative significance of the natural processes which control the distribution of PCBa. The strong focus on fallout as the primary input souroe of PCBa to Lake Michigan suggests the need for furtimr study of the nature of the processes by which PCBa baucine airborne and thus become part of the available atmospheric reservoir. Hie attapt to model the atmospheric reservoir of PCBs, in Section 2, yields results that indicate significantly greater emulative at mospheric loads than the preliminary estimate, made by Nlsbet and Sarofira, ^' of a emulative atmospheric reservoir of 3 x 10" tons ip to 1970. The estimate of Nisbet and Sarofim leads to a half-life, from the model, for PCBa in the atmo spheric reeervoir on the order of eight years. This value is considerably in . excess of the repoiLed lifetime measurements, cn the order of 20 to 40 days, for (29) atmospheric PCTs. However, the obeaevetion that significant levels of POs are found in preeant snowfalls and in padcsd snow in Antarctica suggests that the applicable half-life itey indeed be considerably longer titan 20 to 40 days. It is suggested that further refinement of the ewircmental distri bution model presented in Section 2 will lead to a resolution of this apparent discrepancy. This refinsnent will focus attention cn the nature of the physical processes involved in atmospheric transport of PCBs and may suggest methods of reducing PC3 fallout in the future. The observation that evaporation and/or co-distillation sans to be a significant process by which PCTs are returned to the atmosphere is of impor tance. It should be noted thet the magnitude of the evaporation rata constant necessary to achieve tnaaa balance in Lake Michigan is in excellent agreement with that computed from the simple kinetic theory of gases and also with that ocqputad from the theory of co-distillation discussed by MacKay and HbUcoff. D-37 HONS 209379 The observation that the KB input to LaJca Michigan fron point souroea sen to bs a rather snail part of the total i/put suggests that reduc tion of point source PCS effluents may only slowly correct the present problem. 5.2 Conclusions The first-order mass balance nodal described teiein sears useful in describing the historical situation as it explicitly addresses the qisstion "How did we get here?". Hie nodal requires refinensnt before it can be used to allow a reasonable estimate of future conditions. Significantly more detailed data axe required as to the taeporal variation of irputs and concentrations as well as on the interval transport processes by which local inert concentrations are soothed and distributed over the whole body, ttiile the present model mm to deal very well with the situation that cbtaina during an interval of rising aqueous acncentraticns, there aeons to be little dqerimantal or theoretical guidance as to whet will happen if, in the future, aqueous concentrations begin to fall. It is not known whether the biota and the sadimnts will act as reservoirs to return their P3 loads to the systan. 'As processes, if any exist, which will eventually mn or inactivate tha PCTs already in the lithosphere are not known. Hie application of this nodal to the situation in Lake Michigan sans suooassful. It will be of interest to apply it to regions which axe more <T1** or of larger scale. 5.3 Discussion of haeulta with regard to take Michigan, tha mass balance indicates that this fceeh water system (water, sediment, biota) same as a significant sink for P3e; this oust also apply to many other fceeh water system. in tha case of toxic matala, tha aoaana axe g--**'iiy rarrxyilaad as an important ultimate sink, but this nay not be the case for PCTe. Hie theory developed by Madfey and Wblkoff, as applied to Lake MLchign conditions, yields a lifetime against (until) evaporation of about D-38 HONS 209380 ten hour*. For seaater, this Lifetime is greatly reduced by lower solubility of PCBa and higher evaporation rate, so that the calculated lifetime of PCBa in seawater against evaporation may be as low as ten minutes. Although attachment to organic and living material may well be a factor, the above result indicates that PCBa tend to evaporate fran salt water mjch more quickly than fron fresh water. Then, an this basis, the terrestrial system, such as fresh water lakes, forests, etc., nust be regarded as partial sinks for PCBa in fallout; the PCBa lost from these system reenter the atmos phere via direct evaporation or transport by risers to salt water from which furtiar evaporation occurs. New PCBa are added to the atmoepheric load by direct evaporation, through inadequate incineration ptorestea, or via water from runoff, industrial discharges, landfill leachate, etc. D-39 HONS 209381 6.0 GLOSSAW OF SYMBOLS USED A B(t) cw(t) D G K ma(t) Q <Wt} ^electrical(t) Wt} SW*1 s t a a Y* e 9 Surface area of reference body of water (ft1) PCS injection rate with reference body of water (lbs/yr) Aqueous PS concentration Sediment rate in reference body of water (lb/ft Vyr) Mass of biota in reference body of water (lbs) PS evaporation rate constant (lhe/yr) emulative envizcnnental PS load (Ibe) emulative free environwntal PS load (lbs) Instantaneous atmospheric reservoir of PSe (Ibe) Mass of water in reference body of wetar (Ibe) emulative PS sales for capacitor application (lbs) emulative PS sales for electrical application (Ibe) emulative PS sales for production application (lbs) emulative PS sales for all applications (lbs) emulative PS sales for transformer application (lbs) Hater outflow rate from refarenas body of water (lba/yr) Tims (yrs), (t - 0 in 1930) Fraction of PS sales directly lost to the anvirtnnnt Fraction of PS sales devoted to electrical applications Average in-service life of electrical oenpenants (yrs) Average in-sarviae life of non electrical products (yrs) Fraction of production wests initially free Fraction of initially free PSe that axe vaporized 0-40 MONS 209382 Decay constant for discarded PCB-containing elactrical aarpenents (yr~1 > Decay aonstant for discarded PCB-containing ncn-lectrical products (yr"") Decay aonstant for vaporization of free PCSs (yr~l) Decay constant for fallout of atmospheric PCSs Patio of biota PCB concentration to aqueous PCS concentration Patio of sediment PCS concentration to aqueous PCS concentration Fallout rate per unit area (Iba/ftVyr) Half-life of containment of discarded PCB-containing electrical corporanta (yr) Half-life of cantaiment of discarded PeB-aentaining ncnelectzical ocsponsnts (yr) Half-life of free PC8e for vaporization (yr) Half-life of atmospheric PCSe against evaporation (yr) D-41 HONS 209383 7.0 BIBLIOGRAPHY The literature resulting from analytical measurements on a wide variety of biological and geological specimens has become very large. Tf* following list, while in no sense oonplete, represents those sources used in this work. 1. Addison, R.F., S.R. Kerr, J. Dale, and D.E. Sergeant, J. Fish Fes. 9oarri Can., 30, S95, 1973. ------------------------'--" AncnynDus, "Chemicals Fond in Lake Fish: State PCS Ban Urged." Michigan Out-of-Ooors, July, 1975. Bailey, S., P.J. Ekiryan, and F.B. Fishrfick. Qwdstzv and Industry 22.* 70S, 1970. Bowes, G.W. and C. Jankal, in PCS in the Srrvironment, Martel Dekker Inc., New York, 1974. Carey, A.E., G.B. Weirsma, H. Tai, and W.G. Mitchell. Pesticides Monitoring Jbumal 6(4): 369*376, 1973. CrusHSeianer, H.J., H.R. Felts, and M.L. Yates. Pesticides Monitoring Journal 8(3): 157-161, 1974. Dogudli, M., New Methods in Ehvirornsntal Chenistry and Toatlooloqy. Proceedings of the International Sjeposiini, Suaono, Japan, 1973; Coulatcn, F., Korte, r., and Goto, M., Eds., International Acadenic Printing CO., TOfcyo, Japan, 1973. Duka, T.W., J.l. Lowe, and A.J. Wilson, Jr. Bulletin of Brvironnental Contamination and Dacinologyi 5(2): 171-180, 1970. nlwenle i R. "Polydilorinatad Biphenyls, Their Oocurenoe and Significance: A Revise. (Smistzy and InAistry (Mo \taluae) Issue 47: 1340-8 (21 Nowtasr, 71), 1971. Fog, M., and I. ICraul, Acta VSt. Scsnd., 14, 350, 1973. Frank, R., K. Ranald, and H.E. Braui, J. Fish Res. Board Can., 30, 1053, 1973. C.S., M.K. Hong, A.R. Hanks, and W.M. Sadcett, Bull. Environ. Gontaa. Trndml , 9, 376, 1973. Qnichus, Y.A., A. Qnichus, and R.J. Qnerick, Bull. Envirpn. Contam. Tadool., 9 , 321, 1973. Oatafson, C.G., Bwiramental Sdsnos and Technology 4(10): 814-819, 1970. Harvey, G.R., H.P. Mlklas, V.T. Bowen, and W.G. Steinhausr. Journal of miina naeaarrh 32(2): 103-118, 1974. 0-42 HONS 209384 Happleston, P.B., Mar. Pollut. Bull., 4, 44, 1973. Hidaka, K., T. Che, and K. Fujiwara, Shokuhin Eiseiqaku Zasahi. 13. 523 1972: C.A., 79, 028100, 1973. ------------------ ' Huschenbeth, E., Schr. Ver. Wasser-, Boden-, Lufthyg,, Berlin-Oahl. 37. 103, 1972. ------ ------------------- Han, w., R.w. Risebrough, A. Soutar, and D.R. Young. Scierre 184 (4142). Interdepartmental TaaJt Force on PCBa. "Polychlorinated Bipfcenyla and the awirornent." CCM-72-10419. 1-192. National Technical tnfonreticn Service, Springfield, Virginia (U.S. Dept, of Agriculture, Caimerce, Health-Education and Welfare, EPA, and other agencies), 1972. Lunds, G., J. Gerber, and B. Joeefsecn. Bulletin of Environmental Ccntanination and Toxicology 13(6): 656-881, 1975. ban, L.M., and D.P. Cbarlitz. Pesticides Monitoring Journal 8(1): 33-36. 1974. Marta11, J.M., D.A. Ridcert, and F.R. Siegel, atvirotmental Science and Technology, 9: 872-75, 1974. `-- Oloffs, P.C., L.J. Albright, and S.Y. Szeto. Canadian Journal of Microbiology 18(9): 1393-1398. 1972. Oloffs, P.C., L.J. Albright, S.Y. Szeto, and J. lau. Journal of Fisheries neeeardi Board of Canada, 30(11): 1619-1623. Panel on Hazardous Trace Substances. "Polychlorinated aiphartylsEnvoxoreental Inpset." awirormental Research 5(3): 249-362. 1972. Peel, DJ4., Nature, 254 : 324-325, 1975. Riaabrough, R.W., P. Raid*, D.B. Peakall, S.G. Harman, and M.N. Kirven, Nature (12/14): 1098-1102, 1968. Risebrough, R.w., and B. deiappe. Bwixonnsntal Health Perspectives Ezp 1: 39-45, 1972. Saachenbrecker, P.W., Can. J. Carp. Med., 37, 203, 1973. Smith, W.E., K. Its*, and M.E. Zabik, J. Fi^i. Rts. Board Can., 30 , 702, 1973. Walker, W.H., "Vtoara Have All the Toxic Cheirlnala Gone?" Ground Water 11(2): 11-20, 1973. Monsanto Irriustrial Qeedcals ocnpsny, "PS Manufacture and Sales-Monsanto Industrial Chsedcals Genpeny - 1957 thru 1964." (unpublished data), 1974a. Monsanto Industrial Owmicals Ccnpany, "P<3 Manufacture and Sales-Msnsanto Industrial QmLcals Ccnpeny - 1965 thru 1974." (unpublished date), 1974b. 0-43 HONS 209365 3. Rurn>, D.J. and V.J. naCarlo, U.S. Qivironrental Protection Agency, Washington, D.C. - Privets caamnication. 4. Nisbet, C.T. and A.F. Sarofim, Envirorirental Health Perspectives, ekd l 21-38, 1972.---------------------------------------- ----------------- ^ ' 5. Section V, "Industrial Characterization" and Section IX, "PCBs Release and Cumulative Environmental Loads" of this report. 6. Section V, "Industrial Characterization" and Section IX, "PC3s Ftelease and emulative Environmental Loads" of this report. 7. Nisbet, C.T., and A.F. Sarofim. Environmental Health Pm--pectives Exp 1; 21-38, 1972. 8. Annan., world Almanac, Washington Star News, Washington, D.C., 1975. 9. National Water Quality Inventory. Raport to the Congress. Vbl II. EPA-440/9-74-001. Office of Water Planning and Standards. Appendices C-l to C-69, D-l to D-55, E-l to E-76., 1974. International Joint Ccmnission an the Great Lakes. Pollution of Lake Erie, lake Cntano and the International Section of the St. Larcenoe River, Vbl 3, 1969. 10. liesee, J.L. Statue Report an Polychlorinated Biphenyls in Michigan Waters. Rspoil to Michigan water nasmii'ihas Ccnrdiainn., 1973. 11. Anncn, Wbrld Alnenec, Washington star Nsws, Washington, D.C., 1975. 12. Greet Lakes Fisheries. Suamsry of United States and Canadian landings (Preliminary Data)1974. Michigan Dapartment of Natural Resources Fisheries Division. Estimates of Sicnass of Principal Fish Spades in.the Great Lakes (first report). Fisheries Rueerch Raport No. 1813., 1974. 13. State of Mlchlgst Water Resources Oamdsaicn, Bureau of Water Management. Polychlorinated Biphenyl Survey of the Kalamazoo River and Portage Creek in the Vicinity of the City of Kalamazoo, 1972. State of Michigan Water Resources Ccnmisai.cn, Bureau of water Management. Jtnitoring *nr` Polychlorinated Biphenyls in the Aquatic Enviroment. to lake MLchign Tteodr Substsnoss Gaanittee, May, 1973. Haile, CX., G.D. Vtaith, G.F. Las, and W.C. Boyle, Otlorinatad Hydrocarbons in the Lake oxtario Ecosystem., 1975. 14. Ueith, G.D. Baviromental Health Persnartives Exp 1: 51-54, 1972. D-44 MONS 209386 Uaith, G.D., and G.F. Lea. Water lhaanrrh. 5(11): 1107-1115, 1971. Sctmidt, T.T., R.W. Risebrough, and F. Grass. Bulletin of Envirorronr*) . Contamination and Toxicology 6: 235-243, 1971. ------ 15. Panel on Hazardous Trace Substances. Environ, tea., 5, 1972. 16. Bengston, S.A., Atrfcio, 2 No. 2, p. 84, 1974. 17. Bevenue, A., J.M. Ogata, and J.W, Hylin. Bulletin of Owironrantai Cnn- tenination and Toxiooloqv 8(4): 238-241, 1372" ------ --- --------------- Bidlanan, T.F., and C.E. Olney. Scienoe 183 (4142): 516-S18. 2ni Copy, Bidlenan, T.F., and C.E. Olney. Bulletin of Environmental Contaminaticxi and Toxiooloqy 11(5): 442-450, 137T---------------------------------- ------ ----------------------- Harvey, G.R., and W.F. Steinhauer. Atmoeoheric Envirorment at SI? 777-782, 1974. Holden, A.V. Nature 228 02/19): 1220-1221, 1970. Sfidargran, A. Nature 236 ; 395-397, 1972. Tarrant, K.R., and J.O.G. Tatton. Nature 219: 725-727, 1968. 18. United States Geological Survey. Water Reeoureee Data for Michigan. Part 1. Surface water Raoorda, 19711 19. United States Geological Survey, water Resources Data far Wisconsin. Part 1. Surface water Records. 1974. ~ 20. United States Geological Survey, water Reeoureee Data for Illinois, part 1. Surfsce water Records, 1973T 21. United States Geological Survey, water Raeourcee Pete for Indiana. Part 1. Surface water Ifrcorda, 197TT 22. ftjttner, F., Fir**--"ntals of Lianology. University of Toronto Press., 1952. 23. Saylor, J.H., and P.W. Sloes, water ^olune Transport and Perillatory Currant now through tha Straits of Machine. (Contxibutian No. 38, Great Takas Qxviranmwtal ThaenrA Laboratory)., 1975. 24. Rutzingar, 0., S. Safa, and v. ZiXto. "His Oemistry of PCSa." CSC Press, Cleveland, Chio, 1974. 25. Monard, E.H., "Kinetic Theory of Gases", McGrw-HUl, N.Y., 1938. Lm^adr, "Phnom, Atone and Molecules", Philosophical Library, N.Y. Oiapt. 15., 1950. 0-45 M0NS 209387 26. Maduy, D., and A.W. WbJJeofff. Envirorinantal Science arai Technology 7(7)s 611-614, 1973. 27. Haque, R., and D.W. Schmadding. Bulletin of 5wironnantal Gontanunaticn and Toxicology 14: 13-18, 1975. ^ ' " ' Hague, R., D.W. Schmeddinq, and V.H. Freed. Envirorcental Scierce and Technology 8(2): 139-142, 1974. Wallnofer, P.R. , M. Koniqer, and 0. Hutzinger. Analabe, Inc. R^earch Notes 13(3): 14-16, 1973. ' 28. Ouce, R.A., J.G. Quinn, C.E. Olney, S.R. Piotrowicz, B.J. Ray, and T.L. Wade. Science 176(4031); 161-163, 1972. 29. Sodergxan, A., Nature 236 : 395-397, 1972. Risebrough, R.W., et al; Nature (12/14), 1098-1102, 1968. Harvey, G.R., et al; J. Marine flaaaariii 32 (2): 103-118, 1974. Harvey, G.R., and W.G. Steinhauer. Atmospheric Envlronnent. 8(8): 777-782, 1974. 30. Peel, D.A., Nature 254(3/27) s 324-325, 1975. 0-46 HONS 209366 APFEUDDC E BJOQCCt DATA USED TO OtSTRJCT THE MODEL FOR PSs d LAKE MICTUGSM Table E-l Concentration of PCBs in Sediments ,,, Along the Southwestern Shore of Lake MicJugan (197Q-1971)(1) Sarfle Locations Along SW shore of lake; saipling 1-3 mi. off-shore* (see Figure E-l). PCBs fppb) CD 00 13.09 A 6.73 A 11.81 26.07 A A 130.27 26.61 B 64.32 A 3.72 A 3.87 A 35.8 A 8.31 A 15.24 B 16.09 "5 12.69 23.53 A 17.53 A 36.7 y 58.81 A 41.06 A 132.61 A 80.63 ? 29.29 A 13.34 A Total 896.01 Ave. (PCBi - 37.3 NOTE: Estimated Location of smiling sites with respect to thexmccline; A - above thesnocline B - below thesnocline ? - questionable * Soiling sites are looted in an area with several known STP discharges. Data were not available an PCS aonosntratians in these S effluents; how ever, judging feat PS data for other area STPs, it is probable that these plants dlsrftanjs PSe, thereby producing higher concentrations in the adjacent sedimnts. E-l HONS 209389 p<3* in 3*dimnts of Laka Mtdugan 6 Tributary straan*, ravin** sadirranta. HONS 209390 E-2 Strean St, Joseph Kalamazoo Grand Miskegan Manistee Boaninan Elk Portage TODVL Table E-2 Concentration off PCSa in Micjiigan Stream Tributary to Lake Micjiigan*2,3'^ PCB (pob: nean 1971-72) Strun Discharge (1974) KTS) (M3)) PCB* lb/day 0,013 0.065 0.041 0,010 0.014 0.017 0.012 0.47* 4,204 2,162 5,814 2,489 2,047 187 575 18 17,478 2,716 1,397 3,756 1,608 1,322 121 371 12 11,291 0.29 0.75 1.28 0.13 0.15 0.02 0.04 0.045 105.9 275.1 466.5 47.5 54.8 7.3 14.6 16.5 988.2 *Q-tixre maasuranent taken in 1972. E-3 HONS 209391 State Midiigan wisaonsin Wisconsin Indiana Illinois Total Table E-3 PCBs altering Lake Michican Fran Krwn Industrial and STP Disciiaraag* PCB Load (lb/yr) 217.2 1170<1 130.3 122.3 3.1 1643 Souroe STPs Industries STPs STPs STPs *Sh Tables E-4 - E-9 for tabulations of the individual waste disciiarge*. E-4 MONS 209392 TABLE E-4 Conuntration of PCBs iji Fteportarf Michigan STP-Jlffluants Tributary to lake ,, , , STP Location Albion Battle Creek Benton Harton, St. Joseph Plant Menominee Miskagcn Mile* Portage East Lansing Escanaba Holland Jadcsan Kaleoasoo Lansing Ttotal Design Flow {MGD, 1974) 4.0 22.0 13.0 1.2 10,0 10.0 3.6 8.5 2.2 4.5 20.0 34.0 34.0 147.0* (PCBI <PPh, 1971-72) 0.44 0.39 0.65 0.35 0.28 0.68 1.9 0,5 0.29 0.6 <0.1 0.66 0.18 BO lead m 0.595 lb/dmf - 217.2 Ib/yr. PCB Lead (Ib/day) 0.015 0.017 0.070 0.004 0.023 0.056 0.057 0.035 0.005 0.022 0,186 0.051 0.595* * Total 3om not include flow* with [PO] <0.1 ppb. E-5 HONS 209393 TABLE E-5 Concentration of PCBs in Reported Wian->nin Paper Plant Effluents Discharging to Green a^y (1974-75^ (5* Plant Badger Paper Mills 3aott Paper Marinette Oconto Falla Sh&rarto Paper John Strange Paper Bergatran Paper Kimberly Clark Thilmany Paper Fort Howard Paper Mill Effluent Deinking Deinking 6 Mill Effluent Anerican can Sulfite Sewer Paper Mill lagoon ChAxsriji paptr Green Bay Packaging Total* Flow (npd) 4.78 5.91 11.03 2.43 1.11 5.22 4,30 25.1 7.3 11.04 18.1 2.23 10.35 16.3 1.77 77.65 [PCS] (ppb) <.l <.L <.l <.l 4.00 28.40 0.28 <.l 2.60 6.40 7.07 0.1 0.14 0.14 0.45 PCS Loai flb/day) - * - 0.037 1.26 0.010 - 0.158 0.586 1.06 0.002 0.012 0.019 0.006 3.15 P<3 load *3.15 Ib/day - 1,150 Ib/yr. * lbtaL does not include flow with [P<3] <0.1 ppb. E-6 HONS 209394 TABI E-6 Concentration of PCBs in Sewxted Wisaan*tn Miscellaneous Industrial Effluents Disctiarcsd to Lake Michigan (5) Plant Jtotor Casting Co. Grey Iron Foundry, Inc. Hcwnstt, Qorp. - Crudbls Steel Maynard Steel casting Qorp. Milwaukee Solvay Oaks Oo. Briggs t Stratton wehr Stssl Oo. SST Oo. Milwaukee Ota casting Oo. Mst*-told Daton Mallsabls Inc. Babcodc a WUocdc Oo. ) Tubular Predicts Dlv.( Tbtal** Flow (mgd) 0.22 0.339 0.796 0.133 4.3 1.523 0.228 0.069 0.012* 0.033* 0.6 0.714 [PCS] (ppb) <0.1 <0.2 <0.1 <0.1 <0.1 <0.2 <0.1 2.95 32.2 170.3 0.9 PC3 Load (Ib/dayi 0.001 0.003 0.047 0.004 0.055 PQ load - 0.055 Ib/dwy 20 .1 lb/yr* * Avsrags of tee reading*. ** Ttrtal doss not include flows with [PCS] <0.1 ppb. HONS 209395 E-7 TABLE E-7 Concentration of PCBs io_ Feporbed Wisconsin ... ST7 Effluents Diadiarced to Green Bay (1974-751 STP Location Marinette Portage Oshkosh yeenak-Menash Appleton Kaufcauna DePere Green Bay Kewaunee TWo Rivers Manitowoc Sheboygan pact Washington Milwaukee (South Shore) Milwaukee (S. Mtlwuhee) Racine Kenoeha Tbtal Flow (mqtl) 2.5 0.736 8.49 12.75 11.05 1.25 23.45 30.64 0.315 2.28 9.3 11.04 1.59 66.7 2.42 16.92 18.88 119.8* [PCB1(ppb) <0.1 5.0 0.1 0.16 0.12 <0.1 0.5 <0.1 0.18 0.2 <0.1 1.1 0.2 0.29 0.12 <0.1 <0.1 PCB Loajj (Lb/day) 0-031 0.007 0.017 0.011 0.01 0.001 0.004 O.U 0.003 0.160 0.003 0.357* PCB lrtd - 0.357 It/day 130.3 It/yr. * Total Jom not include fleams with (POl <0.1 pjb. -8 HONS 209396 TABLE E-8 Qaiaentration of PCBs in Reported Indiana STP Effluents Tributary to Late Michigan l6' STP Location Midiigan City Valparaiso Hobart Hamend East Oticago Qiestsrtown Gary South Band Mistwaka Elkhart Goahan Nappanaa Kandallvilla La Granga Ligoniar Angola Syracuaa Total* Flaw I'mgd) 12.2 4.0 2.9 42.6 18.7 1.6 50.5 35.8 10.39 17.5 4.8 0.9 1.2 0.185 0.434 0.784 0.305 99.8 [PCB] (ppb) 1.32 0.24 0.23 <0.1 0.1 <0.1 0.38 <0.1 0.13 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.17 0.13 PCB load - 0.335 Ib/day - 122.3 Ib/yr. PC3 teal (Lb/dav) 0.134 0.008 0.006 0.016 0.159 0.011 0.001 0.0003 0.335 * Total daaa not inelud* flows with(P(SI <0.1 E-9 HONS 20939? TABLE E-9 Ccnoentzaticn of FC3a in Seportad illlnnia STP Effluents Discharging to Lake tti.ciu.qan (1) STP Location N.S.S.D., Waukegan N.S.S.D., North Chicago Plant Total Flaw (mflg) *** 0.002 1.2 1.202 tPCBI (ppto) ' 2.635 0.331 PC3 Load (lb/day) .00004 0033 0.00834 p<3 load 8.34 K 10* 3 lb/day 3.04 lb/yr. * Data for 1975 ** Data for 1971 -10 HONS 209398 TABI E-10 - Lake Michigan Basin Hydrology(7'3,9,l0,11) Total mean river discharge (1974) of the 4 states (Midiigan. Illinois, wisaonsin, and Indiana) into Lake Michigan 34,SOS cfs - 1.1 x 1012 c/yr Total flow of water in the basin - 9.4 billion gpd Flow diverted from Lake to Oiicago - 2 billion gpd Flow diverted through Straits of Mackinac -'67,000 cfs Other withdrawl's fran the Lake - 11.7 mgd Volume of STP effluents entering Lake: from Illinois 27.6 trgd from Indiana - 110.5 mgd from Midiigan - 161.6 mgd from Wisconsin 183.4 mgd E-U HONS 209399 TABUS E-ll Estimates of Fish Bianass in Late MiiAigan (1972-73)tl2) Midiigan waters of Lake Michigan - 11.2 x 10 1b. of lake trout (aga grtxqp II i older); 1972 Northern Lake Michigan - 55 x 10 Lb. of whitefish (age grotpa I-VI); 1972 Fran bottom trails of the Lake - 220 x 10 lb. of alewife (age grcupe I i over); 1973 - 15 x 10 lb. of chubs (age groups I i over); 1973 Total (1972-73) - 3x 10 lb. g' If mi&ieter alewivee are included, the total oould be in the range of 2.3 x 10 lb. E-U MO NS 209400 Backorcund Calculations Used to Construct the Vfadel for PCBs in lake 'MitfUgin The concentration and total weight of PCBs in Lake Michigan at the present wee calculated on the basis of PCS input to the lake Cron the following sources: 1) atmospheric fallout directly an the lake, 2) atmospheric fallout over the drainage basin of the lake, and 3) dooxmnted point souros disOiarges fran tributary industries and swage treatment plants (STFs). The derived axicentraticn in the water of 0.078 ppb PCS (or 8.4 x 10S lb.) represts the expected maxima enoixit of the chemical in the water, asuning a constant annual input PCBs over the past 40 years, and no lose of PCS from the lake. A. Estimation of PCBs In the Lake water Phase. 1. PCB load frtxn atmospheric fallout directly cn the lake surface: ares of lake - 22,400 mi2 - S.8 x 1010 m2 (13) Assum that the atmospheric fallout of PCBs has a aonatent annual rate of 50 mg/ta.2/yr., that PCSe ace evmly distributed agues tie lake surface, and that the total aoamilati.cn the pest 40 years represents the present load; than the annual P fallout on the lake (50 wg/m2/yi) (5.8 x 1010 in2) 2.9 x lO^2 ug/yr. - 6.4 x 102 Ib/yr of PCB The total fallout on the lake after 40 yrs - 2.6 x 105 lb. of PCB. 2. p<3 lotit froe atmospheric fallout on the lake drainage basin: fallout (at a ccmtant annual rats of 50 ug PCB/m2/yr) ow the bmln contributes the majority of the PCBs to the lake via runoff, ml that all of tha PCBs falling on the drainage basin evmtually enter tha lake, tlen tha annul p load - (50 ug>2/yr) (area of drainage basin) Tox the MiAigan portion of the drainage basin -t7> P load - (50 ug/ta2/yr) (6.0 x 1010 m2) 3 x 1012 ug PCB/yr - 6.6 x LO2 lb PCB/yr E-13 HONS 209VO1 Ebr the Wisconsin pr rtian of the drainage basin -(8) PCS load (SO jg/m2/yr) (3.7 x 1010 nt2) 1.9 x 1012 -g PC3/yr 4.1 x 103 lb PCB/yr 1' For the Illinois portion of the drainage basin PCB load (50 ug/tn2/yr) (8 X 10 m2) 4 x 1010 -g PCB/yr 88.1 lb p(3/yr For the Indiana portion of the drainage basin PCS load * (50 ug/7n2/yr) (1.85 x 108 m2) 9.3 x 109 ug PCB/yr - 20.4 lb PCB/yr Total annual PCB fallout fran all four sectors of the basin 1.03 x 10* lb/yr and total fallout on the basin after 40 yrs (1.08 x 104 lb/yr) (40) - 4.3 x 105 lb PCS. 3. Total annual PCS load in the lake due to fallout " PCS ioi fran drainage basin + PCS load from lake surface - 1.08 x 104 lb/yr + 0.64 x 104 lb/yr - 1.7 x 104 lb PCB/yr 4. Total fallout Load of PCS after 40 years " (1.7 x 104 lb/yr) (40 yrs) 6.9 x 105 lb PCS 5. PCS load entering the lake via tributary stream discharges Assune that the conositraticn of PCSa in the streame has remained constant avmc the past 40 years, with an annual PCS load equivalent to that in the most recently recorded data. Data di PCS concentrations are available only for eight tributary stress fran the stats of Michigan (see Table 2). PCB measuronents along the St. Joseph, Kalmnazoo, Grand, MisJcegon, Manistee, Boardnan, Elk, and Portage Rivers indicate a total of 988.2 lb PC3/yr. *2'3'4> E-14 MONS 209402 6. PCB load entering the lake fran reported industrial art! STP discharges: Assure that the ooncentration of PCBs in the industrial and STP effluents has renained aonstant over the past 40 years, with an annual PCS load equivalent to that in the moat recently recorded data, and that all the POs in the disdiarges eventually enter the lake. The annual PCB load from the four tributary states is as follows: (see Tables 4-9) {2,3,4) Michigan - 217.2 lb PCT/yr (fran STPs) Wisconsin - 1150.0 lb P<3/yr (fran paper plant effluents) - 130.0 lb PCB/yr (fran STPs) - 20.1 lb P<3/yr (fran raise. industry) Indians - 123.3 lb PCB/yr (fran STPs) Inline - 3.1 lb PCB/yr (from STPs) TOTAL - 1644.0 lb PCB/yr * 1.6 x io3 lb/yr 7. The total PCB load in the water phase fran all the above souross (i.e., fallout, industry, STPs, Midiigan straans) - 1.98 x 104 lb/yr. 7.9 x 10 lb PCT after 40 years of aonstant aocwulatien at this annual rate. 8. Qanoantraticn of PCSa in the lake water phases Calculation based cn the lake water voliane - 4.91 x 1015 1. Annual ocnoaxtraticn of PCSa (1.98 x 104 lb PCB/yr) (454 x 10 ug/lg) - 0.002 pph/yr 4.9 x 10i5 1 Total ccrcaitratian of PCBe at pzeaant (after 40 years of constant acoanulation) - ^ (7.9 x 10 lb PCB) (454 x 10. ug/lb) * 0.073 ppb PCB 4.91 x 10i? 1 E-15 MONS 209403 9. Ths above calculations estimate PCB fallout over the drainage basin baaed on the size of the drainage areas as oaiputed from USGS stzeen iq 2 flow data, and totaling 9.8 x 10 m . These data were detained fran flow gaging stations, whidi were not all located at the mouths of the tributary stream; therefore, the calculated size of the drainage basin may be underestimated. AS an alternative to the above, the same calculations were oerfarmed, but using a value of 1.76 x 1011 m2 for the area of the ' drainage basin (this area was estirnatsd by the Lake Midiigan Federation! Then, the annual PCS fallout over the basin " (50 ug PCS/m2/yr)(1.76 x 1011 m2) 454 x 10 - 1.9 x 104 lb PCB/yr. After 40 years of constant accumulation at this rate, PCS load 7.6 x 10 lb PCS (from fallout) For this larger basin, the total PCSs in the water phase (i.e. fallout + industrial STP discharges) - 1.9 x 104 lb/yr + 0.16 x 104 lb/yr - 2.1 x 104 lb/yr of PCS After 40 years of oonstant aocuailaticn at this rate, the PCS load would ba 8.4 x 10 lb. Tbs PCS oonomtrmtlen in the water phase is: on an wnual basis (2.1 x 104) (454 x 106) 0.002 jpb 4.91 x lO1^ 1 After 40 years of oonstant aocunulatlon at this rata (8.4 x 105)(454 x IQ6) - 0.078 ppb 4.91 x 1015 1 E-16 HONS 209404 B. Estimates of PCS Transport in Lake Ontario, with ABoHca*-im to Lake Miaiigan. Sufficient data were not available for Lalce Michigan to ctetennine the relationship of PC3 concentrations between the water, sedirrent, and biotic phases. Adequate data v*re available to deteonine this relationship for Lake Ontario, and due to the similarities between the two lakes, the calculations were then used to estimate the present situation in Lalce Michigan, 1. Sampling of Lake Ontario, conducted in 1972 at several near-shore and mid-lake sites, indicated the followings *14,151 PCS in fish (alewives, smelt, slimy sculpin) 2.35 - 5.13 x 106 ppt. PCB in water (total concentration dissolved + particulate) 55 ppt. Average PO in sediments * 1.2 x 105 ppt. Average PC3 in net plankton " 7.2 x 106 ppt. Average PO in benthos " 4.71 x 105 ppt. It was asrrad that these aoncentrations are the result of PO aaamulatians at a constant rats far ths pest 40 years. 2. Determination of ths rats of PO deposition in ths sediments: Ths average sedimentation rats of Lake Ontario is 1.2 rsq/yr (as carpeted to a rata of 1.0 mn/yr for Lake Midiigan. Tferafore, ths thidaisss of sediment today in Lake Ontario, after 40 years of deposition " 48 inn. At this constant rats of deposition, PCBs acemulate in the sediments at a rats - 1.2 x 105 ppt PQ/40 yrs - 2.5 x 103 ppt PC^ of 48 nn sediment/40 yrs sediment 3 x 103 ppt PO/yr. 3. Annual accunulation of PCBs in the biota " * ^^Planktcn * ^^benths (3)(40 yrs) * - (5.13 x 106 ppt) + (7.2 x 106 ppt) (.471 x 106 ppt) (3) (40 yrs) - 0.11 x 106 Fpt/yr. E-17 HONS 209405 4. Annual accmulation of PCSs in the water - 55 ppt - 1.38 ppt/yr 40 yrs 5- Concentration ratios of P(3s in the three phases are: t^sed. ]_ 3 x 103 ppt/vr fPO--------- -------- . L waterJ 1,38 ppt/yr 2.2 x 103 [PCBbiota] - PP^Y* - 3 C^dTj 3* x 103 ppt/yr 6. Applying these ratios to Lake Midiigans [^Wd PV.1" * lo` - (.078 ppb) (8 x 104) 6.24 ppn - C^sedJ " [Pwater] (2.2 x 103) - (.078 ppb) (2.2 x 103) 0.172 ppn C. Estimates of Plankton Bigness in Lake Michigan: 1. Asswne a density of 300 kg. pl*Jctcn/h*ctars of lake(16) Axes of lake - 22,400 ml.2 - 5.8 x 10fi hectare Therefore, plankton bigness - (5.8 x 106) (300 kg) - 1.74 x 1012g - 3.8 x 109 lb E-18 HONS 209406 Estimate of Flow of PCBs Through the Straits of Jfcdcinac: 1. Water flows out of the lake via Straits at a rate - 67,000 cfs. 1.3 X 1014 Hi of water/yr. Using the atnoentraticn of PC3 in the water as 0.013ppb,(17* the loss of PCBS through the Straits is: (1.3 x 10^4 Lb/yr)(0.013 ppb) - 1.7 x 103 lb PCT/yr. Assisting a aonstant loss or the past 40 years, 6.8 x 104 lb a? PC? would ha\w been lost through the Straits. E-19 MONS 209407 bibliography 1. Schacht, R.A,; Pesticides in the Illinois Haters of Lake Midiigan Project *16050 ESP., 1974. 2. State of Michigan water Resources Ocrmissicn, Bureau of Water Managsrent, Polychlorinated Biphenyl Survey of che Kalamazoo River arei Portage Creek' in the vicinity of the City of Kalamazoo 1972. 3. Hesse, J.L.; Status Report cn Polydilorinated Biphenyls in Michigan Waters. Report to Michigan Water Resources cormission., 1973, 4. State of Midiigan Water Resourass Oatmission, Bureau of water Managwent, MDnitoring for Polydilorinated Biphenyls in the Aquatic Envirerrant. Report to Lake Midiigan Toxic Substances Cornuttee, May, 1973. 5. Kleinert, Stan; Chief of Water Quality Surveillance Section, CNR Wisconsin, Personal Ccmmication, 1975. 6. Winters, John; Acting chief of Water Quality and Standards Branch of Illinois EPA, Personal Ocnouiication, 1975. 7. united States Geological Survey, Water Resources Data for Midiigan. Part 1. Surface Water Records, 1974. ' S. United States Geological Survey, Water Resouroes Data for Wisconsin. Part 1. Surface Water Records, 1974. 9. United States Geological Survey, Water Resources Data for Illinois. Part 1. Surface Water Records, 157T! ' 10. United States Geological Survey, Water Resources Data for Indiana. Part 1. Surface Water Records, 157TI 11. Saylor, J.H,, P.w. Sloes; Water Volume Transport and Oscillatory Current Flaw through the straits of Mackinac. (Contribution Mo. 38, Great Lakes Envirumental Research laboratory), 1957.12 13 14 12. Michigan Oepartcmrrt of Natural Resouroes Fisheries Division, Estimates of Bianass of Principal Fish Species in the Great Lakes (first report). Fisheries Raseardi Mport no. 1813, 1974. 13. The Midiigan Federation, "The Lake Michigan Basin", March, 1975. 14. International Joint amission cn the Great Lakes. Pollution of Lake Erie, Lake Chtaxio md the International Section of the St. Lwrenoe River, Vtol 3, 1969. E-20 MONS 209408 15. Hail*, C.L., G.O. Veith, G.F. Lea, W.C. Beyle; Chlorinated Hydrocarbons in the Lake Ctitario Ecosystan, 1975. 16. ftittnar, F., 1952. Fundanentals of Limcloqy. University of Toronto Press. 295 p.,1952. 17. Mealy, Brock; Chemist with Da? Chemical Oo., Midland, Michigan. Personal Ccnrrtinication, 1975. E-21 HONS 209409 APPENDIX F . TOXICOLOGICAL ASPECTS 1.0 TOXICOLOGICAL ASPECTS OF POLTOHLORDWTED BIPHSJYLS (PCBs) 1.1 Introduction A critical biological effect of polychlorinated biphenyls (PC3s) is the induction of tutors in mice and rats, which inplies potential hunan activity. Cancer is typically progressive and irreversible, in the absence of nodical inter vention. Virtually all chanicala known to cause cancer in man have been shown to cause tuners in animals, including mice and rats. The use of experimental animals to test chemicals is generally accepted as a reliable basis for estimating potential carcinogencity to htxnns. Pathological development of chanically induced tumors in experimental animals and in hunana is very similar, and most of the major types of htrnan cancer can be reproduced in animals by chemical induction. Mice and rats are generally the preferred experimental animals because their relatively short lifespan permits lifetime testing within two to three years, whereas chem ical carcinogenesis in hunana is usually manifested by a latent period of 30 to 40 years batnei exposure and the appearance of symptoms. This long latency period oouplad with the lack of adequate tnxnen data, and the lack of identifiable con trol groups for widespread agents such as PCBs, make it difficult to identify PCSs as a "hunsn" carcinogen by conventional epidemiological studies. However, most experts in chemical carcinogenesis, including researchsre at the National Cancer Institute of NIH and the world Health Organisation, accept animal data as pre dictive of potential human activity. To date, no effective dose or maxunxn safe dose has bean estab lished for carcinogenic dmicals in man or animals; therefore in approaching the problen of fomniating regulatory action all maomelian systems are considered sensitive and man oust be considered the target systam. Altfaougi in at least one positive study an PCBs the dosage level used would be considered Low, high levels are generally used in animal tests because the i rasher of animals may mder the teats relatively inconclusive. In addition, the strain or species used may also render the tests cooperatively insensitive. Failure to denonstrata response at low doses of an oncogen is not an adequate basis to establish a "no-effect" level. F- 1 HONS 209410 Virtually no chenical that has been adequately studied is krown to cause only benign tuners. Furthermore, oncogens may cause tuners at different sites in different animals species or strains depending upon factors such as routes of metabolism and excretion. In considering the current status of medical knowledge, a lack of understanding of the carcinogenic mechanism within cellular biochonistry is evident. One issue that must be resolved in order to establish effective control legislation is whether or not there is a level of carcinogenic exposure below which there are no effects. The Do points of viw are known as the "threshold" and the "no-threshold" concepts. The threshold concept is based an the theory that there is a ctose level below which no effect will occur regardless of the nurbtr of test animals exposed; since this no-effect doee level would be higher than any resultant legally-established exposure limit, hunens would not be harmed by doses at or below the limit. The assumption is made that the nuntoer of animals affected will decrease at a greater rate than the rate of decreaee in the doee wtil a zero-point is reached. This assmption is unverified. Proponents of the threshold concept believe that for every toxic chemical there is an exposure level below which no effect can occur in a given organien, and that no effect, or possibly even beneficial effects at subthreshold doses, gives wey to tndesirable effects as the doee is raised. No valid data have beei developed to support the concept of safe levels of exposure to carcinogens since the axtrenely large nulfcers of animals needed for such ex periments preclude such testing, and extrapolation of animal data to man is tenuous. The no-threshold pcopcneits insist that any substance which is carcino genic at any level met be regarded as such at all levels. They further insist that it is not possible to predict safe levels of carcinogens based on an arbitrary fraction of the lowest effective animal doee, regardless of how many test animals are used. For those dmicals which hove been shewn to be carcinogens in experimental aninels, no thresholds have been demonstrated. Thus neither the no-threshold theory (or zero1 doee concept.) nor the threshold concept can be demonstrated or disproved at the present time. F- 2 HONS 209411 In the development of a standard for a carcinogen, the following racoranandations, taken fron tha Aoril 22. 1970 reoort to the Surgeon r^neral bv the Ad Hoc Ccnnittae on tha Evaluation of Low Lewis of Ehviromsntal Chanical' Carcinogens, National Institutes of Health, should be considered: 1. No level of exposure to a chanical carcinogci should be considered taxioologically insignificant for man. For carcinogenic agents, a 'safe level for ran' cannot be established by application of our present taowladge. The concept of 'socially acceptable risk' represents a irore realistic notion. 2. The principle of a zero tolerance for carcinogsiic exposures should be retained in all areas of legislation presently covered by it and should be extended to cover other exposures as well. Cnly in the cases where ccntanination of an oRvixomntal source by a carcinogen has beai proven to be inaraidable should exception be made to the principle of zero tolerance. Seaptions should be made cnly after the most extraordinary justification, including extensive docutantation of uhaniral and biological analyses and a specific statamant of the estinated risk for man, are pre sented. All efforts should bo made bo reduce the lewl of contamination to tha mini nun. Periodic caviar of the degree of contamination and the estimated risk should be made mandatory. 3. A basic distinction should be mode batman intentional and unintentional exposures. (a) NO sifeetaaoa developed primarily far uses involving exposure to men should be allowed for wide-spread hunan intake without having bean properly tested for carcino genicity and found negative. F-3 HONS 209412 (b) Ary siiutanoe developed for use not primarily involving exposure in man but nevertheless re sulting in such exposure, if found to be carcino genic, should be either prevented fran entering the environment or, if it already exists in the environment, progressively eliminated. The same report states: The production of specific carcinogenic chemicals for uses that do not primarily involve an intentional exposure of man, but which result in such environnsntal contamination that extensive hvxnan exposure beoanes inevitable, must also be controlled. The most effective prevention of exposure in men is the elimination of carcinogen production, or control of entry into the anvtronmnt. More recently, the Subcommittee an Estimation of Risks of Irreversible, Delayed Toxicity to the Department of Health, Education and welfare Cannittas to Coardinats Toxicology and Rslatad Programs publiahsd their report (Hoel et al, J. Toxicol. Ehvlron. Health 1, 133, 1975). The Suboormittee suggests (an an interim basis only) a procedure to assist in setting levels of qualitatively unavoidable chemicals (both natural and mnnade) in the environment ccnpatibls with a socially acceptable level of risk. It includes a simple arithnetic procedure to confute an exposure dose of a chanical for hums so that there will be a high probability that this dose will give a risk equal to or below the specified level. Date from experiments designed to datact irreversible salfraplicatlng changes (carcinoganasis) in e^erimental animals will be used. Through this arithmetic, the results will be txanslsbad to appropriately low levels for humans. In F- 4 MOMS 209413 addition, hunan exposure data need to be considered. All the knowledge necessary to evaluate these factors does not yet exist, Me suggest here an interim procedure to be used until research points to better procedures su* as methods for obtaining direct or best estimates of risk at a given dose with their corresponding confidence limits. Sane of this research is nw under way. These suggestions must be reviewed as new research is available, but not longer than within two years. Specifically, the so-called linear straight-line arithmetic method cattoined with a 99% confidence level for extrapola tion to very lew levels works this way:* 1. Say an e^eriment at a dose, d, using 100 animals has sham no induced tutors, for exarple, in the animals, that is, 0/1000%. 2. The upper 99% confidence limit on this result (which can be found in standard statistical tables} is 0.045, that is, 4.5%. 3. Far a dose, dg, that will produce, as an upper limit, fewer than 1 in 1,000,000 tutors, divide 1/1,000,000 by .045. This gives (in standard notation} 2.22 X 10"5i as the appropriate dose, if one were to aim for fewer * For certain ccnpouvle, knowledge of the carcinogenicity process may be available, such as with renal concretions resulting in bladder tutors, in these instances, nodals othar than the linear modal my be nore appropriate. For illustration we consider only the case of one e^erimantal dose. In practice, however, it is that several dose levels will be available and their treat ment can be found in the literature (Gross et al., 1970; Mental and Bryan, 1961; Mental et al., 1975}. F-5 HONS 209414 than 1 in 100,000,000, (i.e., 1 x 10~8), the appro priate dose would be 2.22 X 10~7cfr for fewer than 1 in a hundred thousand (1 X 10~5), the appropriate dose is 2.22 X 10 4i, etc. If 10 of the 100 animals showed a response (i.e., 10/100 - 10%), then the 99% confidmce limit is 0.19, that is, 19%. The appropriate dose for 1 in a million is then 5.3 X 10~6d and for 1 in 100,000,000, the dose would be 5.3 x 10"8d. For corrections to a 'natural' incidence, the normal distri bution is used to approximate a 99% confidence interval on the difference bets>ean the response at dose d and the back ground. Suppose at dose d 0 of 200 (30%) animals were affected while the natural incidence gave 20 of 200 animals (10%). The upper 99% confidence limit is than approximately .3 - .1 + 2.327[.3(.7)/200 + .1(,9)/200]1/2 - 0.29 where 2.327 is the 99% point of the standard nonnel distribu tion. Far a dose, dgt that will produce as an upper limit of fewer than 1 in a million changes in excess of the natural incidence, 1/1,000,000 is divided by 0.29. This gives 3.4 X 10"d as the dose, and far 1 in 100,000,000 excess changes the does is 3.4 X l0-8d. Two questions need to be answered in converting results in animls to men: 1. In what units should the does conversion be made (i.e., weight basis, surface basis, etc.)? At present it appears that tha appropriate doss unit is the 'surface' unit, that is, use tha 2/3 power of tha weight of tha bn aparlaa (test animal-man) as the surface area con version factor. For exarple, if a 2S-g neuse receives a dose stated an a milligram basis, then the corral- F- 6 HONS 209415 ' ponding dose (mg) for a 70-kg nan would be (70 kg/25g)2/^3 " 200 times the mouse dose. Thus, on a mg/kg basis, the use of surface units would require that the corresponding relative dose become (70 kg/25 " 14 times the rouse dose. Dose expressed in concentration (ppm) should lead to approximately the same levels as dose expressed in surface area units. 2. Should any addifinnal safety factor be added in going frcm animals to man? Yes, but not the same factor for all substances. This species conversion factor should be determined substance-by-substance using appropriate biological considerations (and allowing for any safety factors implicit in other parts of the calculation). A statutory provision exists, however, which provides seme sanction to the no threshold concept. This is, of course, the "Delaney clause", Section 409(c) (3) (A) of the Federal Pood, Drug, and Qoanetic Act (21 U.S.C. 321 et sag.), which became law in 1958. This clause provides "... that no additive shall be deemed to be safe if it is found to induos cancer when ingested by man or animal, or if it is found, after tests which are appropriate far the evaulation of the safety of food and additives, to induce cancer in man or animal..." In spite of all of the furor concerning this clause, it is interesting to note that since its introduction in 1958, it has bean invoked only twice to ban food additives and both of these were trivial oaeperants of food packaging. The Food and Drug Mfadnistration, in addition to its responsibility for regulating food additives, is supposed to protect the public from carcino gens which appear naturally or Incidentally in our food. These substances are not covered by the Delaney clause. Aflatoxins, COT, aldrin, nitrosamines, and vinyl chloride are mcasples. Presently, these problems are handled an the basis of practicality and not an any assessment of risk. That PCBe presently exist in our diet has bean anply dmmstrated. But the pressure to eliminate such carcinogens from entering our food oust fall upon other regulator agencies such as EPA. F- 7 HONS 209416 - In sunnary, there is no generally accepted toxicological basis upon which to establish a no-effect level for any carcinogenic material. >tethods which arrive at estimates of acceptable exposure levels for carcinogens in ran are, there fore, based on the concept of a "socially acceptable level of risk." In general, the methods arploy statistical extrapolation of laboratory animal test data to man, whereupon a political decision as to the socially acceptable incidence of tumors is mad*. Such estimates of socially acceptable level of risk to determine human exposure tolerances to ionizing radiation have been arployed by the Atctnic Energy Ccrcmission and adopted by the Environmental Protection Agency. Estimates based on acceptable level of risk are only conceptual and trust not be taken as calculated no-effect levels. 1.2 Mammalian Toxicity The curmt knowledge of the interaction of PCS# with life fonts will not be reviewed in detail in this report; an exhaustive review will be submitted in the final report on Task I. This report will highlight only those data re lating tutor induction. This review, however, is complete in the sense that major adverse effects are mentioned including those within the major target organs. PCBs have low acute toxicity. But because of their near complete ab sorption, high lipid (fat) solubility, low water solubility, and relative chemical inertness, PCBs tend to concentrate in the food chain, accumulate in body fat, persist in biological tissue, and show persistent toxicity. Consequently, shorttern studies are not adequate indicators of the long-term effects of PCB exposure. Latent effects, those effects thet occur some time after exposure has ceased, and cumulative effects, those effects that occur only after a threshold level of PCB or tissue damage has been reached, may be easily missed over the short term, since most toxicity studies with PCBs have bean short-term, there is limited scientific evidence establishing or predicting the chronic effects. 1.2.1 SiPacuta and Qgonic Ttadcity "No-effect" levels of PCB* in rats and doga fed three Artxlors for on years ware reported by Monsanto in 1971. A swmary of their results is presented her*. F- 3 HONS 209417 Rata - Method A ti*>*year chronic toxicity study was ooreiuctad using rats fed diets containing Aroclors 1242, 1254 and 1260. The animals alloyed in the test were Charles River strain albino rats. Four tamdred rata (200 male and 200 female) were selected for each of the experiments. Group Control T-I T-II T-III CXotline of Each Detriment Number of Animals Mala Female 50 50 50 50 50 50 50 50 Dietary Level (ppm) None Administered 1 10 100 Rat Results - Arcelor 1242 At sacrifice after 3, 6 or 12 months an test, organ weights, organ to body weight and organ to brain weight ratios disclosed several randanly occurring intergroup difference*. The lack of any consistent dose-related res ponse and the absence of any deleterious tissue changes confirm that these differences were not related to the ingestion of Aroclor 1242. At the final sacrifice after 24 months an test, the liver weights and liver to body weight or brain weight ratio* were significantly elevated in fsnales from the T-III group. Histologic examination of the livers from the T-III group revealed several animals with vacuolar changes indicative of fatty degenera tion. Specific fat stains confirmed the pressno* of fat in these vacuoles. Focal hypertrophy and focal hyperplasia were also found in the livers from animals fed Aroclor 1242. {jypecplAeift of the urinary bladder was found in animals fron the ocntrol grop and from each of the test groups. This hyperplasia was usually associated with cystitis. F-9 HONS 209418 . The incidences and type* of all tutors were about the sane in all groups, including the control group, and are considered normal for rats cf this age. Rat Results - Aroclor 1254 At sacrifice after 3, 6, or 12 nonths on test, organ weights, organ to body weight and organ to brain weight ratios disclosed several randomly occurring intergitup differences. The lack of any consistent dose related res ponse and the absence of any deleterious tissue changes confirm that these differences were not related to the ingestion of Aroclor 1254. At the final sacrifice after 24 months on test, the absolute liver weight and liver to body weight or brain weight ratios were significantly elevated in both T-III males and famiss. Histologic examinations of Che livers from the T-III group revealed several animals with vacuolar changes indicative of fatty degeneration. Specific fat stains confirmed the presence of fat in these vacuoles. Focal hypertrophy and focal hyperplasia ware also found in the livers from animals fed Aroclor 1254, Hyperplasia of the urinary bladder was fowl in animals from the control group and from each of the test groups. This hyperplasia was usually associated with cystitis. None of the tutors found aould be related to the ingestion of Aroclor 1254 and are considered normal for a randan population of rats this age. Rat Results - Aroclor 1260 At setsifice after 3, 6, or 12 months on test organ weights, organ to body weight and organ to brain weight ratios disclosed several randomly occurring intergroup differences. Ths lack of any consistent dose related res ponse and the iheerre of any deleterious tissue dungs confirm that these differences were not related to the ingestion of Aroclor 1260. At the final sacrifice after 24 months on test, the liver weights and liver to body weight or brain weight ratios were significantly elevated in the rats from the T-III group. Histologic examination of the livers from the T-III F - 10 HONS 209419 m group revealed several animals also with vacuolar change indicative of fatty degeneration. Specific fat stains confirmed the presence of fat in these vacusles Focal hypertrophy and focal hyperplasia were also found in the livers from annuals fed Arcelor 1260. Hyperplasia of the urinary bladder was found in an aninal frern the control group but not in any of the test aninals. . the incidences and types of all tutors were about the same in all groups, including the control group, and are considered normal for rats of this age. Dogs - Method Ths two-year toxicity study utilized an mtreated control group three test groups, each consisting of eight purebred beagle dogs (four males four females). Ths beagles vmrs all eligible for A.K.C. registration and bean previously imunissd. Ths material to be tested, Aroclors 1242, 1254,aand 1260 were incorporated into a stock diet and fed to the dogs seven days a week in three graded dietary levels. Ths levels were 1, 10 and 100 ppm. An outline of the test organisation is presented here: Group UC I II III cut-line of Each Bgeriaent Males 4 4 4 4 Fsnales 4 4 4 4 Dietary Level (ppm) None 1 10 100 Deg Results - Arcelor 1242, 1254 and 1260 Ho significant abnormalities ware observed in the following F - 11 HONS 209420 Body weight Food Consumption Behavioral Reactions Hematology L'rine Animals receiving 100 pan of Arcelor 1260 exhibited increases in serum alkaline phosphatase activity at the conclusion of the investigation. A fanale receiving 100 ppm of Arcelor 1242 was sacrificed in extraitis after 60 weeks of testing; gross and histologic examinations revealed severe chronic peritonitis. A male receiving 10 ppm died after 32 weeks of testing; death was attributed to chronic pnaunenia. Histologic examination revealed no abnormalities related to the test material ingestion. Two fatalities occurred during the Arcelor 1254 study: a 100 ppm female after 33 weeks of testing and a 10 ppm fsmale after 37 weeks. The fanale receiving loo ppm died frnn injuries received in a fight. Gross and histologic examinations of the 10 ppm fanale revealed chronic peritonitis. Two fatalities occurred during ths Arcelor 1260 study: a 100 ppm fanale after 29 weeks and a 100 ppm mala after 33 weeks. Gross and histologic examinations revealed severe chronic peritonitis in ths fanale and acuta pneurciua in the male. AH animals receiving 100 ppm of Arcelor 1260 exhibited elevations in liver to body weight ratios. Gross and histologic examination of all ronaining animals re vealed no significant abnormalities. work by Or. Jones Allan {U. of Wisconsin) on simians is dis cussed in ths following paragraphs. Simians - Method Tha hazards to simians of low level FQ exposure have been donenstrated only very recently. Allan in 1974 reported the results of feeding F - 12 HONS 209421 six adult fatal* rhesus monkeys a diet containing 25 ppm of Aroclor 1243 for two months, the average total intake of PCBs for five animals fed for two months was approximately 250 mg, or 0.78 mgAg body weight per day. The sixth monkey aonsvrad a total of 450 mg at 1.34 mgAg/day? this animal died 68 days after feeding was stopped. The effects in all six animals included facial swelling, severe hyperplastic gastritis and liver necrosis. All but one of the surviving were un able to conceive. The one live birth was a smaller than averace infant. The surviving monkeys continued to have high adipose tissue levels, acne, tissue swelling and hair loss two years after this short term, low level exposure. As will be seen, these signs were similar to those encountered in humans during the "Yusho" intoxication in Japan {described later in this report). 1.2.2 Reproduction PCBs have been shown to affect reproduction in several different species. Egg production, egg hatchability, and shell thickness were decreased by feeding low levels of various PS formulations bo diicksns. Fatale rats fed 20 ppm of Aroclor 1254 (1.5 rag/kg/dsy) had a decrease in the nvnber of litters and in litter site. In a two-generation study, 5 ppm wee the no effect level for rat reproduction. Higher dietary levels caused decreased rat offspring survival and decreased mating performance. Evan at 1 ppm, male rats were born with enlarged livers. In a more recent study, Allan has reported that levels in the diet as low as 2.5 ppm resulted in a marked decrease in the ability of monkeys to conceive. 1.2.3 Pathology Ona of tht most studied bade effects of PCBs has been in liver pathology in rats and rabbits. PCBs cause similar damage whan administered by injection, inhalation, or by south. In cases of PC3 poisoning, early liver damage has been noted. Mny Tseeairtmn have described the now classical pathological changes in the liver of animals exposed bo PCBs. These include infiltration by fat, increased end liver size, dagawration of rellnlar contorts, and ulti mately en death. The latent nature of these effects is dononstratad by the fact the most severe histcpethology known occurred 5 bo 13 weeks after PCT ingestion had ceased. F - 13 MONS 209422 Additional pathological changes have recently been noted. These were classified as adenofihrosis and are often seen in association with liver carcincma. Abnormal growth and development of the gastric TMcosa has also been reported and is further evidence of the carcinogenic potential of ?C3s. For reasons ccrpletely independent of any possible association with cancer, the significance of fibrosis, adenofibrosis, and liver necrosis are very grave. These lesions may be associated with carcinanas in rodent liver. 1.2.4 Carcinogenicity Unfortunately, statistically sound dose-carcinogenic response studies necessary to treat many environmental problems, including PCBs, are currently not available. A review of the world scientific literature reveal only six studies pertinsit to carcinogenesis. These are listed and discussed below. 1. Kinbrough, R.D., Linder, R.E., and Gaines, T.B., "Morphological changes in Liven of Rats Fed Poly chlorinated Biphenyls", Arch. Ehvon. Health 25, 354 (1972). An extensive chronic study of Sharrmn rats, using Aroclors 1260 and 1254, with dietary levels of o, 20, 100 , 500 and 1000 ppm, docmentad a variety of histopathclogical effects after months of ex posure. Degenerative liver changes observed in both amis and fmnele test animals at all dosages of both PCBs included hypertrophy of individual liver cells, hyperdnematic pleonorphic nuclei, cytoplamnic lipid vacuoles, and porphyria, all characteristics of chlorinated hydrocarbon (DOT, dieldrin) intoxication. In sabs cases, adenofibrosis (uncertain significance) v*s observed. All of the mortalities that occurred during exposure to the Aroclor 1260 were fenela. In nearly all gross F - 14 HONS 209423 pathological examinations, males dmonstratad enlarged livers, while females did not; liver effects of Aroclor 1254 were adjudged more pro nounced than those of Aroclor 1260. The short duration of this study is a drawback for its inclusion in evaluation of carcinogenic effects. 2. Kimira, N.T. and Baba, T., "Neoplastic Changes in tha Rat Liver Induced by Polychlorinated Biphenyl", Gann 64, 105 (1973). Fallowing the observation, by electron microscopy, of specific morphological alterations {previously observed with other carcinogens) in liver cell nucleoli of animals ingesting FQe, a preliminary study an PS carcinogenic activity wee instituted. Using rets of tha Oonzy strain, Kanechlor 400 mixed in oil was fed at dietary lwals ranging upwards fxnn 38.5 ppn. Tan male and tan fnala rats were in tha experimental grc*g> with five of each sex in tha control gzocp. Using body weight gains {coo pered to controls) tha concentration of the Xanechlor wes lnoeesed or decreased according to the following sdiadule. Period of Feeding (days) "2T 57 21 21 39 29 98 28 82 Concentration of Kanechlor-400 77 154 308 618 462 0 462 0 462 Total 400 F - 15 HONS 209424 Multiple adenanatous nodules were observed in all livers of the ferale experimental group ingesting more than 1200 mgs of Kanechlor 400. In sharp contrast, however, the liver specinens of the male experimental rats revealed rc such changes even in animals receiving caiparable or higher anoints of Kanechlor 400 than females. Although these authors refer to this lesion as benign in nature, further discussion of this lesion is presented later in this report. The variable dosage schedule and the snail nurtbers of animals used present drawbacks for its inclusion in evaluation of carcinogenic effects. Ito, N., at al. "Histopathologic Studies an Liver Ttxeriganesia Induced in Mice by Technical Poly chlorinated Biphenyls and its Prccoting Effect cn Liver Tutors Induced by Benzine Hexactilori.de", J. Natl. Cancer Inst., 51, 1637 (1973). This paper reports the histopathologic and ultrastructural observations of livers of dd mice fed PCBs in their diet far a period of 32 weeks. Twelve male mica were used at each of three dosage levels. Three PQe were investigated, Kanechlor 500, 400, and 300. The results indicats hepatocellular careinonas and nodular hyperplasia were induced by Kanechlor 500 but not by the two other PCBs, as seen belm: F - 16 HONS 209425 PCBS ' Diet (pp*n) Kanechlor 500 (500) Kanechlor 500 (250) Kanechlor 500 (100) Kanechlor 400 (500) Kanechlor 400 (250) Kanechlor 400 (100) Kanechlor 300 (500) Kanechlor 300 (250) Kanechlor 300 (100) Control Cellular Hypetrophy + i f+ + ; ; - - Nodular Hyperplasia 7/12 0/12 0/12 0/12 0/12 0/12 0/12 0/12 1/12 0/6 Hepatocellular Carcinoma 5/12 0/12 0/12 0/12 0/12 0/12 0/12 0/12 0/12 0/6 The effect of PCS* an neoplastic changes induced by isomers of bens** hsaarhlorids {a, S and i) in the livers of mice fed a diet containing BHC with and without FCBs far 24 weeks wes also studied. The authors concluded that in addition to the carcinogenic activity of PCBSr these materiala, also pconote tutors induced by a EHC and S EHC. 4. Klabrough, R.D., and Linder, R.E., "Induction of Admofibrosis and Hepetcnaa of the Liver in BALB/cj Mioe by Polychlorinated Biphenyls (Arcelor 1254)", J. Natl. Cancer Inst., 53, 547 (1974). Two groups of 50 BALB/cj inbred mala mice were fad 300 ppm of Aroclor 1254 in the diet far 11 and 6 months. The six-months grotp wee given a recovery period of 5 [tenths. The results are presented below: Dietary Level (ppn) 0 0 300 300 Exposure Time (Mo.) 0 0 11 6 Total Survivors 34 24 22 24 Hepatoma 0 0 9 1 F - 17 HONS 209426 In addition, all 22 mica in the group receiving Arodor 1254 daronstratad adenofibrosis which was not observed in any other group. 5. Makiura, S., et al, "Inhibitory Effect of Poly chlorinated Biphenyls on Liver Tumorigenesis in flats Treated with 3 ' -Methyl-4-Diithylarriirca2obenzena, N-2-Fluorenylacetamide, and Diethylnitzosamine", J. Natl. Cancer Inst., 52, 1253 (1974). The effect of PQJs (Kanechlor 500) an liver carein&> genesis induced by 3-methyl-4 dimethylami rrazchenzene (3* Me-QAB), N-2-fluoranylaoetaniijde (2-FAA) and/or diethylnitrosamine (DEN) was studied in male SpragueDawley rats. Duration of exposures were 20 weeks. Liver tuners developed with the three loom liver carcinogens, i.a., 3' Me-OAB, 2 FAA, and DEN. No timers developed in the animals fed PCBa alone and wtun fed with the above mantioned carcinogens a narked reduction in tutor incidanoe wee observed. The lack of tutors in tha PCBa fed rats nay have been the result of low dose (500 ppn) and/or the short period of ad ministration sinos these same authors had induced tutors in rats treated with Kanechlor 500 at 1000 ppm for 72 weeks. Histopathology findings of tha livers were similar as previously reported; i.e., fatty changes and call hypertrophy. 6. Kimbrough, R.D.; Squire, R.A.; Linder, R.E.; Strandberg, J.D.; Montali, R.J. and Burse, V.W., "Induction of /) Liver Tutors in Fats by Polychlorinated Biphenyl Aroclor 1260", J. Natl. Cancer Inst, (in press, 1975). F - 18 HONS 209427 TVo hundred Sherman Strain female rata were fed 100 ppm of polychlorinated biphenyl (Arcelor 1260) for approximately 21 nontha, and 200 fanale rats were kept as oontrols. The rata were sacrificed when 23 nontha old. Twenty-six of 184 surviving experimental rata and 1 of 173 surviving control rata examined had hepafonel Inlar carcinoma. Nona of the oontrols, but 146 of the 134 experimental rats, had neoplastic nodules in their liver. Areas of hepatocellular alteration were noted in 28 of the 173 oontrols and 182 of the 184 experimental rata. It was concluded that Arcelor 1260 had a hepatocarcinogenic effect in fatale Sherman strain rats. The incidence of tumors in other organs did not differ appreciably between the experimental and control groups. 1.2.5 Bryan Mantel and cna Hit Model Calculations of Animal Data for Bctiapolation to Humans As indicated previously, statistical handling of experimental data helpe resolve quaetiers of experimental design and the problem of threshold in setting safe doses. Wt have applied the Bryan-Mantal and Crs Hit Model calculate to two studies. The results of thase analyses are presented in Tables I and II. Therefore, using the recanmndations set forth previously, we '-rreiurt* that the use of the Bryan-Mantal Probit Model should be used to calculate the "safe" level of PQs using a theoretical maxirun acceptable lifetime risk of 1/10 of developMRt of hepatomas (neoplastic nodules). This dose is 167 ppt at the 99-percent aonfidenoe limits if the latest data in rats (Kintacugh 1975) is used. In the case of developMnt of tmpatocarcincnas, the level vreuld be 11,387 ppt. The rather lew "safe" dose relative to the hepatomas reflects that the doeage level used in the experiment (i.e., 100 ppm) wee too high for that inji'iee (146 twpetomas in 184 rats). Thase neoplasm are nostly benign tutors F - 19 HONS 209428 Table I Analysis of Carcinogenic Risk to Humans from Ingested PCBs Based on Kimbrough 1975 Study (Rats) Analytical Method Bryan-Mantel Bryan-Mantel One Hit cm Hit Confidence Limits 95 99 95 99 Intake Level in ppt for Specified Levels of Risk for Kepatocarcircmas 1/10* L/107 1/10* L/L0S 1963 1645 4 4 5080 4257 45 39 14,187 iu lai7J 447 391 43,640 36,566 4,472 3,906 Analytical Method Bryan-Mantel Bryan-Mantel Che Hit CM Hit Limits 95 99 93 99 Intake Level for ppt for Specified Levels of Risk for Neoplastic Nodules 1/10' 1/107 1/10* 1/10' 27 70 122, 605 23 60 fieTl 512 0 2 21 205 0 2 13 130 Method Bryan-Mantel Bryan-Mantel CM Hit CM Hit Limits (t) 95 99 95 99 Intake Level for ppt for Specified Levels of Risk for Foci 1/10' 1/107 1/10* 1/103 01 3 0 12 000 000 10 6 3 1 *Risk level of one tutor per 10',107,io`, or 10s population F - 20 HONS 209429 Table II Analysis of Carcinogenic Risk to Hunans fron Ingested PC3s based on Kirrferouqh-1974 Study (Mice) Analytical Method BryanrMantel cne Hit Confidence Limits Intake Level in ppt for Specified Level of Risk for Hepatana (Neoplastic Nodules) (t) 1/108* 1/107* g* l/icr 1/10' 95 451 1167 3258 10022 99 297 763 1 2145 1 6597 95 2 21 214 2140 99 2 16 160 1596 'Risk level of one tmcr per 1>8, 107, 10, or 10 population. P - 21 HONS 209430 occurring lata in life. Thera is little time left for than to beoone malignant in the mining life-time of the rat. Until further data beoane available or other means are used to handle existing data, one should assune the "safe11 ctose in lifetime hirren diet to be between 0.2 ppb and 12 ppb. It is interesting to rote that if the simian reproduction data is used and the classical 1/100 safety factor is arolied to the lowest dose studied (2.5 ppm), a "safe" dose of 25 ppb is obtained. This <tose (2.5 pjm), towever, appears to be a minimal effective dose, whereas normally the hiahest roeffect level is used. Use of minisun effect levels and even other safety factors have bean used; e.g., 1/10 to 1/5000. These would result in dosage levels ranging from 250 ppb to as low as 0.5 ppb. These calculations must be considered preliminary since time has not permitted consideration of other factors, such as: 1) Body surface area instead of body weight in determining daily intake 2) Ccnperison with most likely hunan daily intake 3) Further calculations of existing data 4) Gcobinetion of all existing animal data 5) Consideration of metabolism, storage and excretion data among animals species as centered to men 1.3 Observations in Humans In Edition to data provided by continuing studies of the various effects of K3a on laboratory animals, seem information is available on the subacute or chronic effects of PCBs on humms. hi-- intoxication with KatMchlcr 400, a PCB manufactured in Japan (48-percsnt dUocine) wee observed after a heat exchanger leaked fluid into rice oil whidi wee than oonsunad by Japanese families in 1963. Approximately 1,000 parsons were affected, and typical clinical findings included: F - 22 HONS 209^31 1. Increased eye discharge 2. Acne-lika eruptions 3. Dark brown pigmentation of nails 4. Pigmentation of skin 5. Transient visual distuxbanoe 6. Feeling of weakness 7. Numbness in linbs 3. Headache 9. Weight loss 10. vtmiting 11. Diarrhea 12. Fetal toxicity Items 5 through 3 represent symptoms of dmoage to the nervous systm seen in "Yusho" patients. PCBs are known to enter the brain, but they <to not have a predeminant central neurotoxic effect like the related hexachloioptane. Laboratory findings in the severe cases included: 1. Red blood cells and hemglobin decreased; leukocytes increased 2. Total serin lipids, triglycerides, alpha 2-globulins increased 3. Slight increase in alkaline phoaphatese 4. Liver biopsyreduction of rough endoplaenic reticulum; hypertrophy of moth ndoplasnic reticulum; giant mitochondria were fre quently snocuntered Mn 159 "Yusho" patients were examined in 1969 and 1970, it was found that 50 percent showed no clinical upromont and 10 parent ware worse, another indication of the persistence of POa in the human body. The chemical was found bo be stored primarily in the adipose tissue tat also passed into the placenta and fetua. A very early and mmm synptan in these patients was chloracns. dOoncns Is an oosi^ational akin disease ratmad by many chenirails. Chloracne lasmtolas adolesoant asm in seme ways, but is generally more severe. Its synptans consist of oomsdonss with ar without cysts and pustules. The openings of the hair F - 23 HONS 209432 follicles are filled with oil and protein material. Darkening of the skin and secondary inflammation may also occur. During the 1930s arti 1940s several large outbreaks occurred in workers engaged in the manufacture of PCBs an! closely related chonicals. The disease can be produced by both direct skin exposure and by oral intake of PCBs. The ability of oral consurpticn of PCBs bo cause persistent chloracne was convincingly demonstrated in the "Yusho" incident, where chloracne was still present in several people three years after oral aonsmptian of PCBs had ceased. The same study showed no significant difference among sexes, but a significant differenos in clinical severity by age was observed, with the 13- to 29-year-old group being the most sensitive. Of the 11 babies bom to affected mothers, 2 wars stillborn, 9 had dark-brown stained akin, and increased eye dis charge was noticeable in most. Growth rates of affected childrwi, as measured by both height and weight gains, wars ncnitcred and corpared with unaffected class mates; a significant decrease in growth rats was detected in the melee who wars poisoned, but no definitive change wee observed in the fomelee. Rice oil exposure levels wars calculated at approximately 15,000 mg/day (average); the oil itself was reported to be contaminated at about 2,000 ppm Kanechlor 400 (derived fan the known organic chlorine oontent of rice oil in relation to the known organic chlorine content of the PCB). The average total dose of PCBs causing an effect in these victims wee reported as 2,000 mg. Tht lwest PCB lsvel that productd human effacts (50 kg man) was 500 mg ocnsunad over a period of 50 days at a rate of approximately 200 u^kg/day. The effect level wee based, however, on overt synpbsms, rather than an sensitive biothnirsl indicators that might have deuaatested effects at even lower levels. Sinos PCBs probably have a long biological half-life in humane, a toxicological analysis of the htzcan data must be based on the assumption that ingested PCBs would aontinus to accunulate in tissues for a long period of time. The apparent human health threat from chronic ingestion of PCBs prtnpted the U.S. Food and Drug Administration to issue proposed limitations on the levels F - 24 HONS 209433 of PCS* In foods, animal leads, and food packaging materials. on July 6, 1973, final regulations were promulgated that established terporary tolerances for PCS residues arising from unavoidable contamination. These tolerances are: 1. 2.5 ppn in milk {fat basis) 2. 2.5 ppn in manufactured dairy products (fat basis) 3. 5 ppn in poultry (fat basis) 4. 0.5 ppn in eggs 5. 0.2 ppn in finished animal feed for food-producing animals (except the following finished animal feeds: feed concentrates, feed supplements, and feed prefixes) 6. 2 ppm in animal feed ocrponents of animal origin, intluding fistmaal and other by-products of marine origin and in fish animal feed concentrates, supplements, and premixes intended for food-producing animals 7. 5 ppm in edible portions of fish and shellfish (the edible portion of fish esrlndes head, scales, viscera, and inedible bones) 8. 0.2 pc*i in infant and junior foods 9. io pest in paper food-packaging material intended for or used with hum food, finished animal feed and any oorponanta intmdad for animal feads (the tolerance does not apply to paper fbod>packaglng natarial asperated from the food by a barrier Inpsm--hie to migration of PCBs) 1.4 Ooneluaicns cnn im14m in certain and do not break dOMi easily in the body. parsietSMS leads to emulative toxicity. Early toxiaological evidence the adverse health affects of FQs from experimental animals such as mice and rats and from nhsenntimsl data in humans has baan more recently P - 25 HONS 209434 egjil trmMd by tunnel experimental findings in monkeys. A clow correlation scuts bstu--i ths synptxxns noted in hunans and those noted in the itcmkeys, suggesting thet the dose response relationships and metabolic and secretion pheno mena of FSi are similar in both hunans and monkeys. According to seme pathologists, PC3 exposure can cause cancerous liver lesions. Evidence from relatively short-term exposure (several months) and chronic exposure in animals or hunans danonstrate* that PCSs are a significant health hazard. F - 26 HONS 209435 . EVALUAXICN OIF RISK FOR POIHnTAL SLESTITUIES FOR K3s 2.0 nmooocricN Altnough unattainable, absolute safety (i.e., absolute control) is the goal society would like to achieve with regard to all chemicals introduced by industry. Safety as practiced, hcwever, always entails seme degree of risk. But experience has shewn that maximization of chenieal, physical, and toxicological informtion will minimize risk. For exanple, if a given conpound is known to end up in man's food supply, information on its chemistry and potantial chronic toxicity would be essential to minimizing the public health hazard. The experierce with FO illustrates the enormous range of complexity of risk evaluation that many w compounds may require for mexinun ptislic safety. Me believe no one oould have foreseen the present situation with PCBs. Thus we strcngly feel all aubetanoes should not be subjected to a single rigid routine of study, as sudi action would be self defeating. Instead, we propose that an orderly step-wise approach be made. Information gathered on specific chemicals should show the direction far the acquisition of additional information. The continuous use and especially the increasing use of w chemicals should be by additional tasting of the chenicals. Such a hierarchy or sequential testing will: (1) result in avoidance of unnecessary test procedures and (2) answer those questions which will in the long run reveal the most productive Information. 2.1 Estimation of Doee to the Target System Mass production of chenicals invariably results in sens degree of enviroraantal contamination, but the route by which a given contaminant affects htnens varies according to the type of ccupound. Vinyl chloride, far instance, presents a hazard almost rnitizely on the occupational level - that is, among workers dealing with vinyl chloride. For P05s, on the other hand, exposure through direct *<** is not the issue: bioaocurulation through the food chain is the exposure routs of interest. F - 27 HONS 209436 The pattern of use is ana of the most significant factors in deter mining the exposure of tha target system. Tha usa of PCBs in carbonless pper prior to tha voluntary ban on this usa in 1971 has proven to be an wcellent example of tha devious routes by which pollutants find their way into our food -- carbonless paper is recycled to paperboard for food packaging, and, in addition to PCB release to the waterways during the recycling process, the paperboard itself leaches P3i to food it contains. The method of disposal of waste also presents problem, especially with sudi highly stable cccpounds as PCBs. Ease of disposability and rapid deccrposition to inert carpounds after disposal are characteristics which are hiahlv desirable in substitutes for PCBs. FOr sene PCS substitutes an elaborate examination of their movement through the environment, their transformation by chenical, physical or biological . interactions and tha diseenination and transport of the resultant ccrpounda may be eiseitial. The nature of injury nuet be considered. A reversible functional effect, though undesirable, would be of vastly leas oonaaquanoe than irreversible and fatal effects. Mitagmsis and teretogneais are mere subtle forme of injury, but the testing methods for these grew threats generally are elaborate and involved. This field, however, is advancing rapidly. With respect to wildlife, considerations are substantially different than with ten. Because of tha impossibility of pretesting all species with all nm chemicals, oenuam oust of necessity be on the endangermant of a species or of a local animal population. This type of Information frequently can only be obtained by constant surveillance of the anvirenmant within which a carpound is released. 2.2 Nature of Teste needed to Evaluate Hunan Health Effects The major determinants of the affects of chemicals upon the health and well-being of tha individual and society are: 1. Tha nature of tha chenical per se F - 28 HONS 209437 2. The duration of asqposure 3. The quantity of tha chanieal if a ralativaly Larga amount of a toxic chemical acts for a short period of time, the effects are acuta, while relatively stall amounts acting over long periods tend to produce chronic effects. Other more subtle effects have bean noted, and cancer, modification of behavior, genetic effects, potentiation of the toxicity of other environmental oerpounds nay also have to be investigated. Clearly there is no one protocol by which to evaluate toxicity of every chemical. Ihs following protocols are presented as guidelines only. 2.3 Rtysical and Oarelcal Properties Basic information on physical and chemical properties are, of course, essential, these data are needed not only far analysis and monitoring, but to assess stability and determine whether and where a chemical is likely to be found in the anvirmiant. the following data can be easily gathered in a laboratoryi 1. Chemical preposition 2. Cannon name, if established 3. Chemical nans (Oieaical Abstracts, wishester nonanclature) 4. Trade nan 5. structural foaiula 6. Melting point 7. Bolling point 8. vapor pressure 9. Density or specific gravity 10. Solubility in water and in selected organic solvents and oils 11. Dissociation constants (p(Ca or pto) 12. Physical state U. Color 14. Odor 15. pa 16. Flashpoint 17. Visoosity F - 29 HONS 209438 Reactions and other characteristics of a chemical in relation to other anpuunds sudi as, water, air, and soil should include the following: 1. Oxidizing properties 2. Reducing properties 3. Corrosive hazard 4. Explosive characteristics 5. Hydrolysis rate 6. Ehotochamistry 2.3.1 Structure and Reactions Elemental opposition, structure, and formula weight ney suffice to suggest various reaction a onprund is capable of, but the chemistry of new compounds nay be highly specialized, and predictive characteristics may not be apparent. In addition to tha oxidative, reductive and hydrolysis reactions, reactions of biological importance should also be considered; for ample, alkylation, dealkylation, esterification, leaner!ration, and conjugation with animal and plant constituents nay eld in the choice of future tasting procedures. Rates and degree of ocrpletion of reactions also are useful; far exanple, the rate of dehydrchelogenetion of organochlorine compounds at high pB could provide leads to relative persletaea. 2.3.2 Physical Properties Knowledge of physical properties assists not only in determina tion of purity, but more importantly, aids in assasmnant of the potential behavior in and flow through the emrlrorwit. ftyeical properties are also useful to the toxicologist in the desi^i of hie studies. 2.3.3 ttpuritiee Bpuritlee si^i as residuse of reactants, residual solvent and congeners* end the products of side reactions must be identified. Many final ^aaiuets are deliberate mixtures. The toxicologist nust recognize tha pcoblae of impurities and mixtures. The remit experience of 2,4,3T having dioxin contamination is an sample. This impurity later was shewn to have an LO^g for F - 30 HONS 209439 guina* pig* of 1 ug/Kg. Oilorobenrofuran appears to be not only a lively iitpurity of the parent PCBs, but may also ba produced in the intended u of tte ecbs; indaad it may even ba a metabolic transformation product. 2.4 Information on Manufacturing Procaa* and Posaiblt losses The following data on manufacture will ba useful in the aasesarat of PC3 substitute*! 1. Description of the basic manufacturing process 2. Purity of starting and intapnadiata matarials 3. Daacripticn of quality controls 4. Composition of the tedmical product including the names and anounts of impurities 5. Annuel production reports 6. Present and anticipated usaa 7. Means of transportation to site of use 8. Pi appeal of waste of production 9. Disposal of "spent" material that may contain the chemical 10. Accidental losses likely to occur 2.4.1 Production. Use, Disposal Knowledge of the production, use and disposal of a chemical will be extremely helpful, along with physical and chenical properties, to estimate exposure levels to specific target syetens. These estimates thro can be used to idrotify the control syetroe that might be instituted to minimize release to the roviranrot. In general, releasee associated with production are amenable to controls an merufaccurate > releases associatsd with uss are asenable controls on users. Voluntary control over releasee during use (equivalent to the voluntary controls exercised by Monsanto with regard to production) warrant further investi gation, because the use of a is intimately related to its potrotial re lease tVthesRvironBrot. Etoleasee associated with disposal are also related to production rod use, but are most easily controlled at the nwieipaj level. F - 31 HONS 209440 2,4.2 Production Specifics Production is tbs first level at which a chertical is likely to be introduced to the environment (i.e., through nissions) ? it is iyi at this stage that hunan toxicological data nay be first obtained, through exposure. Records of health and e^oaura levels of oiployeas as now required by the Occupational Health and Safety Mftinistration will be of inestimable value in assessing health effects; the discovery of hatangiosaroona in workers exposed to vinyl chloride is an example. Data an production and production losaes must be obtained fran manufacturers. Inventory statistics and data on methods of transport to major clients will be essential in quantifying losaes. All data should be eqiressed on the final product, i.e., oaumcial grade, since impurities may prove more harmful than the product itself. Data on the losses fran production and transport pro cesses are of oritical importance. Mudi of these data are oarpany confidential and allowances will ba necessary to protsct confidentiality. 2.4.3 Pass Oy far tha most important information needed to estimate tha exposure of a target population is a knowledge of the uses of a chemical. Tha first stap in understanding how chemicals get to the cnviroment would be to classify tha uaaa into two categories: (1) contained uses, and (2) dispersive uses. In g1**--1 those usee designated as contained will not introduce large quantities of choaicals to the srviroment. However, experience with PCBs has shown that accidanta, whan they occur, fraquejtly result in massive spills. Information on methods and amounts of release during normal contained should be carefully considered. The ultimate air route of dispersal of ECBs was never aonaidared a serious threat, though it new appears this may ba tha major route of dispersal. The use of consumer products containing toxic materials can result in significant direct ag^osure as well as affect the disposal pattern of these material!. F - 32 MONS 209441 2.4.4 Disposal The disposal of dimicals in contained uses is, of murs*, a major ooncam, especially with persistant materials such as PCBs. Labelling and refund incentive* may be necessary in order to get "spent" materials into the hands of persons knowledgeable in proper disposal techniques. Tt* flow of dis carded consular products, hnwuer, presents a nuch nore serious threat. Lack of ability to control this type disposal is obvious. For products having a short life, disposal rates are approximately equal to production rates. For products with a longer life and rapidly growing oensmption rata, the rate of disposal will be mailer than tha rate of production and may be estimated fran the service life of tha product and from production records. 2.5 Environmental Rate - Chmodynaalcs, Envlromantal Alteration, and Bioaocumlatton ' 2.5.1 Outline Qm following outline lists tha type of information needed to investigate adequately tha toxicological aensequanoa of introduction of a new cftmical such as a PCS substitute, it is not meant to be aonclt'<ve but is only intended as a guideline. These date will assist tha toxicologist in relating tha advene affect levels in animals to appropriate exposure levels for hunens. I. Mjvepent and fate in water A) Dissipation rata in distilled water 1. hydrolysis rate at acid, basic, and neutral pH 2. ytipuadagrerit'tnn 8) Degradation in water containing suspended solids C) Degradation in bottom sediments D) Rate vti. extent of nevt in flowing water -- chmical analysis of water down*tram E) in aquatic micxoorgmims F - 33 HONS 209442 H. Mawrt and fata in soil A) Soil metabolism studiaa -- aerobic and anaerobic B) Soil persistence atudiaa C) Leaching atudiaa IH. Covenant into and fata in air A) volatilization from water, soil and normal use B) Photodagradation IV. Fiat tptake -- in flowing water until plateau is reached and clearing in clean water v. aioriegrariafrility under aeimga traatnent conditions 2.5.2 Behavior in Aquatic Envirotnent the major factors contributing to the partition of a chanical into the aquatic environment are its snhhiUty and latant heat of solution. Bat cauaa so nany organic i.ui|Uiid are hydrophobic, exact solubilities are difficult to obtain. 1-bny of thaae oapjads tend to aoasulata at tha air/water interface and to form clusters of varying particle size. TeMperatura, pa, salt content, and othar variables affect solubility. Microbial, [**ww*mh<*i and chanical transformations in aquatic systems play an important role in the ultimate fate of cdwrinal a. Bioaocmilation occurs through: I.) Direct, active (*intended") tranaport into anorganiea's 2. ) Active transport, whsra tha oapotnd is mistakan for one with similar propartias (e.g., arsenic being tskan V In piece of phoaphotus) 3. ) Passive 1 fannation, with ligands in tha organism 4. ) Solubility equilibrium bah man fat (in tha organinn) and water F - 34 HONS 209443 Hie inportanoe of it*n #4 can be appreciated by cbaarvaticn of the PCSa data timing that bioaccinulations exceeding 100,000 times the anfeient level ara reached in aana microorganisna that are tha primary food sourca of fiah. 2.5.3 Bahavior in Soil Tha major prooaaaaa affecting tha bahavior of chenicals in soils ara adsorption and laartiing rllffininr both of vdiich ara influenced by tsnperature and moisture. Another process that affects transport of a chemical in soil is tha chasical's moment with water. Although downward moment is most cannon, lateral and even upward uuwaiL are rmsMines significant. The upward movement, which oftan is ths result of svsporatian at tha surfaos, is affactive in moving chenicals frail ths root tons, thus preventing poesible rnv--t into the food chain. P - 35 HONS 209**4 tltUetUPHIC BATA [T Report No, SMCCT *. T<c(4 ia4 Sublet* PCB* In tbm uiitfld state* Industrial Cm and EStvirarmentAl Distributions 3. RCJF:flM'* *C*f4.on Nu 1 RtOOrt Uatr February 25, 1976 7. burner* 11 ftatare L. Durfee, Gsysnah Contos, frank C. whicicra, Janes D. Bardan. E.E. Hactanan, III, and Robert A. Wtatin t. Pprlprrftiflt Uf4A4JtL0* N** and Adtfrtst Varsar Inc., 6621 Electronic Drive Springfield f Virginia 22151 . P*rtorffifla Orr*n<ftnaA ft(0* Se* 474.1' " *0. Praitet JjrI iai! \j 1 1 . CflAtTiact Crant No. EPA Mo. 68-01-3259 12. fpomorm* Ocaaniaanon Name juJ AJdresa u.S. Elrvircrnentzl Protaction Agency Offica of TOxic Substances Washington, D.C. 20460 t~13. T,p ji ft, p.rr * i *:jj OrfreJ Final it. Ij, Supplementary Note* EPA Project Officar - Ttm Kopp 14. Abiinfii This dsewant praeits tha currant stata of knowledge about tha production, usage and distribution of polychlorinated biphiyls (POe) in tha Unitad Statas. Tha inform ation presented is derived from data11ad atudiaa an tha production and first tier usar Induatrias, tha past and peasant generation and disposition of PCB-ocntaining wastas, nviroraantal transport and emulative loads, potential altamativaa to PCBa usage, inadvertent Iciaaai to and potantiai formation in tha anvirermant, and currant regulator; authoritiaa for POa control. Thaaa results indicatad that, although PCBa oontant of industrial wastaa can ba redocad through various approaches (treatmant, substitution, ate.), than mists a petitially savers futura hazard in tha fan of lsrgs aiounts of POa currently contained in land dlapnaal sites, further definition of this and of tha PCTs peobli, and, datanolnation of ways to minimize tha hazard, Propartiaa Manufacture Ua ! Auly.ii. IT*. On.nftM Polychlorinated Biphenyls (FO) Polychlorinated Tarptwnyls (PCTs) Production A Distribution Substitutes environmantal Loads Ehvimaantal Transport. Madal Regulatoryj 17k Umii> 17t, C 05ATI field Croup It AmliliUtr buw M- ENDORSED BY AN* AMO UNESCO. If. Security"?!*** Re*uni fffe- PTwi ...IF1.0 THIS FORM \AY RE RETtODCCEO 21. No, or 487 11. Pr.cr MONS 209445