EPA Uosted States -600/2-81- Envonmental Protection pe cone ol oes ‘Agency February 1981 Research and Development GUIDELINES FOR THE DISPOSAL OF PCBS AND PCB ITEMS BY THERMAL DESTRUCTION Prepared for OFFICE OF PESTICIDES AND TOXIC SUBSTANCES AND REGIONS 1 - 10 Prepared by Industrial Environmental Research Laboratory Research Triangle Park NC 27711RESEARCH REPORTING SERIES. Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into nine series. These nine broad cate- gories were established to facilitate further development and application of en- Vironmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields The nine series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4, Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7. Interagency Energy-Environment Research and Development 8, “Special” Reports 9. Miscellaneous Reports This report has been assigned to the ENVIRONMENTAL PROTECTION TECH- NOLOGY series. This series describes research performed to develop and dem- ‘onstrate instrumentation, equipment, and methodology to repair or prevent en- vironmental degradation from point and non-point sources of pollution. This work Provides the new or improved technology required for the control and treatment of pollution sources to meet environmental quality standards. This document is available to the public through the National Technical Informa- tion Service, Springfield, Virginia 22161EPA-600/2-81-022 February 1981 GUIDELINES FOR THE DISPOSAL OF PCBs AND PCB ITEMS BY THERMAL DESTRUCTION by D.G. Ackerman, L.L. Scinto, P.S. Bakshi, R.G. Delunyea, R.J. Johnson, G. Richard, and A.M. Takata TRH, Inc., Environmental Engineering Division One Space Park Redondo Beach, CA 90278 Contract No. 68-02-3174, Work Assignment No. 1 EPA Program Element No. C1YLIB Task Officer: David C. Sanchez Industrial Environmental Research Laboratory Office of Environmental Engineering and Technology Research Triangle Park, NC 27711 Prepared for: U.S. Environmental Protection Agency Office of Pesticides and Toxic Substances and Regions I Through x Washington, DC 20460 US. Environmental Prot ion V, Library os 230 South Deardorn a Chicago, Minois 6960:DISCLAIMER This report has been reviewed by the Industrial Environmental Research Laboratory, the Office of Toxic Substances and Regional Offices of the En- vironmental Protection Agency and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or comercial products constitute endorsement or recommendation for use. US. Environmental Protection AgencfABSTRACT This report is a resource and guidelines document intended to aid U.S. Environmental Protection Agency Regional Offices in interpreting and apply- ing the PCB Disposal Regulations to thermal destruction of PCBs. As background material, this document describes fundamental processes of combustion, thermal destruction systems, sampling and analysis methodo- logy, and flame chemistry relative to PCB incineration. Administrative considerations, including public involvement, are discussed. Detailed guidelines on evaluation of Annex I incinerators, high efficiency boilers, and the several stages of the approval process are presented and discussed. This report was submitted in fulfillment of Contract No. 68-02-3174, Work Assignment No. 1, by TRW, Inc., Environmental Engineering Division, under sponsorship of the U.S. Environmental Protection Agency. This report covers the period 12 October 1979 to 12 April 1980, and work was completed as of 12 April 1980.CONTENTS. Page Bee iv 0605005000 d0GK GG nb bdbduduuGu5G vit ee vill 1, Introduction. 2... ee ee eee 1 Vl Background. ee ee 1 1.2 The Problen ss... et 1 1.3 Purpose... 2 ee ee 6 V4 Scope. ee iit 7 2. Thermal Destruction Technology... 2... ...-0% 9 2.1 Combustion Theory... . 2.222. ee ee 9 2ulenbe combust iantatsUtquids\-aepeparmresanes inet 10 2.1.2 Combustion of Solids. st 2B 2.2 Thermal Destruction Systems... .. 2... 00 4 2-2nlbeIncinerat lonisystens iene are anes anea 15 2.2.2 High Efficiency Boilers >. Lt 48 2.2.3 Summary... 2... ee 54 2.3. Sampling and Analysis Methodologies for PCBS... . 54 2.3.1 Sampling Methodologies... 2.2... 0. 56 2.3.2 Analytical Methodologies... n 2.4 Stack Monitoring Instrumentation... 2.0... 83 2.4.1 Oxygen Monitors... 83 2.4.2 Carbon Monoxide/Carbon Dioxide Monitors . .. 85 2.4.3 NO, NOD Monitors... 2... 2. eee ee ee 86 2.4.4 Use of Monitoring Equipment... ......- 86 HB Cro cooggsdsdcoude 4s 87 2.5.1 Fuel Characteristics. 2... ee ee 87 2.5.2 Combustion Process Characteristics... . . . 88 2.5.3. Formation Mechanisms... . 0. wee 2 2.5.4 Thermochemical Equilibrium Analysis... 7 2.6 Other Pertinent Literature... ....-----5 102 2.7 Summary... ee ee ee 103 3. Administrative Requirements... 2... 6.2.2 eee 105 3.1 Federal Rules and Regulations. . 105, 3.2 State and Local Rules and Regulations. . 2.2... 108 3.3. Spill Control and Reporting Requirements . 2... 108 3.4 Public Notification and Participation... 2... . 109 4. Evaluation of Annex I Incinerators 2... 6. ee eee m iv4d 4.2 4.3 44 Evaluation of High Efficiency Boilers... .... 5.1 5.2 5.3 5.4 CONTENTS (Continued) Evaluation of Initial Report... ... . 1.1 Incinerator System Design. . . Operational Data Capability. - Effluent Monitoring Capability Sampling Locations... . Storage Capability. ..... Evaluation of Trial Burn Plan... ... 4.2.1 Operational Data... . Ae 4.2.2 Monitoring, Sampling, and Analysis . Evaluation of Trial Burn... .. 2... 4.3.1 Completeness of Data... ... 4.3.2 Data Reduction... ... . fe 4.3.3 Data Assessment... .. ~~ hoe Criteria for Incinerator Permit Approval. . 4.4.1 Design and Operational Criteria. . Site Specific Concerns... 1... Waste Characterization and Feed Rate | |. | 4.4.2 Monitoring and Record Keeping Criteria . 4.4.3. Sampling and Analysis... .. 2... 4.4.4 Waste Composition... 2... 2. 4.4.5 Compliance Criteria. |... 1 4.4.6 Waiver Criteria... 2... Evaluation of Notification Information. . 5.1.1 Boiler Design and Operation Evaluation . . . Operational Data Capability. . . Effluent Monitoring... ..... Storage Capabilities 1... |. Site Specific Concerns 1... 1 ation of Trial Burn Plan... .. . Operational Data... .... 5.2.2 Monitoring, Sampling and Analysis. Evaluation of Trial Burn Data... ... 5.3.1 Completeness of Data. ...... 5.3.2 Data Reduction. ...... wee 5.3.3 Data Assessment... 2221. Criteria for Approval of Boilers for PCB Destruction 5.4.1 Design and Operational Criteria. . 5.4.2 Monitoring and Recording Criteria. . 2 3 4 5 Sampling Locations... .....- 6 7 ual 1 Waste Characterization and Feed Rate . | . 175 178 179 186 188 188 191 196 196 199 200 201 201 202 203 203 205 210 2n 212 22 213 213 214 215 216 218 28 218 29 220 223 223CONTENTS (Continued) Page 5.4.3 Sampling and Analysis... 2.2... eee 224 5.4.4 Compliance Criteria... 2.2.2... 2% 22a References... ee ee ee eee 226 Appendices A, PCB Regulations... ee ee eee ee ee eee 232 B. Environmental Assessment ee ee 209 C. Sample Calculations... ........0.0000004 302 viFIGURES. Disposal requirements for PCBs and PCB Items... . . « Schematic of Rollins Environmental Services rotary kiln incinerator... ee ee es Typical vertically fired liquid waste incinerator . . . Horizontally fired liquid waste incineration system . Multiple hearth incineration system... ....... Fluidized bed facility schematic... 2.2... ae Retort multiple-chamber incinerator... 2.2... In-line multiple-chamber incinerator... 2... 00. Schematic diagram of a catalytic combustor... .. . Schematic diagram of a pyrolysis system... ..... Atomic International Div. molten salt reactor - process flow and sampling schematic. 2... eee ee ees Pulverized coal firing methods... .. 1.2... 5 Cyclone firing of crushed coal... ee. ee ee ee Schematic of EPA Method 5 train. 2... 2. ee eee ESUGW cL ub oo ooo 0uGcucDGoG0nG Schematic of modified Method 5 stack sampling train . Preferred PCB sampling train configuration. ..... . Assembled sampler and shelter with exploded view of the Mii ito pd pdobddcoduGe0dGa0a Flowchart of Annex I incinerator approval process . . . Examples of wet scrubber types for emission control . . Overall penetration versus cut to mean particle diameter rotiOyae et tie emer ce PCB incineration waste disposal... .......-. vii 16 27 29 33 37 40 40 2 43 46 53 53 58 59 62 64 69 ue 139 145 151TABLES: Number. Page 1 Operational Data from PCB Tests at Rollins Environmental Services. 2 2. ee ee ee wwe 20 2 Operational Data from PCB Tests at ENSCO..... 2... © 24 3 Results of Incineration Tests of Ethylene and Hexachloro- cyclopentadiene Wastes at the Marquardt Company... .. 31 4 Results of Several Incineration Tests of Organochlorine Wastes Onboard the M/T Vulcanus...... 2.2.2... 31 5 Incineration System Summary... . . eee oe a7 6 Summary of PCB Thermal Destruction Tests......... 58 7 (0, (0p, 0, Monitoring Instrumentation... ....... 84 8 Percent of PCBs Remaining After Exposure at Different Temperatures. 2 ee te eee ee ee 89 9 Percent PCBs Remaining After Treatment at 704°C... .. 90 10 Theoretical Combustion Efficiencies and Equilibrium Concentrations of Major Species from Combustion of Two PCB ee een ae eee erate ne es rar eterna Ce eared Stee erent cede err 98 n Pyrolysis of Chlorinated Hydrocarbons: Equilibrium Product Distribution as a Function of Temperature. ....... 100 12 Pyrolysis of Highly Chorinated Hydrocarbons: Equilibrium Product Distribution as a Function of Temperature... . 101 13 Federal Laws/Regulations Pertaining to PCBS... . . .. 107 iT) Checklist for Evaluation of Initial Report........ 7 15 Theoretical Oxygen Requirements and Product Gas Yields for Complete Combustion. ....... wee ee 125 16 Configurations of Selected Gas Cleaning Devices Applicable to PCB Incineration Facilities... 2... 1... ee eee 138 v7 Packing Depth Required to Achieve Specified Removal Efficiency. 6... eee ee ee ee ee 142 8 Murphree Vapor Phase Efficiency for Plate Towers... .. 143 19 Typical L/G Ratios... ee ee eee ee ee 19 20 Partial List of Liquid Samplers. ...-..--.--- 163 a Partial List of Flow Rate Measurement Instruments... . 167 2 Checklist for Evaluating a Trial Burn Plan... ..... 176 23 Suggested PCB Trial Burn Plan Outline... ....... 177 24 Types of Data from Trial Burn... ..- see ee 189 25 Checklist of Trial Burn Results... ......--.. 195Number. 26 27 28 29 30 3 TABLES (Continued) Page Requirements for Approval to Incinerate Liquid PCBs... . 197 Requirements to Incinerate Non-Liquid PCBS... ..... 198 Information for High Efficiency Boilers... ....... 204 Recommended Types of Data from Trial Burn in a High Efficiency Boiler... eee eee eee ee eee 219 Requirements for Burning PCB-Contaminated Dielectric Fluids in High Efficiency Boilers. 221 Requirements for Burning PCB-Contaminated Non-Mineral Oi1 Dielectric Fluids in High Efficiency Boilers... . 222 ix1. INTRODUCTION 1. BACKGROUND Polychlorinated biphenyls (PCBs) are derivatives of the compound bipheny! in which from one to ten of the hydrogen atoms have been replaced with chlorine atoms. PCBs synthesized for commercial use are mixtures of isomers. PCBs are not naturally occurring compounds. PCBs have extremely high thermal and chemical stability. They are of low volatility (decreases with increasing chlorine content), are relatively non- flammable, and have excellent electrical insulating characteristics. Commer- cial mixtures are liquids at room temperature. They are insoluble in water, have a low degree of hygroscopicity, and are soluble in most common organic solvents. There are 209 possible PCB isomers, ranging from three monochloro isomers to one decachloro isomer. The commercial mixtures are very complex, each con- taining many isomers. Sissons and Welti (1) identified 69 isomers in Aroclor 1254, a conmercial mixture produced by Monsanto. Aroclor is a trademark of Monsanto, the principal U.S. manufacturer of PCBS, for a series of PCB mixtures. The digits "12" refer to bipheny? as the parent compound. The digits "54" in- dicate that the chlorine content of Aroclor 1254 is approximately 54% by weight. From 1971 through 1974, Monsanto produced Aroclor 1016 (an exception to this nomenclature) which was similar to Aroclor 1242 but greatly reduced amounts of penta-, hexa-, and hepta-chloro isomers. Other tradenames for PCBs or PCB fluids are: Chlorextol (Allis-Chalmers), Clophen (Farbenfabriken Bayer), Dy- kanol (Federal Pacific Electric Co.), Fenclor (Caffaro,S.P.A.), Inerteen (Westinghouse), Kanechlor (Kanegafuchi Chemical Industry Co.), Noflamol (Wagner Electric Corp.), Phenoclor (Prodiec), Pyralene (Prodlec), Pyranol (General Electric), and Santotherm (Mitsubishi-Monsanto). 1.2. THE PROBLEM The excellent stability characteristics of PCBs made them highly usefulin numerous commercial applications: particularly dielectric fluids in capa- citors and transformers, but also in heat transfer and hydraulic systems, pigments, plasticizers, carbonless copying paper, electromagnets, components in cutting oils, and others. Their wide use coupled with a lack of recogni- tion of their hazards has led to PCBs being ubiquitously distributed world- wide in virtually all compartments of the environment (2). Highest concen- trations are found in industrialized urban areas; but PCBs are found in air, water, soils, and marine samples in remote, unindustrialized areas. Experi- mental evidence, summarized in Reference 2, indicates that atmospheric trans- Port is the major means by which PCBs have been so widely dispersed. Although PCBs have ow acute toxicities, other adverse effects have been found in humans, laboratory animals, and other organisms (3). A summary of toxicological and epidemiological data on the effects of PCBs, adapted from Reference 3, is given below. More detailed discussions are given in References 2 and 3. PCBs appear to cause tumors in laboratory animals. There are limit- ed human epidemiological data, but excess carcinogenic effects have been ob- served in several large groups of people exposed to PCBS. Several studies in animals have shown that PCBs cause fetal resorption, birth defects, and high offspring mortality rates at levels of 1-5 mg/kg body weight. There is evi- dence that PCBS produce inmunosuppressive effects in laboratory animals. PCBS have been observed to cause liver damage. PCBs have caused chloracne in human workers occupationally exposed to air levels as low as 0.1 mg/m?. Adverse effects observed in laboratory tests also occur in wild animals. PCBs are known to bioaccumulate and to biomagnify. Effects noted in mink fed PCB contaminated fish include reproductive failure, reduced weight gain, increased mortality, and enlargement of liver, kidneys, and heart. PCB mixtures are extremely toxic to several species of aquatic inverte- brates and fish. Aroclor 1254 is toxic to several shrimp species at levels of about 1 ppb. Increased mortality of sheepshead minnows was observed in water containing 0.16 ppb of Aroclor 1254. Concentrations of Aroclor 1242, 1016, and 1254 as low as 0.1 ppb have been demonstrated to depress photo- synthetic activity in phytoplankton.The principal sources (2,3) on health effects of PCBs used in this report indicate that there is very little information on the relative ad- verse effects (toxicity, oncogenicity, mutogenicity, etc.) of individual isomers or mixtures. It might be argued that the more highly chlorinated isomers or mixtures are more harmful, if only by virtue of the facts that they are less readily metabolized and eliminated than the less highly chlori- nated species. However, EPA has not established standards for the differ- ent mixtures because all PCB mixtures: 1) can induce toxic effects at low levels, 2) include highly persistent components, and 3) include components that are subject to significant uptake and storage. The realization of the widespread distribution of PCBs in the environ- ment and growing knowledge of their hazards led Monsanto in 1972 voluntarily to restrict sales of PCBs to the manufacture of electrical transformers and capacitors. Monsanto ceased all production in 1977. A few data points serve to illustrate the magnitude of the environmen- tal contamination problem. It has been estimated (2) that over 400,000 metric tons (mt) (900 million pounds) of PCBs were sold domestically in the U.S. during the period 1957-1974. Nisbet and Sarofim (4) have estimated that cumulative sales of PCBs in North America from 1930 through 1970 amount- ed to 450,000 mt (1 billion pounds). Data from Reference 2 indicate that domestic sales from 1971 through 1974 were 60,000 metric tons (133 million pounds). Total domestic sales may thus be estimated at 510,000 metric tons (1.1 billion pounds). Nisbet and Sarofim (4) also estimated that during the period 1930 through 1970 cumulative losses of PCBs to the environment amount- ed to 354,000 metric tons (770 million pounds) distributed as follows: @ Air ~ 27,000 metric tons @ Fresh and coastal water - 54,000 metric tons © Dumps and landfills - 270,000 metric tons EPA has estimated (5) that up to and including 1975, between 136,000 and 181,000 metric tons (300 to 400 million pounds) of PCBs had entered the en- vironment.