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EPRI Electric Power Research Inatitute Topics: PCB Chemical analysis Flras Transformers Pollution control Insulating oils EPRI CS/EAIEL-4480 Project 2028 Proceedings March 1986 Proceedings: 1985 EPRI PCB Seminar Prepared by Electric Power Research Institute Palo Alto, California HONS 018832 REPORT SUMMA R Y SUBJECTS Hazardous/toxic substances / Risk assessment / T&D: Substations TOPICS PCB Chemical analysis Fires Transformers Pollution control Insulating oils AUDIENCE Environmental managers / Distribution engineers Proceedings: 1985 EPRI PCB Seminar New regulations have increased the complexity of virtually all phases of PCB management. In this EPRI-sponsored seminar, participants discussed the latest advances in methods and equipment to facilitate and Improve PCB disposal, cleanup, replacement, and risk assessment. BACKGROUND This industrywide meeting constituted the third EPRI-sponsorad seminar to update utilities on equipment and processes for dealing with the complex problems of polychlorinated biphenyl (PCB) management. As in the previous seminars, held in 1961 and 1963, discussion topics ranged from equipment and methods In the initial stages of development to processes now on the market. OBJECTIVES To provide a forum for discussing equipment and methods for PCB management. To avoid unnecessary duplication of research efforts through exchange of Information. To Inform equipment suppliers of utility PCB management needs APPROACH Approximately 460 representatives of utilities government agencies, research groups and private Industry In the United States and other coun tries attended a PCB seminar In Seattle October 22-25,1986. Major subfects of discussion weie PCB destruction, mineral on decontamination. PCB anal ysis PCB spill cleanup and management, risk analysis and management. PCB fires and retrofill and replacement fluids RESULTS This report contains more than 60 papers presented at the seminar. Those discussing PCB destruction addressed such topics as the thermal treatment of PC8s and PCBcontaminated soils and the sampling and analysis criteria for evaluating the effectiveness of PCB destruction methods topics m other discussion areas Included processes for removing PC8s from contaminated transformer oil and coolants, equipment for tasting PCBcontammated soils PCB environmental transport, pyrolysis and combustion of PCB contaminated transformer fluids and preventive measures for reducing sir borne PCB contamination. Several papers described pilot plant projects or cpmcs/EArEirraos HONS 018833 case studies to demonstrate the use of new equipment, processes, and cleanup methods. EPRI PERSPECTIVE The large number of people attending the 1965 PCS seminar reflects the need of all those involved in PCS management to discuss common prob lems and goals. Participants--nearly 200 of whom were from member . utilities--came from the United States. Canada. Great Britain, Prance Italy, and Sweden and represented a variety of disciplines. The meeting thus provided for a comprehensive review of the Issues faced by those responsible lor PCS analysis, risk assessment, and disposal--and by those planning research or developing equipment to make these tasks easier. This report presents the proceedings of the seminar. The proceed ings from the 1961 and 1663 seminars are contained in EPRI reports EL-2572 and EL-3661, respectively. PROJECT RP2026 EPRI Project Managers.' Ralph Komai; Vic Nlemeyer, Gil Addis Coal Combustion Systems Division; Energy Analysis and Environment Division; Electrical Systems Division For further Information on EPRI research programs, call EPRI Technical Information Specialists (415) 856-2411. HONS 018834 Proceedings: 1985 EPRI PCB Seminar CS/EA/EL-4480 Research Project 2028 Proceedings. March 1986 Seattle. Washington Octooer 22-25.1985 Edited by R. Y. Komai. Coal Combustion Systems Division V. Niemeyer, Energy Analysis and Environment Division Q. Addis. Electrical Systems Division Electric Power Research Institute 34t2 Hiilview Avenue * Palo Alto. California 94304 EPRI Proiect Managers fl. Y. Komai Heat. Waste, and Water Management Program Coal Combustion Systems Division V. Niemeyer Economic and Environmental Integration Program Energy Analysis and Environment Division G. Addis Transmission Substations Program Electrical Systems Division HONS 010835 ORDERING INFORMATION Requests for copies of this report should be directed to Research Reports Center (RRC), Box 50490, Palo Alto, CA 94303. (415) 965-4081. There is no charge for reports requested by EPRI member utilities and affiliates, U S. utility associations. U S. government agencies (federal, state, and local), media, and foreign organizations with which EPRl has an information exchange agreement. On request, RRC will send a catalog of EPRI reports. Cooyngnr 4 '9M Efeeir>e Rower Research institute. toe ah ngnis reserved NOTICE This reoori wm oreoereo bit the Etectne R>wer Research insiriuie me lERfli) Neither gpm memoers ot ERRt nor any person acting on fte* behalf tatmewes any warranty. ecm ot mcMd with resoeei to tna use ol any mtormelon apparatus. method. or oocnt d<loosed tn th*s reoort dr tnet suen use mey not minn^e private* owned rights o> fbl assumes any haMmes with resotet to the use at o* tor damages tesuttmg from the use ot any ictormetion aeoaratut method or orocesi wetoseo m ihs reeert. or ici reeponsieie tor statements meoe or oprtuons ewessed Dy rri>vual author* HONS 048836 ABSTRACT The 198S PCB seminar continued EPRI's series providing timely Informetlon on PCS resetrch to utilities, regulators, and contractors. The papers In this seminar showed a significant Increase In technical level over those presented In the 19(1 and 1983 meetings. Subjects covered In the three and one-half days meeting were: PCB Destruction Mineral Oil Decontamination Analytical Techniques for PCBs Spill Cleanup and Management Risk Analysis and Management PCB Fires and PCDF Analysis Retroflll and Replacement Fluids Miscellaneous Subjects HONS 018837 111 ACKNOWLEDGMENTS Wc rnuld like to acknowledge the help of our session chairmen who kept the long meeting on schedule throughout. Ellen Lanun and Claudia Runge did a superb Job on meeting arrangements and administration. Babs Ryan and Barbara Cole contributed both to the preparations for the meetings and these proceedings. Thanks to all. HONS 018838 CONTENTS Section Part 1: BACKGROUND 1 FIRE INVOLVING PCS TRANSFORMERS - FURTHER REGULATIONS, MANAGING THE RISK--H. C. Manger Pjjj 1-1 Part 2: DESTRUCTION Ralph Koaal, Chatman 2 SAMPLING ANO ANALYSIS CRITERIA USED TO EVALUATE THE EFFICACY OF POLYCHLORINATEO BIPHENYL (PCB) OESTRUCTION-John H. Salth 3 PYROPLASMA DETOXIFICATION OF ASKAREL FLUIDS-- T. G. Barton 4 THERMAL TREATMENT OF PCBj ANO PCB-CONTAMINATED SOILS--JlBiy Boyd 5 PCB INCINERATOR USING MOLTEN GLASS BATH AS HEAT SOURCELarry Penberthy 2-1 2-3 2-7 2-11 Part 3: DECONTAMINATION OF MINERAL OIL Gilbert Addis, Chatman t NON-SOOIUM PROCESS FOR REMOVAL OF PCBs FROM CONTAMINATED TRANSFORMER OIL--Robert L. Peterson and George P. Adaas 7 AN ELECTROCHEMICAL PROCESS FOR OECOMTRMINATING PCB-CONTAINING TRANSFORMER COOLANTS--Michael J. Massey and Fraser M. Walsh 3-1 3-S HONS 018839 vl 1 Section 8 CHEMICAL DESTRUCTION OF POLYCHLORINATED BIPHENYLSSteven C. Vick and N. S. Chu Pam 3-IO Part 4: ANALYTICAL PANEL - PCS* Tom Rouse, Moderator 9 EVALUATION OF A PORTABLE TEST KIT FOR TESTING PCB-CONTAMINATEO SOILS AND OILS IN THE FIELD--Gary Gauger, Gary C. Smith, and Judy M. Sullivan 10 EVALUATION OF THE CLOR-N-OIL' TEST KIT AS A PC8 SCREENING TOOLDavid W. Mills and Klrt Rhoads 4-1 4-7 11 FIELO TESTING OF THE S-CUBEO GAS CHROMATOGRAPH, PCBA-102--0.C. Hein 4-1S 12 COMPARISON OF PCB ANALYTICAL METHOOS--Lansing H. Wong 4-17 13 BPA SUBSTATION SOIL PCB TESTING PROGRAM--David Plath 4-21 14 AN ANALYTICAL METHOO FOR THE ANALYSIS OF CHLORINATED BIPHENYLS IN LIQUIDS AND SOLIO- Mitchell 0. Erickson, John S. Stanley, J. Kay Turman, Gil Radolovlch and Daniel T. Heggem 4-42 15 FIELO MEASUREMENT OF PCBS IN SOIL AND SEDIMENT USING A PORTABLE GAS CHROMATOGRAPH- Thomas M. Splttler 4-44 16 DISTRIBUTION OF POLYCHLORINATED BIPHENYLS WITHIN BONNEVILLE POWER ADMINISTRATION SUBSTATIONS--David W. Baker 4-46 Part 5: SPILL CLEANUP W. Corey Trench, Chairman 17 PILOT PLANT STUOIES FOR SOLVENT EXTRACTION OF POLYCHLORINATED BIPHENYL (PCB) FROM SOIL-Margaret B. Saunders 5-1 HONS 018840 V1 11 Section 18 POLYCHLORINATED DIBENZOFURAN CONTAMINATION OF THE STATE HIGHWAY DEPARTMENT OFFICE BUILDING IN SANTA FE, NEW MEXICO, AS A RESULT OF A PCB TRANSFORMER MALFUNCTION--Fred L. OeRoos, Susan C. Watson, and Joseph A. Hatchel piat 5-S 19 DEVELOPMENT OF A SPRAY-VACUUM HEAD (ANO SUPPORT SYSTEM) FOR THE REMOVAL OF PCB CONTAMINATION FROM WALLS, FLOORS, ANO OTHER SURFACES--Karl C. Ashley 5-13 20 SORPTION/OESORPTION OF POLYCHLORINATED BIPHENYLS IN SOILSDon C. Glrvtn, 0. S. Sklarew, and C. C. Ainsworth 5-17 21 DESORPTION OF PCBs IN A SOIL-AqUEOUS SOLUTION SYSTEM-- Mark Cl lath, M. E. Esslngton, M. R. Resketo, A. A. Elseewl, and C. P. Ooyle 5-23 22 SOLVENT CLEANING OF PCB-CONTAMINATED SOILS- Leo Weltaaan 5-27 Part 6: RISK ANALYSIS ANO MANAGEMENT Abrahaa Silvers, Chalnaan 23 PCB EXPOSURES - THE INSURANCE INDUSTRY ANO THE PCB EXPOSURE SITUATION--Richard G. Clarke 24 PREVENTIVE MEASURES FOR REDUCTION OF AIRBORNE PCB CONTAMINATION RISK--Brian W. Wast and Warren G. Hansen 25 ENVIRONMENTAL FATE OF PCBs IN MINERAL OIL SPILLSStuart M. Brown and Arteals Antipas 26 MANAGING ECONOMIC RISKS DUE TO ELECTRICAL EQUIPMENT CONTAINING PCBs--David Cohan, Deborah A. L. Aaaral, Dean W. Boyd, Michael S. Johnson, and Oonald S. Wilson 27 THE TRANSFORMER/CAPACITOR RISK MANAGEMENT MODEL: 'TRIM*-- Donald S. Wilson, Dean W. Boyd, and David Cohan 5-1 5-4 6-7 6-12 6-16 lx HONS 018841 Section 28 HUMAN HEALTH RISK FROM PC8-C0NTAM1NATED MINERAL OIL TRANSFORMERS-- Alan Q. Eschenroeder and Edward J. Faeder Paoe 6-20 29 OCCUPATIONAL EXPOSURE OF ELECTRIC UTILITY PERSONNEL TO PCBs A CASE STUOY--J. 0. Sahl, T. T. Crocker, M. 0. Saperiteln, and E. J. Faeder 6-23 30 PCB ENVIRONMENTAL TRANSPORT ANO FATE MOOELING-James W. Llngle 6-26 Part 7: PCB FIRES Mitchell Erickson, Chairman 31 MEASUREMENT OF PCOF/PCOO IN UTILITY EQUIPMENT-- Sydney H. Gordon, Michael Miller, Fred L. DeRoos, Marcus Cooke, Jacques Guertln, and Gil Addis 32 FORMATION OF PCDFs ANO PCOOs IN ELECTRICAL DISCHARGES-- Tom Rouse, R. E. Koch, and F. L. DeRoos 33 SAFETY OF NON-PCB RECLASSIFIED TRANSFORMERS IN FIRE INCIDENTS A BUILDING SCALE ENGINEERING STUDY--Marcus Cooke, Fred L. DeRoos, Bruce Rising, and Will 1am H. Martin 34 PYROLYSIS AND COMBUSTION OF PCB-CONTAMINATED TRANSFORMER FLUIDS--George Eadon 35 PCB ACCIDENT IN FRANCE-Chrtstoffer Rappe, L.-O. KJelltr. S. Marklund, M. Nygren, and R. Fournle 36 PCB FIRES - CORRELATION OF CHLOROBENZENE ANO PCB CONTENTS OF THE FLUID WITH PCOF ANO PCOD CONTENTS OF SOOT-Paul des Hosiers, 8. Westfall, B. Campbell, and A. Lee 7-1 7-7 7-11 7-20 7-22 7-26 HONS 018842 Section Port 8: RETROFILL AND REPLACEMENT FLUIDS H. C. Manger, Chairman 37 FORMEL, A NEW, SAFER, NONFLAMMABLE DIELECTRIC AND COOLANT FOR TRANSFORMERS--David SI Inn 38 STATE-OF-THE-ART REVIEW OF COMBUSTION/PYROLYSIS BY-PROOUCTS OF PCB SUBSTITUTES--J. Rodney Marsh 39 DIFFUSIONAL MOOELING DURING TRANSFORMER RETROFILL--G. R. Atwood. I. R. Moore, and P. R. Dillon 40 DECONTAMINATION OF PCB TRANSFORMERS USING ENSCO, INC.'S RETRO-1 PROCESS-J. Lee Tlnney 41 PROOOCTS OF PARTIAL COMBUSTION OF PCB ALTERNATIVE DIELECTRIC FLUIDS--C. Clair Claiborne 42 PCB TRANSFORMER DECONTAMINATION RATHER THAN BURIAL--Ted Topolskl 43 RETR0F1LLING ASKAREL TRANSFORMERS - WORDS OF CAUTIONJames P. Kinney 44 DECONTAMINATION OF AN ASKAREL-FILLED NETWORK TRANSFORMER0, T. Drew Dunlop 45 PCB REMOVALS - OPTIONS AND IMPLEMENTATION--Francis E. Silvia Page 8-1 8-30 8-34 8-41 8-47 8-57 8-S3 8-60 8-64 Part 9: SPILL MANAGEMENT PANEL Harry Onlshl, Moderator 46 AFTER A PCB FIRE - CLEANUP INSIDE BUILDINGS CONTAMINATED WITH DIOXINS AND FURANS-KIrk Blackmon 47 PCB SPILL RESPONSE AND CLEANUP RESULTS-Paul J. Etsele 48 MANAGING A PCB FIRE DECONTAMINATION--Chris Kwoka xl 9-1 9'5 9'9 HONS 018843 Section 49 MANAGING CLEANUP OF MAJOR PCB-CONTAMINATEO SITES-- Nicholes .A. Speed, Denny S. Parker, and William E- Glister 50 PCS CAPACITOR FIRE AT IREQ'S HIGH-VOLTAGE LABORATORY AND SUBSEQUENT DECONTAMINATION--Oavld Train, A. Chamber land. 0. Oupont, and J. Castanguay 51 GUIDELINES AND ALTERNATIVES FOR PCB SOIL-SAMPLING PROGRAMS-- Warren G. Hansen, Thomas L. Johnson, and Karen A. Sahatjlan 52 VERIFICATION OF PCB SPILL CLEANUP BY SAMPLING AND ANALYSISDaniel T. Heggem, Richard A. Levy, John H. Smith, Mitchell D. Erickson, Stephen E. Swanson, Gary L. Kelso, J. Kay Turman, David C. Cox, and Bradley D. Schultz 53 RISK ASSESSMENT DEVELOPMENTS FOR PC8/PC0F DECONTAMINATION PROJECTS--Richard Wade 54 A SYSTEMATIC APPROACH TO PCB CAPACITOR SPILL CLEANUP COMPLIANCE SAMPLING-Mark J. Knight, Bohdan I. Dmyterko, Steven K. Wlnshlp, and Thomas E. Hemmlnger 55 COMMONWEALTH EDISON COMPANY'S PCB SPILL CLEANUP PROCEDURESThomas E. Hemmlnger, Mark J. Knight, Bohdan I. Dmyterko, and Steven K. Wlnshlp 56 COMMONWEALTH EDISON COMPANY'S TRANSFORMER SPILL RESPONSE PREPAREDNESS--Bohdan I. Dmyterko, Thoaws E. Hemmlnger, Steven K. Wlnshlp, and Mark J. Knight 57 AN ANALYSIS OF PCB CAPACITOR SPILL CLEANUP EFFECTIVENESSSteven K. Wlnshlp, Mark J. Knight, Bohdan I. Dmyterko, and Thomas E. Henalnger Peae 9-13 9-17 9-21 9-25 9-28 9-37 9-40 9-43 9-46 MOMS 018644 Section - Pert 10: MISCELLANEOUS Victor Nlemeyer, Chairman 58 IN SITU VITRIFICATION OF PC8-C0NTAMI MATED SOILS-C.L. Timenun 59 EPRI'S WORK ON PCS HEALTH EFFECTS--Walter Weyzen 0 HUMAN ANO ENVIRONMENTAL BIODEGRADATION OF PCBs--John F. Brown,Jr., Donna L. Bedard, Lawrence H. Bopp, Janes C. Carnahan, Richard W. Lawton, Ronald 0. Untenaan, and Robert E. Wagner tl COMPUTER AIO FOR COMPLIANCE WITH THE RECORD KEEPING AND REPORTING REQUIREMENTS OF THE PCB REGULATIONS--Kent D. Hedrick 82 RADIOACTIVE ANO NONRADIOACTIVE PC8 MANAGEMENT AT HANFORDWesley W. Leonard, Robert F. Gretzlnger, and Gary R. Cox APPENOIK LIST OF ATTENDEES Peee 10-1 10-5 10-7 10-11 10-27 A-l xllf HONS 015845 MOT t: MCKUOUW HONS 018846 FIRE INVOLVING PCB TRANSFORMERS FURTHER REGULATIONS MANAGING THE RISK H. C. Manger The Environmental Protection Agency (EPA) issued a final rule on August 25, 1982, authorizing the indefinite use of certain electrical transformers containing polychlorinated biphenyls (PCBs). At that time, information available to the EPA indicated that fires involving electrical transformers were rare, isolated incidents. Because of the notoriety of several recent transformer fires and upon reconsideration, EPA has amended the 40 C.F.R. regulations with regards tot 761.3 761.30 761.40 Definition Authorization Marking Requirements The changes established three important dates for action: October 1, 1985 December 1, 1985 October 1, 1990 October 1, 1985 After October 1, 1985, EPA prohibits the use or storage of PCB trans formers where there is exposure to food or feed, in addition, the installation of PCB transformers in or near commercial buildings is prohibited, and defines "in or near commercial buildings". December 1, 1985 By December 1, 1985, all PCB transformers must be registered with the local fire fighting authority with specific information such as location, principle dielectric fluid, name and telephone number of person to contact in case of a fire. By the same date, PCB transformers located in a commercial building (commercial buildings are defined) must be registered with building owners, noting the specific location, principle dielectric fluid, and type of the PCB transformer (radial - network). For PCB trans formers located near commercial buildings, the same information must be registered with all owners of buildings located within 30 meters of the transformers. HONS 018847 1-1 October 1, 1990 EPA has amended authorizations in CFR 40 - 761.30 Prohibitions . As of October 1, 1990, the use of Network PCB Transformers with high secondary voltages (4B0 - 480/277 or greater) in or near commercial buildings ir prohibited. Allowed (with "enchanced" protection) Redial PCB Transformers with high secondary voltages 480V and above, in use, in or near coiranercial buildings after October 1, 1990 must be equipped with protection to avoid high current faults, and a method to detect and avoid sustained low current faults. Network and Radial Transformers with voltage less than 480 need only be equipped with protection to avoid high current faults. These amendments are a result of an EPA Risk Analysis. EPA with data available, as stated in the preamble of the latest rule, "undertook an evaluation of the fire-related risks posed by the continued use of PCB Transformers, and the costs and benefits of measures designed to reduce those risks". MANAGING THE RISK Aside from the regulation, the fire incidents publicized and the ensuing costs from fires involving PCB should suggest an evaluation of each specific risk with PCB equipment, particularly in buildings. Some of the potential cost are: Litigation Costs and Injury Awards The potential presence of PCDF's (Furans) and PCDD'e (Dioxins) essentially causes every incident to turn into a piece of Agent Orange controversy. Business Interruption Costs The building owners in Sen Francisco and Tulsa have claims against the utilities involved for damages. Cleanup Costs In Binghamton, the cost for cleanup exceeded the cost of the building. Sampling and Analysis Costs Each dioxin and furan analysis cost as much as $1,000.00. It is evident that industry generally is not prepared to deal with a PCB fire. In order not to make costly mistakes, one should consider what steps could be taken before a PCB incident, and possibly prepare a plan in order to respond expeditiously to potential PCB fire emer gencies. 1-2 HONS 018848 Examination of the PCB fire incidents suggest that proper pre-incident preparation and post-incident emergency response can greatly reduce the risks and liabilities associated with PCB fires in buildings. Pre-Incident Preparation should include: (1) Form a corporate response team to develop pre-incident preparations and plan post-incident actions. This team should include employees who encompass these disciplines: Legal Insurance Claims Environmental Operations Maintenance Media Relations U) Make an inventory of, and collect detailed information about all major PCB equipment installations owned by the Company. (3) Record the location of all PCB transformers and prepare maps identifying major PCB transformers in public buildings or areas accessible to the general public. (4) Identify the owners of buildings which contain PCB trans formers . (5) Develop a risk assessment and transformer phase-out priori tisation scheme. (6) Determine the responsibilities and authority of local Fire, Health, EPA and Natural Resource departments. Discuss the plan with the local agencies and determine limits of autho rity. (7) Discuss plans and execute contracts in advance with experi enced PCB-cleanup service companies. (B) Prepare operation procedures which will ensure the proper and immediate reporting of all PCB incidents. If an incident occurs? (1) Take charge immediately. When governmental agencies assume control, they may act so slowly that nothing is done by the time the media is involved. Public opinion can then dictate procedures and cleanup levels. One must convince the agencies, preferably in advance, that you can handle all problems. (2) Call in cleanup companies. MOWS 018849 -3 (3} Sample to analyze the extent of the problem promptly. It is important to determine the extent of the problem as soon as possible, not only from a PCB, furan, and dioxin standpoint, but what portion of the building is actually contaminated. (4) Get in touch with building owners. Building managers have the primary interest and responsi bility for communicating with the tenants of the building and for arranging alternate accommodations if the building must be evacuated during the cleanup. Therefore, the building manager should be kept completely informed, and should be both the spokesman for the tenants and their major source of information. (5) Get statements from persons who claim exposure or may have been exposed describing their feelings and symptoms. (6) Follow predetermined plan for press releases. Caution all involved not to make statements which will add confusion and adverse publicity. How one handles such a serious situation is never cut and dry. nor do I infer that this approach is the only way. However, adopting a well thought out plan in advance can show that you are competent and knowledgeable. It can also provide tangible benefits, such as re ducing human and environmental exposure, and can serve to signifi cantly reduce the risks of liabilities associated with PCB accidents. REFERENCES: 1. PCB Fire Emergency Response and Management by Joseph E. Shefchek. Wisconsin Power and Light Company and Louis Kosek. Public Service Company of Oklahoma . Proceedings of Pollution Engineering's HA2PR0 '85. Baltimore, Maryland HONS 018050 1-4 PA*T 2: OESTWCTIMI HONS 018851 SAMPLING AND ANALYSIS CRITERIA USED TO EVALUATE THE EFFICACY OF POLYCHLORINATED BIPHENYL (PCB) DESTRUCTION Author: John h. Smith For PCB Disposal Permits in more than one United States Environmental Protection Agency Region, the Office of Toxic substances (OTS) has the responsibility to negotiate demonstration conditions for, examine demonstrations for, and write permits for PCB destruction efficacy demonstrations in accordance with Toxic Substances Control Act Section 6(e) regulations. To carry out this responsibility OTS reviews documentation submitted by permit applicants. This documentation includes: existing state and local permits, equipment diagrams, equipment operation procedures used, operating specifications, proposed personnel, PCB destruction validation, waste disposal, a schedule of demonstration activities, and expected use(s) of treated material. This talk discusses information obtained in and prepared by the U.S.E.P.A. Headquarters PCB Disposal Permitting Program. one of the key factors in evaluating the demonstration of PCB destruction efficacy is the review of the permit application and analysis of the treated and untreated PCB matrix. The PCB Disposal Section evaluates the sampling and analysis of different process materials in order to meet several regulatory objectives. Sampling of a matrix, from which PCBs are to be destroyed or removed, must be representative of that kind of matrix and the distribution of PCBs in the matrix. Sampling must be controlled such that (1) PCBs are not destroyed in the sampling process, and (2) contaminants interfering with PCB analysis must not be introduced in the sampling process. Samples must be of a large enough size to provide sufficient material for instrumental analysis. Analysis includes the preparation of the sample for instru mental analysis, the instrumental analysis, interpretation of inetrunental data, and reporting of the results of the analysis. As with sampling, contaminants interfering with PCB analysis are not introduced In the analysis process. Minimum quantitation levels must meet regulatory requirements. The maximum level of PCBs in the treetnent matrix must be specified in many permits, and thus the permit applicant must demonstrate the repeatable capability to treat and analyze PCBs at the maximum level to be permitted. In all demonstrations the materials from which PCBs have been removed or destroyed must be proven free, at levels required in the regulations, of PCBs by definitive, confirmatory chemical analysis. In many cases waste products from the process must also be analyzed, the specifications of wsste product analyses depend on the proposed method of disposal. office of Toxic Substances senior officials use the results of the sampling and analysis from the PCR destruction efficacy demonstrations in making final decisions on PCB Disposal Permits. HONS 018852 2-1 If the treated material and waste fron a PCB disposal process are below designated treatment levels, there are no regulatory requirements for disposal of the treated material. If waste material or material treated as part of PCH disposal does not have a PCH concentration below designated limits, the waste material or treated material must be disposed inthe sane manner as the regulatory requirement for the original untreated material. That is, for original untreated material greater than 500 parts per million (ppm) disposal is incineration and for original untreated material between 50 ppm and 500 ppm disposal is in an approved PCb landfill. According to the regulation (40 CFR 761.60 and 761.70), there are several requirements for a PCB incinerator. Some of the sampling requirements are the monitoring of oxygen, carbon monoxide, carbon dioxide, volatile organic halides, PCBs, polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzodioxins (PCDDs) in the stack emissions. The temperature and the residence time are also regularly monitored. The regulation also allows alternative methods of disposal if those methods have been determined equivalent to incineration. Equivalence includes not only destruction eficiency but also potential for environmental exposure to, potential hazards from, and contamination from material fron which PCBs are to be removed and PCB disposal processing wastes. As an example, PCB materials treated by mobile alternative methods do not have to be transported. The matrix containing PCBs, once completely treated to below the levels required by regulation, may be reused. The non-PCH wastes generated are generally not hazardous. For separation processes, PCB wastes, in which PCBs have been concentrated to much lower volumes are incinerated. Alternate technologies demonstrated to the office of Toxic Substances to date include the general classifications of chemical reduction, physical separation, and solvent washing for metal recovery. The demonstrations of the alternate technologies include representative sampling of the untreated PCB matrix, the treated matrix, and process emissions and wastes. Initial PCH matrix concentrations are quantitated based on the original PCB formulation present. Where the treatment process changes the chemical natura of PCBs, the analytical method for treated material must be quantified based on representative individual PCB compounds at each level of chlorination. If the treatment process does not change the chemical nature of the original PCB formulation, quantitation of the treated material is based on the original PCB formulation. Completeness of PCB disposal in conjunction with metal recovery (and assumed metal reuse) is addressed in a case by case basis. For capacitor casing by solvent rinse, a solvent concentration based on estimated metal surface area is used to determine the equivalence to incinerator removal of PCBs. For the recovery of copper from transformer cores, the content of PCBs in the copper must be below regulated disposal treatment waste levels of 2 ppm for each individual PCb compound. 2-2 HONS 018853 PYROPLASMA DETOXIFICATION OF ASKAREL FLUIOS Thomas G. Barton INTRODUCTION During the pst year, a mobile PyroplasmaTM unit has been undergoing a series of waste destruction demonstrations using organic fluids. This demonstration project has been Jointly funded by the New York State Department of Environmental Conservation (NYS/DEC) and the Environmental Protection Agency Industrial Environmental Research Laboratory (EPA/IERL). The Pyroplasma unit Is a plasma based system which uses a Westinghouse high enthalpy plasma device to chemically atomize organic fluids. Following their atomization, the elemental components are allowed to recombine to form fuel gas, acid gas and carbon. A caustic soda scrubber is used to quench the gas, neutralize the acidic products and capture the carbon. A schoaatic of this process is shown in figure 1. The entire process is controlled and monitored by a process control computer which provides a continuous check on all operating parameters and provides operator warnings should these parameters deviate from preset values. The computer is also programmed to shut down the process in the event of deviation set by critical parameters. Two onboard gas chromatographs monitor for bulk gas constituents as well as trace residual compounds of Interest. The entire mobile unit Is housed in a forty-five foot moving van end requires hookup to power, water and sanitary sewer as well as waste fluid and caustic soda supplies to function. THE TEST PROGRAM A three stage test program was Jointly developed by NYS/DEC, and EPA/IERL in conjunction with Environment Canada and the Ontario Ministry of the Environment. The first stage Involved system shakedown with organic solvents as the feed material. The second stage had two main objectives. The first was to determine the ability of the Pyroplasma system to destroy a refractory chlorinated compound. HONS 018854 :-3 The second objective was to verify the mechanical operation of the system when using chlorinated feed material and demonstrate the capture of the hydrogen chloride product by the caustic soda scrubbing system. The third stage Involves the destruction of Askarel fluids by the Pyroplasma unit with stack monitoring for residual PCB, dioxin and furan residuals. At the time of writing this abstract, only the first two stages have been completed. Figure 1. Pyroplasma Process Schematic RESULTS TO OATE During the first stage, approximately twelve hours of operation. Including a three hour and a four hour test, pyrolyzed over 3000 litres of ethanol. A further eighteen hours of testing were conducted using 3500 litres of methyl ethyl keytone (HEX). Once the operating temperature of the reactor had reached 1000*C, virtually no adjustments by the operator were required. Product gas composition was very constant from run to run. In the ethanol testing the concentrations of the two major components of the product gas, hydrogen and carbon monoxide, varied by only three percent from the mean concentration. During these shakedown tests, no external stack monitoring was conducted. 2-4 HONS 018855 Theoretical values for the composition of the product gas from the pyrolysis of ethenol were calculated using kinetic equilibria equations. This theoretical composition was then compared with the gas chromatographic analyses of the product gas to determine the accuracy of the computer predictions. Excellent agreement within the 95 percent confidence Interval of the experimental data Is Indicated. This agreement supports the hypothesis that the pyrolytic gas leaving the reactor has a composition close to that defined by kinetic equilibria. As a result, computer modelling based upon such kinetic equations should provide a good estimate of the product gas composition. Discrepancies may be caused by the assumption that the composition of the cooled product gas as analysed by the gas chromatograph Is equivalent to the composition of the hot product gas as It leaves the reactor. This hot product gas composition may not be Instantaneously "frozen" by the scrubbing mater system. During cooling, kinetics mould favour an Increase In methane and a reduction in hydrogen concentrations. A "reverse shift" to reduce methane concentration to a theoretical value provides higher concentrations of hydrogen and carbon. This calculated product gas composition mhen compared to the theoretical composition shotted differences of less than one percent for the major bulk gas constituents. During the second stage of testing, a solution containing 38 percent carbon tetrachloride and 62 percent MEK on a mass basis mas fed to the reactor at a rate of 2.6 kg/mln. This represented a chlorine loading of 36 percent by mass. The reactor exit temperature mas maintained at 1000'C with a plasma torch operating power of 300 kti. The product gas had a combustion energy value approximately three times the plasma energy put Into the system. Operational stability mas demonstrated during this series of tests. At the 95 percent confidence level, parameters such as feed rates, plasma power and cooling water flows varied by less than four percent, whereas the reactor temperature varied by less than one percent. The 6CA/Technology Division, under contract to EPA provided external monitoring of the scrubber water and flared product gas effluent streams. The scrubber water was analysed for residual CC1a>. The post flare product gas was monitored for ecu, HC1, 0], CO, CO] and N0X. The temperature and flow rate of the flared gas were also monitored. The data collected by GCA are to be considered as preliminary pending review and approval by EPA. HONS 018056 2-5 Preliminary results showed that the Pyroplasma system repeatedly achieved for CC1<. a destruction efficiency greater than 99.9999 percent in triplicate tests. Recovery of HC1 by the scrubber system was better than 99.3 percent during these tests. Stack emissions for HC1 were also less than 8 g HCl/mln and easily complied with the EPA emission requirements of 99 percent removal. On average, the stack loading for N0X was typically less than 100 ppm and met CPA standards. Ourlng these tests, particulate carbon was captured In the scrubber at a rate approaching 2.5 grams of carbon per litre of scrubber fluid. As this carbon absorbs residual organics. Its presence In the water is considered beneficial In the overall objectives of environmental protection. At a detection limit of 5 ppb, no organics were detected In the liquid phase of the scrubber effluent. When this effluent stream Is discharged to the wastewater treatment plant, the carbon Is physically separated In the plant and sent to the anaerobic digesters for final treatment. At the time of writing, stage three tests with Askarel fluids are not complete. I hope to be able to report on their success during the Fall meeting In Seattle. The success demonstrated by the Pyroplasma unit with carbon tetrachloride Indicates that Askarel fluids should offer little additional technical challenge. However, the controversy surrounding these wastes often creates Interesting political challenges. 2-6 HONS 018857 Theraal Treatment of PC81 na PC8-cont*n1nated Soil* Jlawny W. Boyd* J. M. Huber Corporation Hubor Technology Group (HTG) of J. M. Huber Corporation has developed an Advanced Elactrlc Raactor (AER) which la highly of fact I for decontaminating solli contawInatad alth polychlorlnatad btphanyla (PCS) and tlnllar hazardous natarlaH. Tha AER hat boan utad to conduct PCS taats undar tha auspicas of tha Toxic Substances Control Act (TSCA). and demonstrations with carbon tatrachlorlda (CC14>. oetachlorodlbanzo-p-dloxln (CCDD). and tetrachlorodlbenzo-p-dloxln 1TC00). Tha AER It a pyrolytic procnas which rapidly haatt waataa to temperatures batwaan 2E00O-2500OC using Intansa tharaal radiation In tha naar Infrarad. Solid faad It transfarrad fro* an air-tight hoppar to tha top of tha AER. Raactants ara Isolatad fro* tha cylindrical graph 1to raactor cora by a gasaous blankat fontad by flowing nttregan Inward through tha porous cora wall. Carbon alactrodas hast tha cora to Incandascanca. Tha cora transfara hast to tha raactants by radiative coupling. Two post raactor treatment zonal intTZ) laaadlataly balow tha raactor provlda addi tional hlgh-taaiparaturo rosldanca ttaa at about 13?0C and cool tha product gas to about 540OC. HTG currantly maintains a pllot-scala AER (AER-12) with a 12-Inch dlaamter cora and a portable 3-Inch AER (AER-31. Tha AER-12 usas a cyclone* baghouse* caustic scrubber* and activated carbon bads for particle reaoval and gas polishing. Tha AER-3 uaas one PRTZ* a baghousa* and carbon bods. Tha technology Is designed to be highly mobile and wall suited for on-site treatsient. A transpor table AER with a throughput of IB-27 alii Ion kg/yr Is readily feasible. In Saptaaibar 1983* HTG conducted a trial burn treating approxlaately 6400 kg of soil containing 3000 ug/g PCS. All TSCA requirements ware exceeded Including PCS destruction and reaoval efficiencies (ORE) In the range of 99.99999* (7 nines). Evan destruction efficiencies (DC) aeasured In tha product gas before downstreaa cleanup exceeded the TSCA ORE raqulraaant of 6 nines In 3 of 4 tests. Chloride and particulate loading In tha gaseous effluent ware also wall balow EPA Incinerator standards. Gas-phasa polychlorinated dlbenzodloxlns and furans (PCOO l PCPf> be fore downstreaa cleanup uere balow detection Halts of 0.03-0.06 ug/SCM. The AER received EPA certification for destruction of PCBs In May 1984. AER Tests were also conducted alth CCl^ as a surrogate on soil and with dioxincontaminated soil taken from Tines Beach* Missouri. CC14 was chosen for tasting bated on Its refractory properties* reflected by Its high position on EPA's 2-7 M0NS 018858 hierarchy of Inclnerabllity. CC14 tests were conducted to demonstrate the AER's capabilities over a wide range of operating conditions and waste concentrations. DREs >99.99998 were achieved for CC14 feed concentrations up to 998. The Times Beach tests* conducted on site with the AER-3 In November* 1904 was the world's first successful field demonstration of dioxin treatment technology. The Tims Beech tests are supported by 0C00 tests conducted with the AER-12 and AER-3 at Borger, Texas. On-site tests and tests conducted with the AER-3 in Borger achieved OREs >99.9998. Dioxin concentrations In the process effluent were below detection limits In all cases. Higher DREs could not be demonstrated due to low feed concen trations. However* OCOO tests with the AER-12 resulted In DREs of >99.99998* Indi cating that In an actual claanup operation using a full-scale unit* DREs of greater then 6 nines for dioxins are achievable. A summary of tests conducted Is given In Table 1. Detailed results of the PCS and CC14 tests aro given In Tables 2 and 3* respectively. PC8* dioxin* and CC14 concentrations were determined by gas chromatography-mass spectrometry (GC-MS), GC-MS-MS* and GC with electron capture detection* reepectlvely. Other species concentrations were determined using EPA reference methods. Rotary kiln Incineration (RKI) Is presently touted as an attractive technology for treetmMt of soils contaminated with hazardous wastes. The AER has Inherent safety and performance advantages over RKI. Safety features Include! the absence of com bustion air* eliminating the possibilities of txploslon and formation of toxic com pounds such as PCDOs* PCOFs* and dioxins; high thermal Inertia to process time ratio* assuring continued waste destruction and safs clearing of feed from the process In the event of a temporary power failure; operation at low to slightly negative pressures* greatly reducing the probability of an outward gas leak; and the ability to economically equip the AER with high-efficiency ges treatment units such as carbon beds to provide redundant treatment of stack amissions In case of emergency. Performance advantages include; increased gaseous residence time at higher temperatures resulting In Improved DEs and DREs and reduced sensitivity to process upsets; pyrolytic decomposition which essentially eliminates normal pro ducts of combustion such as N0x S0x* and oxygenated organic species and also elim inates the problems of fuel carbonization on burner surfaces* caking and fouling* and variations In fuel properties; and very low process flow rates which reduce atmospheric emissions and allow using low-cost* off-thm-shelf gas scrubbing and cleanup units. AER versus RKI Job total cleanup costs for contaminated soils ere comparable. Asswing 20*000 ton/site and on-site operation* an overall cost com parison Including setup* treatment* site excavation* end site restoration Indicates a total cost of S700/ton for tho AER and $765/ton for tho RKI In 19S5 dollars. 2-8 HONS OiB*59 Table 1 A SUMMARY OF HAZARDOUS WASTE TESTS CONOUCTEO WITH THE AER Pat* Unit Faad Cone. --tUQ/fll__ FMd Ret. (kg/.lnl Avartga - QBE PCS CC14 OCOD ocoo TCOOb Nov. 83 May 84 Oct. 84 Oct. 84 Nov. 84 AER-12 AER-12 AER-12 AER-3 AER-3 3000 0.37-100* 17.9 0.25 0.08 7.1 l.s-ie.s 5.4-7.8 0.1 0.1 99.999997 99.99998 >99.99996 >99.999* >99.9992* 01 oxln* at tha process stack war* balov datactlon Units for all tasts. &Taat parfornad on alta. Tabla 2 OETAIIEO RESULTS FOR THE PCS TEST SERIES T--t 1 T--t 2 Tit 3 T--t 4 Tast Ouratlon (nln) Avaraga Faad Rata (kg/nfn) Total Faad Mass (kg) PCS Coneantratlons Fnd (ug/g) Treated Faad (ug/g) 6eMeu> Efflumt (ug/SCM) Stack Gas , (mg/SCM) Chlorld. (mg/SCM) Parttcl. Loading (mg/SCM) Reactor Outlet PCOD* (ug/SCM) PCOFa (ug/SCM) PC8 DE (X) PCS ORE (X) NS Net Sampled. 271 7.0 1910 3000 0.0005 0.23 271 7.1 1930 3000 <0.0005 0.03 225 7.1 1610 220 7.2 1580 3000 0.0006 0.10 3000 0.001 0.30 16.0.26 <0.010 <4.5 <0.05 <0.05 99.99992 99.999995 6.2*.8 <0.016 <7.1 NS <0.012 <5.5 8.0+6.6 <0.012 <5.8 <0.06 <0.06 99.99992 99.9999994 <0.03 <0.03 99.9996 99.999996 <0.05 <0.05 99.99995 99.99994 2-9 MONS 018860 Tabl. 3 DETAILED RESULTS FOR THE CARBON TETRACHLORIDE TEST SERIES Rsactor Faadrata loot <0C> (kC/1n) F.d Trsatd F*d Stack Gas fcui fuq/fl ram <ug/srai DC XU 1 2100 14.9 2 2100 10.0 3 2090 3.0 4 2260 10.1 5 2260 2.5 6 2420 2.6 7 2100 2.5 a 2060 18.5 9 2060 10 2060 9.8 2.0 11 2260 10.4 12 2270 2.1 13 2440 14 2090 2.3 0.5 15 2100 1.4 16 2090 1.5 17 2090 1.5 1.37 1.37 1.37 1.37 1.37 1.37 1.37 0.37 0.37 0.37 0.37 0.37 0.37 13.8 13.8 99 99 0.69 0.47 NS 0.47 NS NS 0.07 0.14 NS 0.56 NS NS NS NS 0.18 NS NS NS Not Sampltd j NO Not DotarntnoO. 0.0023 0.0019 NS 0.0071 <0.0002 0.0007 0.0004 0.0018 <0.0009 <0.0004 <0.0004 <0.0004 <0.0004 <0.0006 <0.0006 0.0054 0.0027 99.99992 99.99996 99.99991 99.9992 99.9990 99.9997 99.9993 99.99991 99.99992 >99.99992 99.99995 99.9964 >99.99967 99.99996 99.99992 98.3 97.1 ORE XU 99.999992 99.999990 NO 99.99996 >99.999996 99.99999 99.999996 99.99996 >99.99996 >99.99996 >99.999992 >99.99996 >99.99997 >99.999991 >99.999997 99.999997 99.999999 HONS 018861 PCB incinerator using molten glass bath as HEAT SOURCE * Larry Penberthy * The toxicity of polychlorinated biphenyls was grossly overstated during the environmental hysteria of the 1970s. It has since appeared that the culprit was Impurity dioxin. Even that has not been demonstrated to be very hazardous to humans (]J. Ironically* cigarettes may be burned in closed rooms freely, whereas PCBs are under strict burning regulations with which we must comply. Dioxins and furans can be formed during burning of PCBs If there is a deficiency In oxygen as in a smokey transformer fire {Figure 1). {) (2) Figure 1. Smokey Transformer Fire In the presence of excess oxygen* temperature above the cracking point for the carbon-carbon bond, and turbulence* the benzene rings burn to carbon dioxide* never to form benzene again. These considerations of chemistry guided our work in development of a furnace to destroy PCBs. Our long background In electric melting of glass (4) was Ideal In providing such a furnace for destruction of PCBs. Figure 2 shows our engineering and demonstration furnace {). It Is a tunnel. 3 ft $q by 22 ft long. The basin holds five tons of glass which Is kept molten by heat from the burning PCBs* supplemented by electric heat as needed. This size can burn 20 gallons per hr of PCBs. The author Is president of Penberthy Electromelt Co.. Seattle. WA. He has a BS in physics and chemistry, and Is the recipient of the Geijsbeek Award of the American Ceramic Society for his development of electric melting of glass using molybdenum electrodes (5J. 2-11 HONS 018862 Figure 2. Glass Furnace Incinerator PCB liquid Is sprayed or poured onto the hot glass surface. The organic portions vaporize and bum In air supplied from side jets. The Jets are arranged to give high turbulence to the fire. The organics bum to completion and Inorganic residues, such as metal oxides or soil, fall on the glass and dissolve In It. The range of allowable feed material is very broad. The furnace can even handle contaminated mud or soil. Soda ash Is added to soil to flux It down to make glass. When the glass level builds up a few Inches, the excess is tapped off and sent to beneficial use or to landfill. Our demonstration furnace Is small but Is still a practical furnace. It Is also practical to build larger furnaces such as 20 ft wide x 50 ft long x 15 ft high, volume 15,000 cu ft (Figure 3). The burning capacity Is 150,000,000 BTU/hr. corresponding to 3,000 gallons of PCBs per hour. Intermediate sizes can also be built readily. __________________ 50 ft ,, "1 29 ft x 50 ft x 15 ft high Volume 15,000 cu ft Rating: 150,000,000 BTU/hr 30.000 lbs PCB/hr 3.000 gal/hr Figure 3. Plan View of Large PCB Furnace The heating value of PCB-mineral oil mixtures as commonly found In transformers Is amply high to reduce electric power consumption to about half a kilowatt-hour per gallon of PCB liquid. Where power costs 8< per KWH, the electric cost is thus *4 per gallon. This is a lot less than has been rumored. 2-12 HONS 018863 Th chlorine pert of the PCS Is converted to hydrogen chloride, which must he scrubbed out of the offgas. Figure 4 shows a series of scrubber towers. They are filled with limestone rock. .1 recirculating water spray absorbs the h'Cl to form hydrochloric acid which then reacts immediately with the rock to form calcium chloride. When the solution In the first tower rises to commercial concentration (33* CaCl2), it Is tapped off to be filtered and sold. The weaker solutions In the second and third towers are moved upstream and fresh water is added to the third tower. The fourth tower contains a Brink filter for mist and particulate removal. This filter Is a cylindrical cup of fiber glass 2 ft diameter * 10 ft high. The walls are densely-packed, and are 4.S'* thick. Alternatively the HC1 can be captured In water-spray towers to form hydrochloric acid, also a commercial product. RAINDROP SHOWERS FOR COOLING ______ i_______ BRINK FILTER (FLUSHABLE) Figure 4. Scrubber Towers There are several advantages of the Pyro-Converter4"1 System for the destruction of PCBs: 1. The burning conditions are highly oxidative (12* excess oxygen) and hence products of Incomplete combustion cannot form if the temperature Is held above the auto-ignition temperature and there is turbulence. 2. There cannot be a flame-out with loss of temperature because electric heat comes on to maintain the correct temperature If the feed stops or If a low-heating-value material Is being burned. Even plain water can be "burned". 2-13 MONS 018864 3. The tunnel can be made as long as required for absolute totality of destruction of the PCBs. 4. The molten glass provides a ''home" for any inorganic material that might be in the PC8 oil. The glass thus made is a superb non leaching form for the inorganic residues. 5. Valuable chlorine compounds can be recovered and sold. REFERENCES 1. J. F. Brown. "The Search for PCS Health Effects." Proceedings: 1983 PCB Seminar. Electric Power Research Institute, pp. 6-35, 6-39. E. T. E. Siedhoff, C. A. Zale, and H. E. Morris. "Destruction of High Concentration PCBs in a Utility Boiler." Ibid.. p. 5-15. 3. J. R. Marsh and J. Zbozinek. "Chemistry of PCDDS/PCDFs." Ibid., p. 6-41. 4. Larry Penberthy. "Electric Melting of Glass." Handbook of Glass Manufacture. Vol. II, 1960, pp. Z57-271 , and 2nd edition, Vo 1. 1, 1974, pp'. '387-400. 5. Larry Penberthy. Electrode Assembly for Glass Furnaces. U.S. Pat. 2,693,498, Nov. 2/1954. 6. Larry Penberthy. Converting Hazardous Material to a Relatively Harmless Condition. U.S. Pat. 4,299.611, Nov. 10, 1981. 2-14 HONS 018865 PART 3: DECONTAMINATION OF MINERAL OIL MONS 018866 HON-SODIUM PROCESS FOR REMOVAL OF PC8S FROM CONTAMINATED TRANSFORMER OIL G. P. ADAMS, Niagara Mohawk Power Corporation R. L. PETERSON, Galson Research Corporation INTRODUCTION Currently acceptable methods of disposing of PCB contaminated oil Include either Incineration In specially permitted Incinerators or use of metallic sodium decontamination processes. Niagara Mohawk Power Corporation (NMPC) through It's contractor Galson Research Corporation (GRC) has developed a non-sodium process for oil decon tamination as an alternative to current methods. This patented (I) process has been demonstrated at both laboratory and pilot plant (60 gallon) scales, and a 2200 gallon/batch mobile prototype unit is currently in the start-up phase. BACKGROUND Incineration and sodium treatment of PCB contaminated transformer oil have significant disadvantages. Disposal of PCB oil by incin eration Is expensive and depletes the limited supply of replacement naphthenic transformer oil. Application of the Goodyear process (2) or similar sodium based dechlorination systems Is an Improvement on Incineration In that It allows recovery of the naphthenic oil for re-use. However, such decontamination processes require the expense and hazard of handling potentially explosive metallic sodium. The use of metallic sodium in such processes has resulted In safety re lated operating problems. The NMPC process, like the Goodyear process and It's variations, allows recovery of decontaminated transformer oil. Unlike the Goodyear process, the NMPC process does not use metallic sodium, rather a mixture of potassium hydroxide, glycol and sulfoxide. but APPROACH The objective of the NMPC study was to find and develop a commer cially viable non-sodium process for dechlorination of PCBs and other aromatic halides In transformer oil. Dechlorination of aliphatic halides using potassium hydroxide and alcohol Is a standard tech nique (3). Researchers at General Electric demonstrated that aromatic halides such as PCBs and chlorobenzenes can be dechlorlnated In the same fashion as aliphatic halides by use of an alkali metal hydroxide/alcohol mixture If polyethylene glycol Is used as the alcohol (4). MONS 018867 3-1 Tests conducted by GRC confirmed that PCBs mixed directly with a hydroxide/glycol reagent were rapidly dechlortnated to <Z ppm. EPA regulations require that chemically decontaminated transformer oils contain<2 ppm PCB. However, in GRC tests hydroxide/g1yco1 reagents used to dechlorinete PCBs in transformer oil reacted very slowly (6-7 hours from 500 ppm to <2 ppm). This slow rate of reaction made the hydrox1de/glycol process questionable from a commercial view point. The large difference in reaction rate between PCB added directly to hydroxide/alcohol reagent and PCB dissolved in transformer oil indi cated that the rate controlling step in the process was the transfer of the PCB from the oil phase into the immiscible reagent phase. The NMPC research therefore focused on methods of improving the rate of extraction of aromatic halides into the hydroxide/alcohol phase. Two major areas of investigation were studied. The first area Involved tests of the effects of using varied rates of agitation on reaction rates. The second major area studied the effects of various co solvents on the reaction rate. Co-solvents tested Included sulf oxides, amines, ketones, and various mixtures of alcohols. RESULTS OF AGITATION TESTING Initial laboratory testing of the agitation effect used l,2,A trichlorobenzene (TCB) in place of PCB. This simplified the analysis of the oil. Mixtures of TCB in the transformer oil were allowed to react at 100C with agitation supplied by a paddle stirrer turning at either 400 or 2500 rpn. Additional tests of agitation effects were conducted using a 60 gallon pilot plant equipped with a 2 hp high shear mixer with a variable speed 0-7000 rpm motor. Use of this equipment allowed higher agitation rates than were practical In laboratory glassware. The results of both the laboratory and pilot plant (PP) tests are shown in Graph 1. HONS 018868 3-2 Laboratory and pilot plant results are graphed using reaction rate, calculated as (10,000/time in minutes to reach 2 ppm), and agitation calculated as (rpm/1000)3. While increased agitation produced in creased reaction rates, the magnitude of the agitation effect was small. A 90 fold increase in agitation was required to yield a 3 fold Increase in reaction rate. These data indicate that changes in agit ation are not sufficient to produce the desired improvement in react ion rate. RESULTS OF CO-SOLVENT/CATALYST TESTING In an effort to improve the rate of extraction of contaminant from the oil phase into the reagent phase, a variety of co-solvents were tested, including sulfoxides, amines, alcohols and, ketones. The most promising results were obtained with sulfoxides such as dimethyl sulf oxide or sulfolane and amines such as ethylene diamine. The toxicity and potential carcinogenicity of the amine reaction products led to the selection of the sulfoxide series for further development. The addition of sulfoxide to the hydroxide/alcohol mixture in labor atory testing caused a substantial increase in the overall rate of reaction, as shown in Graph II for the reaction of a mixture of po tassium hydroxide (KOH) and polyethylene glycol 400 (PEG) with PCB 1254 In transformer oil at 100C. GRAPH II - REACTION OF PCS 1254 M TRANSFORMER Ot THE .MW The reagent with DMSO reached <2 ppm PCB after 30 minutes, vs about 400 minutes for the reagent without DM$0. Much the same result was obtained using sulfolane, a chemically similar and somewhat more ex pensive sulfoxide commonly used to extract aromatic compounds from crude oil in refining operations. These data formed the basis for the patent (1). After the laboratory work on co-solvents was completed, additional tests were conducted in a 60 gallon batch capacity pilot plant. These tests confirmed the results of the laboratory experiments, with re sults in the pilot plant being slightly better than those from labor atory runs, probably due to better agitation. MOWS 018869 3-3 SCALEUP The successful results of the pilot plant co-solvent tests led to the construction of a full size 2200 gallon/batch prototype unit. Proto type construction was completed in August 1985. with Initial field trials scheduled for September. Field trials with PCB contaminated oil will commence with receipt of EPA and NYDEC permits. REFERENCES 1. Peterson, "Method for Reducing Content of Halogenated Aromatics In Hydrocarbon Solutions", U.S. Patent 4,532,028 2. Parker and Stelchen, "Process for the Removal of Low Level (ppm) Halogenated Contaminants-, U.S. Patent 4,284,516 3. Morrison and Boyd, "Organic Chemistry", Allyn and 8acon Inc. 1966 plS7 4. Brunelle, "Method for Removing Polyhalogneated Hydrocarbons from Nonpolar Organic Solvent Solutions", U.S. Patent 4,351,718 HONS 018870 3-4 AN ELECTROCHEMICAL PROCESS FOR DECONTAMINATING PC9-CONTAINING TRANSFORMER COOLANTS . Drs. Michael J. Massey and Fraser M. Walsh* Environmental Reseacch t Technology, Inc. (ERT) and Tracer Technologies, Inc. (Tracer) ate developing an electrochemical technique for the controlled dehalogenation of a wide range of halogenated organics, including PCB's.** Feasibility studies, design, and prototype field test programs are being conducted to integrate this technique into processes tailored to address the full range of PCB problems from fluids contamination to equipment and soils contamination. The present paper focuses on application of the technique to the in-situ decontamination of PCB-containing mineral oils and mineral oil transformers. CHARACTERISTICS OF ELECTROCHEMISTRY ERT/Tracer's electrochemical cell consists of pairs of working electrodes operating at a controlled potential in an electrochemical solution. A range of inexpensive non-noble metal materials serve as suitable electrodes, cell operating voltages range from about S to about 15 volts depending upon the overall conductivity of the electrochemical solution. The electrochemical solution consists of the pcB-contaminated fluid, a chemical medium for the proper conductance of current, and a proprietary reagent. Although a variety of sources are feasible, the most convenient *Dr. Massey is General Manager of Engineering Product Develop ment St Environmental Research a Technology, Inc., 696 Virginia Road, concord, Massachusetts 01762. Dr. Walsh is President of Tracer Technologies, Inc., 225 Needham street, Newton, Massachusetts 02164 "Patent pending. 3-5 HONS 018871 medium is usually a combination of the proprietary reagent and accumulated electrochemical reaction products. The proprietary reagent is an inexpensive, readily available organic chemical. Products of electrochemical dehalogenation of PCB's are substituted biphenyls and chloride salts. Treatment of the chlorinated benzenes typically present as solvents in a PCB system yields substituted benzenes and chloride salts. Chloride salts can be washed from the electrochemical solution and concentrated to a small volume brine for disposal. Electrochemical reactions involved are rapid, highly specific to halogenated organics, and proceed at least to detection limits of PCB's in organics, viz., about 2 ppm. Reaction systems function well over a tested range of temperatures from room temperature to 95C. APPLICATION TO MINERAL OIL DECONTAMINATION Application of CRT/Tracer electrochemistry to mineral oil decontamination involves simple equipment and avoids the need for extraction equipment to remove PCB's from the mineral oil (see Figure 1). PCB~contaminated mineral oil is mixed with conducting medium (about 1:3 ratio) and fed to two electrochemical cell circuits connected in series. Because mineral oil and conducting medium are largely immiscible, the combination is recirculated between the electrochemical cell and a pump which continuously remixes the two fluids. The first reaction cell removes the bulk of the PCB contamination: the second completes the reaction to detection limits of 2 ppm. The bulk of the conducting medium is then recovered and recycled by simple phase separation. The remainder is recovered with chloride salt reaction products by washing. Buildup of reaction products is regulated by a process blowdown stream. ERT/Tracer system* for mineral oil treatment are low cost, extremely compact, can be sized to treat either small or large quantities of oil and can be operated unattended. The total systam required to treat 500,000 gallons per year of oil containing 250 ppm of PCB would: fit in a 10 ft. by 15 ft. apace 3-6 HONS 01d8?2 with 10 ft. of clearance, cost less than $200,000 in capital, and produce 1,000 to 10,000 gallons pec year of concentrated chloride blowdown.- Smaller systems can be made fully portable, with packaging that will pass through conventional doorways. Total treatment costs to a client are expected to be about $1 pec gallon. ILLUSTRATIONS OP MINERAL OIL TREATMENT SYSTEM PERFORMANCE Laboratory-scale data on the performance of the ERT/Tracer system are presented in figure 2. Pigure 2A indicates that the three chlorinated organic contaminants in mineral oil are all dechlorinated over time. Pigure 2B shows that, as PCB dechlorination proceeds, measured accumulations of chloride salt product represent essentially 100% of the chlorine removed from PCB and chlorinated benzenes. Pigure 2C illustrates the favorable kinetics Involved in the electrochemical reaction, and indicates a lack sensitivity to the presence of either mineral oil or reaction products. COMMERCIALIZATION PROGRAM AND SCHEDULE ERT is seeking to complete the commercialization of its mineral oil treatment technology by January 1937. a key contribution to the accomplishment of this objective is a costsharing contract now in progress between ERT and the U.S. Navy for field demonstration of the technology, as a part of this contract, ERT is presently constructing a 10 gallon per hour prototype mineral oil treatment unit. During the fourth quarter, this unit will be installed at Northeast Utilities in Hartford, Connecticut. Shakedown testing will occur there during the first quarter of 1986. The unit will then be modified as needed and moved to the Naval station in San Diego and operated during the second quarter of 1986. Based upon the results obtained, an EPA-approved commercial demonstration of the system is planned for the third quarter of 1986. Arrangements for the manufacture of process systems will be made during the third quarter of 1986, with target date for the delivery of commercial equipment of first quarter 1987. HONS 018873 3-7 Reactor Loop 1 Nmw Leeel Figure 1. Schematic Flowsheet of ERT/Tracer Process for the Electrochemical Decontamination of pCB-contanlnated Mineral Oil HONS 018874 3-8 DCCMlOfttNAnON AtACTlONS WFICTlVI OH MX CHlOMWAraO COMAOUNOI CHiomoc iaunci OIMONSTNATtA COMAHTiMISS KMtnet atthactivi Aon TM MCMWM O# MMTUU DMitTMINT UWT Fljur* 2. Illuaetatlona of tha Facforaanca of 8RT/Tcac*c Pcoctii SiM??Cnf?Ch**1C*1 D*eont*i'*tion of FCB-Contalning 3-9 0*iS 018875 CHEMICAL DESTRUCTION OF POLYCHLORINATED BIPHENYL N, S. Chu and S. C. Vick INTRODUCTION Polychlorinated biphenyls (PCBs) are widespread environmental pollutants. The molecules are characterized by their extremely high chemical stability* low water solubility, low vapor pressure and nonflammability. These properties render them Ideal heat transfer, hydraulic and dielectric fluids. However, the same factors also account for widespread contamination of our environment. Because of the toxicity associated with PCBs and PCB derived products. Congress In 1976 banned the further manufacture and use of PCBs In the United States. However, an estimated 750 million pounds still are In service, awaiting a cost effective, safe means of disposal. PRIOR PCB DESTRUCTION TECHNIQUES Although high temperature Incineration offers an effective way to dispose of PCBs, of the numerous generally approved waste Incinerators In the US, only three have been approved by the EPA for the destruction of PCBs. Furthermore, because an Inadequately designed and/or Improperly operated Incineration process can lead to Incomplete destruction and formation of highly toxic compounds such as dioxins and dlbenzofurans. Incineration continues to Incur some public opposition. Alternatively, PCBs can be destroyed or detoxified by chemical means. The chemlcal destruction of PCBs contained In contaminated transformer oil has the advantage that It allows the recovery of the valuable transformer fluid, while Incineration Is simply a disposal strategy which does not allow for recovering valuable components. Several approaches have been studied to destroy PCBs che mically* For Instance, Laplere and co-workers studied the catalytic dehydrochlorlnatlon of PCBs using either 61% nickel on Kleselguhr or 10% palladium on charcoal (equation 1) (Ih They reported that approximately 90% of the chlorine may be removed from PCBs in five hours at i00-200*C. *1985 UNION CARBIDE CORPORATION AH rights reserved 3-10 HONS 018876 ArCln xHj Nl/Pd ArHxd,,.x *HC1 (1) However, the reaction requires the handling of relatively high hydrogen pressure (30-50 atm), and the HC1 liberated has to be removed with base to prevent cata lyst deactivation and corrosion problems. Sodium (2) or organosodium such as Na-naphthal ide (_3) and Na-PEG M) have been used to dehalogenate PCBs at low con centrations. But because sodium and organosodium can react violently with water with Increased potential for fire, and polytethylene glycol ether) containing sodium alkoxyglycolate (ROCH^CHjONa) is hazardous to handle, these processes are not suitable for the destruction of PCBs in high concentrations. Other PCB destruction approaches such ts by ultrasonic energy (). electrocatalytlc dechlorination (6), and biodegradation (7) are all still undergoing research and development. NICKEL CATALYZED REDUCTION Of PCBs Ne now wish to report a chemical method which allows the destruction of PCBs in both dilute form such as PCB contaminated transformer fluids and In concentrated form such as Askarel wastes. This chemical method can be carried out In conven tional equipment and is, therefore, less capital intensive. In addition, this would provide a mobile service eliminating the potential transportation risks associated with incineration. The process was developed based on a nickel cata lyzed zinc reduction of aromatic halides reported by Colon (equation 2) (8). Nl-cat 2 ArCl Zn ------------------------- 2 ArH ZnCl2 (2) Destruction of Pure PCB. Using pure Aroclor* 1260 as a model, we have success fully demonstrated that after reduction, at least 99.5* of the Aroclor* 1260 originally added was destroyed. It was further estimated that of the Aroclor* 1260 destroyed, 95* was converted to biphenyl. The remainder was converted pre dominately to chloro- and dlchloro- biphenyls. These chloro- and dtchloroblphenyls and the minor amounts of remaining PCBs can be recovered together with catalyst components and can be recycled for the next reaction, thus providing for PCB destruction efficiencies approaching 1001. Because solvent and catalyst usad for the reaction are recyclable, biphenyl and a concentrated aqueous metal halide solution are the only waste products of the process. Destruction of PCB In Dilute form. Similar results were obtained when mixtures containing Aroclor* 1242, trichlorobenzenes and tetrachlorobenzenes were used 3-11 HONS 018877 (Aroclor* nlatures with chlorobenzene diluents were commonly used In transfor mers) as well es when Union Carbide Silicone Fluid* 1-305 contaminated with PCB (10,000 ppm) ms used. Although In the litter case the reaction miiture con* talned two liquid phases, the destruction of PCBs ms Just as effective, and the silicone oil recovered after the reaction ms free from PCBs (l.e. less than 1 ppai). Gel permeation chromatographic analysis of the recovered silicone revealed no change In molecular Height distribution, shooing that the recovered, PCB free silicone fluid oould be reusable In transformers. OPTIMUM CONDITIONS FOR PCB DESTRUCTION The destruction of PCBs uorks best uhen a SO/SO mixture (by Height) of dfmethylformamlde (D) and isopropanol Is used. The presence of a protlc solvent Is essential for the reduction of PCBs. In the absence of a protlc solvent, coupling of the aromatic halides oill become a major pathvay (equation 3) and an Insoluble polymer Hill form due to coupling of the polychlorinated biphenyls and benzenes. 2 ArCl Zn-------------------- . Ar-Ar ZnCl2 (3) Formation of polymers should be avoided because it renders the recovery of unreacted tine more difficult and because the polymers still usually contain unreacted chloro-groups, the disposal of which might also be a problem. Although water can also be used as a protlc solvent as Indicated by previous Union Carbide work, alcohol is a much better choice for the current objective. The low mutual solubility of PCBs and water prevents water from being used effectively. On the other hand, the presence of a polar aprotic solvent Is important In order to obtain reasonable reaction rates. Polar aprotic solvents such as DMF, dimethylacetamlde (OMAC) and N-methyl-2-pyrolldinone (NMP) all work well as the aprotic solent for this Nl-catalyzed reduction. Solvents such as acetonitrile and tetrahydrofuran do not give as good results, but they may be used together with DMF. Both the ratio of reduction to coupling reaction and the rate of these reactions depend on the ratio of protlc to aprotic solvent used. A mixture of 50/50 per cent DMF/lsopropanol was found to promote the reduction of PCBs and still give reasonable reaction rates, so that the destruction of PCBs can be completed within a few hours at 70-80`C. 3-12 HONS 018876 *CHANI$TIC CONSIDERATIONS Based on 51s chroMtogrephtc (gc) analysis of the reaction, the highly substituted chloroblphenyls appear to be more reactive toward the Nl-catalyzed reduction. Significant amounts of chloro- and dlchloroblphenyts acre found together with biphenyl as long as Aroclor* was present In the reaction mixture. Upon depletion of the high PCB congeners, the mono- and dlchloroblphenyts themselves are consumed. The fact that the same dlchloroblphenyl Isomer Is always formed no matter which of the three Aroclors* (1242. 1254 or 1260) were used, and that the gc retention time of this dlchloroblphenyl Is different from the three dl chloroblphenyl Isomers generally present in Aroclor* 1242 suggests that there might be a substitution effect. The two chloro- groups of this dlchloroblphenyl are located In such positions that they are less reactive toward the reduction reac tions and therefore are reduced at a much slower rate. The Ni turnover rate for the reduction of biphenyls with 3 or more chloro groups Is estimated to be approximately 60 while for chloroblphenyl and the mentioned dlchloroblphenyl It Is about 37. The positions of the two chlorines on the biphenyl skeleton for this dlchloroblphenyl are unknown at the present time. The mechanism of the Nl-catalyzed reduction Is not yet fully understood. However, based on Colon's work and other related literature data, a working hypothesis for the reaction Involves:1 1. a reduction of Ni(II) to a lower valent state by line 2. oxidative addition of aryl halide to the lower valent nickel and 3. reaction of the aryl nickel species with alcohol to form the dehalogenated aromatic compound, regenerating a Ni(II) species. Transition metals such as palladium and ruthenium are also known to catalyze the reductive dehalogenatlon of aromatic halides using hydrazine (g), amines (10), formates (11) and alcohols (12) as hydrogen sources. But our current process Is more effective end repulres no expensive, precious metels as catalyst. CONCLUSIONS This technology represents a new approach for PCS destruction vta the nickel catalyzed zinc reduction of PCS to biphenyl. By this process, PCBs can be destroyed with efficiencies approaching 100S. The process has the advantage that It destroys PCBs In dilute solutions In transformer fluid but leaves the transformer fluid intact. The recovered PCB free transformer fluid Is reusable In transformers, thus limiting the destruction only to the toxic PCBs. This Is 3-13 HQNS 018879 In contrast to incineration, which by necessity, must destroy both the PCBs end the transformer fluid. Furtherenre, the ease with which the reaction can be carried out, the mild nature of the Nt-catalyst toward water and the recyclabi lity of the recovered reactants and solvents make the technology suitable for the destruction of PCBs in concentrated for*. The latter development is impor tant as it represents the first viable technology for the safe and economical chemical destruction of concentrated PCBs. Alternate technologies are useful only for the destruction of dilute solutions. Thus, one process may be used to eliminate the hazard from both concentrated and dilute PCB solutions. Finally, this method of PCB destruction utilizes an inexpensive nickel catalyst and does not require the use of expensive, precious metals as catalysts. REFERENCES (1) D.G. Acherman, L.l. Scinto, P.S. Bakshl, R.G. Oelumyea, R.J. Johnson, G. Richard, A.M. Takata and E.M. Sworzyn, 'Destruction and Disposal of PCBs by Thermal and Ron-Thermal Methods", Ch. 3, p. 300, Moyes Data Corporation, Park Ridge, NJ (1983). (2) U.S. patents 4,465,590 and 4,340,471. (3) U.S. patents 4,284,516 and 4,326,090. (4) U.S. patents 4,447,368; 4,353,793; 4,430,208 and 4,417,977. (5) U.S. patent 4,477,357. (6) (a) T.F. Connors and J.F. Rusllng, J. Electrochem, Soc., 130, 1120 (1953); Analytical Chem. Sec., ACS Fall Meeting Abstract, 1984. (b) European patent 27,754. (7) Reports in Research and Development, p. 41, July 1985 and Chemical Engineering, Feb. 4, 1985. (8) U.S. patent 4,263,466. (9) W.L. Mosby, Chemistry and Industry, 1349 (1959). (10) H. Imat, T. Nishlguchi, M. Tanaka and K. Fukuzumi, J. Org. Chem., 42, 2309 (1977). ~ (11) N.A. Corteze and R.F. Heck, J. Org. Chem., 42, 3491 (1977). (12) T. Okamoto and S. Oka, Bull. Chem. Soc. Jpn., 54. 1265 (1981). 3-14 AG*(S 018880 NUtT 4: MMLYTICM. HKL - PCs HONS 018881 EVALUATION Of A POETASLI TEST KIT POE TESTING PCS CONTAMINATED SOILS AMD OILS IN TEE PISLO Gary A. Gauger, Gary C. Saith and Judy M. Sullivan ' McQraw-Sdleon Company INTMDOCTXON Tha McGrsw-Edlson PCS field taat kit was initially davalopad by tha Cantae Corp. in Easton, VA. to aeraan oil saeplee for PCSa in ordar to sllelnate tha naad to taat avary saeple cacalvad by gas chcoawtoqcaphy. Tha kit waa avaloatad initially by Cantae and indapandantly by tha U. S. Aray Envlroruaantal Hygiene Agsncy (AEHA)* to dstsralne tha aefactivanaaa of tha kit. Prior to acquiring tha PCS taat kit technology, MeGraw-Edison aada an avaluation of tha kit using fiald aaaplas of PCS contaalnatad oil. saaad on this avaluation and tha previous tudlea, it was datarainad that tha kit could ba a fall aafa aoraaning tool provided that tha intarpratatlon ba baaad on a aora conearvativa Aroelor 1242 calibration curva. McGraw-Edison introduced this curve in lata 1983. Shortly after tha kit was introduced tha u. 8. Air force, which had bean actively using tha kit to screen oil saaples in tha field, expressed an interest in being able to screen soil aaaplas at various reaote spill sites in Alaska. Cantae, in conjunction with tha 0.8. Air force, proceeded to develop and evaluate edaptatlona to tha kit which allowed soil screening. In tha procese of thia avaluation, over 27 different soil types ware teatad, apikad at SO ppa, 2SQ ppa and 1000 ppa, with Aroelor 1260 to deteraine tha effectiveneea of tha fiald extraction procedure by correlation of tha kit results with gss chroastogrsphy. Tha results of this study indlcstsd s worst csss extraction efficiency of 40%. for aoraaning purposes, therefore, whan taking into account th worst caaa extraction efficiency and solvent density, s aultiplicstion fsctor of four was found necssssry to give a safe aoraaning value. The initial study also dstsrelned that the test procedur# was not subjsct to intsrfsrancs fcoat inorganic *ABMA Pestlcids Monitoring Special Study Mo. 17-44*0409-83, *Laboratory and field Evaluation of s Coaearcially Available Plaid Test Kit", Jan.-July 1983. HONS 018682 4-1 chloride In the environment. The results of this study concluded tbet ths dsvslopsd procedure provided s rslisbls screening tool for rapidly assassin? ths sxtsnt and Isvsl of PCB contamination at suspsetsd spill sites. Because of the oomplsx nature of soils and the potential for contamination by Aroclors other than 1260, namely Aroclor 1242, McGcaw-Bdlson has continued this evaluation to further evaluate the performance characteristics of the kit. This study assesses the effects of soil coapoeitlon and aolsture levels on the kit performance. REVIEW OP TECHNOLOGY The aethod involves eheaioal dechlorination of the PCS molecule with an orgeno sodiua reagent* The sodium chloride which results is extracted into an aqueous medium and detected with a chloride ion specific electrode. The concentration of chloride le then related aatheaetically to the concentration of PCS either as Aroclor 1242 or ae Aroclor 1260. When testing aolla. the PCS is initially extracted from the soil aetxix and the solvent extract la then evaluated. SCOPE OP WOM This evaluation involves side-by-side PCB analysis using standard laboratory methods and the McGrav-Edison PCB Pield Test Kit. A summary is presented depicting both the oil and soil tsst capabilities of the kit. Oil ssaples were tested which had been submitted to our lab for analysis. The samples represented a large variation in PCB concentration* Arocloc blend and oil condition. The soil evaluation was accomplished In two stages. Thm fleet stage Involved the evaluation of the soil tsst metbod under varying soil conditions. A multldimanslonal experiment was designed and completed to evaluate the effects of soil type* moisture and PCB concentration on ths ability of the PCB field Test kit to screen for PCB content. The second stage involved the analysis of actual field temples. OIL TSSTING 70 oil samples which wers sent to our laboratory for PCB analysis by more than 50 different cuetoamrs wers analysed by both gee chromatography and the teet kit MOMS 018S83 4-2 method. The total PCS concentration by GC was compared to tha value obtained with tha taat kit. RESULTS POR OIL SCREENING Overall tha daU lndleataa interpretation aa Aroclor 12(0 will be more accurate in 9(1 of samples taatad in a typical sample population. In tha remaining 4% of tha aaaplaa interpreted aa 12(0, the anaweca will be lower than actual. Interpretation aa Aroclor 1242 on tha other hand will eaaentially five no falae negatives but will give values that are higher than actual if Aroclor 12(0 la present. A falae positive or negative aeana that the kit classified the staple into a higher or lower range than did the G.C. SOIL SELECTION AND PREPARATION Soils testing la ouch eore complex than oil evaluations, due to the diverse soil types and conditions encountered in field situations. Soil texture and particle else, ranging from the larger site of sand particles to the oinute clay particles# all with varying organic contanta# provide an inconsistent unpredictable oatrix. Texture aa wall as porosity is an important soli chsrsctsrlstlc becauae it will, in part, determine water intake and tha accessibility of tha extraction solvent to adsorbed PCSa. Surface erea and the activity of adeorbtlve aitaa alao play an Important part in both water and PCS access and removal. Sandy type soils have higher poroeity and have relatively low surface ares and adsorptive affinity coopered to clays which are noted for high surface area and wida range of active adeorbtlve sites. Organic soils have very high water holding capacity and strongly adsorb PCS molecules in the lipid portion of cellular residues. Selection of soils from each of the categories sand, clay and organic for the evaluation was, except for sand# a difficult task because of the almost infinite variety of pocslblllties available and tbs lack of defined standards. Use of a refined industrial type clay wee not practical, for axanple, because of the extremely high abeorbtivlty of these materials. Therefore, high clay toll end organic past wars selected and characterised. 4-3 HQNS 016684 Theoretically# tha combinations of soil taxtura# organic content and moisture content contribute to the strength of adsorption of chemicals to soil and accordingly to the extraction efficiency of KBs from soil. Bach soil wee air dried and sieved then contaminated to the desired level using PCI (1242) standards. Oil was added to a level of 5% w/w oil to soil. These oils were used in all subsequent testing. The *wet" soils were spiked to a level considered to be the field moisture capacity for each particular soil type Bach soil type was spiked with KB to three different contamination levels (IS# SO# 500 ppm 1242). Bach of these samples were tested when air dried and also at maximum field moisture capacity. Somhlet extraction and subsequent gas chromatographic testing per ASTM D3J04 (proposed) was used as the standard analysis method. Throughout this evaluation D3104 was considered to be 100% efficient In extracting PCBs from soil. The KB test kit extraction was compared to it in order to determine extraction efficiency. By evaluating the extraction efficiency of the test kit method using extremes of soil type and moisture content# the minimum extraction efficiency could be determined. Once determined# it could then be compered to the factor of four used in the kit method. The characterisation of the sand# clay and organic soils used in the evaluation are shown in Table X. h blend which contains equal parts of the three basic types was also evaluated. BBSOITS or TBB SPIKSD SOIL BXFBBIMSMTS h summary of the results for model soils spiked with Aroclor 1242 under air dry end water saturated conditions is shown in Figures l and 2, rsspectlvely. Xt was not possible to modify the test soils with the same high moisture levels because of the wide variance in their moisture holding ability. Moisture content of saturated sand is little more than S% where as the clay soil was around 20% moisture and the organic soil saturated significantly above 20%. HONS 018885 4-4 Soli Typa Sand Clay Oryanlc land ' Oceanic Mattar (%) .02 2.S4 20.72 6.06 Table I Plaid Moistura Capacity () Air Or lad Molatura Laval <%> .07 2.2 S4 20 Partlcla Slsa valuation Sand Silt aay (1) (%) (%) SO 13 7 30 27 43 60 27 13 53 27 20 Figure 1. Air Dried Soil 4-5 HONS 0X8886 The results on the sir dry soils indicate that all soil types show 401 or greater recovery with the test kit. This impliea that using the standard multiplication factor of four with the kit all screening values would be at the level of the 'expected C.C. reeult or greater. The results with the spiked soils indlcete that the kit will not consistently detect PCS levels below about 20 ppm in some soil compositions, however, the limited experience with air dried field samples indicates a slightly better detection limit than observed with the artificially contaminated samples. Soils evaluated in a water saturated condition do show a distinct reduction in extraction efficiency. The reduction for sandy soils is only slight but is more pronounced for both clay and organic type soils. Clearly it is more desirable to test air dried or moderately wet soils when screening for PCh'e with the test kit in order to obtain optimum results. To more effectively deal with situations of extremely high moisture content, physical removal of the water by desiccant or mechanical techniques will enhance the capabilities of tha kit in handling wattr saturated samples. Sines the final stap in using tha soil test is sending the last sample back to the lab for analysis, no strious problem is anticipated even under the worst case conditions. PISLO SAMPUS Soil samples which wars sent to our laboratory for PCS analysis were analysed by both gae chromatography and fcha test kit method. These samples reprasentad a large variation in soil type, moisture content, Aroelor blend end concentration. Tha rslatlve extraction efficiency of the various samples follows the trend established with the synthetic (laboratory prepared) soils. The samples which contained minimal molstura showed excellent extractabillty. The *wet* samples, however, showed decreased extractabillty, especially thoae samples of high clay and high organic content. MOMS 016807 4-6 CLOR-N-OILTM TEST KIT AS A PCB SCREENIMC TOOL DAVID W. HILLS and KXRT RHOADS UTAH POWER 4 LIGHT COMPANY INTRODUCTION Utah Power 4 Light (UP4L) haa ban facad vleh tha nacaaalty of tasting larga numbers of transformers and othar equipment to determine tha PCB contant of tha dlalactrlc fluid. EPA promulgated narking and dlapoaal regulations of PCBa in 1978 and in 1979 consolidated chase Into the Use Prohibition Regulations. These regulations established tha transformer categories of non-PCB (leas than 50 ppm); PCB-contaalnated (50*500 ppm); and PCB (greater than 500 ppm), These regulations have been further refined, mostly aa a result of court actions, to Include: Periodic Inspection of PCB transformers, Identification of PCB transformers In food and feed locations. Removal of such by October 1, 1985, Identification of PCB transformers in commercial buildings. Notification of building ovnera and flra dapartmanta by December l, 1985, and finally. Removal of some by October 1, 1990. In addition, UP4L instituted a program to remove end dispose of ite PCB transformers by December 31, 1968, e program which requires testing of ell Company transformers. In the scramble to meet ell of these requirement*, UP4L hea inves tigated every method of testing or screening of PCBa that research has brought to light. So far tha Clor-N-OilTM cast kits have been found to be the most affective screening system for UP4L applications given the time limitations imposed by the regulations. DISCUSSION The Clor-N-Oil^* teat kite were developed by General Electric under contract from the Blectrle Power Reeeerch Institute (EPRI), DEXSIL Cbemleal Corporation hee exclusive license from EPRI to mass-produce the kits for Industry-wide use. This kit sveuletsd by UF4L is dssignsd to give sn indication of whether e mineral oil contains more then or lees then 50 ppm PCBa. The kit does not measure PCBa but rather measures chlorine content of the oil. It is designed to reed positive if the chlorine content of the oil le greeter then 21 ppm. 4-7 HONS 018888 The cut-off point of 21 ppa it based on tht chlorino content of the ltttt halogenated Aroclor (1242). In oehtr words* SO ppa of Aroclor 1242 will contain at laaat 21 ppa chlorine. The kit la hand-held and portable. Each kit haa ita own eat of lnatructlona end can be uaed in the field. The teat only takee a few minutes, and the reault la an eaay-co-read colorimetric determination of the pretence of chlorine. The kit will only work on FCB-eontemlnated alneral oila end Aekarel flulde; it will not work on aolla, waters, or other notarial. One kit will teat one oil eaaple and eoeta from $3 to $6, depending on quantity purebated at ooe clae. Laboratory Gaa Chromatograph (GC) analyaia of one aaaple of alneral oil currently coata $20 to $40. Teatlng prograaa can generally be completed much aooner if the teat kit la utilised* aince it la not neceaaary to tend all aaaplea to the laboratory for CC analyaia. UP4L uaea the teat kit to screen its distribution transformers for PCI content. In the past* UP4L haa not purchased or utilised PCB-type transformers in its distribution plane. It haa, however* classified these* by rule* as PCB-contaalnated transformers. From our experience* between 80Z and 90S of all distribution-type transformers are screened out (classified as non-PCB) by the test kit* Currene computer records show 198*464 distribution transformers in lx reglona throughout the UP6L system. Some of the regions cover aetropolltsn areas such as Salt Lake City* and others cover remote areas in Wyoming. In most of the regions, there is considerable irrigated agriculture* with substantial distances between each transformer. Line crews have been cowlaaloned to collect the samples and deliver them to a central location for testing, or run the test themselves in the field* They taka the sample by inserting a piece of polyethylene tubing into the pressure relief valve of the transformer. The oil sample is then collected in new 2-ounce glass vials. They also label the vials and complete the paperwork which will bs used to enter the teat information into the company-wide computer. HONS 0188*9 If the inplti tt positive (SO ppm or greater) with the Clor-N-OilTM kit, they or* sent to a Utah State-certified laboratory to b* taatad by GC methods. If a sanpla eaata negative, It la aant to a control facility vhara It la permanently atorad In caaa CC analyala on eha aaapla la naaded at some point in tho futura, such aa In tha caaa of an oil spill. If a aaapla taata positive with tha taat kit (ovar 50 ppa PCB) and negative (loaa than SO ppa KB) by GC aathoda. It la taraad a "false positive.M If It la negative by the kit and positive by GC, It la considered a "false negative". Falaa positives are axpactad but tha rata of falaa negatives should be very low If the kit la to be considered an effective screening tool. EPA Region Vill has bean contacted regarding the use of the teat kit as a screening tool. Region VIII said they had no problea with using the kit, but when asked to put this In writing, hesitated. UP4L then Inquired further of EPA in Washington D.C. They responded: ".....the Agency presently finds gas chromatography to be the alnlaua acceptable method for determining the concentration and nature of KBs In most samples. There la no prohibition against the use of test kits utilising total chlorine analysis as rough field screening devices to determine If further testing la required. However, any analytical errora resulting from such testing would not Insulate a company against prosecution should the Agency obtain evidence of a violation of the KB rule." Since UP4L Intended to use the test kit extensively la a testing program to be completed in 1986, and since EPA took the position that test kit results could not be used to insulate the Company from prosecution should an analytical error be made with the test kit, UP4L decided to study ths probability that such an error might occur. The goals and objectives of the study sto aa follows: U. S. EPA correspondence to Utah Power 4 Light Co. dated February 16, 1985, signed by John $. Seltx, Chief Executive Officer, Office of Compliance Monitoring, Pesticides and Toxic Substances Branch. HONS 018890 4.9 COALS AW) PROGRAM OBJECTIVES 1. Determine what percent of a largo random aamplt of distribution transformers could be expected-fto be "screened out," l.a., test negative. wich the Clor-N-Oil PCS Case kit. 2. Determine whether the portion of transformers screened out by the east kit varies with the transformer manufacturer. 3. Determine what portion of those samples testing positive with the test kit will test positive by GC methods. 4. Of thosa samples testing posielve, determine whae portion would be expacted to cast between 30 and 500 ppm; over 300 ppm PCB. 5. Of those samples testing negative with the kit, determine how many would be expected to teat positive by CC methods; l.e., the portion that would be false negatives, and compara this false-negative rata with that which would ba expected from the Clor-N-Oil^ test kit. 6. Evaluate the probability of e false negative with the kit vs. che probability of a falsa nagatlve by GC methods. METHODOLOGY 1. There art approximately 198,000 transformers on the UP4L system. Soma of thass transformers have been Installed since the PCB regulations became affective In 1979. It la company policy to raly r on tha individual mamufacturtr's non-PCB certification rather chan test these transformers. However, 31,032 trentformers have beam tasted with tha kit or with both the kit and the GC. The samples taken to data have bean taken from transformers selected at random. Tha number of transformers sampled so far represents approximately 352 of all the transformers to be tested. 2. Records on each transformer sampled Indicate the manufacturer as well as other data. This data has bean compiled on the computer and la accessible by various tort programs. 3. All samples taatlng positive are tasted by GC methods at a Utah otato*certlied laboratory. Tha results of tho GC teste ere entered Into tha coa^uter data base along with tha other information mentioned In "2" above. 4-10 HONS 018891 4. The results of Ch GC teats, once entered into the computer data beta, can be sorted into the ?C8-contaminated (30-500 ppm PCB) and PCB (ovar 500 ppm PCB) categories. 5. Ninety-nine aaaplee coating negative with tht kit wart taatad with cha GC to dactrmlne If any vara actually positive. 6. Twenty staples were prepared by an Independent Utah State-certified laboratory to accomplish objective 6. They conteined 30 ppm of Aroclor 1260 plue or alnua 5*. These samples ware than tasted by GC methods ec enocher laboratory end by the test kle. Th# number of test kit negetlvee waa compared with the number of negatives by the GC method. Various computer sort programs wars used to accomplish objectives l through 4 tad e simple tabulation of the teat results satisfied Objectives 5 and 6. RESULTS 1. Of the 51.032 tests run with the Clor-h-011TM kit, 6,523, or 8.91, teetad positive. Therefore, 91.IX of ell samples tested were "screened out" with th teat hit. 2. From the information in Table 1, the teat kit aaama to be able to screen the transformers made by certain manufacturers slightly better then those made by others. Tit Electric end Standard do not seem to screen ea well with the test kit ee some of the other manufacturers, since they have e higher rate of false positives. The date shove Northwest to have e 1002 positive rate; however, only one Northwest transformer wee tested. Alehough ehara wee some variability In the rate of false positives among tha various manufacturars, no slngla manufacturer wee considered to have e false positive rate high enough to significantly reduce the ueefulaeee of the teec kit ee e screening cool. 4-11 HONS 01SB92 TABLE I Total Toatod Kanufacturor Allla Chalvora v/Clor-H-Oil 2,2*4 Bullock l Chance 42 Control Moloney 4,846 Colt 46 Dovter Electric 28 Delta Star 49 Conorol Electric 14,635 Howard Induatry 901 Hill 3 Kuhlaan 2,512 Larkin 16 Lino Material 1,592 McGrow Ediaon 2,213 Moloney 1,185 Horthveet 1 Pacific Electric PenneyIvanla 2 393 Port.r 61 Polo Star 262 EXE 3,961 Soronoon Electric 33 Spokane 3 Square D 2 Standard 233 TAR Electric 31 Vagner 3,512 Weotlnghouee 12,029 No. Toatlng Poo. v/CNO 82 - - 811 l 14 1 1,986 10 - 20 - 32 39 233 1 - 90 2 12 143 2 36 27 119 1,466 Total Toat. Poo. v/CC 9 - - 43 - - - 1,241 4 - - - 2 2 14 1 - 15 l 2 1 - 30 15 38 562 Z Pooltlvo by GC 0.40 . 0.88 _ . 8.48 0.44 - - 0.13 0.09 1.18 100.00 3.82 1.64 0.05 3.03 12.88 48.38 1.08 4.67 TM 3. Of the 4,523 aavplee tooting pooltlvo with the Clor-N-011* kit, 2,537, or 56.IX, tooted negative by CC methodo. 4. Of the 4,523 aavplee tooting pooltlvo, 1,830, or 40.45X, voro botveon 50 and 500 ppa by GC vethoda, and 158, or 3.49X, voro grootor than or equal to 500 ppv by CC nothod. 5. Of 99 oavpleo tooting negative with tho kit, 5 voro actually found to bo pooltlvo vhon tootod by CC vethoda. All voro run again by CC and tho roaulta^coefirved. When tho 5 oavpleo voro rotootod with tho Clor-H*OilT toot kit, thoy all toatod pooltlvo. 6. Tvoaty oaaploo proparod by an lndopondont Utah Stata-certlfled laboratory voro eortlfiod to bo 50 ppv Aroclor 1260 pluo or vlnuo 5X. Thooo oavploa voro tootod by both CC vethodo and with tho toat kit. 4-12 MONS 018893 The reaulca vara at follova: a. Tha CC teat raaulta on cha 20 known samples vara as follova: ' TABLE 2 PCI Cone. IPP) 47 48 49 52 53 54 55 56 57 56 59 61 62 Frequency 2 1 2 2 1 2 2 2 1 2 1 20 Aa can be aaan froa Tabla 2 above, cha GC taat vaa negative on four aaaplea. b. Tha saae aaaplaa vara tested with cha Clor-9-OllTM taat kit. Savantaan tested poeltlva and three taatad negative. Aa can ba aaan froa tha data above, tha GC taat actually did not predict aa vail aa tha taat kit In tana of falaa nagatlvaa. (4 falaa nagatlvaa veraua 3 falaa nagatlvaa.) It aust ba emphasised that cha 50 ppai aaaplaa vara plue or alnua 5* and that 20 la a fairly aaall aaapla also. 4-13 HONS 018894 CONCLUSIONS 1. The teat kit la an economical PCB acraanlng cool ainct ovar 90X of all aaaplaa tested vara "acreaned out". 2. Tha probability of falaa nagaeivea with tha eaat kit aa dttaralnad by the data haraln la noe higher than tha probability of a falaa negative by CC taat method*. Hovaver, tha rata of falaa negative* experienced by UP6L (5X) la higher than that experienced by othar 12 raaaarchara (1.2X, 2.SX). * Sinea all of tha falaa nagatlvaa taatad poaltlva vhan rataatad vith tha Clor-N-011TM kit, tha analytical praclalon of tha kit la probably batter than Indleatad by thla experiment. 3. Thara la lnaufficiant variability In tha rata of falaa poaltlvaa among manufacturer* to conclude that tha Clot-H-OilTM kit vill not acraan tha transformers from a particular manufacturer economically. 4. Tha Clor-H-011TM taat kit la an analytically acceptable method for acraanlng PCBa in dlatrlbution transformer olla. * Riley, Michael T., Detroit Ediaon Co., "Utility PCB Practlcea", praaantad at 1965 T 4 D Exposition May 14, 1965, Chicago, Illlnole (aaa Table 5) found falaa negative rata of l.SX out of 247 taata. 2 Tahlllanl, Vaau H., EPtI "Field Determination of PCB In Tranafonar Oil, Volute 2: Clor-N-011 PCB Screening Kit", EP11 Bl-3766, October 1964, Appendix B, pg* 8-10, found falaa nagatlva rata of 2X out of 1,506 taata. 4-14 MOHS 018695 Field Testing of the S-Cubed Gas Chromatograph, PCBA-102 J. C, Hein Brown and Caldwell 1255 Powell Street Emeryville, California 94608 Background In many field situations, the analysis of polychlori nated biphenyls (PCB) in transformer fluids and in soils must be accomplished under severe time con straints. Often, highly trained analysts are not available. Field instrumentation (PCBA-102) re cently developed for EPRI under RP1263-9 by S-Cubed is intented to circumvent both difficulties in the sense that their instrument is highly portable and does not require an experienced analyst operator. The manufacturers have simplified the sample prepara tion steps by providing prepackaged reagents. The Interpretation of results, which is often the most demanding of the analytical tasks, is performed by pattern recognition software. Furthermore, the amount of time between injections has been significantly reduced, thereby permitting greater sample through put. Objectives The Electric Power Research Institute has elected to support field testing of this instrument. The objectives of the project were to evaluate the S-Cubed PCBA-102 instrument for accuracy and precision, con venience, technical expertise for operation, and the ability to handle PCB'a in a variety of matrices. Study Design The field test program had two aspects, a series of comparisons between laboratory and field measurements of PCB in soil from a contaminated site and an instrument loan program to utilities where they ran oil or soil samples of their own choosing. The site study was in Sacramento, California, utilization of the PCBA-102 allowed on-site 4-15 HONS 018896 definition of the contamination zone at a number of transformer substations* Confirmation analyses were performed by conventional laboratory methods. The instrument loan program allowed the utilities to apply the PCBA-102 to applications of their own choosing. Confirmation analyses by approved EPA methodology were used to evaluate precision and accuracy. Speed and convenience of operation was evaluated by each utility. Conclusions The performance of the PCBA-102 during the utility loan program was subject to both instrument downtime and operator error. In general, adequate precision and accuracy was achieved with experienced gat chromatographers as operators. Downtime, imprecision and inaccuracy increased dramatically whan inexperi enced personnel were asked to perform instrument start-up and operation. The site study is being conducted in September and October of 1985. Results will be available for the EPRI PCB Seminar in Seattle, Washington. 4-16 HONS 01809? COMPARISON OF PCS ANALYTICAL METHODS Lansing V. Wong * Pacific Gas and Elactric Company Tha purpoaa of chit work was to evaluate several PCB analytical systems as altarnatlvas to gas chromatography (GC). Sinca tha promulgation of PCB ragulatlons undar tha Toxic Subatancaa Control Act, thara has baan a naad for a rapid and accucata mathod of datarmining KB concantratlona. Gas chromatography has baan tha aecaptad mathod for KB analysis. It requires an oparator trainad in tha oparation and maintananca of a gas chromatograph, sampla praparation, and intarpratation of KB chromatograms. Bacausa of tha labor involvad, it Is an expensive analysis. Savaral altarnata mathods ara now availabla which ara faster, portabla, and lass axpansiva. Thasa ara tha MeGraw Edison spaciflc ion alactroda mathod, tha CLOR-N-OIL colorimetric mathod. and tha S-Cubed KBA-102 gas chromatograph/computar. MeGraw Edison Chlorida Spaciflc loo Elactroda KB Tast Kit This mathod is basad on tha maaauramant by spaciflc ion alactroda of tha resultant chlorida ion activity whan ehlorlna is chemically removed from tha PCB molecule. Any chlorida from other sources will also be measured as KB. which can result In higher results. Tima required par analysis is about five minutes, not including mater calibration, which takas about tan minutes. Tha detection limit is about 6 ppm as Aroclor 1260. aOj-H-OIL PCB Screening Kit This KB measurement method is tha fastest to perform, requiring about five minutes. It gives a quick determination as to whether an oil is over 50 ppm in KB or not. This analysis Is basad on color changes caused by different 4-17 HOMS 018898 concentration* of PCB. The color range* from a deep purple for low PCB concentration* and gradually lighter to colorleas for high PCB (over SO ppm) concentrations. As with the HcGraw Edison method, other chlorinated compounds can contribute chloride, which can give high results. S-Cubed PCBA-102 Gas Chromatoeraoh The system is basically a gas chromatograph with an electron capture detector coupled with a computer which 1* programmed for interpretation of PCB chromatograms and calculation of concentration. Aa programed, the PCBA-102 can detect PCB down to 10 ppm. Modification of the sample preparation procedure can extend this dectectlon limit to 1 ppm, but this requires some calculations by the operator. The PCBA-102 eliminates the need for the operator to analyze the chromatograms. Addition <?f a recorder to the PCBA-102 Is helpful In that it gives a visual trace of the sample, and would give indication interfarencas not evident in the numerical printout. Time for analysis Is about 12 minutes. Results Some two hundred samples were run by the different methods. Of these, seventy-seven were run by all three, which allowed comparison. Results obtained by conventional gas chromatography were used as a basis for comparison. Results generated from the PCBA-102 were much closer to those obtained by conventional GC than that of the McGraw Edison. They averaged 1.12 times that obtained by regular GC. This is probably due to the feet that the PCBA-102 procedure la basically the same as the conventional GC procedure, the mein difference being the computer interpretation and calculation of the results. For the McGraw Edison, results averaged 1.25 times that obtained by GC. This la In large part probably due to other chlorinated compounds other than PCB (such as trlchlorobensene) In the sestples. 4-18 MONS 018899 No numerical results can be given for tha CLOR-N-OIL rasults, as it tests as only over or under SO ppm. In any case, the CLOR-N-OIL successfully screened any oil over 50 ppn as determined by GC. Gas chromatography remains the accepted method for PCS analysis per EPA regulations and A5TM methods. The PCBA-102 appears to be a logical choice as an anelyticel alternative to GC. Semple preparation and calibration are easier than the other methods. Its weak points are Injection of the sample, which requires a consistent technique for reproducible rasults: snd the use of sulfuric scld, which requlrss cere In handling for safety. The CL0ftN-0IL and McGraw Edison are bettor suited for screening samplec for approximate PCB concentration. 4-19 MOWS 018900 Summary of Results of Comparisons of PCB Methods Table 1 AVERAGE OF RESULTS OF METHODS RATIOED TO CONVENTIONAL GC ANALYSIS Method McCraw Edison S~Cubd PCBA-102 Avereee Ratio and Standard Devletto 1.25 0.43 1.12 + 0.25 Table 2 COMPARISON OF MISCELLANEOUS METHOD PARAMETERS GC Tim per analysis, minutes 30 Tim per calibration, minutes 30 Frequency of calibration - (samples between calibration) 10 Detection limit, ppm NA PCBA-102 12 12 10 10 McCraw Edison 5 10 5 6 CLOR-N* 5 NA NA NA 4-20 HONS 018901 DEVELOPMENT OP THE BPA SUBSTATION SOIL PCB TESTING PROCRAM David C. Plath INTRODUCTION Polychlorinated biphenyls (PCBa), because of thair stability and roslatanct to oxidation* vara uasd for ysara aa dlalactrlc fluids in slsctrloal equipment. Due to thair chemical stability thay hava bean datarainad to ba a parsistent environmental pollutant. As thay ara ralatlvaly nonpolar* thay tand to accumulate In fatty tiaauss and hanea ara paaaad through ths food chain. Tharafora, aa atatad by Toxie Subatancaa Control Act (TSCA), tha Environmental Protactlon Agency has implemented rulaa for tha handling, storage, and disposal of contaminated asterlals. Two Halts (50 and 500 ppa) hava baan sat vhich dlvldas insulating fluids into thrs# catagoriaa, non-PCB contaminated fluids, (lass than 50 ppm) PCB contaminated fluids (bstvsso 50 and 500 ppa). and PCB fluids (ovar 500 ppa). In addition, a racant ruling (July 1965) of tha Washington Pspartaant of Ecology has sat tha lovar Halt of ragulation on vaata insulator fluids at 1 ppa. Sine# thaaa laglalativa limits vara sat, a graat deal of vorfc has goo# into dtvtloplng aathoda for accurataly and raliably dataraining tha concantratlons of PCBa in a variaty of aatricaa. Major problaaa hava had to ba ovarcoaa in tha clsan-up, analysis, and quantitation of PCBa. Thaaa lncluda diffsrsntlatlng PCB congaaara froa eoaluting paaticldaa (2,4-D, POP, ate.), suppraaalon of tha electron capture detector by tha elution of tha oil matrix, and tha quantitation of aixed Aroclor aolutlona. In addition, tha povtr utllitlaa involvad in this analysis had aa obligation to limit tha coat, and thus tha analysis tin# due to tha extraordinary number of samples being handled. MOMS 018902 4-21 INSTRUMENTATION AND INSTRUMENTAL CONCERNS At Bonneville Power Administration we became involved in PCB analysis 3 years ago because private laboratories could neat neither our sampling obligations nor our turn-around-tlnt expectations. Now, 3 years later, the capabilities of many west coast laboratories have improved to the point where we now have additional options. Our program has completed over 9000 samples providing a data base on over 4000 pieces of oil-flllad equipment. Ve feel that the problems we have encountered and solved in the course of developing our approach to PCB analysis might provide help to utilities in a similar poalton. Since ve were starting on this analysis from scratch, we were in the enviable position of being able to choose the instrumentation and methods to beet suit our needs rather than having to adapt existing hardware. Noting the necessity of high resolution to the separation and the quantitation of these complex mixtures, ve chose to develop our method around the capillary gaa chromatograph. Excepting "on column" injections, the two main mathods of sample introduction for ceplllery chromatography ere splltleaa and split Injection. As split injection tends to differentiate betveen the high and lov boiling fractions and would thus tend to skew our results, ve chose splltleaa Injaction which has been identified in the literature ea a more quantitative approach. Ve vers hoping to automate this system, therefore, "on column" injection wee not considered because it has not yet been ahovn to be compatible with autosaaplers. At this point, it should be pointed out that it has been written in several well-respected sources, (Ref. 1 and 2), that the method of injection (a very slow, 5-10 second Injection) it eeeeatlel for a proper splitlees injection. Vhlle we do not dispute thia claim, wa have found that due to changes va have mads in the flow system of the chromatograph, we are able to achieve leaa than 5 percent relative standard dsvlation in raplicata injections of both standards and samples whan using an autosampler end splitlees injection. The changes made involved primarily replacement of tubing connections that were found to develop mall leaks, end the use of ultrapure carrier end makeup gases with oxygen scrubbers. As e consequence, our normal BCD background current hae dropped from approximately 600 p. saps to 100 p. eape indicating a clean system with very little air leakage. One phenomena that wm noted early on In this method 4-22 HONS 010903 development, was that the response factors for chlorinated hydrocarbons In an BCD were higher when ir leeks wars evident. khtle this tended to lover our PCB detection Halt it was impossible to reproduce end increase the error of the analysis considerably. Recently, work was presented in the literature that Indicates that doping the aake-up gas with low levels of oxygen will increese the response of an BCD. Sines this would give a reproducible increase, it could he valuable for this analysis, especially for low level work, now thet the system leakage has been minimised. QUALITY ASSURANCE In order to assure the absolute concentration of PCBe in a saaple oil, it la necessary to have a regular quality assurance progrea. This includes, in our case, both standard oil saaplea as well aa documented standards. Early on in this method development we noted variability In the relative concentrations of individual PCB congeners for standards from different sources. Since this variability would affect the use of single peak or peak group calculations necaaaary for nixed Aroolor samples we decided that it would be prudent to base our analysis on a well-defined standard. Ve requested samples of pure Aroclors from the Food and Drug Administration (FDA) that had been well characterised In the literature by Leon Sawyer of the FDA (Ref. 3 end 4). In addition, we received PCB standards end diluent oil froa the National Bureau of Standards in order to prepare standard oil aaaplea. To enture repeatability with the autoaaapler without sacrificing sample output, we designed our analysis schedule such that after every six eaaplee run, two standards, nominally 0.1 and 0.5 ug/ml of a tingle Aroclor were run followed by a blank rim of solvent. The Aroolora were then alternated so that in a series of 100 runs there were approximately three sets of each standard run. The solvent rune give an indication if carryover is occurring froa saaple to sample and when eyringee should be cleaned or changed. The absolute magnitude of standard runs indicate the condition of the eplitleee injection system (i.t., septum leaks, etc,). Of course, when the sample wee of a known Aroclor type, the autoeeapler table was adjusted to reflect this case (standards ware shifted). Once it hat been determined that the system la giving reproducible results, it is necessary to determine the accuracy of the data. The signal suppression in the 4-23 HONS 018904 ECD da* to the pasting of th* transformer oil fraction, has b**a noted in several articles and was a basis for the development of the ASTM procedure that involve* preparation of standard Aroclors with a known transformer oil, (Ref. 5). As reliable sources had noted that the degree of suppression varied with the transformer oil, w* chose an alternate rout* to account for suppression. Using a sample of new Shell transformer oil, representative of the oil used at 8FA, and FDA Aroclors, we prepared 5 and 50 ug/g standards of Aroclors 1260, 1254, and 1242 in oil. These standards were then run through our procedure to determine the "recovery" due to suppression. This recovery was found to vary between approximately 50 and 80 percent. Aa the recovery falls toward the 60 percent level or below, it indloates the existence of air leaks in the deteetor systems and as such signals th* need for corrective maintenance. In a series of 99 autoaampler runs, 5 ppm and 50 ppm standards prepared in oil are run three times for each Aroclor type. It should be noted that the oil suppression recovery is e function of retention time end when individual peak areas are used in calculations, aa thay are for Aroclor mixtures, the suppression recoveries are individually calculatsd for aacb peak. Effaots auch aa oil suppression recovery variation are masked when all standards ara prepared with oil ee in the AST!! procedure. Vhile theee effecta may not result in different quantitative result* by the two methods, they do add to tha fundamental understanding of the measurement system aa a whole. Sample chromatograms of Aroclors in solvent, in oil, and aa mixtures are shown in Appendix B. If thecalculated concentration fells on or near a regulatory limit (50 or 500 ppm), th* sample is rerun using standard additions. In most cases this involves using tha asms atoek or standard solutions used in tha normal standards. Tha preparation time for standard additions is lee* than 5 minutes sad with the use of aa autoaampler the operator time is negligible. Standard Aroclore in ell run by thia method ehov a recovery of 100 percent ^ 5 percent. Ve consider this aceuraey to bo more than adequate. CALCULATIONS Th* calculation of mixed Aroclor samples was tha next problem to be addressed. Slnoe ve had choean to use tha capillary system, we found that for two Aroclor mixtures ve had significant non-overlapping regions In the chromatogram from which Indlvldmnl peak arena could bo dotarminod for quantitation versus tha standard or by standard additions. 4-24 HONS 018905 For mixtures of Aroelore 1242, 1254, and 1260, this seme method can be employed for tha determinations of tha first and last Aroclors. V* r currently investigating tha uaa of a mini computer to "subtract out" tha araaa dua to Aroclora 1242 and 1260 In ordar to caleulata tha remaining fraction of Aroclor 1254. Sinoa tha ovarlap of Aroclor typts is dua to tha praaanca of tha aaaa congener in both mixtures (as opposed to different compounds coeluting), it la not possible to completely resolve Aroclor mixtures by capillary GC. However, it ehould be poaaibla to calculate by relative peak area ratios tha contribution of each Aroclor type to a given peak using peaks in tha noQ-overlapplng region as refarance. In tha fall of 1902, ws participated in an MBS round robin study on the enalysls of PCBe in oil. It was our relatively poor performance in this study which prompted tha changes in our chromatographic system as wall as the adoption of the current quality assurance program. Aa a result, reanalyaie of these samples has shown the system and mathod to be reproducible and accurate. Stepwise procedures for oil sample preparation end calculations can be found in Appendix A. Instrumental parametara for this analysis are given in Appendix C. Methodology for the Analysis of PCBe in Substation Soils The aethods currently being used by BPA for the sampling and analysis of PCBe in oil are modifications of those used by CPA. The EPA extraction method (Bo. 8060) uses a 16-hour Soxhlat extraction with a mixture of acetone and hexane. This extraction la intended to recover PCBe and pesticides from a wet soil sample. Since we ere not interested la volatile pesticides, we have modified this procedure. Ve first dry tha cample et 50*C and then eleve it with a 40-mesh screen in order to remove rocks leaving a homogeneous sample that is representative of the true adsorbing matrix. Rocks In the sample (tuck as substation gravel) being nonporoue, will merely dilute the effective PCS concentration bp virtue of their weight. A 10 gram sample of this preparation la then Sohlet extracted with 2, 2, 4-trlmethyl pentane (lao-Octane) for 6 hour* to remove PCBe. Ve have done serial extractions on samples of known KB content end established that the first 6-hour extraction will capture 97 percent of the PCBe in the sample. In turn, each additional 6-hour extraction will capture 97 percent of the remaining KB contant. 4-25 HONS 018906 Next the sample is reduced la volume, ia the extraction flask, on a hot plata such that tha iso-Octane (boiling point 90*C) will reflux in the neck of the fleek. This reduces the volum* without loss of PCBs (boiling point approximately 2$0*C) without having to resort to the time-consuming, Kuderna-Danlah aethod. Ia many cases a large percentage of the solvent can be captured in the upper level of the Soxhlet extractor coapletely eliainating the boil down step, Finally, the aaaple is brought to voluae with leo-Octane in a 100 al volumetric fleek and analysed by eaplllary gas chromatography with electron capture detection following the protocol we have eatabliehed for the analysis of PCBs in transformer oil. One of the tools wa havt baen using in tha analysis of soils is to dataralna the difference of the aoil sample weight before end after extraction. Tha percentage of ieo-Oetene "extractables" calculated from this difference can b# cautiously used to eoapars the amount of oil present to tha PCB content. This comparison can give information concerning tha contamination aoda of tho PCBs in soil. For example, a aoil sample showing e high Level of PCBm but a low percentage of oil would indicate either that thm source did not contain transformer oil (i.e.. a capacitor spill) or that soma mechanism was occurring that separated tha oil from tha PCBs after tha soil was contaminated. This information ia mleo of valuo analytically since tha response of PCBs in an electron capture detector ia reduced whan analysed in tha preaenee of transformer oil through e process previously referred to as suppression. Suppression la accounted for when analysing PCBs in transformer oil by preparing PCB standards in oil and calculating tha auppreaaion based os standards prepared in iso-Octane. For aoil samples wa can determine the extent of auppreaaion visually on the chromatogram and compare this to tha expeoted auppreaaion baaed on the percentage of Iso-Octane extrmctables. We can than dataralna if the use of an oil suppraaalon factor la warranted. Wa have determined in our lab that oil auppreaaion ia not a linear function of oil concentration. Therefore, dilution of the sample by e factor of 10 will not causa a corresponding decrease in auppreaaion. Our preliminary findings are that It is a log-log function. 4.26 HONS 018907 Praparatlon of Sampling Plana for th Analvala of PCB'a la Substation Soils Factd with tb prospect of characterizing the PCB contamination patterns of over 90 of BPA'a 450 substations, we flrat had to daeida the extent to which va would ample. Our first calculations, baaed on Ref. 6 indicated that in ordar to have a 90 parcant chance of finding a PCB "hot spot" of 1 aatar radiua in a substation of 100 metsra length on a aida we would need to set up a square sampling grid and taka over 3,000 aaaplaa Just to analyst the surface soil. Obviously, for temporal and financial reasons, this would be unacceptable. Therefore, it was nscsssary to make some assumptions to reduce this burden. The first assumption that wa mads la that a spill would be vleibla. With our substations being cowered with coarse gravel, a stain from an oil spill is gtnsrally visible for many ysars. The next assumption made wee that once deposited on soli, PCB contamination would not migrate horizontally. While some reports of airborne PCB migration have been mads concerning open hazardous waste dumps, our results of thousands of soil samples (approximately 20 percent of which were taken at the perimeter of highly contaminated fenced capacitor yards) Indicate that horlsontal migration simply Is not occurring at any reasonable level. One of the "knowna" we had going Into this program was that, baaed on the analysis of PCBa In Insulating oil from approximately 4,000 pieces of large oil-filled equipment (transformers and oil circuit broakors), only 2 percent of this equipment was contaminated with PCBe above the 50 ppm level. Also, with the geometric layout of the substations, large areas could be disregarded ee potential treat of PCB contamination. Referring to figures 1 and 2, It la apparent that with increasing voltage rating (sad consequently alas) the levels of PCB contamination in general dropped. Since thla equipment, greater then 69 kV in voltage rating, occupies the majority of apses is the substation yards, we can expect that PCB contamination of the surrounding soil will be mlnimnl. In fact, if oil at the 50 ppm level oontamlaatea soil end comprises 10 percent of its weight, the resultant soil would have a PCB content of 5 ppm. Ve would consider thla level of contamination in a substation to be nlnlmnl. Our current practice for construction In area# of PCB contamination of leas than 5 ppm it to place this material to the aide of the construction and use it as backfill after construction la oomplatad. 4-27 HONS 018908 It should bo saphasistd that circuit breaker and transformer oil (froa equipment greater than 69 kV in rating) accounts for at least 90 percent of oil used in the BPA syatea. In addition, this large equipment has the potential for causing auch larger spills. ` Saall equipment, on the other hand, has historically shown a higher level of PCB contaalnatlon. Figure 3 shove the results of oil analysis in aaaller equlpaent. The aoat significant result of this figure Is that over 16 percent of the aaall equlpaent teeted shoved PCB contaalnatlon above 50 ppa. Therefore, spillage froa this equlpaent would have a greatar probability of causing significant contaalnatlon to the surrounding soil. However, this contaalnatlon would be spread over a sore Halted area than the large equlpaent due to the saaller aaount of fluid In the low voltage equlpaent. The previous analysis has resulted In the developaent of sampling plana which concentrate sampling around the lover voltage equlpaent and visible oil stains. Figure 4 shove e typical substation with its resultant aaapllng plan. The second area of concentrated sampling haa been around capacitor yards and houses. Capacitors In the BPA syatea, with e few exceptions, ere Isolated In the yard by enoloaure with fencing or metal houses. This was done primarily for safety reasons due to the low electrical clearance of this equlpaent. However, this Isolation has also prevented the distribution of PCBe throughout the eubetetlon. It has, therefore, been our practice to staple the periaeter of these locations, especially by gateways (in the case of capacitor yards) and close to pads (la the cate of capaoltor houses). The results of thsss tssts have shown that migration of PCBt horizontally is virtually nonexistent, with the exception of actual tracking of PCB froa the locations by substation personnel end the contamination resulting froa the peat practice of storing felled capacitor cells along the outside of the capacitor yard fenoea. Results of aaaples taken within the oapacltor yards (during periode of de-energisatlon) have shown levels of PCBe exceeding 10,000 ppa and additional testing would be expected to yield similar results. All soils froa those locations are assumed to be highly contaminated but contained. The Use of Contract Labe In tho euMor of 1964, It was learned that our laboratory would bo responsible for the tooting and profiling of PCBe in soil froa 90 of BPA's 450 substations. Tho 4-28 HONS 016909 substations Identified in thia program ware those which had or still have capacitor installations as vail as those substations containing equipment filled with PCB oil. Since this program would have taxed the laboratory beyond its ability to plan and execute such an undertaking, it was decided the actual sapling and analysis would be performed by contract laboratories. The responsibility for preparing the sampling plana and assuring the quality of the enalyeie, however, reaained in our control. Since we began contracting analysis, we have noted several quality assurance problems with our contrect labs. In general, the probleas have not been with basic methodologies because ws provided each laboratory with the sethod we had developed In our lab. Rather, the problea hae been that of record keeping during analysis. We have, with tone labs, had probleas of dilution factor trrors due to poor record keeping, the reported results being aa much as a factor of 10 below the actual value. I believe thia la a record keeping problen which is associated with saaple "overload" in the saaller labs. Kany of tha labs that wa deal with are etsall organisations which do a variety of analytical work in addition to PCB analysis. PCB analysis in this region hae recently increased, drastically overtaxing record keeping ayeteaa that were devlaed for handling fewer samples. Therefore, it is important to keep in alnd. vhsn evaluating contract labs, the level of work they are currently doing versus what you will be expecting of then. Their quality assurance procedures should be designed for the increased sample load. is a quality control procedure we are currently requesting contrect laboratories to provide u# with duplicate eaaples of approximately 10 to 20 percent of selected samples following receipt of their report. These samples are then run by the same procedure in our laboratory.' The acceptable Halt of deviation froa our results la 50 to 100 paroant, depending on the level of PCSa found. Duplicate analysis by tha contract lab Is rsquirsd when these limits are exceeded In order to recooelle the deviations. Since soil samples are not inherently homogeneous we feel these limits are eoaaervative. It ie our intention, in the future, to develop a homogeneous soll/PCB standard to usa for additional quality control. 4-29 HONS 01891 BIBLIOGRAPHY 1. Walter Jennings: Gas Chromatography with Glass Capillary Coluans Sseond Edition 1980 Acadsaic Prsas 2. R. R. Frssnan: High Rssolution Gas Chroaatography 11/79 Ksvlstt Packard 5. Lson D. Savyer: Quantitation of Polychlorlnatsd Biphsnyl Rssidus by Elsetron Capturs Gas-Liquid Chroaatography! Rsfsrsncs Material Characterisation and Prsliainary Study, J. Assoc. Off. Anal. Chea. (Vol. 61, Ro. 2, 1978). 4. Lson D. Savysrt Quantitation of Polychlorinated Biphenyl Residues by Electron Capture Gas-Liquid Chroaatography: Collaborative Study, J. Assoc. Off. Ansi. Chea. (Vol. 61, No. 2, 1978). 5. Analysis of Polychlorinated Biphenyls in Mineral InauUtlnc Oils by Css Chroaatography; ASTH Standards, Part 40, 4059-92, pg. 1051, 1982. 6. L. Zirsehky and R. Gllbsrt - Chaaieal Engineering 7/9/84 pgs 97*100. HOHS 018911 4-30 11- 5--50 ppm OCB'S OF 69 KV OR LESS (500 PIECES TESTED) 52X OCB'S 110-130 KV (409 PIECES TESTED) 5-50 ppm 55% 0-5 ppm 64% 50-500 ppm 1% OCB'S OF 220 KV OR MORE (319 PIECES TESTEO) Figure 1. Comparison of FCB*% In Oil Circuit Breakers HONS 018912 z t-t 50-500 ppm 5-50 ppm 50-500 ppm XFORMERS OF 69KV OR LESS (162 PIECES TESTED) XFORMERS 110-130 KV (443 PIECES TESTED) 0-5 ppm 72*' 5-50 ppm 27* 50-500 ppm 'l* XFORMERS 220 KV OR MORE (344 PIECES TESTED) .Figure 2 Cunpurlou of PCI's In Tranafomera HONS 018913 ttt 50-500 ppm 5-50 ppm 38% 50-500 ppm 2% 58% SMALL EQUIPMENT (1591 PIECES TESTED) LARGE EQUIPMENT (1515 PIECES TESTED) Flgurt 3. tuipniMn of FCB'o In U[|< and full Eqoipaanc HONS 018914 k iS l L fifurc 4. HONS 018915 APPENDIX A PCB SAMPLE PREPARATION; OIL SAMPLE 1. For each saaplt to b# analysed prepare two - 20 ml disposable culture tub#* vlth Teflon-faced acre* cap#. Tub# A contain# 9 *1 0f 2, 2, 4-triaethyl pentane. Tub# B contain# 9.00 al of 2, 2, 4-triaethyl pentane and 5 al conc#ntrat#d HjSO^. All voluaes ar# delivered 1 parcant bp autoaatlc pipetting equipment. 2. To Tub# A pip#tt# 1.000 al of oil to b# analysed. Mix v#U on a vortex mixer. 3. Pip#tt* 1.000 al of th# solution froa Tub# A into Tub# B and alx veil on th# vortex alx#r. Centlfug# to ##parat# alcrodropa of H2S04 and pr#par autoaaapl#r vial with th# aup#rnat#nt solution. STANDARD PREPARATION 1. V#l(h 0.5000 ( to the n#ar#st .0001 g of pur# Aroclor otandard obtained froa PDA. Dilute to 500 al vlth 2. 2, 4-trinethyl pentane. Stor# this solution is the refrigerator away froa light. This solution is nominally 1000 ug/al. 2. Proper# working standard by pipetting 0.5 al and diluting to 500 al vlth 2, 2, 4-tria#thyl p#ataa. Thl# solution la noainally 1.000 ug/al. 3. Actual ataadarda ar# pr#par#d by 1:10 and 1:2 dilutions of the working standard vlth 2* 2, A-tria#thyl pentane. Proper# actual standards in th# as# typ# of disposable cuitur# tub# and vlth th# #aa# volumetric plpott# at the eaapla eolutiona. Thaaa solutions ar# noainally 0.1 ug/al and 0.5 nc/al. 4-35 HONS 018916 CALCULATION 1. Single Aroclor Samples When sample has been identified ee e single Aroclor the celculatlon is quite straightforward. Linear Recreation Analysis la uaed to prepare a standard curve using the total area of all the peaks due to that Aroclor at both standard concentrations. The sane total area is calculated for the eaaple and using an HP-11C calculator the concentration is "picked* off the curve. This value is then divided by the density of the oil eaaple (approximately 0.86, an average velue determined by aeaeureaent of 10 normal oil samples) and multiplied by 100 (the dilution factor). This concantration (now in ug/g) is then divided by the oil suppression reoovery. This fsotor is a "recovery* to account for the suppression of the BCD signal due to the passage of the transformer oil fraction. Thia factor haa been determined os 5 ppm and 50 ppm Aroelor 1260, 1254, and 1242 standards prepared in oil and normally runs about 50-80 percent. Vhen the final calculation le close to e Halt the eaaple should be rerun by standard additions. Therefore, the calculation for a single Aroclor 1st (Concentration of eaaple from regression analysis) ug/al x dilution factor (100) .86 g/ml Suppression Recovery 2. Nixed Aroclor Samples Nixed Aroclor samples ere calculated by individual congener peak areas or peak grouping sums chosen from non-overlapping regions of the chromatogram. These areas are compared with the same standard areas using s regression snslysls program as for single Aroelor samples. This method Is sufflclsnt for tvo-Aroclor mixtures. For three-Aroelor mixtures 1242 mad 1260 eaa be determiaed as before. Aroclor 1254 can be determined by subtracting the Aroclor 1260 component of a single congener peek in the overlapping region from the sample peak area. This 1260 componsnt is ealculatsd by multiplying the congener peak ares from the sample by the ratio of the same peak in the 1260 standard end another peak fros a non-overlapping region of the 1260 standard. This vslus thsn subtracted fros the cogener peak area vlll give the congener peak area 4.36 HONS 018917 contribution of Arocior 1254. With this a'rsa tha concantration can than ba eaeulatsd by coaparln* with Arocior 1254 standards and completing tha calculation as for two-Arqclor slxturss. This assuass that ralativa paak concantratlona in a (Ivan Arocior standard ara constant. Vs hava found this to ba rsasonably trus for standards. 4-37 HONS 018916 Appendix 8 ::. ">4 4-38 HONS 018919 t. 79 4 . <5 0 0.33 z.n -- 3.33 fi 7 3 > - 7.73 3.42 ,, -, :e.42 Arcelor 1242/1260 M4.iturt la 2,2,4-tnaothyi plBUoi 4-39 MONS 016920 t.ll 4-40 HONS 018921 Appoadix c K IWWMWMi PMWIilt Uit ouNcrtu 3VIM TCRR UNIT 403 JVlN flNN *0 OVt* Ul*R ON ur j tcin unit n 9CT 2 Tin* 133 8CT 2 HR* t)H sJ i tcnn unit oi luj I TCNN MO 1**J I reno on 2IttJ J TWO l|"IT 09 iiu nn mo IMJ 3 H*F 04 -KHCT9N 0 On KTUTOft c ON Kin Mm m RUM IK On RUM IK ftNNOTRTtOM ON RUN Tim 4.11 VM.VC * ON RUN ttm 0.00 VNCVC t 0ft rum tim o.io cmwt imi o.t RUN fine 0.90 *MVC 0 Off RUN Tim 0.90 VNiUt 9 ONN RUN ll 0.09 OVtN TCNN 040 run Tim o.oo cmnnt pui i Run Tim 10.09 CMNNT imi 0.1 RUM Ttm 04.09 VM.VC 0 ON run Tim 20.tt myt s on RUN Tim 19.00 9T0N 1ICWH. C MVICCR tt 1ICNNL ON MVlCCO 12 9TON RIOT MVICCR 12 chrot inn i.oo Huieto n NTTN 9t J MVlCC* 12 90NNKT 19 HVlCtO 12 21R0 On KVICC9 12 1ICMM > KVICCR 20 1ICNM <M MVICCR 20 Hon mi Nvtcct to NTTN 2tO BCVICCO 10 WMIT 0 MUtetO URO ON OCVICtO to ! ClCflM C 9/mC ONN RUN Tim RNNOTOTION ON OvCN 'CNN touto Tine I.M JtLiTt r/tH TCNN VMVt 9 022 vmvc 4 orr VMVC 0 ONN RIM HIOTN 0.04 TNHMOkl 1 CNONT ON MVICCO 0 CNONT ON RCRONT RMHOTNTIOM OH MUTC KMNT TK CNOOT ftm 0.10 NNCN OUN ON RCNOOT Tim 2.29 NNfR 0UN ONf CNOOT TINC 0.20 NNCN OUN ON RCNOOT Tim 0.09 NNCN OUfT ONN NLNUNI lim *.00 MN4N UUN UN CNOOT Tim 10.10 NNCN OUN ONN RCNOOT Tim 12.29 NNCN OUN ON NOUN ' SCUM CNUO COIT CNLIO *7 coit emu o.i ioit emit -i.o COIT CM.II *2.9 CUT CM to s.o coit emio hit emio o*o 4-41 HONS 018922 AN ANALYTICAL METHOD FOR THE ANALYSIS OF CHLORINATED BIPHENYLS IN UQIJIOS AND SOLIDS Mitchell O- Erickson, John S. Stanley, J. Kay Turman, and Gil Radolovich Midwest Research Institute 425 Volker Boulevard Kansas City, Missouri 64X10 Oaniel T. Heggem U.S. Environmental Protection Agency Office of Toxic Substances Field Studies Branch, TS-798 401 M Streets, S.W. Washington, 0C 20460 This is a gas chromatographic/electron impact mass spectrometric (GC/E1MS) method applicable to the determination of chlorinated biphenyls (PCBs) In liquid or solid samples cf environmental, human, or commercial origin. The PCBs may originate either as contaminants derived from commercial PCB products (e.g., Aroclors) or as synthetic by-products. The PC8$ may include any of the 209 congeners from monochloroblphenyl through decachlorotoiphenyl and may be present as single isomers or complex mixtures. The use of GC/EIMS yields qualitative information which not only readily differen tiates among the PCB homologs but also permits elimination of other compounds from quantitation. The other common PCB analysis technique, GC/EC0, does not discrim inate between PCBs and many common interferents. Thus, GC/ECD results are less reliable for complex matrices. A variety of general and specific sample preparation options are presented in this method. In some cases, these options are taken from other standard procedures for PCBs. In other cases, no standard procedure exists and general guidance is given with appropriate literature references. This method takes a different approach from those which rely on Aroclor mixtures for calibration and quantitation. In this method PCBs are detected and quantitated by homo log group. The results can be summed to give a total PCB value comparable to results generated by other meth ods or they may be presented as 10 individual homolog values. This homolog dis tribution can provide additional quantitative information on the composition and source of the PCBs. For example, the relative homolog distributions nay indicate how closely the sample resembles a commercial mixture. The method consists of the following steps: 1. The process or product must be sampled such that the specimen collected for analysis is representative of the whole. Statistically designed selection of the sampling position, time, or discrete items should be employed where appro priate. The sample must be preserved to prevent PCB loss prior to analysis. Room temperature storage may be adequate for some samples if biological degra dation will not occur. Otherwise, subembient storage is recommended; refrig eration for aqueous samples and freezing for all others. 4-42 HONS 018923 2. The snapIt is mechanically homogenized and subsampled If ntctssary. The sam ple must then be spiked with four 13C PCB surrogates (4-ch1oro-13C-biphenyl; 3,3' ,4,4'-ttrcr>loro-l3Cl2-Diphenyl; 2,2' ,3,3' ,5,5' ,6,6' -octachloro-l3C,2' biphenyl; and decachloro-`3C12-biphenyl) and the surrogates incorporated by further mechanical agitation. 3. The surrogate-spiked sample is extracted and cleaned up at the discretion of the analyst. Simple dilution or direct injection is permissible. Possible extraction techniques include liquid*!iquid partition, liquid-solid partition, thermal desorption, and sorption onto resin columns followed by solvent de sorption. Cleanup techniques may include liquid-liquid partition, sulfuric acid cleanup, saponification, adsorption chromatography, high performance liquid chromatography, gel permeation chromatography, or a combination of cleanup techniques. The sample Is diluted or concentrated to a final known volume for instrumental determination. 4. The PCB content of the sample extract must be determined by high resolution (preferred) or packed column gas chromatography/electron Impact mass spec trometry (HRGC/EIMS or PGC/EIMS) operated In the full scan, selected ion monitoring (SIM), or limited mass scan (LMS) mode. 5. PCBs are identified by comparison of their retention time and mass spectral intensity ratios to those in calibration standards. 6. PCBs are quantitated by the internal standard technique, using response fac tors for a mixture of 10 PCB congeners. The recoveries of four l3C surro gates are used to monitor for losses in workup and determination. 7. The PCBs identified by the SIM technique may be confirmed by full scan HRGC/ ElMS, retention on alternate GC columns, other mass spactrometric techniques, infrared spectrometry, or other techniques, provided that the sensitivity and selectivity of the technique are demonstrated to be comparable or superior to GC/EIMS. 8. The analysis time is dependent on the extent of workup employed. The time required for instrumental analysis of a single sample, excluding instrumental calibration, data reduction and reporting, is typically 30 to 45 min. 9. A quality assuranct (QA) plan must be developed for each laboratory. 10. Quality control (QC) measures include laboratory certification and perfor mance check sample analysis, procedural QC (Instrumental performance, calcu lation checks), and sample QC (blanks, replicates, and standard addition). The method Is available through NTIS: Erickson, M. 0., J. S. Stanley, 0. K. Turman, and G. Radolovlch, "Analytical Method: The Analysis of Chlorinated Biphenyls In Liquids and Solids," U.S. Environmental Protection Agency, Office of Toxic Substances, Washington, 0C, EPA-560/S-85-023 (February 198$). Tha work was supported by the U.S. Environmental Protection Agency under Contract No. 88-02-3938. 4-43 HONS 018924 FIELD MEASUREMENT OF PCB'S IN SOIL AND SEDIMENT USING A PORTABLE CAS CHROMATOGRAPH Thomas M. Spittler INTRODUCTION With the recent Increase in activity at hazardous waste aitaa vhera cleanup and remedial action is underway, a need has emerged for rapid analaytlcal methods which can be used in the field. Often there is need to assess the impact and extent of eontaalnatlon right in the field. This enables a sampling crew to collect meaningful samples for later laboratory analysis. A second, more pressing need for field data is in the actual cleanup process. Where a problem has been identified and removal is planned, it is loglstlcally difficult to perform adequate analytical work to direct a thorough cleanup prior to the actual cleanup operation. Few pollutants leave adequate visible traces to guide cleanup. Therefore, analytical work must often be performed during the cleanup operation to guide the contaminant excavation and subse quent removal process. Because removal end transportation of hazardous materi als to a safe disposal sits La often very costly, It would be preferable to remove only the contaminated materials snd stop excavation whan elean material or soil is finally reached. In order to achieve this end va have devlaad a field method for extraction and measurement of PCB's from soil and sediment which can be performed In as little as seven minutes after the sample Is collected. EQUinCNT AND METHODOLOGY While there ere several serviceable small gas chromatographs on the market, we have found that the Model 511-06 made by Analytical Instruments Development is one of the most practical for field work. This instrument is equipped with a sensitive Electron Capture Deteecor and hat a long history of reliable field operation both in our laboratory and elsewhere. A stainless steel column Is held in s well-insulated Isothermal chamber. If the column and oven art raised to 210 degrees Cantlgrada on AC power, the unit can main tain these conditions on battery power for a full sight-hour working day. However, it Is usually possible to supply soma alternative source of elelctrlcsl power such as battery-inverter supply or a portable generator. Overnight charging of the Nl-Ced batteries will prepare the unit for an 6-hour workday. The unit has three lecture bottles stored in the power pack baas and these can quite easily be manlfoldsd together to supply carrier gas for aavaral days of field operation. Again, an auxlllalry carrier gaa bottle of moderate capacity la advleeable for longer field use. Overnight charging of the Ni-Cad battery peck will prepare the unit for en 8-hour workday. 4-44 HONS 018925 For general field uM we employ 3 or *-foot x t/8" stainless teeel coluan packed wlch 3X SC-30 on 80/100 mesh chromosorb U-HP. The coluan is held ac about 200 - 213 degrees centigrade, depending on the particular Arochlor which is to be analysed. Adjustment of teaperature and carrier flow as well as proper choice of coluan length can provide rapid elution of even Arochlor 1260 In as little as seven nlnutes. Injections are typically aade using 1*3 ul of the hexane extract of a soil, sedlaenc or standard saaple. FICL0 EXTRACTION TECHNIQUE A field settle Is prepared for analysis as follows. Depending on soil homo geneity, 100 - *00 og of soil Is used for analysis. Typically, 200 mg of soil Is weighed (or estimated by volume when high accuracy is not important) and placed In a 2 cc septum vial. To the soil sample are added sequentially 100 ul of water, *00 ul of methanol and 500 ul of hexane. The sample is than agitated for about 60 seconds. This Is easily achieved in the field by holding the vial to the tip of a vibrating engraver . RESULTS AND DISCUSSION This method has been applied in the field at several PCB sollls and cleanup operations. Results of some of this work will be dlseuased. Also, several samples were analysed by the field technique and chan subjected to standard PCI analytical procedures In our laboratory. Finally, a study Is underway to more accurately determine the sxtrsctlon efficiency of the field method on different Arochlore. Results of this work will also be reported ac the seminar. 4-45 HONS 018926 DISTRIBUTION OF POLYCHLORINATED BIPHENYLS WITHIN BONNEVILLE POWER ADMINISTRATION SUBSTATIONS David W. Baker INTRODUCTION Tha Bonneville Power Administration (BPA) la a fedaral power distribution and marketing agency for some 30 hydroelectric dame in tha Columbia Rivar Baaln. Tha BPA transmission system interconnects public and private alactrical utilitlaa in tha Pacific Northwest and eonaiata of about 14,200 circuit ailaa of high voltaga tranaaiaaion linaa and approximately 450 aubatationa. BPA alao auppliaa diract aarvica to alualnua raduction plant# and othar induatrlal customers with high povar load#. Tha alactrical industry bagan using polychlorinated biphenyl# (PCBa) in capacitora, transformers, and othar equipment in 1929 with production continuing until about 1977. Tha pereletence of PCBa in tha general environment haa created a national concern regarding tha impact of these bloaccumulatlng chemicals both to public health aod to aensltive ecological systems. As a result, a voluntary cooperation agreement was recently entered into by BPA vith tha Environmental Protection Agency (EPA) for the purpose of clarifying mutual responsibilities and commitments for conducting actions required and authorised by the Toxic Substances Control Act (TSCA), PCB Regulations, and the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). Provisions under this agreement include the implementation of a tasting program to determine the extent that soils in BPA facilities have been contaminated over the yeara by equipment leeks end failures. Beemuse very few Aakerel transformers (PCB's over 500 ppm) were used within the BPA system, emphasis of this soil survey ia toward the 85 eubetetlona where PCB empmeltorm are nov, or have In tha past bean, in service. 4-46 MONS 018927 APPROACH AND OBJECTIVES Stapling procedures and analytical requirements developed to carry out this testing program are presented In the coapanion report, with hundreds of samples needed to fully characterize an average substation, certain assumptions regarding PCB soil contamination patterns were made to reduce testing requirements. ?o confirm the validity of theme assumptions and their use In sampling plans for the 65 substations, 15 BPA substations ware sampled extensively. Type and site of electrical equipment, maintenance history, environmental setting, and past construction prsctlcss ware factors considered In selecting these substations. This pspsr is intended to provide insight into overall PCB soil contamination patterns within fenced BPA subetstloas based on a continuing PCB atudy which is about one third completed. Results are included on the 15 substations identified for comprehensive sampling and the findings from these substations are reviewed in detail. A total of 15 substations, analyzed according to the reduced sampling protocol, are now completed along with 26 other BPA substations sampled in specific treat for construction projects. This report will not cover those substations tested for construction purposes or thorns sampled under the reduced plan. Levels of soil contamination will be considered In relation to the general equipment locations within the substatione and maintenance history, in order to Chech basic assumptions used in developing the reduced sampling plans. It is important to remsmber that this survey focuses on presenting s worst csss scenario for PCB contamination within fenced BPA substations. Semples Include those taken from capacitor areas which are generally inaccessible, but traditionally show high levels of PCB contamination (e.g., soil adjacent to capacitor houa# pads and locations beneath rack-mounted capacitors) and sites used In the past for temporary storage of failed capacitors. Sampling plana and instructions to aamplara also call for prefarentlal collection of soil with visual evidence of pset oil spills. Sampling la also selective towards oil-filled equipment, such as distribution and metering transformers, known to contain the highest PCB concentrations. OVERALL RESULTS AJIB DISCUSSIOR Extensive sampling was performed on the following substations to form foundational Information on PCB distribution patterns in soil; 4-47 HONS 018928 BPA Substation No. PCB Cape No. Snail Oil No. Large Filled Oil Circuit Equip .* Breakers No. Powe r/ Converts r Tranef. Total No. Soil/Cor* Samples Albany Anaconda 1782 2178 Boll Big Eddy 12663 1998 Longview 8178 Maple Valley 3246 McKary Olyapla 0 2667 Port Angeles 1085 Bose 7628 Snohomish 3021 St. Johns 1764 Troutdal* 5814 33 40 189 109 129 70 77 79 74 120 106 69 118 12 7 35 12 34 9 14 21 17 31 30 23 18 7 38 6 29 22 315 34 33 12 103 7 49 25 33 13 62 7 50 15 101 16 59 11 66 19 149 Tost results for the 13 subetations tested under the initial phase of this survey euaaarlsed below: PCB Contamination Level Surface Soils (0 to 6") Soli Cores (Blov 12") Sedlnent Samples Total Samples Leas than 1 ppm 1 to 4.9 ppa 5.0 to 49.9 pp 50 to 499 PP Over 500 ppa All Concentration* 468 (66.1*) 148 (20.9*) 61 (8.6*) 10 (1.4*) 21 (5.0*) 706 283 (89.3*) 17 (5.4*) 16 (5.0*) 1~ (0.3*) 0 (0*) 317 31 (50.0*) 17 (27.4*) 13 (21.0<) 0 (0.0*) 1 (1.6*) 62 782 (71.9*) 182 (16.7*) 90 (8.3*) 11 (1.0*) 22 (2.0*) 1067 "Includes dietrlbution/aetering transformers and oil circuit breaker* lea* than 69 kV. "Single oore sample exceeding 50 ppm (283 ppm) wee fron Bell Substation at drill aits near capacitor house. 4-48 HONS 019929 Ths results from 709 surfscs soil samples indicate that moat (95.6 percent) of the substation locations contain less than 50 ppm PCBs, with two-thirds of these sites having less than 1 ppm. Of the 317 samples taken below the soli surface (12" or more) only 1 (0.3 percent) had more PCBs than the 50 ppm regulatory level. The higher number of sediment samples with 1 to 49 ppm contamination is consistent with the property of PCBs to tightly bind to orgsnic fines which in turn tend to colleot in quiescent environments such as electrical manholea and oll/vater aeparmtor tanka. Overall surface soil and sedlmsnt rssults for the individual facilities tested are given in Table Bo. 1. PCBS IB CAPACITOR AREAS The test rssults for sslscted substations having extensive sampling have shown that the highest levsl of PCB contamination is in locations adjacent to capaoitor banks, and of thesa areas ths highest levels era associatsd with enclosed capacitor houses. Older direct customer service substations, such as Longview, Bell, St. Johns, sod Troutdtle had certain vintages of lower voltage capacitors which were more prone towards violent failure or leakage. Clean-up of spills within these enclosures is difficult end led to practice# which either spread PCBs directly (steam cleaning), or laft enough compound within the structure toeventually flow into ths soil outside thehouse. Initial test rssults have shown that thssoil next to capacitor house foundation pads may have extremely high concentrations of PCBs (mostly Aroclors 1242 and 1254). At this point PCBs could be readily tracked by workmen to other substation arses. One example of this phenomena la shown by three Ross Substation sidewalk samples, taken in an eras with no history of capacitors or contaminated (over 50 ppm PCBs) oil-filled equipment, showing between 5 and 9 ppm of Aroolor 1242. Apparently, operator personnel caused this pattern of contamination by their dally rounds through contaminated areas. fenced capaoitor yards with a history of failures will of course have concentrated PCB compound in the soil directly below the capacitors involved, but limited access reduces spread by foot traffic. Cora samples (which ws define as soil collected deeper than ths 0 to 6 inch surfscs samples) have shown that concentrations of PCBs drop off rapidly with depth, indicating that the contamination appears to b contained at ths surfscs soil through strong 4-49 HONS 018930 adsorption. An exception was a single cor* sample exceeding 50 ppm which was fro* th* Ball Substation at a location near a 13.3-kV capacitor house. The saaple was takas at 12 Inches and tested at 283 ppm. Deeper cores for this drill site at 5, 10, 20, and 25 feet were found to contain 1.04, 39.3, 3.28, and 0.18 ppa PCBs respectively. Past asintenancs practices which includsd storing ruptured cells st convenient locations (usually near the gate for fenced cspacitor yards) no doubt has contributed to contamination beyond restricted access areas. This is illustrated by two samples from Longvisw Substation, collected next to gates leading to capacitor yards, which were tested and found to have 28,500 opr. (1254) and 22,100 (1242) ppa PCBs. Results for the capacitor locations in the 13 subatstiona are summarised in Table No. 2. In the cess of McBary Substation, no date is shown since this facility has never had capacitors. For those 9PA substations with rack-mounted capacitors, most could not be ssaplsd within the fenced cspacitor yards because of the reduced electrical clearance during operation. Surface soil PCS contamination profiles, based on 83 snd 133 samples from capacitor houses snd fsncsd yard arsas respectively, are illustrated in Pigurs 1. Of these 216 samples mors then half (55.6 percent) contained less than 1 ppm PCBs snd 66.1 percent were lees than the 50 ppm regulatory level. PCBS IB OIL-FILLED EQUIPMENT AREAS In addition to PCBs from capacitor cells, another source of soil contamination within substations is from oil-filled equipment. For purposes of assessment, sample -date from lover voltage (69 kV end below) arses is being considered separately from those of higher voltages. Of course, within s 230-kV yard, for esaaple, there is often lower voltage aetsring snd station service transformers which typically contain such higher PCB levels then the asjor breakers or power transformers. As ssntionsd earlier, s critical element of this survey is to taks these factors into account and to preferentially oollect eaaplea from sitae aoet likely to have significant contaainatlon. The information developed on the group of 13 substations la summarised in Table 3. This date suggests (see Figure 2) that the lower voltage oil-filled 4-50 HONS 018931 equipment inn ere sore contaminated by PCBe than the 115-kV (end above) locations but the Halted number of eaaplea for the 69-kV end below arena make thie conclualon atatletlcally invalid, aa doea the overwhelming influence by one faelUty to thie data. It la clear, however, that oil-filled equipment aectlona within 8PA aubatatlona are significantly lean contaminated than oapaeltor areas. Only one eubatatlon of the 13 showed high PCB levels in surface samples collected near oil-filled equipment (aa opposed to seven for capacitor bank locations). The exception was a single Longview sample which contained 1OT0 ppm PCBe identified aa Aroclor 1246. Not withstanding, the sample serves to illustrate the fact that although this survey may provide valuable Insights into tha extant of PCB contamination within substations, there is always the possibility of undetected hot apots. SEDIRENT SAMPLES Although PCBe have a vary low solubility in water, they are known under oartaln circumstances to migrate in runoff water while tightly bound to organic "fines.' Tha analysis of sadimanta found in electrical manholes and oil water separator tanks, could provlds s diagnostic tool related to past levels of substation contamination. Average PCB results for the 62 sediment aaplts collected from 6 of the 13 substations ere presented in Table 1. PCBS IN OTHER SUBSTATION AREAS Surface samples from bulk oil storage locations within BPA aubatatlona appear to have similar PCB toil contamination levels aa the oil-filled equipment areas, Tha 39 samples collected from 6 of tha 13 aubatatlona, bad no results above 50 ppm and 26 pareant batwean 1 and 49 ppm aa shown in Figure 3. Core samples wars taken at two of tha aubatatlona around oil storage tanka because these areas may have bean subjected to apilla over tha years. Ball substation was extensively sampled in tha oil storage area with a total of 12 holes drilled, moat of them reaching 50 fast in dspth. On# drill sita showed 4-51 MOWS 018932 heevy oil contamination with fairly low PCB levels down to spproxlmately 15 feet. a maximum of about 6 ppm appearing at 6 faat. However, deeper than 15 foot aaw an Increase to a maximum of 43 ppa at 30 faat. Below this tha PCBa drop off to a* nlnlaua of 0.09 ppa at 50 faat. Tha other core samples showed soaa agreement but did not have tha PCB levels of tha described site. It should b# noted that ths soil is glacial moraine and is thought to account for the depths of penetration. The other substation aaapled below surface near oil storage tanks was Port Angelas. Analysis of the soil at the two sample sites showed 0.02 and 0.04 ppm at the surface, and 0.14 and 0.26 ppm at IB and 16 inches respectively. These results suggest that further work is needed to characterise below surface contamination around oil storage locations. Surfaoe aaaples taken in substation areas away from existing or past electrical equipMnt and storage tanks are referred to as background aaaples. The saaple category dlagraa (refer to Figure 3) shows less PCB contamination than other substation locations. CONCLUSIONS Sampling parameters identified for this system-wide PCB soil survey appear to be valid based on reviewing 1067 saaple results froa 13 eubetetlons. Movement of PCBa away from areaa of highest expected contamination (e.g., PCB capacitor inatallatlons) has been shown to be limited both horlsontally and vertically through the toll. Contamination levels have been demonstrated to be predictable baaed on the general location within the subetation with highest contamination associated with capacitor installations. Taata to data, with vary few exceptions* have not shown PCB contamination to sxlst above the 50 ppm level outslds capacitor use areas in BPA substations. Oil contaminated soil samples associated with higher voltage equipment (115 kV and above) appear to have lower contamination than samplea collected near lower voltege (69 kV and below) equipment but additional work it needed to confirm this. 4-52 MOWS 018933 Tati* Wo. 1 Surfacs Soil (0 to 6 Inches Dapth) and S*dl**nt Results for 13 Substation* Tested Substation Total So. Sanplaa Sanplaa Sanplaa Surfaoa *50 ppa 1 to 49.9 <1 PP* 2*Stii*____ PCI# non PCBs PCS# 11K*"* 31 ______*_ 6-5# 93.5* Anaconda _?2____ ____i-if.. 51.7# 41.4# Ball _i_______ 8-3* 16.7* 75.0* Bla Iddv 0* ___ 3.* 97.0* Lontvlav 00 7.5* 63.8* 28.8* Mania Valley 44 o# 6.a* 93.2* Total So. Sadlaant Sanplaa 0 0 1 , 22 5 Sadlaant Sanpla Aaerates _ Tfpa Capacitor Installations fanead tacka Only Panead Backs Only Sousas sad 32.5 m Panead Sacks Panead Saeka MD Only Bonssn and 4.68 . Panead Sack# Paacad Racks 0.03 nan Only ScBary 3? 01r.pl. Port Ancelea loss Snoboalah 57 36 101 50 0* 1.0# M< 3.0# 0 93.9*___ 0 28.1* 11.1# 42.6* 0 70.2* 83.3* 54.5* 100* 5 0 1 10 Boa# Paacad Backs Reuaaa 0.26 ana Previously . Paacad Saaks Only Sousas and 8.6 m Paacad lacks Paacad lacks 0.36 tm Only St. Johns Troutdale 40 70 2.1# 11.4# 83.3* 22.9* 14.6* 63.7* 0 17 Bouses Rosass sad 7-87 .! Passad Saeka cs-* HONS 018934 Table No. 2 Surface Soil (0 to 6 Inchea Depth) Results In Relation to General Subatatlon Locations BPA Bakstatloa Albany Anaconda Bell Bif Bddj Lonayloe IUdI* Valley McNary Olympia Port Anaelea Roaa Soohoalab St. Johaa Troutdale Total Kncloasd Capacitor House Areas Saaplaa la PCB Catacory l to 49.9 < l Total Bo. . 7 29.2* . 3 37.5* 1 11.1* _ 3 30* 1 12.5* 8 33.3* 23 27.7* . 3 12.5* _ 4 50* _ _ 3 33.3* _ 6 60* _ 5 62.5* 8 33-3* 34.9* 14 58.5* _ 1 12.5* _ _ 5 55.6* ,, 1 10* 2 25.0* 8 33.3* 31 37.4* 0 0 24 0 8 0 0 9 0 10 0 8 24 83 Fenced Capacitor Back Areas Saaplea In PCB Cateaorv fc50 n 1 to 49.9 < 1 P* 00 26 4. 100* 4 14.3* 57.1* 28.6* 19 9 5.3* 47.4* 47.4* 6 00 100* 24 2 25* 50* 25* 16 00 100* Total Bo. 4 14 19 --r 8 16 . 0 2 25* 0 0 _ 0 7 5.3* _ 1 9.1* 2 25* 11 55* 0 _ 2 14.3* 37 27.8* _ 10 90.9* 4 50* 9 45* i3 100* _ 12 85.7* 89 66.9* 0 11 8 20 ___ LL 0 14 133 HONS 018935 SPA Substation Albany Anaconda Bell 1* Wi Lonrele* Neale Valley RcNary Olynpla Port Anceles Ross Snoboalab St. Johns Troutdala Total Tabla No. 3 Surface Soil (0 to 6 Inchaa Depth) Results in Relation to General Substation Locations Oil Pilled Kaulpnent Areas 4 69liT--- Samples la PCB Catstory * 49-9 < i tm 2 Total No. 0 0 100* 2 . _. 0 _. 0 _ __ 0 __ 0 __ 0 1 0 0 100* 1 __ 0 0 0 loo4 t 4 8 0 0 100* 8 _ ._ 9 0 - ii _ 0 0 9 . .0 0 9 15 Of __3?.51 . 62.5* __21__ Oil Pilled Equipeoat Areas fc 1 5 H Saaples in PCB Cat*lory TCiaT <1 to 49.9 1 MB Ba. 2 14 0 12.5* 87.5* 16 4 i\ 0 40* 60* 10 2 35 0 5.4* 94.6* 37 1 22 0 4.3* 95.7* 23 1 4.2* 14 56.3* 3 9 37.5* H 24 0 10.7* 1 8269.9* 2H 0 3.7* 9*. 3* 28 9 21 0 y2* 70* 30 T" 0 18.2* si .at 11 22 51 0 41.5* 58.5* 53 32 00 100* 32 18 3 0 85.7* 14.3* 21 6 0 28.6* 71.4* 21 1 84 "245------- 0.3* 74.5* 333 HONS 018936 w *> ENCLOSED CAP. HOUSES (83 SAMPLES TOTAL) FENCED CAP. RACKS (133 SAMPLES TOTAL) (FIG. 1) GENERAL SUBSTATION SURFACE SOIL SAMPLES (0M--6") IN EACH PCB CATEGORY HONS 018937 4-57 1-49 ppm 37X 63X 75X OIL FILLED EQUIP. <69kV (24 SAMPLES TOTAL) OIL FILLED EQUIP. 2>115kV (333 SAMPLES TOTAL) (FIG. 2) GENERAL SUBSTATION SURFACE SOIL SAMPLES (0"-6") IN EACH PCB CATEGORY HONS 018938 1-49 ppm 72% OIL STORAGE AREA (39 SAMPLES TOTAL) 74% OIL FILLED EQUIP. AREA (357 SAMPLES TOTAL) 1-49 ppm 18% 82% BACKGROUND SAMPLES (56 SAMPLES TOTAL) (FIG. 3) GENERAL SUBSTATION SURFACE SOIL SAMPLES (0"-6") IN EACH PCB CATEGORY 4-58 018939 PART 5: SPILL CLEANUP HONS 018940 PILOT PLANT STUDIES FOR SOLVENT EXTRACTION OF POLYCHLORINATED BIPHENYL (PCB) FROM SOIL M. B. Saunders *So11ex" Is a process for the solvent removal of PCB from soils. PCB will be trans ferred from the soil to the solvent phase when the two are mixed together. Kerosene and water were determined to be the solvent of choice. Kerosene can be recovered for recycle by steam-stripping. The mixing study was Initiated to determine the Importance of component (soil-water-kerosene) variables and mixing time. A pilot plant was operated, and results are reported. Soll-to-water ratios of 3 to 5 and sotl-to-kerosene ratios of 3 to 5 are best. No difference In extraction performance could be determined between IS and 30 minutes mixing times. The kerosene retention In the soil was about 2S vol X. A three-stage batch pilot operating with a 6 to 1 volume ratio experienced soil feed PCS con centrations of 300 mg/L and discharge soil levels of 10--15 mg/L. Lower soil values could be obtained using additional stages. The soil contaminated with 300-600 mg/L PCB also has a high concentration of oils and tars, resulting In a total organic carbon concentration of 10-20X. The PCB and oil was solubilised* using the kerosene leaching solvent. Water was also added to the solvent mixture to help break up the soil particles. About 26-30 wt X kerosene was absorbed Into the leached soil. The PCB extraction from the soil as a function of so 11-water-kerosene ratios and the mixing times were performed. The purpose of these tests was to define areas of acceptable operation. In order to minimize operation and equipment cost, the water and kerosene-to-soll ratios must be as low as possible. The data Indicates that a water-to-soll less than 1.0 and/or a kerosene-to-soll ratio less than 1.0 fall Into 5-1 HONS 018941 an irn which docs not have enough fluid to allow for adequate mixing and, there fore, not acceptable for operation. A ratio of water-to-sotl and kerosene-to-soll greater than 5.0 requires processing a high voluma of material. A ratio of 3.0 to 5.0 for the water-soil ratio and kerosene-soil ratio resulted In a system having good hydraulic alxlng characteristics and yielded a PCS leaching percentage of MX. The pilot plant (Pig. 1) consists of three stages of mixing equipment. The plant Is operated In a counter-current mode; soil and water are added to Stage 1 and clean kerosene to Stage 3. Each mix tank has a 200-1 capacity and an air-driven mixer. An Interstage solvent pump and a 120-1 solvent-hold tank allows the kerosene to be transferred In a counter-current mode. The distillation-packed column system was 7.6 cm In diameter by 2.4-m long with an 18 L steam-heated reboller and product con denser (See Fig. 2). The distillation unit was used to steam-strip the recyclable kerosene from the other oils and PC6. The pilot plant Is a one-day batch-cycle operation. Each day the solvent Is pumpid from each of the three mix tanks to their solvent-hold tanks. The water-soil mixed phase Is transferred by gravity to the next stage, untreated soil and recycle water to Stage 1, and fully treated soil and water are discharged from Stage 3. The kero sene Is then drained from the hold tanks to the next lower numbered mixer. The transfer operation takes about three hours to complete. The tanks are mixed for four hours. Samples removed from the mix tanks at 30-minute Intervals Indicate that tha mix tanks ara at staady-statt after 90 mlnutas. After mixing has been stopped, the mix tanks are allowed to phaso-soparato for 16 hours, thus consuming out day per batch. The pilot plant was operated for 19 batch days. Successful steady operation was obtained after four days. A 25-1 batch of PCS and oil from the solvent-extraction pilot plant was staam-strlpped to recover the kerosene In throe hours, using $00 aL/aln of water food to tha boiler operating at 110C. Twenty-two liters of korosono wore recovered at a PC8 concentration loss than 5 mg/L. Tha PC8 was con centrated to 15 mg/L. 5-2 mons 018942 A preliminary cost estimate of the entire solvent loach and PCB removal from 10II process has been completed. This cost estimate shows a very small (two to five) percentage of-the total operating cost results form the loss of 25% of the kerosene to the soil phase. The cost estimate also compares cost of the solvent extraction process to direct Incineration of the PCB-contamlnated soil. The solvent extraction process cost was about half of the direct Incineration cost. 5-3 HONS 018943 80ILEX PILOT PLANT RECYCLE KEROSENE IN NONS 018944 SOILEX STEAM DISTILLATION UNIT TOP CUAN KEROEEME l(/L POE HONS 018945 POLYCHLORINATED OIBENZOFURAN CONTAMINATION OF THE STATE HISHMAY DEPARTMENT OFFICE BUILDING IN SANTA FE, NEH MEXICO AS A RESULT OF A PCS TRANSFORMER MALFUNCTION Fred L. DeRoos, Susan C. Watson, and Joseph A. Hatchel Battelle Memorial Institute Columbus, Ohio 43201 USA INTRODUCTION On June 17, 1985. an electrical malfunction occured In the New Mexico State Hlghuay Department Office Building In Santa Fe. New Mexico. A transformer containing 245 gallons of Askarel consisting of Aroclor 1260 (87X) and a mixture of trtand tetrachlorlnated benzenes (13*) overheated resulting In the release of vaporized Askarel through the safety valve. The duration of the release Is unknown, however It continued for at least 65 minutes after Initial detection until the transformer was de-energized. Although there was no fire, charred paint on the transformer casing Indicated that the casing nay have reached a temperature of approximately 300 *C. Examination of the transformer and metal analyses of the coolant Indicated that arcing had not occured. The State Highway Department Office Building Is a two story building of approximately 70,000 ft? connected to an annex building of approximately 30,000 ft2. The Askarel vapor was distributed throughout the building by convective air currents and by mechanical transfer via the heating, ventilation, and air conditioning systems. In some areas, such as those adjacent to or above the transformer vault, the Askarel vapor condensed when It reached cooler surfaces and `rained* onto the floors and horizontal surfaces. 5-6 HONS 018946 INITIAL CONTAMINATION LEVELS Air and surface wipe samples, as well as ccplant fluid saaiples, were cpllected within seven days of the malfunction. The airborne concentrations of PCBs In the transformer vault were approximately 42 pg/m3. The PCB concentration ranges In the rest of the main building were: Other 8asement Areas First Floor Areas Second Floor Areas 0.3-26 ug/m3 1.0-19 ug/m3 0.7-6 ug/m3 The total concentrations of polychlorinated dlbenzofurans (PCDF) In the air ranged from approximately 10 to 500 pg/m3 with the tetrachlorlnated dlbenzofurans (TCDF) ranging from approximately 1 to 55 pg/m3. Although polychlorinated dlbenzo-p-dfoxlns (PC00) were detected In the range of 7 to 21 pg/m3, no tetrachlorodlbenzo-p-dloxlns (TCOD) were found. The surface concentrations of PCBs were as high as 280,000 ug/100 cm2 in the basement areas. The highest PCB surface concentrations In the first and second floor areas were 98.000 ug/100 cm3 and 190 ug/100 cm2 respectively. POTENTIAL PCDF INTERFERENCE During the analyses of samples which were collected following the cleanup of the building. It was noted that the PCDF Isomer elution patterns were not typical of PCB fire samples. This Is Illustrated by the heptachlorodlbenzofuran (Hepta-CDF) elution patterns shown In Figures 1A and IB. The heptachlorodlbenzofuran chromatogram from the Santa Fe sample. Figure 1A, contains additional peaks as compared to the chromatogram from a sample from Tulsa. Oklahoma, Figure IB. Since high levels of polychlorinated dlphenylethers (PCDE) can Interfere with PCDF analyses, selected extracts from the Santa Fe site were screened for PCDE. As can be seen In Figures 2A.B, 3A.B. and 4A,B, PCOC Isomers account for a significant percentage of the observed PCDF response. Standard analyte enrichment procedures remove the majority of the PCDE Isomers, however high levels of PCDE can result In residual concentrations In the final extract usad for analysis. HONS 018962 5-7 Although PCOE Isomers ire comaonly observed In biological samples, they are seldom seen In high concentrations In samples from soot producing PCS fires. The Santa Fa Incident Is somewhat unique In that It was a non-soot producing discharge of PCBs. It Is postulated that the unique conditions of the Santa Fe Incident, that Is the relatively long term refluxing of the coolant, resulted In the conversion of a portion of the polychlorobenzenes to polychlorophenols. The chlorophenols then reacted with the remaining chlorobenzenes to produce the polychlorinated dlphenylethers. As a check, extracts from other PCS Incidents, Including Binghamton, NY, Boston, MA and Tulsa, OK were also screened for PCOE Isomers. They were not detected In these simples. Several coolant fluids from In service transformers that were approximately 40 years old were found however, to contain relatively low levels of PCOE Isomers. These low levels may have been produced slowly under normal In service conditions during the life of the transformer. SUMMARY An apparent difference In the levels of PCOE Isomers In samples from soot producing and non-soot producing PCB Incidents has been observed. Since the toxicity date that regulatory agencies use to select cleanup criteria are based on PC00 and PCDF levels. It Is Important to be certain that the detected levels do not result from Interferences. It Is recmmeded that all PCDF analyses from non-soot producing PCB Indicants Include a PCOE screening to validate the PCOF Identifications. HONS 018948 5-8 santa re Figure 1A. Heptachlorodtbensofurans In Santa Fe sample. TULSA SAMPLE Figure IB. Heptachlorodtbensofurans In Tulsa Sample. 5-9 HONS 018949 SANTA FE 5-10 HONS 018950 SANTA FE Figure 3A. Selected Ion current chromatogram for pentachlorodlbenzofuranj (m/z 339.860) ^- i S-ll HONS 018951 SANTA FI Figure 4A. Selected Ion current chromatogram for heptachloro* dibenzofurans (m/z 407.782) Figure 48. Selected Ion current chromatogram for nonachlorodlphenyl ethers (m/z 477.719) tT HONS 018952 DEVELOPMENT OF A SPRAT - VACUUM HEAD AND SUPPORT SYSTEM FOR THE REMOVAL OF PCB CONTAMINATION FROM WALLS, FLOORS, AND OTHER SURFACES K. C. ASHLEV QUADREX HPS INC. Work is underway to develop equtpaient for field use by utilities to remove PCB dielectric fluid contamination from floors, walls, and related surfaces. Current techniques for such removal are both labor-intensive and time consuming and have varying degrees of effectiveness. SURFACE CLEANING One conmon approach Involves scrubbing the surface with a selected detergentwater solution, followed by wiping the area with absorbent cloths. Wiping is important in this approach to thoroughly remove residual cleaning solutions (which now contain PCBs) from cracks, crevices, and other typical surface irregularities. Any residual liquid film or surface wetness of contaminated cleaning solution effectively limits the degree of surface decontamination that can be achieved. This phenomena of residual surface wetness is particularly evident with textured and porous surfaces such as unsealed concrete, cement, asphalt, etc. A basic limitation of this static or batch-type of cleaning action Is that as contaminants are removed from the surface, their concentration rises In the cleaning liquid. Alternately, a continuous flushing of the surface with uncontamlnated cleaning liquid can be seen as a mechanism to significantly reduce the amount of contamination which may remain on the surface. However, a con tinuous flushing action necessitates some simultaneous method to remove the copious cleaning liquid. In addition, some support system Is required to supply, store, and perhaps clean-up for recycle, the cleaning liquid. TECHNOLOGY TRANSFER The general problem of removing contaminants from surfaces challenges many Indus trial operations. These include semiconductor and computer manufacturing, aero space, and nuclear materials processing. 5-13 HONS 018953 Early engineering work by Quadrex HPS addressed the unique problem of removal of plutonium waste materials which coated the Interior surfaces of a glove-box type assembly chamber. A prototype surface-decontamination system was configured which consisted of a cleaning head and support equipment. Within the cleaning head were spray nozzles angled 30 from the surface; liquid Freon*-113 was pumped through the nozzles to provide continuous cleaning and flushing actions. The head had Internal passages and a connection port for a source of vacuum. The edges of the cleaning head which contacted the contaminat ed surface, were designed so that the vacuum-Induced In-flow of air prevented liquid leakage beyond the head. The vacuum removed contaminated cleaning liquid, flushing liquid, and dried the surface. The cleaning head was equipped with a trigger valve to control Freon* flow; the head was simply moved across the surface to achieve effective contaminant removal. The support system (solvent storage, pumping, vacuum generation, vapor control and spent solvent handling) was specifically designed to handle radioactive materials, which meant that certain geometric and mass configurations must not occur anywhere In the system. These design restrictions do not apply to the handling of non-radtoactlve materials such as PCBs, thus providing the oppor tunity for design Improvement and overall optimization. DEVELOPMENT PROGRAM HIGHLIGHTS The objective of this program Is to develop equipment for the fast and effective removal of PCB contamination from various surfaces such as walls and floors. It Is assumed that any free PCB liquids would have been removed prior to using this equipment. The overall program has been divided Into a series of fact-finding and develop ment steps with review and assessment occurring at key stages. An Initial key evaluation will be the effectiveness of the spray-vacuum head technique for surface PCB clean-up. Target clean-up levels for PCBs will be established. Surface sampling techniques will be evaluated. Including the NIOSM method. Samples of various surfaces (brick, asphalt, concrete, cement, wood) which have both fresh and aged PCB liquid exposures, will be obtained. A literature search Is Included as well as a focused survey regarding current PCB clean-up practices, and current work by others whose results can be made available. 5-14 HONS 018954 Two general types of cleaning liquids will be used in conjunction with the eval uation of the spray-vacuum head. These Include Freon-113 and water-detergent solutions. The effect of spray pressure for each selected cleaning liquid Is being evaluated; two pressure ranges established are: 50i psl and 1000 to 2000 psl. For porous surfaces, core samples will be taken to profile cleaning effec tiveness relative to substrate depth. An additional sample set will evaluate PCB leachback over time from the substrate, thus potentially recontaminating the surface. Operator safety concerns Include vapor or liquid releases, equipment control, airborne PCBs and conditions Imposed by an actual application site, l.e., poor ventilation, nearby energized equipment, public exposure, etc. The program's next development step addresses cleaning liquid recovery, process ing, and possible PCB waste concentration. Three scenarios have been established for processing contaminated cleaning liquids: 1. local recovery, with purification and recycle at the site; 2. local recovery with purification occurring at some central location; 3. local recovery with disposal In lieu of purification. EVALUATION CRITERIA Evaluation criteria for the contaminated cleaning liquid processing (or disposal) alternatives Include equipment acquisition and usage costs, overall costs, practicality, and technical feasibility. Assuming the development program proceeds to this point, prototype equipment will be fabricated and shop tested. Suitable utility host sites will have been iden tified for field testing. Field evaluation criteria Include equipment portability and handling ease, surface decontamination and support system performance, and maintenance require ments. 5-15 HONS 010955 PR06RAM GOALS The broad goal of this program Is to develop equipment and techniques of prac tical use to' utilities. Clear user benefits of a successful prototype would Include savings of clean-up labor, time, and overall costs. As this project progresses, we will be working with representatives of the user comunlty to obtain Input. We regard such Input as essential for the development of equipment which would be broadly acceptable by the Industry. 5-16 MO NS 018956 Sorptlon/Dtoorption of PolychlorInated 81 phenylt <i> Soils 0. C. Glrvln, 0. S. Sklerow, and C. C. Afntworth * Earth Sciences Department Settollo, Pacific Northwest laboratories Polychlorinated biphenyls (PCSs) have found their way Into wide variety of Industrial appli cations, a Major on* being coolant-insulation fluid* in transformers. Because of th* ubiquity and persistence of PCS*, eh* ability to 1) predict th*lr long-tana nobility In th* toll-water onvtronoont and 2) d*crib* th*lr ranoval fron contaminated aol I via toil nothing technologist, when r*n*dial action it required, la of particular {ntarait to th* alactrlc utility Induttry and regulatory agencies. Thia paper turnerIsos, for both typical and low organic carbon (OC) soils, th* adequacy of currently available data and estimation technique* and model* for describing PCS torptlon/deaorption In tell-water tystams. Deficiencies or gapt In avallabla data and hoy unresolved ittuo* *r* alto dltcuttadi 1) the rov*r*tblltty of PCS torptlon/deaorption and 2) the extent to which terption limits the nobility of PCSt in low OC toil*. Soils for *tieh th* woight fraction of OC (f ) > 0.00} ora oc operationally defined hart a* 'typical' OC aollt, end toils for vdtich f^ < 0.001 art defined at 'low* OC toils. Finally, th* offoct of turfactantt on Aroclor sorption in typical OC sella is briefly dlacuasod. ESTIMATION Of SOSPTiOW PAttdCTEIIS FWOH PHYSICAL COWStAHTS Typical OC Soils Sorption of hydrophobic nonionizabl* organic compounds (HNOCs) such as PCS* at low environmental coneontretIona can be doecrlbed by a I inoar Isotherm aodal, whor* th* amount of congener sorbed {$*) 1* related te th* equilibrium solution concentration |C*) by a conatant IK*) terwod the equilibria partition coafflclant, P S KC P m Phon doocriblng th* sorption of Aroclor mixtures, whor* the total analytical concentration of th* PCS* sorbed (S^) and In aolutlon (C^) are measured, the diatributlon ratio (K^) it the appropriate 5-17 HONS 018957 parameter for describing sorption end Is defined ss $ lil c (2) Relatively few x date are available for Individual PCB congeners; however, en abundance of K values Pd (or Its nonlinear eewlvelent, tha freundllch are available for various soil type* [1]. This situation Is unfortunate because is not an appropriate parameter for describing mobility unless the X s for the major Aroclor congeners are known. The distribution ratio (K ) Is not appropriate for pd describing nobility because X s Increase by many orders of magnitude with Increasing chlorine ~j~Sir P and thus the changes as a PCS mlsture moves through soil because of the chroaietogrephtc separation Of congeners of differing chlorine number. based on extensive data for a wide variety of hydrophobic compounds (Log K > ) and water sol* ubllltfes < 10 Kerlekhoff (2] concluded that soli organic carbon dominates observed variations In K for surface soils with f^ > 0.001 to 0.002, Soli particle site distribution snd expendable clay content (CM) In these soils are of secondary Importance. Thus, to a first approximation, K Is P proportional to the weight fraction (f ) of organic carbon In the soil, l.o., where Is the carbon*referenced partition coefficient; It Is relatively constant over a wide range of tells. for linear carbon*raforancad sorption, regression equation* of tho form, Log X a leg X b oc ow |b) have been extensively used In the literature, where Is the octeno1*water partition coefficient. The a and b correlation coefficient determined for various desses of hydrophobic compounds differ significantly (2*5). It Is strongly recommended that tho coefficients for one class of compounds should not bo used for another class (2). These coefficients have net been explicitly derived far e series of PCS congeners; however, both equations 3 snd b should bo appl(cable to PCSs. Once the a and b coefficients end their limits of accuracy ere established for e variety of tolls. X valuta end therefore X valuta for congeners for which no X or X date exist, can be estimated from experimental {<) or calculated (7) values. Development of thle Information would represent a significant advance because K s are far aasiar to measure than K values, it should be ew pt noted that X snd X are equilibria* coefficients. There Is strong evidence that X values reported P oc p in the literature for PCS congonora and other HNOCa may not bo equilibrium valuta and thus may bo s factor of two to three lower than If equilibrium wera reached. This evidence, in addition to tho paucity of data, currently preclude* determination of tho a and b coefficient* in equation b. 5-18 MONS 018958 BCVMSIBIUTV AW RELEASE RATES FWQH TYPICAL X SOUS The reversibility of PCB sorption In aqueous-soil systems Is an Important unretelved i(ue typ ified by conflicting Information in tho literature [9]. It is oftan reported for PCBs and HNOCs that both tha sorption and dasorptlon processes rapidly roach equilibrium, and that the overall process Is reversible, ret, others report, in addition to a rapidly released labile fraction <Q^), the existence of a highly release-resistant 'nonlebtle' or nenreversfbla fraction (0R), eomprlslnq $0% to 90% of the total tor.ed PCB [9). This resistant fraction is reported to require eatended and often harsh eatrec* tlons for complete removal of the sorbent from the solid pheso (10,11,12]. Those reports end others note that the qwenttty of this reslstont fraction end the difficulty of Its eatrectlon usually in crease with the duration of tho sorption stop. A key element in resolving theta conflicting ebaervetiona Has In tho fact that for both sorption and dasorptlon, tho time required to reach equtllbrtui Is much greater than commonly believed [2]. As a consequence, reported K values for PCBs may be as b much as a factor of two to thro* too low (9]. From a practical standpoint, tho question Is whether this resistant fraction Is truly fixed In tho sell matrix, or whether a alow release of PCSs (vie diffusion plus sorptton/desorptlon) occurs over o span of months or years. For soils containing Aroclors, the questions to bo addressed ere 1) nhet ore the relative quantities of sorbed PCB In tho labile ond resistant fractions (0 , 0^); 2) what Is tha release rata of tho labile fraction (k^) from the soil; and 3) is the resistant free* tlon an artifact ef not having reached equilibrium, end, if so, whet 1 the release ret# (k ) from this fraction. To directly address those questions, gos stripping technique ean bo used on aqueous suspension* of PCB-contamtneted soils. Using this technique, 0^, 0R, k^, kR, tha reversibility, and tha true equilibrium K values can bo determined simultaneously for 30 to AO of the major congeners In Aroclor P mixtures that hove sorbed onto sells. Tho gos stripping technique has bean used to measure these parameters for several HNOCs from sediment (2,1,11]. Tho release rates, determined in this way, represent the upper limit or maximum release rates that could occur In e sol 1'water system. TMe information directly quantifies the slgnlflcsnee of a given spill site as a PCB source term for subsequent migration In soil-water or aquifer-groundwater systems. PCB SOBPTION ON LBN OBCANIC BOILS Tho quantity of OC In soils typically decreases rapidly with increasing depth. Thus, within a few maters of the surface, the might function of OC con drop below 0.001. In addition, the OC frac tion In subaurfoco aquifer Mtorlel* often fella below this value. The sorption of HNOCe end PCSs on theee lew OC auterlels Is not well understood. Few dote exist In the literature for PCB sorption on low OC soils, and those available are for Aroclor sorption on pure clay minerals (1], Aa a result, no bates exist for prodlctlng the Influence of torption/deserptlon on the mobility of PCBs in those cases whore PCBs may contact low 0C softs and aquifer materials. 5-19 HONS 018959 A we l I-tested predictive model egulvelent to the carbon-reference model for HNOCe on typical 9C lolls (toot not OJiiit for low OC toil*. However, expendable cloy minerals (0.9., smectltea) art con* eldered to do the major aorbant for HNOCa in Ion OC materials [3,13]. 8y analogy with the carbon rafaranca .nodal, it has boon suggested (2] that K for low OC aoila may ba of tha form R R f 9 p cm cm where ta tha weight fraction of expendable clay nfnorala In tha aoll, and K la 0 day-referenced partition eoofficlant. IPvathar K la relstlvsly constant for apocific clay nlnoraia In a wlOa cm variety of aoila ramalnt a gveetlon. without aoma wall-tasted boat a for describing PCB aorption in low OC aoila, tha movement of PCBa through low OC aoila or agutfer natariala cannot ba aatlnatad with any dagraa of certainty aa tha following hypothetical example demonstatea. Consider tha retardation of henechloroblphenyl (2,*,5,2',*',S', x 10*) movement through a soil eharactarlaad by # 0.0005, 10b expandable clay, a porosity n 0.3, and density p 2.0 g/cnJ. Tha retardation la given by whore P la the ratio of the aater velocity (v) to tho velocity of the advancing PCB front {>) [it]. If wo make tha gueetlonable aaaumptlon that K can ba aatlmatad by tha earbon-roferonced R K f P P oc oc S00, than I M x 10J. Given thlt R and a water velocity of 100 em/d, we would expact PCBa ta ragulre approximately 700 yaara ta move 100 meters. This estimate la baaed on tho carbon rafaranca modal that wo know does not apply to low K soils [2]. besad on our currant lack of Information in oatlmotlng a K value for this low OC, 10b, clay aoll. It la not unroeaoneble to poatulato that tha R PP used above could bo In error by as much aa a factor of *50. In this ease, tho 100-motor transit time could bo aa lew aa IS years or aa high aa 35,000 years. Thus, wa currently have no basis with which to estimate tha tranapart rata af PCBa In low 0C sella. Tha point hora Is that additional Information on IM0C/PC8 sorption in low 0C soils Is cloorly needed. Iffoct of Surfoctonts an Aroclor Sorptlon/Posorptlon ark by ana of tha authors [IS] haa domanstrotod that Aroclor 12S2 aorption from aguooua solution onto a soil containing *% OC and 21b clay la significantly reduced In tha presence af an anionic turfactvit. Aa the.concentration of this surfactant la Increased, tha aorption steadily doereases. Surfactant concentrations examined ware all wall below the critical micella concentration (cac) at which a discrete laailaclbla phase (micelles) form. in addition, tha pH dependence af Aroclor 12*2 sorption hes boon examined on an Iran on Ido ca--only found In aoila. In tha abeence af cationic or anionic surfactants, Aroclor 12*2 aorption does net vary with pH. In the presence of either tha cationic or anionic surfactant studied (below emc), Aroclor 12*2 sorption shows a strong pH Papondance and la found to bo completely reversible for sorptlon/deaorptlon times on tho order of days. Tho influence of surfactants on tho release rates of tho slowly desorbing or 'resistant' fractions af PCBa In aoila haa not aa yet boon examined. 5-20 HOMS 018960 Theae obeervatlona may hove algntftcant Implications for aqueous-based soil-meshing methodologies In nhlch single* or *laed*b1edegradoble surfactants art uaod. Currently, aork sponsored by the Electric Power Research Institute with thla objective In mind la under may at Battalia Northwest to determine the Influence of surfactant* on PCS sorpelon/dasorptlon and tho roltaao rates for soils that hove boon fn contact with Aroclora for extended tlmoa. sugwMtf Wo hove Idontlflod specific aroaa mhoro additional aorptlon/doaorptlon information rolatod to tha mobility of HNOCa and PCta In aolla would bo oaoful to tho oloctrlc utility Induatry and regulatory agencies. Specifically, thoao aroaa aro 1) dotormlnatton of K to K correlation coofflclonta to P ow enable eee of extensive X^ end other physlcat dote for ootlmotfng of X ar 2) determination of the reversibility and rolooao ratoa of Aroclora from aolla In aqueous systems, 3) aorptlon/doaorptlon In low OC toll*, end M tho Influence of aurfeetanta on aorptlon/doaorptlon and datorptIon rolooao ratoa of Aroclora from aolla for poaalblo applleatlan In squmout-baaed tol1-mashing technology. Finally, It ahewtd bo noted that although PCSa ara Important compounda to tho utility Induatry, they aloe ropro* lent an Ideal tool for Investigating the Important hydrophobic Interaction* that play o major role In tho ettenuetlon proceaaea of other organic ccmpoundo that My bo of current or futuro Importance to tho utility Induatry. ACKWOWLEPCEXWT Tho outhora mlah to odknomlodgo CPS I for aupport of thla mark undor HP 120*22. Wo ore grateful to Dr. S. Xawal, CPSI Project Manager, for hit technical guldonca, Mnagawant, end aupport. SEFBtOCES 1) Clrvln, D. C. and D. &. Sklorow. Attonuotlon of Polychlorinated Biphenyl* In Solla: Lltoroturo ftevlem. Final Soport for koaoorch Project 120*22, aubmlttod for EPS I publication Auguot IMS. 2) Korlckhoff, S. ff. "Organic Pollutant Sorption in Aquatic Syateme." J. Hydraulic Eng., voi. 10, no. S, IMA, pp. 707*7)3. 3) Hoaoott, J. J., J. C. Meeno, M. L. Sanwort and S. C. Wood. Sorption Prooortloo of Sodlmowta and Enmfv Solotod Pollotomta. Athene, Georgia! Environ. Procoaaoa Branch, Environ. Soooorch tab, 1*0, EPA-400/3-BO-OA1. t) Schmortonboek, S. P. end J. Woatal1. "Transport of Nonpolar Orgonlc Compounda from Surface Water to Groundwater, laboratory Sorption Studloa." Environ. Scl. Tochnol.. vol. IS, 1M1, pp. 1340* 13*7. ,3) Karlckhoff, S. W. "Seal'Empirical CatlMtlon of Sorption of Hydrophobic Pollutente on Natural Sodlmonta and Solla." Chamoiphoro, vol. 10 1M1, pp. S3J*W. () Rappoport, R. A. end S. J. Eloonrolch. "Chromatographic Determination of Octoo1*Wotor Partition Coofflclonta (K_'a) for SB Polychlorinated Biphenyl Conganera." Environ. Sol. Tochnol., vol. 11, IMA, p. 1. 5-21 MQNS 018961 7) Lao, A. J. "Calculation of Partition Coofficlont* llsaful In tho Ev1uation of th Relative Hatard* of Various Chemical* 1ft the Environment." In K, J. C. Sympodaa on Structure Activity Correlation* In Studio* of Tonicity and Sloconcontretlon with Aquatic Qroenlama ad. C. 0. Velth, Wlndtor, Ontario: International Joint Coamission, Koflotowlch, D., Secretariat, 1975. a) Karlckhoff, S. W. and K. A. Horn*. "Sorption Dynamic* of Hydrophobic Pollutant* In Sediment Sutpentlon*," Environ. Sc1 Techno!. (In pro**, t983). 9) Oltoro, D. M. and L. H. Hortempo. "Reversible and Resistant Component* of PCB Adsorption*0o*orptlont Isotherms." Environ. Set. Technol. vol. 14, 1982, p. 59*. 10) Karlckhoff, S. V. and 0. S. Orown. "Paraquat Sorption at a Function of Particle Slto In Natural Sediment*." J. Environ. Quol.. vol. 7, no. 2, 1978, pp. 296-252. 11) Kerlekhoff, S. W, "Sorption Kinetics of Hydrophobic Pollutant* <n Natural Sediment*." In Con taminant* and Sediment*. Vol. 2, *d. R. A. Baker, Ann Arbor, Michigan! Ann Arbor Sctonco Pub* 11after ai Inc., 1980, pp. 199*205. 12) Freemen, 0. H. and l. S. Cheung. "A Col Partition Modal for Organic 0oorptlon from a Pond Sediment." Science, vol. 219, 2981, pp. 790*792. 13) Maaaott, J. J., W. L. Benwort, S. C. Wood and J. C. Moan*. "Sorption of a-Nephthol: implication* Concerning tho Limits of Hydrophobic Sorption." Soil Set. Soc. Amor. J.. vol. AS, no. 1, 1981, pp. 38-*2. 19) Oierry, J. A., ft. W. Cl 11 ham and J. F. Barker. "Contaminant* In Groundwater: Chemical Pro* eetaoe.1' In Groundwater Contamination. Studio* In Ceophyalca Soria*. Weahlngten, O.C.: Notional Academy Proao, 198*, pp. *8*8*. IS) Chou, S. F. J., C. C. Ainsworth and ft. A. Griffin. 198*. "Effact of Surfactant* on tho Sol ubllfty and Sorption of Aroclor 12*2 by Eorth Notorial*." Aaron. Abt.. pp. 2*, American Society of Agronomy 78th Annuel Mooting, Los Vogoa, Nevada, Nevaiaber 25*30, 198*. 5-22 HONS 018962 DCSORPTION OF PCBs IN A SOIL-AQUEOUS SOLUTION SYSTEM M, . Esslngton, M. R. Resketo, M. M. Cllath, A. A. Elseewl and C. P. Doyle The adsorption-desorption behavior of PCBs In soil-aqueous systems has generally only been examined using PCB concentrations well below their aqueous solubilities. The applicability of results obtained from these studies to acciden tal Arodor spills from point sources such as transformers and capacitors and leaks from waste disposal sites are likely to result In localized PCB concentrations that far exceed their aqueous solubilities. The objectives of this study were to characterize the partitioning of capacitor oil Aroclor 12(2 between soil and aqueous equilibrium bathing solutions over a wide range of PCB concentrations. PCB behavior was examined as a function of homolog type and as a function of aqueous solution composition. The results obtained are expected to provide greater Insight Into the environmental behavior of the various PCB homologs and to provide usable data to predict the mobility of PCBs In environ ments exposed to accidental Aroclor spills. Subsamples of a California soil (Llnnd silty clay loam, 2.41 O.M., 33.41 clay), were treated with Aroclor 1242 to Impart the following Aroclor concentrations: 0, 25, 50, 100, 250, 500 or 1000 mg Aroclor*kg-`. Desorption studies were performed by equilibrating 5 grams of Aroclor treated soil with 50 ml of either (1) deionized water (DW), (2) 0.01 N CaC12H20, or (3) California Waste Extraction Test Solution (WET) consisting of 0.2 M citrate and 0.15 M NaCl adjusted to pH 4.5. Solutions (l) and (2) were used to characterize the behavior of PCBs In soil as a result of precipitation or Irrigation with Colorado River water, respectively. The WET solu tion was Included to determine Its effectiveness In extracting PCBs. Aroclor treated L1nn< soil suspensions were equilibrated for 48 hours at 25*C. Following the equilibration period, the suspensions were centrifuged at 35000 x g for 35 minutes for phase separation. The supernote solution was removed and repeatedly extracted with hexane, which was then passed through Na2S0t and reduced In volume by rotary evaporation. The settled L1nn< soil was extracted with 1:1 acetone: hexane which was passed through Na2S0k and reduced In volume by rotary separation. The hexane extracts from both supernate and soil were subsampled and diluted to the appropriate Aroclor 1242 standard range for GC/ECD analysis. A gas chromatograph equipped with a tJN1 electron capture detector was operated under the following conditions: Injection temperature (230*C), detector temperature (340*C), column temperature 180*C. The Aroclor 1242 PCB homologs were separated by a 1.8 m x 2 mm l.d. chromatographic column packed with 31 0V-101 on 100/120 mesh Chromasorb w-HP 5-23 HONS 018963 and with nitrogen carrier gas delivered at 20 ml`min*1. Data collection and peak area calculations were performed by an Integrator. The gas chromatograms were used to quantify PCB compositions on an Aroclor 1242 equivalent basis and on a PCB homolog basis. With respect to the latter, the chro matograms were partitioned according to data presented by Webb and McCall1 and Hutzlnger et al.2 Aroclor 1242 was partitioned Into dlchloroblphenyl (DCB), trlchloroblphenyl (TCB), and tetrachlonoblphenyl (TTCB), composing 17%, 39% and 32% (weight basis) of Aroclor 1242, respectively1. The distribution of PCBs between adsonbed and aqueous phases are routinely eva luated using the Frtundllch adsorption Isotherm model. At equilibrium the adsorbed PCB concentration, x/m (mass of adsorbed PCB/mass of adsorbent, ug'kg*1) Is related to the aqueous PCB concentration c (ug>L-`) by the equation: x/m KFC1/n {1) where and 1/n are empirical parameters Indicative of the relative adsorption capacity and adsorption Intensity, respectively. The constants are evaluated via a logarithmic transformation of the x/m and C adsorption Isotherm data followed by regression analysis to fit the linear form of equation (1). For PCBs, adsorption data are found to fit this model when C Is approximately 60 to 70% of the aqueous PCB solubility. Aroclor and PCB homolog desorption from the Llnnd soli. Irrespective of PCB homolog or equilibrium solution composition, corresponded to the Freundllch model at low solution concentrations Illustrating adsorption-desorption control on aqueous solution PCB content In a slightly contaminated soil. Freundllch para meters. Ky and 1/n. determined through linear regression analysis on the the three lowest system Aroclor concentrations (excluding system blank), are shown In Table 1. Table 1. Freundllch parameters characterizing Aroclor 1242 and homoloq desorption Llnnd soil.________________________ DW CaCl v MET kf 1/n `F 1/n *F 1/n Aroclor 1242 1242-OCB 1242-TCB 1242-TTC8 1063.4 367.3 1044.7 3898.2 1.05 0.96 1.06 1.07 394.5 196.5 301.4 2114.2 1.15 0.96 1.23 1.05 2570.4 414.4 3022.5 3123.8 0.83 1.04 0.77 0.80 5-24 HONS 018964 Aroclor 1242 homolog retention, as measured by the magnitude of KF (ug*kg*>) PCB adsorbed when the equilibrium aqueous PCS concentratln Is 1.0 ug-l->) was found to Increase In the following order: DCB < TCB < TTCB, Irrespective of solution com position, This differential homolog behavior has been noted by a number of Investigators through the examination of specific PC8 congeners In soil-aqueous systems3*5. At elevated Arodor system concentrations the adsorption data appeared to asymptotically approach a maximum equilibrium solution PCB concentration. That Is, a positive change In x/m would not result In a corresponding change In C. This behavior might be Indicative of solubility controlled solution PCB concentrations In highly contaminated soil. Indeed, If the full range of PCB desorption data are considered, one would find an exponential relationship between c and x/m: C - [exp (Sx/m)] * C% (2) where x/m and C are as previously defined, a and t are empirical constants, and Cs the aqueous solubility of the species under consideration. In Table 2 are shown C( values for Aroclor 1242, DCS, TCB and TTCB In the three aqueous systems, as determined from desorption data and Eq. (2) In comparison to published PCB (homolog and congener) data In deionized water2,*-11. Table 2. Aroclor and homolog solubilities. DU desorption published CaCl T >211-0 WET Aroclor 1242 214.6 19 - 340 325.0 480.0 1242-DCB 143.3 43 - 1941* 234.1 169.0 1242--TCB 91.6 17 - 228* 118.4 265.0 1242-TTCB 21.7 7.3 - 175* 38.1 145.0 `Includes solubility values for specific PCB congeners. One finds the solubility values generated from desorption data are within published solubility ranges, Illustrating the solubility control on aqueous solution PCB con tent In highly contaminated soils. Solubilities and Freundllch parameters were affected by the composition of the equilibrating solution. The solubility of PCBs In the CaCl2,2HJ0 system were ele vated with respect to those In the deionized water system. Conversely, PCB reten tion was greater In the deionized water system. The WET solution, developed for use In evaluating the hazardousness of waste materials, was less effective than either deionized water or CaCl2-2HjO solution In extracting PCBs when PCB behavior 5-25 MONS 018965 was adsorption control ltd (l.e., low system PCB contents). However, at elevated system PCB concentrations (solubility controlled) the WET solution provided a higher degree of extraction than did either deionized water or CaCl2.2H20. These findings Indicate that under low and high system PCB concentrations, the WET solu tion would not provide an adeguate assessment of Aroclor 1242 PCBs solubilized by either rain water or Irrigation water. 1. Webb, R. G. and A. C. McCall. 1972. Quantitative PCB standards for electron capture gas chromatography. J. Chromatogr. Scl. 11:366-373. 2. HutZinger, S., S. Safe and V. Zltko. 1974. The chemistry of PCBs. Chemical Rubber Publishing Co., Cleveland, OH. 3. Chlou, C. T., P. E. Porter and D. W. Schmeddlng. 1983. Partition egulllbrla of nonionic organic compounds between soil organic matter and water. Environ. Scl. Technol. 17:227-231. 4. Voice, T. C., C. P. Rice and W. J. Weber, Jr. 1983. Effect of solids con centration on the sorptive partitioning of hydrophobic pollutants In aquatic systems. Environ. Scl. Technol. 17:513-518. 5. Gschwend, P. M. and $. Wu. 198S. On the constancy of sediment-water partition coefficients of hydrophobic organic pollutants. Environ. Scl. Technol. 19:90-96. 6. Haque, R., D. W. Schmeddlng and V. H. Freed. 1974. Aqueous solubility, adsorption, and vapor behavior of polychlorinated biphenyl Aroclor 12S4. Environ. Scl. Technol. 8:139-142. 7. Haque, R. and 0. Schmeddlng. 1975. A method of measuring the water solubility of hydrophobic chemicals: solublltty of five polychlorinated biphenyls. Bull. Environ. Contam. Toxicol. 14:13-18. 8. Dexter, R. N. and S. P. Pavlov. 1978. Mass solubility and aqueous activity coefficients of stable organic chemicals In the marine environment: polychllronated biphenyls. Mar. Chem. 6:41-53. 9. Paris, 0. F., W. C. Steen and G. L. Baughman. 1978. Role of the physicochemi cal properties of Aroclor 1016 and 1242 In determining their fate and transport In aquatic environments. Chemosphere 7:319-325. 10. Cel!alien, M. A., H. W. Sllmek, N. W. Gabel, E. P. May, C. F. Fowler, J. R. Freed, P. Jennings, R. L. Ourfee, F. C. Whitmore, B. Maestri, W. R. Mabey, B. R. Holt and C. Gould. 1979. Water-related environmental fate of 129 priority pollutants. Vol. 1. Introduction and technical background, metals and Inorga nics, pesticides and PCBs. US EPA-440/4-79-29a. Washington, DC.11 11. Miller, M. M., S. P. Waslk. G. Huang. W. Shlu, and 0. Mackay. 1985. Relationships between octanol-water partition coefficient and aqueous solubi lity. Environ. Scl. Technol. 19:522-529. 5-26 HONS 018966 SOLVENT CLEANING OF PCB CONTAMINATED SOILS Leo Weittman PhD Acurex Corporation Cincinnati, Onio Thla paper describes a pilot-scale study of a novel system for cleaning aolls that have been contaminated with PCB. The process uses solvents to extract the PCB from the soil. The PCB Is then concentrated and the solvent reclaimed. Final PCB concentrations of leas than 2 ppm on the soil, have been achieved. The system was designed and built In late 1994. It was operated using non-PCB soils and shown to parfora to design specifications. A permit to operate the system with PCB contaminated soil was obtained In February. 1985. Eight seta of teete were conducted end these demonstrated that soli containing up to 1.983 ppm PCB wart successfully treated to less than 2 ppm. In addition to demonstrating this pllot-ecale ayatem. theae taata provided design data for conatructlon of a full-scale prototypa soil washing system. The results of these tests are summarised in Teble 1. Figure 1 gives the schematic of the pilot soil washing system. It consists of s soil contactor, dirty and damn solvent storage tanks, a solvent reclamation system, eteem generetor end ancillary piping equipment. It also includes vent condensers and an activated carbon adaorptlon system for eir pollution control. Operation proved very simple. One person had no difficulty operating It. Based on the results obtained with thla system, a 7 cubic yard mobile toll washing system was designed and is now under construction. The following sections describe the major components of the system The soil contactor is s semi-cylinder 4 feet in length with a radius of 2 feet. The soil wmmbsr is subdivided Into two wash chambers, along Its axis. The volume of each wash chamber Is 11.5 cubic feat. The isolated chambers allow operation of the soil washer with two different batches of toll at a tlaa. Accasa to each chamber for soil loading and removal, or to obtain soil samples for analyses, is through two hinged Uda which comprise the entire flat side of the semi-cylinder. The lids are sealed with s Neoprene gasket and are clamped to the sain body for oparatlon. 5-27 HONS 018967 Each wash chamber Is subdivided by filters installed In presses Isolated In slotted holders at each end of the central soil ehaaber. The available volume In the soil chaabers la 70 cubic feet, although the chaabers were not filled entirely during operation, Approximately 450 pounds of soil was cleaned during each test. The washer is oounted to a fraae by the shaft along its axis. It is rocked about its axis in order to agitate the soil/solvent alxture. It has a drive aechanlsa for rocking the washer which swings the contactor 90 degrees In either direction. The system was tested on three types of soil, a (1) 502 alxture of sand and clay. (2) 702 clay alxture end (3) dark lossy top-soil. The sand/elay alxtures were obtained froa the local Cincinnati area. These soils were PCB-free and were contaaineted in the washer to the specified aaaount of PCB. The third type of soil, dark/loaay, was obtained froa a contaaineted site that was being cleaned up. It contained up to 1923 ppa PCB in it. The results of the tests were very encouraging. Table 1 shows that all of these aaaplea were cleaned to leas than 2ppa in leas than 12 washes. The analytical results showed excellent closure on the asmounts of PCB reaoved In all but one test. In Run 15. the untreated soil was analysed to be 548 ppa. The PCB removed, however, corresponded to 1941 ppa. It is asssuned that this soil had a pocket of very high concentration PCB In it which waa reaoved by the washing acheae but was not picked up by the saapling procedure used. Based on these successful results, a full-scale system is now under construction. ACKNOWLEDGMENT The wort described herein was sponsored by the Ooel Combustion Systems Division of the Bltctrlc Power ftsseerch Institute. Their support and the technical assistance of the EPKI project manager. Dr. Ralph Kasai,is gratefully acknowledged. 5-28 HONS 018968 DEMISTER XONDENSER REROlLEX u*s Figure 1. SctttMtlc of Pilot Soil Masher HONS 018969 Table 1 RESULTS OF SOIL CLEANING TESTS RUN ft 1 2 3 4 5 6 7 8 BY AMOUNT OF PCS ADDED 37 503 - ppm PCS BY ANALYSIS 38 492 67 135 548 832 773 18 BY AMOUNT OF PCS REMOVED 38 436 72 141 1941 910 678 16 NO OF HASHES 3 10 6 6 12 12 10 5 FINAL PCB cone. ppm <2 <2 <2 <2 <2 <2 <2 <2 5-30 HONS 018970 PART 6: RISK AHALTSIS ARO NANACENEKT HONS 018971 THE INSURANCE INDUSTRY AND THE PCD EXPOSURE SITUATION BY RICHARD G. CLARKE, CPCU INTRODUCTION Dramatic changes are occurring In the Insurance industry regarding pollution re lated risks. Insurance Industry experience with pollution (toxic chemical, hazardous waste, environmental) claims and loss has prompted a wave of policy exclusions for these types of exposures. PCB is Included in the Insurance Industry category of "pollution" exposure. The extensive loss seen with several notorious PCB Incidents clearly indicates that pollution risks are two-fold. In addition to property damage claims. Insurers have been faced with many liability claims (bodily injury as a result of exposure). Due to extensive clean up, EPA Involvement, and the uncertainty of human exposure implications, accurate prediction of loss is nearly Impossible. It is for these reasons that Insurers are excludinn pollution related risks from current policies. Lack of Insurance leaves PCB owners financially vulnerable, and requires that PCB managers play a more significant role in corporate risk re duction. Understanding risk management principles can help the PCB manager to be most effective. WHAT PCB MANAGERS SHOULD KNOW ABOUT TODAY'S INSURANCE MARKETPLACE Never has the axiom "the claim is the eother of the exclusion" had more applica bility than to the general pollution liability exposure. Recent experience with pollution related claims has revealed that the actual extent of exposure for pollution related risks is uncertain. This applies to both property and liability exposure possibilities. Property exposure potential Involves direct damage to Insured property, as well as potential loss of income due to business interrup tion and associated "extra expenses". With PCB incidents requiring extensive clean up, and in one case, closure of a building for several years, it's no wonder that carriers are wary. Liability exposure potential, involving bodily injury claims, holds equal uncertainty. Widespread contamination possibilities coupled with the most environmentally conscious and knowledgeable public yet presents liability exposures of tremendous magnitude. The distinction between property and liability exposure must be addressed by the PCB manager. PCB risk assessment mist ask what damage to property is likely (including business interruption loss), as well as who and how many could be affected by a PCB incident. As previously stated, the answers are difficult to come by. Insurance Industry uncertainty regarding these questions is indicated by two significant Industry developments: 6-1 HONS 018972  The Insurance Industry capacity to provide high limits of liability Insurance and coverage for other than relatively routine property exposures Is very strained now. The traditional source of rein surance (insurance carrier's Insurance coverage on the various coverages which It writes) eminates from London - and there is a shortage of "Investors" who wish to take risks relating to large liability or property losses. The common, traditional source of Insuring bodily injury for busi ness or utility operations Is the general liability Insurance policy. Effective January 1, this particular Insurance contract, considered one of the most standard, will be undergoing extensive change. Most carriers will accept the new position of not being responsible for claims or exposures which are alleged to have occurred rather than just recently and will create severe restrictions on covering pollution liability exposures. Coverage for pollution risk unless sudden or accidental (virtually Impossible to purchase at this time) may become unavailable altogether as the words "sudden1' and "acciden tal'' are redefined. If available at all, such coverage would demand unrealistic premium charges. In light of these insurance Industry developments, and as PCB exposures become better known, the Inevitable result will be "withdrawal" by those carriers still providing some measure of coverage. Many electric utilities are "self-Insured", reducing their dependence on carrier limitations. Self-Insurance, however, does not Isolate utilities from PCB expsosure problems. There Is always a limit on self-Insurance, even if It Is the last available dollar of corporate assets (an unthinkable situation). Certainly, had various utility companies anticipated the extent of PCB caused losses, preventive measures would have been taken. The fact that major carriers are discontinuing pollution related coverage - a business decision designed to avoid technical Insolvency because of the loss involved - should be a warning signal to those who are self Insuring PCB risks. If Insurers won't sustain PCB losses with their tremendous reinsurance resources, how can an electric utility or major industrial facility? THE PCB HAWSER'S ROLE IM RISK REDUCTION Since Insurance or self-insurance cannot be relied upon for total protection from PCB losses, the PCB manager becomes a more Important Influence on prudent pro tection of corporate assets. Although Insurance cannot provide full coverage, the risk management principles used In that Industry can be useful to the PCB manager for risk reduction plans. The science of risk management identifies alternatives for reducing exposure to determine loss potentials. Risk management principles purport that the best possible alternative Is to avoid or elImlnate the loss exposure. If not viable. 6-2 HONS 018973 the second best alternative is to control or retain (partially via deductible amounts, or totally via self-insurance) loss exposure. If this also is not a viable option, transference of the financial effects is then considered. (In the case of utilities and large manufacturers, there rarely are parties to whom the responsibility of loss exposures can be transferred.) Finally, If all else fails, the last option is to purchase insurance coverage. This thought process ensures that effort (and money) is most prudently spent, i.e., when possible, $1,000 is spent once to eliminate the risk rather than $100,000 over a period of years to Insure the risk. For the PCS manager, whose Job has become one of managing risk as well as electri cal eguipaient or environmental affairs, this thought process can be a prudent guideline that is well understood by management. The common communication gap that exists between the corporate risk manager and PCS manager must be closed. Responsibility for protecting and Informing manage ment from the same perspective is shared by both parties. Effective communication will accurately identify PCS exposures and will facilitate decisions to avoid, eliminate, control or retain these exposures. LOOKING TO THE FUTURE Although the Insurance industry is cyclical, it is unlikely that coverage for high exposure areas such as pollution will ever be easily available. As a result, PCB owners must become even more active in eliminating and controlling PCS risks in order to preserve financial integrity and avoid catastrophic loss situations. Options do exist for effectively reducing and eliminating PCB risk. Dyking, vaulting and closure - isolation methods can help control exposure. Reclassification technologies go even a step further toward risk elimination. Control is mandatory because of catastrophic loss exposure. PCS elimination and the prospect of entirely non-PCB systems is the most prudent and reasonable alternative today, and the PCB manager plays perhaps the greatest role in the achievement of this corporate goal. 6-3 HONS 018974 PREVENTIVE MEASURES FOR R0IUCTION OF AIRBORNE PCS CONTAMINATION RISK Brian U. West P.E. - West S Hansen Engineers, Inc. Warren B. Hansen P.E. - Tetra Tech, Inc. INTRODUCTION Electric utilities as well as other askarel equipment owners are Implementing transformer fire prevention measures, either to comply with the July 17, 1985 "PCB Electrical Use Rule," or voluntarily. In recognition of the need to assist menber utilities conducting airborne PCB spill risk reduction programs, EPRI sponsored development of a design manual addressing technical, economic, and environmental aspects of preventive engineering. This document (CS-4094, Design Manual for Reducing Airborne PCB Contamination) Is now available through EPRI Research Reports Center. The Intent of the Design Manual is to describe a variety of cost-effective preventive measures that can be rapidly Implemented. It Is repeatedly emphasized that only aqulpment replacement (l.e., complete removal of all PCBs) will eliminate all spill risk. Other preventive measures, though less expensive, perpetuate a residual spill potential. MANUAL DESCRIPTION The Design Manual Is organized Into four Sections presented sequentially In the order of their occurrence In a risk reduction program. These are: 1. Ranking PCB Installations on the basis of their potential for widespread contamination 2. Selecting the most appropriate spill reduction approach 3. Determining design requirements 4. Preparing design plans and specifications. Each Section Is self-contained, consequently users can select those elaaents applicable to their particular situation for Integration Into an overall risk reduction program. Ranking PCB Installations on the Basis of Their Potential for Widespread Contami nation Utilities that own numerous askarel transformers may require several years to caaplete a system-wide risk reduction program. This section describes a methodology 6-4 MOHS 018975 for prioritizing PCB Installotions based on contamination potential. The results provide an objective basis for scheduling corrective action. The risk ranking methodology utilizes a quantitative scoring format taking Into account both spill probability and consequence. The major parameters affecting spill probab111ty are: a Equipment condition a Electrical system design e Operating environment. The major factors affecting spill a Public safety a Building value a Contamination migration a Cleanup conplexlty. consequence are: potential Selecting the Host Appropriate Spill Reduction approach Preventive measures addressed in the Design Manual Include: a Replacaeent a Relocation a Isolation a Protection (electrical, mechanical, fire alarm, and maintenance). Presented In this Section is a procedure for evaluating the technical, economic, environmental, and regulatory factors affecting each alternative and for comparing those factors to select the most appropriate approach. Determining Design Requirements Upon selection of a risk reduction approach (or combination of approaches), a site Investigation to Inspect design-related conditions Is required. Transformer replacement and relocation are not addressed In the Design manual, as these activities are veil understood by all utilities. Isolation and protective measures are included. A predeslgn Investigation worksheet, utilizing a checklist type format, as developed for survey use. Critical design parameters are Identified to ensure thorough data gathering. Technical guidelines for each alternative are presented, principally In tabular form, for ready reference. 6-5 MOMS 018976 Preparing Design Plans and Specifications This Section Is basically technical In content. Its organization Is similar to the predesign Section to facilitate cross-reference. Those techniques, equipment, devices, and procedures determined applicable to airborne PCS spill prevention are described In detail. Recommended applications and engineering specifications are presented. References and a bibliography are Included to facilitate acquisition of additional Information. Key excerpts from the National Electric Code are also Included. SUMMARY Installation of risk reduction measures can rapidly and Inexpensively lower the probability of extensive airborne PCB contamination. Maximizing the cost-effectiveness of this approach requires a well-planned survey program. Including on-site Investi gations. The Design Manual for Reducing Airborne PCB Contamination Is available to assist member utilities and others conducting PCB spill risk reduction activities. 6-6 HONS 018977 ENVIRONMENTAL FATE OF PCBS IN MINERAL OIL SPILLS Stuart M. Brown and Artemis Antipas* INTRODUCTION At of 1982, approximately 21 million places of electrical equipment, or 08 percent of ell electrical equipment, owned by the utility industry contained mineral oil (IK Some mineral oil equipment has becoew contaminated with low levels of PCS during either manufacturing or routine equipment maintenance. Approximately 93 percent of the mineral oil equipment contains less than 100 ppm of PCB, 70 per cent contains less than 10 ppm and 44 percent contains less than 1 ppm (1). This paper examines the environsmntel behavior of PCB in a contaminated mineral oil spill and shows that volatilisation and leaching losses from a mineral oil spill are significantly less than those from an equivalent askarel spill. Thus, mineral oil spills pose considerably less risk. Existing and pending spill cleanup guidelines apply uniformly to both types of spills. CONTAMINATED MINERAL OIL SPILL MOOEL The behevior of e contaminated mineral oil spill was examined by using e simple model describing the behevior of chemical spills developed by Phyper end Mackey (2). The model divides e spill event into four separate time periods: Psriod A. A relatively ehort time period wherein the chemical penetrates into the soil. Period >. A slightly longer tism period wherein penetration continues end the chemical redistributes in the soil pores until residual saturation is achieved. *Groundvater Hydrologist and Senior Chemist, reapectively, CH2M HILL, Bellevue, Neshington. HONS 010978 6-7 Period C. A relatively long tin* period wherein dissolution of the pur* phase of the ch*nic*l occurs as water percolates through the soil. Period D. A time period of variable duration wherein the remaining chemical dissipates from the soil coluain through volatilization, leaching, and degradation. Th* original version of the modal assumes the ehamical (e.g., PCBJ la preaent as a pur* liquid. In th* css* of a contaminated mineral oil spill, th* PCB is present as a trace constituent in the oil. At th* PCB concentretions typical of most con taminated mineral oil spills, it is reasonable to assume that th* PCB-oil mixture behaves as an ideal solution. Given this assumption, it is possible to show that for two sparingly soluble organic compounds in th* presence of water p^ partial pressura of PCB in th* presence of mineral oil x^g - PCB mole fraction in mineral oil p#* pur* phase PCB vapor pressure C PCB solubility In water in the presence of mineral . oil C pure phase PCB solubility in water At a PCB concentration as high as 500 ppm of Aroclor 1242, th* PCB mol* fraction is only 0.0004. Thus, when a mineral oil spill occurs, the oil will substantially reduce the vapor pressure end solubility in water of the PCB, which in turn leads to rtducsd volatilisation and leaching losses. As th* spill weathers, th* mineral oil will dissipate through volatilisation, leaching and biodegradation producing an increase in the PCB mol* fraction. HONS 018979 6-8 The model developed by Phyper and Mackey was modified to account for the affect of tha mineral oil on PCB volatility and solubility and to estimate the change in PCB mole fraction during each time period. MOOCL RESULTS The model was used to examine the behavior of a 10 gallon mineral oil spill con taminated with 200 ppm of either Aroclor 1242 or Aroclor 1260. The spill was assumed to cover a 100 square foot eree composed of a sandy soil. figure 1 shows the estimated percentage of the mineral oil and PCB (as either Aroclor 1242 or 1260) remaining in the soil with time following the spill. During Period A (i.a., penetration) and Period B (i.e, redistribution) negligible mineral oil and PCB are lost from the spill site. As Figure 1 shows, both periods sre relatively short in duration* combined they took less thsn 3 hours. During Ptriod C (i.e., dissolution), the mineral oil begins to dissipate quite rapidly while relatively little PCB is lost. Once dissolution of the mineral oil is coatplate at the end of Period C, the PCB begins to dissipate. The Aroclor 1260 dis sipates more slowly thsn the Aroclor 1242 because it is composed of more highly chlorinated PCB congeners that ere less volatile, less soluble in water, end less biodegradable. The delay experianced by the PCB illustrates the impact of the mineral oil on reducing volatilisation and leaching losses from s spill site. The effect of the mineral oil is further illustrated in Table l which lists esti mated volatilisation and leeching rates of Aroclor 1242 for the spill conditions discussed above and for an aquivalent spill of pure Aroclor 1242. These results how that volatilisation and leaching losses for the contaminated mineral oil spill are significantly less then those for the pure Aroclor 1242 spill. Losses decrease by three orders of magnitude, in the case of volatilisation during the first three time periods. Once dissolution of the mineral oil is complets, the lose rates for the two spills sre the same. The model results demonstrate that PCB levels in air and groundwatar around a contamlnatad mineral oil spill site will be orders of magnitude less than those around an equivalent eskarel spill site. Thus, potential exposure levels and assoeletad health risks will be lower. HOMS 018980 6-9 PERIODS PERIOD C PERIOD D Figure 1. Percent remaining with time for a mineral oil spill containing 200 ppm of either Aroclor 1242 or Aroclor 1260. Table 1 ESTIMATED VOLATILIZATION AND LEACHING LOSS RATES FOR A 200 PPM CONTAMINATED MINERAL OIL SPILL AND AN EQUIVALENT PURE AROCLOR 1242 SPILL (gm/day) Period A B C 0 Contaminated Mineral Oil Volatilisation 7xlo'3 7xl0~3 IxlO*4 IxlO*1 Leaching - 5xlO*5 6xl0*4 Pure Aroclor 1242 volatilisation Leaching 38 - 7 SxlO*1 IxlO*1 5xl0*3 SxlO*4 6-10 HONS 018981 RPEROiCES 1. USMAG. Co--nt and Studlas on tha Ui of Polyehlorinatad Biphanyls in Msponsa to an Ordar of tha Unitad Stataa Court of Appaals for tha District of Columbia, Voluma 1, Exacutivt Suamary and Intagrstad Cowaants. EEI, Washing ton, D.C., 1982. 2. Phypar, J.D. and D. Maekay. "A Simpla Miero-Computar Modal of Short and Long Tam Chamlcal Bahavior on Land," Procaadings of tha Saeond Annual Tachnical Samlnar on Chamlcal Spills, Toronto, Ontario, 1985. 6-11 HONS 018982 MANAGING ECONOMIC RISKS DUE TO ELECTRICAL EQUIPMENT CONTAINING PC8S: ANALYTICAL TOOLS TO SUPPORT UTILITY OECISIONS by Deborah A. L. Amaral Dean W. Boyd Oavld Cohan Michael S. Johnson Oonald S. Wilson OECISION FOCUS INCORPORATED The PCS Economic Risk Management Model (ASK) and the Contaminated Oil Economic Risk Management Model (COIL) are decision support tools designed to help utility personnel manage equipment containing or contaminated with PC8s. Based on the methodology of decision analysis, the models provide techniques for comparing alter native strategies In terms of equipment costs and the costs of potential Incidents such as fires and spills. INTRODUCTION Electric utilities typically have a variety of equipment containing or contam inated with PCBs. Accidents or failures Involving such equipment may lead to very large economic costs for the utility. These costs can Include cleanup of the facil ity and the surrounding area, repair or replacement of utility and third-party equipment, and possible legal liabilities. The possibility of Incurring such losses may exist even when the PCD contamination Is very low. The need to weigh these highly uncertain but potentially large losses against the costs of various manage ment alternatives prompted the development of the two decision support tools dis cussed In this paper. The development of ASK was motivated by the need to manage askarel transformers and PCS capacitors In the face of the potential for large financial Impacts due to Incidents such as fires. COIL was developed to help util ities choose management alternatives for contaminated mineral oil equipment. Both tools focus on economic risks, whtch Include direct equipment and cleanup costs, and costs that may be Incurred due to real or perceived health or environmental effects from releases of PCBs. Management Alternatives Utilities have a variety of options available to manage equipment containing PCBs, Including replacing existing equipment with one or more alternative types of equipment. Isolating the equipment or installing electrical protection devices to reduce risks, retrofllllng to reduce PCS levels, or retaining the existing equipment 6-12 HONS 018903 ts Is. Replacement may Involve significant costs for a new unit and for Installa tion, but may Improve the operating efficiency and will eliminate the possibility of a PCB Incident. Incidents Involving substitute equipment may occur with greater frequency and with greater risk of conventional damage, but probably will not lead to the larger costs sometimes associated with PCB Incidents. There Is often considerable uncertainty regarding the degree of PC8 contam ination of mineral oil transformers. Testing the equipment can help guide the choice of a management strategy and may help a utility avoid the costs associated with an Incident Involving PCBs. If the likelihood of severe contamination Is low and Incidents are rare, however, the cost of testing may exceed the value of the Information gained. Balancing Equipment Costs Against Economic Risks Choosing the best management strategy requires careful weighing of uncertain losses against known cost and performance considerations, ts an Investment In risk reduction measures or new equipment merited to remove the possibility of a poten tially very expensive but relatively unlikely Incident? Management questions such as these are challenging due to the large uncertainties In the likelihood, severity, and cost of Incidents, as well as the complexity of the cost, performance, and financial considerations. for example, constder the case of a utility that has a number of askarel trans formers In Its generating stations. There Is a small chance that a fault In one of the transformers could lead to a major fire, one In which PCBs and combustion by products would be distributed widely through the plant In the form of smoke and soot. How large would the probability of a major fire need to be, and how great would the likely costs of an Incident need to be, before the company should decide to remove Its askarel transformers and replace them with non-PCB equipment? The cost of Installing new equipment Is relatively easy to determine, but the potential Incident costs are not. Utility personnel may find It difficult to estimate the costs since Incidents are unlikely and the costs could be quite large. The challenges posed by decisions such as this have motivated the development of the risk management models and decision support tools described In this paper. ASK AKO COIL: AIDS TO OECISION MAKING ASK and COIL are designed to help utility personnel make the difficult manage ment decisions regarding PCB and contaminated mineral oil equipment. Both ASK and COIL Incorporate equipment cost and performance calculations, a financial model to account for costs to ratepayers and shareholders, and explicit representation of (-13 HONS 018984 uncertainties In the occurrence, severity, and cost of Incidents. These features are combined In Interactive software packages that Implemant the risk management models. The software Implementations have been designed to facilitate and guide analyses performed by relatively inexperienced computer users, yet remain convenient and efficient for experienced users. They provide complete capabilities for the user to enter, display, edit, save, and retrieve data, to run the models, and to display and save both summary and detailed results. Decision Trees The management decisions and key uncertainties are represented In ASX and COIL using decision trees. The tree for ASX, shown in Figure 1, can be used to calculate expected costs and the range of uncertainty over a large number of scenarios. The tree in this figure Is a shorthand representation of the complete tree, where specific decision alternatives and uncertain events are defined, and each node is connected to every branch of the previous node. The decision tree for COIL Is similar, but Includes explicit representation of the sample/no sample choice prior to the equipment management alternative. If each of five uncertainty nodes shown In the ASK decision tree had three possible outcomes, there would be a total of 243 scenarios, represented as distinct paths through the tree. The likelihood, or probability, of each scenario Is sleply the product of each likelihood associated with the branches along Its path through the tree. Management Incident Alternative Frequency Incident Severity Cleanup Coats Plent ShutDown Coats debility Coate Figure 1. Key Uncertainties Are Represented as a Decision Tree In ASK Models For each scenario defined by the tree, the calculations In ASK and COIL are carried out using the models shown In Figure 2. The equipment model calculates all costs associated with existing and replacement equipment. It can take Into account different operating and maintenance costs and efficiencies for different types of 6-14 HONS 018985 equipment. The Incident occurrence model calculates the likelihood, potential timing, and likely severity of an Incident using values for the uncertain param eters, such as the rate of occurrence of Incidents, from the decision tree. figure 2. A Set of Models Are Used to Calculate Costs in ASK and COIl The Incident cost model calculates all costs of an Incident, given that one occurs. Cost elements can Include equipment replacement costs, cleanup and repair costs, costs of legal liabilities, and costs due to the shutdown of a generating plant during the cleanup and repair period. The model Incorporates utility cost-ofservlce calculations, distinguishes between capitalized and expensed costs, and calculates costs to both ratepayers and shareholders. SIMWtY ASK and COIL are decision support tools that allow utility personnel to eval uate PCB equipment management options for a wide range of situations. Comprehensive analyses can be carried out quickly and efficiently, comparing different management options In terms of direct costs and costs due to Incidents. Uncertainties in Incident occurrence, severity, and cost may be accounted for explicitly, and a wide variety of "what If?* questions can be answered rapidly. In addition to serving as a useful analytical aid, ASK and COIL can help util ity personnel communicate with top management, regulators, and public groups about the complex nature of PCS and contaminated mineral oil problems, as well as provide key Insights from the analyses. The tables produced by ASK and COIL show both the assumptions and the results clearly. The Implications of alternative viewpoints and opinions can be tested and displayed quickly and easily, thus facilitating discus sion and consensus building on difficult PCB management Issues. 6-15 HONS 018986 THE TRANSFORMER/CAPACITOR RISK MANAGEMENT MOOEL: `TRIM* by Dean W. Boyd David Cohan Donald S. Wilson DECISION FOCUS INCORPORATED INTRODUCTION This paper describes the Transformer/Capacitor Risk Management (TRIM) model. TRIM has been developed to facilitate analyses of alternative utility actions and regulatory policies Involving electric equipment containing PCBs (polychlorinated biphenyls). Analyses performed using TRIM can provide a basis for improved under standing and Insight Into the costs and benefits of alternative actions. Based on the methodology of decision analysis, TRIM Includes a detailed structural model and a flexible decision tree allowing explicit representation of key uncertainties. The paper will discuss the methodology of TRIM and review example applications. BACKGROUND PC8s have been used extensively as dielectric fluids In transformers, capac itors, ballasts, and other electrical equipment. The use of PCBs was motivated by a combination of fire-resistant and dielectric properties. Olelectrlc fluid composed largely or solely of PCBs Is currently used In over 30,000 large electric utility transformers and In several million capacitors. In addition, several million mineral oil transformers are potentially contaminated with small amounts of PCBs. Ourlng the 1900s and early 1970s a small number of Incidents occurred which, combined with limited scientific Information, led to concerns regarding potential health effects of PCBs. Although evidence Is conflicting and still far from cornplate, these concerns led to the regulation of PCBs by the federal government under the Toxic Substances Control Act (TSCA). The United States Congress banned the manufacture of PCBs In 1976, and the Environmental Protection Agency (EPA) has developed strict regulations concerning the continued use, phase-out, and disposal of PCB equipment. Recently, a new set of concerns arose regarding potential by-products of com bustion of PCBs that might result when equipment containing PCBs Is Involved In a fire. Possible by-products of PCBs Include PCDFs (polychlorinated dlbenzofurans), and PCDOs (polychlorinated dlbenzo-p-dloxlns). Some of these substances nay be by 6-16 HONS 018967 products of other components of PCB-based dielectric fluids, such as chlorobenzenes. Both PCOOs and PCOFs are suspected of causing health effects In humans, although once again evidence Is Incomplete; in particular there is little direct Information regarding the effects of PCOFs. As a result of these new concerns and questions, the CPA has proposed additional regulation of PCB equipment. These proposals, as well as other potential PCB-related regulatory issues, were the motivation for the development of TRIM. METHOOOLOGY ANO MOOEL STRUCTURE The structure of TRIM was designed to represent the critical elements involved In PCB regulatory Issues, Including PCB transformer and capacitor use, releases From this equipment, human exposure, and human health effects. The model provides an Integrated quantitative tool to test a variety of alternative assumptions. TRIM Includes two key components: a decision tree and a deterministic model. The decision tree, outlined In Figure 1, represents the Interaction of the principal regulatory decision with critical uncertainties that can have a major Impact on the ultimate outcomes. Both near-term decisions and longer-range decisions subsequent to the development of new Information can be Included. The model user may define the alternatives to be considered at each decision point. The deterministic model traces the potential Impacts of PCBs from their use In electrical equipment, through release due to accidents or other Incidents and poten tial human and environmental exposure, to any ensuing health or environmental effects. The deterministic model Is composed of six submodels, as shown In Figure 2, representing equipment use and replacement, spills and other Incidents, human exposure, human health effects, environmental exposure, and environmental effects. The equipment use and replacement model provides a detailed Inventory of the PCB equipment In use at any time given a particular regulatory environment. This model tracks PCB equipment In use In various locations and accounts for units being taken out of service and different units being Installed. TRIM also calculates the costs of phasing out and replacing equipment, and of any special risk management activities. The splll/accldent model specifies the amount of PCB material released during different types of Incidents defined by the user; the frequency of occurrence of these Incidents; the production of by-products during the Incidents, If any; and the residual concentration of the material after cleanup. The human exposure and depo sition model calculates both the number of people exposed and the average lifetime deposition for each of one or more distinct population groups possible exposed to 6-17 HONS 018988 PCBs and by-products, for each of tha savaral types of Incidents In various loca tions. Exposure Is calculated both for the short period during an Incident end cleanup and for multi-year periods after cleanup Is complete. AMITIOMk 'H4SC-0UT, 8A8ID MMC-ICAlt VumcTHm I Mfwiiaft OMtMot-iToEnMs <JUIlSTMTlv) suosiouc!iir Mnewosions. !fOnaritm it osvtionto Figure 1. Outline of the TRIM Decision Tree Figure 2. Outline of the TRIM Deterministic Model In parallel with the calculations of human exposure Is the environmental exposure model which calculates the total exposure to various ecological groups. The environmental effects model calculates average deposition as a surrogate measure for the Impacts on exposed ecological groups. The human health effects model calculates the occurrence of potentially serious health effects due to exposure to PCBs and any by-products or contaminants, for each of the user-specified population groups. 6-18 HONS 018989 TRIM has been Implemented as an Integrated, flexible computer program, incor porating both the decision tree and the deterministic model. It includes options that facilitate sensitivity and decision tree analysis. The program has been designed to run on mainframes, minicomputers, and personal computers, and Is avail able from the Electric Power Research Institute. APPLICATIONS OF TRIM The primary uses envisioned for TRIM are to assist In the evaluation of regula tory policy options at the national, regional, or local levels, and to assess the possible health risks at an Individual utility due to the use of PCI equipment. TRIM has been used to evaluate national regulatory options being considered by EPA. TRIM can also be used by utilities, state agencies, and other Interested parties to analyte the PCS problem on a smaller scale. While much of the attention has been on askarel transformers, TRIM may be readily applied to any other types of equipment that contain PCBs or other related chemicals which may present some health hazard. Olelectrlc fluids that may be Investigated Include askarel, contaelnatedoll, mineral oil, and silicone or other substitutes for PCS fluid. AN EXAMPLE TRIM has been used by the Utility Solid Waste Activities Group (USWAG) to carry out a detailed analysis of potential risks due to fires Involving PCS transformers. The analysis assessed potential health risks associated with Incidents Involving utility-owned askarel transformers, and evaluated a set of alternative regulatory policy options designed to mitigate the risks. The options Included maintaining a normal phase-out schedule. Implementing risk reduction measures, or carrying out an accelerated phase-out of the transformers. The USWAG analysis Indicated that the risks posed by fires Involving utility-owned askarel transformers are very low, even with a normal phase-out schedule. Evaluation of the USWAG analysis results suggests that avoided cates of health effects would have to be valued at almost one billion dollars each before any regulatory actions beyond the status quo was merited. The analysis using TRIM served as the basis for comments USWAG submitted to the EPA regarding proposed additional rules on PCS transformers. 6-14 HONS 018990 HUMAN HEALTH RISKS FROM PC8-C0NTAKINATED MINERAL OIL TRANSFORMERS Alas Q. Eachenrotder and Edward J. Feeder Addraaa correspondence to Dr. Feeder at: Southern California Edison Company, 0.0. #1 Environmental Operational Room *53 Foot Office Box 800 Rosemead, California 91770 Tha objective of this study la tb estimation of human health daks due to the Inhalation of combustion products from accidental mineral oil transformer fires occurring outdoors* Polychlorinated dlbeosofurans (PCDFs) are believed to be the principal toxic products of the pyrolysis of polychlorinated biphenyls (PCBs) sonatinas found as contaminants in transformer mineral oil. This presentation highlights the different exposure levels In sir risk analysis in contrast with a uniform exposure level in drinking water risk analyses. The adverse health effects addressed here are those attributable to the toxic action of PCDPe Inhaled la the neighborhood of the fire. The findings are Interpreted la light of accepted health guidelines for PCDFs. A prototype scenario la based on extreme values of population density, climatology and transformer oil capscity selected from the ranges of those variables within the service arses of the Southern California Edison Company. The analysis follows three main steps: (1) Emissions characterisation, (2) atmospheric dispersion eetineteo sod (3) sxpsctatloaa of health haxards which could arias from downwind Inhalation exposures. Is order to specify tbs amissions In detail we define the firs scenario, determine mese/eaergy balance parameters and introduce the PCD to PCDF conversion efficiency. Baaed on parameters of the prototype system, a subsurface vault location Is chossn, and n one mater pool firs la assumed to burn 25 galloon of mineral oil contaminated by PCBs at the level of 9.9 ppm. The burning rats In dorlvod from a correlation of oboervatlooal data on aaay oil flrsn which glvss 6 x 10** m/s for the average regression rate of the liquid surface for flrea one meter end larger. 6-20 HONS 016991 Th emission rate of FCBFe Is derived from the percent conversion of KBs to PCDFa and the estlasted level of KB contamination In the elnersl oil of 9.9 ppm by mss. This efficiency* based on a conservative Interpretation of experimental data* la at eaxlaue IX. In the case of a transformer fire in Binshasten* NY. where the fluid was sostly KB (63X) with aose chlorinated beoteaea (351). the eatlsated conversion efficiency waa only Q.1X. We can now calculate an appropriate ealsalons rate to be used as a worst case eetlaate for our human Inhalation exposure study. For a mineral oil specific gravity of 0.91 (with the derived veluee of pool burning rate* KB contamination level and KB to KPF conversion efficiency)* we calculate the KDF emission rate from a one meter diameter pool firs to be 4.2 x 10~* g/a. Moreover* the time required to burn ell 2S gallons of mineral oil la calculated from these data to be 34 minutes* The air dispersion calculation uses a Gaussian plus# modal with tht urban dlsptrslon parametara from the Industrial Source Complex formulation. An ensemble of eases for the wind epeed/ecablllty combinations for the local area were run In order to represent an appropriate range of conditions weighted by their frequencies. This procedure generate* a frequency distribution of anbltot concentrations at tha surface In the downwind direction. Combining these statistic* with the population* associated with aach racaptor point* we derive a likelihood parameter which shews the probability of any person exctedlag soma glvsn expotura laval. Wa have maximised tha factor* governing tha exposure of an Individual to KDFa from Inhalation of tha combustion products plume ambient concentration. Combining an inhalation rata of 22 *3/day with the fire duratloi and each locally calculated value of tha ambient comcemtratloa, we estimate tha aoaambla of Inhalation axposura value*. Having defined tht *t*tl*tlc* of expotura* wa Interpret these result* in term* of health hasards, tagulatory agendas ordinarily use conservative extrapolation* of animal toxicological date to human* for affect* suspected of having no threshold ilka *om* form* of cancer. This conservatism 1* intended to allow for uncrtlatl*a 1* extrapolation from on* apeclaa to another, from small orgamlama to large ooaa and from high doses to low dotes. Each of tht three prototype calculation* of aafa laval we have selected is based on this typo of analysis* We have determined tha likelihood of exceeding any of the safe lifetime dose levels of KDD/FCSF compounds as derived from three regulatory agency guidelines: (1) The California permissible level of KDD/KDFs In the sir In a building; (2) Tha 6-21 HONS 018992 California 10~* rlak lavcl of PCDD/PCDFa and (3) the PA vatar quality crltarlon laval for 2, 3, 7, 8 TCDD. Tha llkallhood of aayooa In tha neighborhood of tha flra receiving avan the conaarvatlve EPA aafa lifetime doaa laval la laaa than ona la 7,000,000, *ad llkallhooda atlll lower ara found for azcaadanca of tba California Stata guidallnaa. Therefore, It would appear aa If no algnlfleant health rlak la poaad by Inhalation azpoaura to poaaibla PCDF producta froo alaeral oil tranafornar flraa undar tha ayaten aeanarlo anployad In thla analyale. 6-22 HONS 018993 OCCUPATIONAL EXPOSURE OF ELECTRIC UTILITY PERSONNEL TO PCBS A CASE STUDY J.D.Sahl; T.T. Crocker; M.D. Saperstein; and E.J. Feeder Southern California Edison Company A research project was developed to determine the occupational exposure to polychlorinated biphenyls (PCBs) of Southern California Edison Company (Edison) personnel. Results from this project are presented and include! identification of potentially high exposure jobs; measurement of blood PCB concentrations among Edison personnel; and evaluation of the amount of PCBs on the Edison system in electrical equipment. The data indicate that no significant occupational exposures have occurred among Edison personnel. Personnel involved in the servicing and repair of distribution and electrical apparatus have the greatest potential for contacting dielectric fluids which may contain PCBs. Length of service in these occupations, work practices, the number of Askarel units, and the degree of contamination with PCBs in non-Askarel units will influence the actual levels of exposure for a particular work force. To assess this exposure potential we compared levels of PCB in blood of several exposure categories of Edison personnel and measured the amount of PCB in electrical apparatus on the Edison system. This provides an historical view of exposure in a way that current industrial hygiene monitoring can not. 6-23 HONS 010994 To establish a background blood PCB level for non-occupationally exposed individuals, blood samples from the pre-employment medical examinations of 738 new employees were analyzed for PCB. Blood PCB concentration of this group have a median of 4 ppb and a mean of 5 (SO 4) ppb. These data are comparable to previously published values for blood PCB concentrations of non-occupationally exposed groups. Since the demographic characteristics of this pre-employment sample are similar to those of the general population, and agree with other published data, we conclude that these levels result from exposures to PCBs in the general environment. Blood PCB levels of 1,0S8 current personnel have a median of 3 ppb with a mean of 4 (SO * 4 ) ppb. Two hundred and twenty of this group were in "high exposure potential jobs" between 1979 and 1984. This subgroup of the current personnel is considered to have the highest current exposure potential and should reflect the greatest PCB body burden if occupational exposure is occurring in this work force. Duration of exposure for these personnel averages 14 years, ranging from 1-37 years. Blood PCB concentrations ranges from 1 to 15 ppb with a median of 3 ppb and a mean of 4 (SO 3) ppb. There is no significant diffsrance in blood PCB concentrations between the pre-employment, current employment, and the the subset of high exposure potential groups. wa conclude that employment at Edison has not resulted in the accumulation of PCBs different than that of the general, non-occupationally exposed population. There is no Indication that a blood concentration at thasa levels posst a threat to human health. Investigations of occupstlonal groups with substantially higher blood PCB concentrations have not reported significant health or physiologic effects. 6-24 HONS 018995 The amount of PCB on the Edison system was assessed by quantifying the gallons of PCB in capacitors, transformers, and other electrical apparatus. Capacitor fluid (entirely PCB) and Askarel-coritaining (predominantly PCB) transformers represent less than It of total dielectric fluid in electrical apparatus on the Edison transmission and distribution system. Mineral oil is the predominant dielectric used by Edison. PCB contamination of mineral oil equipment on the distribution system was 6 ppm (median less than 2 ppm) and in substation equipment the mean was 12 with a median of 2 ppm. These data Indicate that no significant occupational exposure to PCBs has occurred among personnel of this utility, and that no significant health impacts would be expected from PCBs. 6-25 HONS 018996 PCB ENVIRONMENTAL TRANSPORT AND FATE MODELING James W. Llngle* INTRODUCTION New mathematical modeling tools have recently been developed through research funded by the Electric Power Research Institute that predict the environmen tal transport and fate of PCBs from spills of dielectric fluid from electri cal equipment such as capacitors and transformers (1). These tools can be used on mainframe or personal computers In order to examine the consequences of a particular PCB spill. They can also be used to evaluate 'what If* questions regarding potential cleanup and restoration actions. The major function of the models Is to predict the movement of PCBs through pathways such as air, surface water, soil cleanup, and groundwater. A model has also been developed to determine the potential exposure and dose of PCB to receptors In a given spill area. This paper briefly discusses the models used, the Input data required, and the application of the models to several PCB spills. The examples Include a PCB capacitor failure In a substation ana a spill from a pole-mounted PCB contaminated oil filled transformer. Analytical data were available for both spills. PREDICTION OF ENVIRONMENTAL TRANSPORT The PCB Off-Site Spill Model (POSSM) 1$ the main core model used to predict the partitioning of PCBs Into various environmental pathways. POSSM Is an adaptation of PRZM, an EPA model used to predict the fate of pesticides. It has been modified to Include a pure phase component In the soil and Imper vious surfaces such as asphalt or concrete. The POSSM model can be used with other off-site models (shown In Figure 1) to predict the movement of PCBs to the atmosphere, rivers, lakes, and groundwater. Other models used In this analysis Include PTDIS, an EPA air pollution model, and EXPOSE, a iodel developed to calculate the dose of PCB to receptors based on potential exposure pathways such as Inhalation, dermal contact, or ingestion. SPILL SCENARIOS The POSSM model was used to analyze a PCB capacitor spill In a substation. About l.S gallons of Aroctor was spilled over an area of about ISO square feet. The Input data were constructed to Include a < Inch layer of crushed stone over a Miami silt-loam soil. Soil profile data Including bulk density, l organic carbon, moisture.content, and soil horizon thickness were obtained from reports published by the USOA Soil Conservation Service. Dally meteoro logical data Including wind speed, temperature, and precipitation were ob tained for the area from Local Climatological Data published by the National Oceanic and Atmospheric Administration (NOAA). Other Information about the spill Is supplied on Table 1. * Principal Environmental Chemist, Wisconsin Electric Power Company, Milwaukee, Wisconsin. 6-26 MQNS 010997 The model Input data were adjusted to Include the average PCS concentration measured In the soil after the first, second, and third cleanup events. The Input data were also modified to account for a new 6 inch crushed stone layer on top of the soil after restoration. PCB concentrations In the air 1,200 feet from the substation (distance to the nearest house) are shown In Figure 2. Model results for a nine-month period are as follows: PATHWAY PERCENT Cleanup Volatilization Runoff Leached to Groundwater 97.96X 2.041 .0000211 None The POSSM model was also used to analyze a spill of 100 ppm PCB contmalnated mineral oil from a pole-mounted distribution transformer. Approximately 6 gallons were spilled over an area of 312 square feet. The total amount of PCB actually spilled was 2 grams or 0.07 ounces. Other conditions are provided on Table 1. Modifications discussed elsewhere were necessary to account for the difference In properties of mineral oil versus pure Aroclor 1254 (2). Soil cleanup factors were based on measured PCB levels In the soil (3.21 ppm average before cleanup, 1.18 ppm average after cleanup). The PCB levels predicted In the air 60 feet from the spill (distance to the nearest house) are Illustrated on Figure 3. The total amount of PCB volatilized during the four-month modeling period was 2.75S. Volatilization was negligible after restoration. EXPOSURE CALCULATIONS The EXPOSE model was used to calculate the dose of PCB for persons living in homes near the spills. Input conditions Included calculating the airborne concentration of PCB with PTOIS at distances correspond!ng to the nearest homes. Exposure was assumed to occur whenever the wind was blowing from the spill site to the house (approximately ISt of the time). No adjustments were made for differences In outdoor versus Indoor concentrations. The potential health effects were estimated using the PCB dose-response function developed by the EPA Office of Toxic Substances and discussed elsewhere (3). The cumulative deposition from Inhalation (In grams) was multiplied by a dose-response function of 4.0 x 10*9 to estimate the likelihood of an exposed Individual Incurring cancer. The results are as follows: SPILL SCENARIO Substation Spill Transformer Oil DEPOSITION (Grams) .483 X 10* .033 X 10* PR06ABILITV OF A HEALTH EFFECT 1.9 X 10*" 1.3 X 10'12 In these examples, both exposures are well below the 1 X 10* risk level which is sometimes used as a gauge of acceptability. 6-27 HONS 018998 CONCLUSIONS New mathematics! modeling tools allow utility personnel and others to conduct more meaningful analyses of PCB spill events than In the past. These tools should help the user determine If PCBs are likely to migrate beyond the area of the spill and what the cumulative dose might be to persons exposed. The models allow the user to examine a variety of cleanup scenarios and the resul tant Impact on exposure potential. Additional work Is necessary to field test the models to determine the accuracy of the predictions. REFERENCES 1. Brown, S. M., and S. H. Boutwell. "PC8 Spill Exposure Assessment Method ology,1' EPRI Report RP 1826-13, December 1984. 2. Brown, S. M., and A. Antlpas. "Environmental Fate of PCBs In Mineral Oil Spills," paper presented at the EPRI PCB Seminar, Seattle, Washington, October 22-25, 1985. 3. USWAG, "Proposed Spill Cleanup Policy and Supporting Studies," submitted to EPA October 15, 1984. 6-28 HONS 018999 Equipment Fluid Spilled Quantity Spilled Spill Area Soil Type Surface Event Dates Spill 1st Cleanup 2nd Cleanup 3rd Cleanup Restoration Table 1 PCS SPILL MODELING INPUT DATA SUBSTATION SPILL PCB Capacitor Aroclor 1016 1.5 Gallons 150 Square Feet Silt Loam Crushed Stone TRANSFORMER OIL SPILL Pole-Mounted Transformer 100 ppm 1254 In Oil 6 Gallons 312 Square Feet Silt Loam Grass August 3 August 4 August 24 October 19 October 26 September 11 October 3 October 10 6-29 HONS 019000 HONS 019001 It-f HONS 019002 U6/M3 Ftjure 3. HONS 019003 PART 7: PCS FIRES HONS 019004 Measurement of PCDF and PCOO In Utility Equlment Sydney H. Gordon, Michael Hiller I IT Research Institute, Chicago, Illinois Fred L. DeRoos, Mercus Cooke lettelle Meaiorltl Institute, Coluabus, Ohio Jacques Guertln, G11 Addis Electric Power Resetrch Institute, Palo Alto, California Introduction There is Increasing Interest In the potential for foraatlon of polychlorinated dlbenzofurans (PCOF) and polychlorinated dlbenzo-p-dloxlns (PCOO) from uncon trolled fires Involving polychlorinated biphenyl (PCO)-contalnlng dielectric fluids. At the tenperatures that prevail In transformer fires, PCO nay react to form PCDF and other toxic oxidation products. Information 1$ sparse, however, on the distribution of PCOF and PCOO In the PCO-contalnIng Insulating fluids used by the electric utility Industry. Even less Is known about the effect of service tine on the contaalnant concentration In PCB-fllled electrical equipment. There Is also the possibility that abnormal operation (arcing, overheating) nay create conditions that lead to the foraatlon of PCOF and PCOO. In order to address this Issue, the Electric Power Resetrch Institute (EPRl) recently Initiated a program to evaluate and develop compound-specific analytical procedures for characterizing PCOF and PCOO In PCB-contalnlng Insulating fluids. Although the toxicological effects of PCOF and PCOO on humans Is not well under stood, tests using laboratory animals suggest that these compounds are much more toxic than PCS. Moreover, they generally occur at very low ambient concen trations, and toxlcltles can vary over a range of five orders of magnitude depending an the specific compound (1.e., degree of chlorination and location of chlorine atoms). Consequently, In order to measure specific compounds at pg/g (parts-per-trl11Ion) levels, the EPRI-sponsored research has three basic goals: e Improve the chemical analytical methods for Individual compounds of PCOF and PCOO HONS 019005 7-1 a Determine the concentration of PCOF nd PCOO In utility equipment that has seen varied use a Oevelop a screening test that determines PCDF and PCDO concentrations rapidly In order to reduce costs and time delays before undertaking cleanup activities after PCB fires. To this end, the program has been divided Into the following tasks: a Round-robin aethod evaluation e Analysis of spiked sample matrices end In-service dielectric fluids a Development of a rapid MS/MS screening technique. This paper summarizes the chemical analytical methods used and some of the early results of these studies. Results of the MS/MS Investigation will be reported elsewhere. Analytical Approach The Isomer-specific analysis of trace concentrations of PCOF and PCOO In PC8contalnlng fluids Is a challenging problem. The analytical difficulty is often compounded by the presence of Interfering substances such as PCB or polychlorinated diphenyl ethers. Combined capillary colunn gas chromatography/mass spectrometry (GC/MS) Is the method of choice for the measurement of PCOF and PCOO In trace amounts. The selectivity of high resolution SC together with the sensitivity of mass spectrometry yields detection limits of 0.5 to 2 ng/g (parts-per-bllllon) for these compounds. Since GC columns cannot handle PCB-contamlnated fluids (sample matrices) directly, the samples must be extracted first with a suitable solvent to teparate the analytes of interest (l.e., PCB, PCOF, PCOO) from them. This Is followed by an enrichment step to remove co-extracted Interferences and to concentrate the PCOF and PCOO In the sample extract. Finally, GC/MS analysis of the sample extracts provides the Identification and quantitative measure of the PCDF and PCOO of Interest, based on the premise that GC separation of each chlorinated compound class can be achieved so that a unique set of mass spectral Indicator ions can be monitored for each of the appropriate GC retention time windows. The use of high resolution GC/hlgh resolution MS (HRGC/HRMS) Improves the Isolation of PCDF and PCDO from impurities and reduces the need fpr extensive sample cleanup. 7-2 HONS 019006 To determine the recovery efficiency end Improve quantitation, appropriate ^3C-labe1ed liotoplc analogs of the 'dioxins" and 'furans' are added to the samples. (13C-.containing compounds are not present In significant quantities In naturally occurring materials and are clearly distinguishable from native compounds by mass spectrometry. Spiking samples with labeled compounds thus provides unique Internal standards for accurate analysis.) Hound-Robin Method Evaluation The round-robin method evaluation Is designed to validate the analytical procedure and to determine the reliability with which specific compounds can be Identified and quantified. It Includes the synthesis of native and Isotoplcally labeled standards and the analysis of spiked sample matrices using the best available In house procedure. Five laboratories are Involved In this effort: Battelle Memorial Institute, IIT Research Institute (IITRI), New York State Department of Health (NYSOH), Radian Corporation, and University of Umea. Radian synthesized the standards and prepared the spiked matrix samples. These have been analyzed by the five laboratories. The laboratories use a variety of extraction-cleanup procedures and analytical DC/MS techniques, the mein elements of which are suaaartzed In Table 1. Five baseline samples (Aroclor 1016, Aroclor 1242, Aroclor 1260, trl- and tetrachlorobenzenes, and aged mineral oil) were spiked with the Isotoplcally labeled Internal standards 13C-2,3,7,8-TC0F, 13C-2,3,7,8-TC00, *3C-l,2,3,7,8-PnC0F, and *3C-OCOO at concentrations of 100 ng/g each. In addition, the three Aroclors and the trl- and tetrachlorobenzene samples were spiked with the native Isomers 1,2,3,4,7,8-HxCDF and 1,2,3,4,6,7,8-HpCDF at concentrations of 100 ng/g each. The aged mineral oil sample contained several additional unlabeled Isomers as well as 510 g/g Aroclor 1260 and 530 vg/g trland tetrachlorobenzenes. A summary of the measured average total congener class concentrations obtained by the reporting laboratories Is presented In Table 2. In general, agreement between the values obtained by the various groups was found to be within a factor of two. In the case of the trl- and tetrachlorobenzene sample, fairly good agreement was also obtained between the expected and measured amounts for the Isomers spiked Into the matrix, and virtually no additional PCOF and/or PCOD was detected. By contrast, the Aroclor 1260 sample contained significant amounts of a large number of PCOF compounds. Lower, but still significant, amounts were measured for the remaining Aroclors, while the aged mineral oil sample had concentrations close to that of the spiked values. 7-3 HONS 019007 Analysis of In-Service Dielectric Fluids A preliminary round-robin study was undertaken by three of the participating laboratories uilng four staples of dielectric fluids taken froa In-service transforaer and capacitor units. The average total congener class concentrations found for PCOF are shown In Table 3. Owing to differences In analytical procedures and variabilities In sample aatrlces, estlaates of detection Halt have not been Included. Saaple ISL10 was a alneral oil contaalnated with 100 ug/g PCS froa a transforaer that had failed In service by arcing. Saaple 1SL2A was an Askarel containing Aroclor 1242, which was removed froa a capacitor that had bulged, but not ruptured. In service. Both staples had PCOF at concentration less than or equal to the Halts of detection. Staples ISL3A and ISL4A both contained 70* Aroclor 1260 and 301 trichlorobenzene. Seaple ISL3A was taken froa an Askarel transforaer after 20 years of service and contained O.S to 2.0 g/g of PCOF. Saaple ISL4A was taken froa a transforaer (of a different aanufecturer) after 31 years of service. It had substantially higher concentrations of these partial oxidation products for all congener classes except total TCOF. Work to date has developed leproved measurement methods for compound specific PCOF and PCOO In PCB-contaalnated Insulating fluids. Thus far. the results do not suggest a preferred analytical technique. Analysis of the four In-service fluids Indicate measurable quantities of specific PCOF compounds In 20- to 30-year old Insulating fluids, however, there Is Insufficient Information for generalization to all utility equipment. Future work will focus on replicate analyses of another three baseline samples as well as 10 In-service samples. MOWS 019008 7-4 Table 1. Suaaary of Analytical Protocols for PCDF and PCDD Measurements Laboratory Cleanup Solvent Extraction Column Chromatography Analysis Capillary Gas Chromatography* Mass Spectrometry** Battelle IITRI NYSOH Radian Unea None None StOj/AljO^VAl^P OB-5, CPS11-88 HAMS. El Gel permeation/ AlpOp/AljO^ SP-2330/CPS11-88 LAMS, El None ch3cn/ hexane Al2i^C/Al203 SP-2330 SIO^A^O^AljO^ OB-5. SP-2340 HAMS, El LRMS, El None C-flber/reverse elutlon/FlorlsIl SP-2330 LRMS, NCI *Fusad-s111ca capillary columns **LRMS - low resolution MS; HAMS > high resolution MS; El - electron Impact; NCI negative Ion chemical Ionization (methane). (All use selected ton monitoring node MS). Table 2. Average Total Congener Class Concentrations of PCOf and PCDO In Spiked Baseline Samples Sample, g/g Congener Class Aroclor 1016 Aroclor 1242 Aroclor 1260 Trl- and tetra- Aged chlorobenzenes Mineral Oil rrew iTCDF tPnCOF tMxCDF ZHpCOF OCOF HD O.OltO.Ol 0.0110.02 0.1810.12 0.0810.01 0.0110.01 HD 0.9410.78 0.3310.24 0.1010.03 0.1210.06 0.6311.12 HD 0.5510.39 1.1510.66 2.7312.08 1.8310.71 2.8111.22 ND NO NO 0.3410.44 0.1110.04 NO 0. OHO. 02 0.1010.02 0.2110.04 0.4410.44 0.0710.05 0.2210.15 NO not detected 7-5 HONS 019009 Table 3. Average Total Congener Class Concentrations of PCOF In Four In-Service Dielectric Fluids Congener Class In- service Sanole. ua/o ISL4A 1SL3A 1SL10 iTCDF iPnCOF zHxCOF iHpCOF OCDF Total PCDF 0.1 2.6 7.6 16.3 9.8 36.4 0.5 1.6 1.6 2.0 U) 6.7 HO 0.01 0.01 NO NO 0.02 NO ND ND NO JO NO ND not detected HONS 019010 FORMATION OF PCPFs AND PCOOs IN ELECTRICAL DISCHARGES R.E. Koch and T.O. Roust General Electric Company F. L. DtAoos Battalia Columbus Division Nlaturas of PCBs and TCBs (chlorinated banzanas), called 'askarals*. have bean used as the liquid dielectric Insulation and beat transfer material In trans formers where fire resistance Is of particular concern. There also has been an Intermingling of askarals and the mineral oils more coamonly used in transform ers. PCOFs are products of partial oaldatlon of PCBs and both PCOFs and PCOOs are products of combustion of TCBs. PCOF and PCOO formation In fires Is being studied widely. Their formation In the dielectric liquid In and near the vicin ity of an electrical breakdown has not been examined. Electrical breakdown represents a malfunction In a transformer which Is neither readily controlled nor reproduced and occasionally cannot be contained. Electrical failure of actual transformers then Is not an acceptable approach to examining PCOr and PCOD formation. This report describes studies of the formation of PCOF and PCOO In controlled simulations of high energy electrical breakdown - 'arcing* - in transformers. Askarals alone and mineral oil containing low concentrations of askarals have been examined. EXPERIMENTAL Test cells were capped, glass filament wound epoxy fuse tubes (t.B cm ID x ao cm L ) containing 1.35 1 of liquid, with a wrap of 0.23 mm thick electrical Insul ating Craft paper Inside the tube; both half saturated with water and fully sat urated with air. The air space over the oil was 17X of the oil volume. Elec trodes were radlused l.S cm D aluminum rods with a 1.27 cm gap. Initially bridged by a small diameter low carbon steel wire to start the arc. Each cell was provided with a connection to a pressure gauge, a pressure transducer and a gas sampling container. Current, arc voltage, duration and pressure excursions were recorded; I*'t products and arc energies were integrated automatically. Askarals tested were electrical grade trichlorobenzene (Hooker Chemical) and Arodors 1254 and 12B0 (PCB mixtures made by Monsanto Company). TCB and a 1:1 ONS 019011 7-7 mikture of TCB end Aroclor 1254 wore toch treated twlco with 3X of tholr weight of activated Fuller's eorth. a normal manufacturing practice In removing polar Impurities -prior to filling askarel transformers. One component usually added to askarels was 0.1SX of 3,4-eposycyclohekyl methyl-(3',4'-epo<ycycloheaane) carboiylate as a scavenger for chlorine or water. The possibility of Its halogenatlon, dehydrogenation and rearrangament to form PCDFs and PCOOs Is remote and It was omlttad here to simplify the testing. Oil samples were made from coammrclally available. Fuller's earth treated transformer oil and Aroclor 1234 [SOppm, SOOppm, 3ppt (parts per thousand), lOppt), Aroclor 1260 (lOppt) or TCb (lOppt). PCDFs, PCODs and some PCBs were separated from the sample matrtses using silica and activated alumina. Analysis was done by capillary column GC/HS with 13C PCDF and PCDD spikes (1). RESULTS Two or more samples of each liquid were subjected to arcing and at least one of each pair was analyied for PCDFs and PCDDs. Arc currents ranged from TOO to 7SO amps ran and durations from 40 to S msec. The Intent was to control the arc energy to less than 10 kJ. The pressure buildup In the cells was proportional to the arc energy, and In two cases. It pegged the pressure gauge at 40 pslg. The energy dissipated In an actual transformer arc might reach 100 kj. However, actual transformer arcs arc not confined to volumes as small as that of these test cells and the test conditions are considered to be more severe. Arcing parameters are listed In Table 1. Tube Muster 2 4 5 6 7 9 9 10 11 TAOLE 1 AKINC TESTS - ASKAOELS AHD OIL COmTAIHlHG ASKADELS Dielectric Llould , ita.... TC0/12S4 1:1 1:1 011/MM SO ppm S00 ppm 3.0 ppt 10.0 ppt 011/1210 10.0 ppt 011/TCQ 10.0 ppt Current ML 74S Arc Parameters___________ Tim Charge Energy iMl 41 It) 36 (kJl 4.3 735 90 St 11.5 125 55 40 3.7 730 72 S3 715 DO 57 705 49 33 715 S3 45 6.5 9.4 3.1 6.4 745 48 36 3.7 730 BO ts 15.6 Final Pressure (PSlU) 12 >60 13 29 52 10 30 14 >90 7-8 HONS 019012 Th concentrations of PCOFs and PCOOs In tht TCB and TCB/1254 alvture bofort (B) nd after (A) arcing ara given in labia 2. A good deal of carbonaceous resi due was foraed In the liquids. A portion of this was filtered froa a TCB saaplt, washed with mathanol. astractad with banzana and analyzed. The results of these analysts are also given In Table 2. Isoagr TABLE 2 PCOF AND PC DO CONTENT Of AMABELS BEFORE ANO AFTER ARCING _________ PCOF or PCDO Content - no/a (oob) TCB 50:50 TCB/Aroclor 1254 PCOF TetraPontaHtxaHepte- OctaTotal B/A 280/270 2000/2500 1700/2000 B30/1000 170/150 S020/S020 PCOO Tetra- 33/24 Penta- ii/n HX- 4/2 Hepta- NO/NO Octa- NO/NO Total 40/47 NO - Not Detected Particles 100 990 1500 1100 560 -* 40 NO NO NO ND -- B/A 357/173 1850/1740 1740/1ISO 2460/1360 217/171 7184/4624 21/24 NO/12 ND/2 ND/ND ND/NO 21/38 B/A 230/46 1200/340 1300/310 520/24 100/S 3350/783 20/6 1/1 2/NO NO/ND NO/NO 23/7 The results of analysis of the oil staples before and after arcing are given In Table 3 (Note - Analysis of the unarced TOppt Aroclor 1254 In oil staple TABLE 3 PCOF CONTENT OF OIL CONTAINING PC8S - BEFORE ANO AFTER ARCING PCDF ISOWEB __________ PCPf Coiittfit - na/q fppbl_____ Aroclor - o/o Foot) 1254 1260 Orlg Tube 0 Tube 4 Tube 10 Tetra- 1000 JDL -- 3 ppt D/4 0.1/ND 10 ppt D/A ~/n 10 ppt D/41/1 (100) (0.5) (2) Penta- -- 3/0.5 --/4 3/2 Hast- (400) -- (4) 1/1 (4) ~n 4/3 Hepta- (400) .. (3) 6/NO (4) --/NO 6/7 Octa- (110) -- (0.3) NO/1 (ND) --/NO 23/15 Total (30) .. (0.1) 11/2 (NO) --n 37/29 (1620) (0) (15) < ) - calculated values, see tent TCB Tube 11 10 ppt B/A NO/M 0.4/NO 1/NO NO/NO NO/NO 1/ND 7- 9 HONS 019013 ms not don*. Tht concentration of PCOF In the Aroclor 1254 was estimated fro* tho analysts of tho TCD/1254 mixture and tho TC8 ttsolf. The concentration In the unarced Tube 9 sample ms then calculated fro* the dilution factor, as a check, this same procedure was folloMd for the 3ppt 1254 sample. The calculat ed and measured values are In reasonable agreement.) PCOF content of the 50 and SOOpp* Aroclor 1254 saaples were below the Malt of detection both before end after arcing, as ms the PCOO concentration In all oil samples. 0ISCUSSI0* The TCI and Aroclors used hero were retained samples fro* the mld-lfTO's. After a laboratory treataent similar to that done on a larger scale In tho manufacture of transformers, measurable PCOF and PCOO remain. It, therefore, seems probable that, if unused transformers could be found and askarel samples taken and ana lyzed , measurable PCDFs end PCOOs could be found. This, In turn, suggests that the Interpretation of analyses of samples fro* functioning transformers and other sources will bo complicated by the presence of an unawasured and variable background. It also appears that arcing TCI and PCts under the conditions hero does not result In the formation of PCOFs and PCIOs. The reliability of the analytical method Is still under study, but clearly there Is no major Increase In the levels found. If anything, there appears to have boon a reduction In the solu tion concentrations. This may. In part, bo duo to adsorption of tho pre existing furans and dioxins on the carbonaceous material forming In tho dis charge. No attempt ms mada to recover all of this finely divided powder. It Is a minor, but very visible, amount. Unless tho extraction with bonxene Is very Inefficient, tho powder Is not e sink for any major quantity of PCDFs and PCOOs which may Neva boon formed In the discharge. ACkNOWUOGMNT This work ms sponsored by the Electrical Systems Division of the Electric PeMr kesearch Institute (EPRI IP 2020-0). He thank Or. 011 Addis for his participa tion In, and support of, the project.1 (1) f. l. Deloos, to be published In a forthcoming EPII report. 7-10 HONS 019014 SAFETY OF NON-PCB RECLAS5IFIE0 TRANSFORMERS IN FIRE INCIDENTS A BUILDING SCALE ENGINEERING STUDY Marcus Cooke, Fred L. DeRoos, and Bruce Rising Battelle Memorial Institute Columbus, Ohio 43201 USA Nil 11am H. Martin (2) Union Carbide Corporation Tarrytown Technology Center Tarrytown, New York 10591 USA INTRODUCTION In July 1985 the U.S. Environmental Protection Agency promulgated new regulations that Impact all electrical transformers containing greater than 500 ppm (w/w) polychlorinated biphenyl (PCB). This regulation, known as the `Fire Rule', was the result of scientific evidence that combustion of PCB containing coolants produce polychlorinated dlbenzo-p-dloxlns (PCOO) and polychlorinated dlbenzofurans (PCOF). Because of the risks posed by a fire Incident, the continued use of certain PCB transformers Is banned after 1990. An economic alternative to the replacement of PCB transformers Is to remove PCB from the transformer cavity and refill the transformer (retroflll) with a nonhazardous coolant that does not produce PCOO or PCOF If an accidental building fire were to occur. Ideally all of the PCB would be removed by retrofllllng, however due to the difficulty of extracting PCB from porous constituents of the windings, a residual amount usually remains. Current regulations consider a transformer to be non-PCB if the residual level Is less that SO ppm (w/w), following a period of 90 days normal service. Numerous publications over the past several years have Indicated that PCB can be converted directly to PCOF by Intramolecular condensation reactions and that chlorinated benzenes can likewise be converted to both PCOO and PCOF by Intermolecular reactlons(l). In all cases, the results were obtained through small, bench-scale experiments, or sealed tube pyrolysis techniques, which did not Involve combustion. Since neither the scale or the experimental conditions of previous programs simulated true fire conditions, Union Carbide and Battelle felt that It was Inappropriate to extrapolate such data to assess the potential for dioxin and furan formation from building fires. Furthermore, all studies were with1 (1) Present address: General Motors, Indianapolis, Indiana (2) Present address: Unison, Dublin, Ohio 43017 7-11 HONS 019015 neat PCB, or neat chlorobenzenes, end no Information existed on the PCDO/PCDF formation when small quantities of these materials were present, such as might exist In a transformer which had been serviced and successfully reclassified as non-PCB, l.e., less than 50 ppm. EXPERIMENTAL Battelle's Columbus Laboratories, under contract to Union Carbide, designed and built a pilot scale combustion apparatus which would simulate the conditions existing In an accidental building fire (see Figure 1). A panel of International experts in the area of fire research and PCOD/PCQF analysis was assembled to guide and direct this program. MUMMY tNJCCTION FOftT Figure 1. Schematic Diagram of the Combustion Test Apparatus 7-12 HONS 019016 Considering the difficulty In controlling and measuring the combustion conditions, and the difficulties In collecting all by-products formed, pool fire techniques were ruled out. Instead, an enclosed furnace was built. The test unit was a 40,000 Btu/hr, vertically fired tube furnace with a combustion zone 131 cm long (4.3 ft), and having a 14 cm Internal diameter (5.5 In.). The combustor was fired using kerosene containing IX (w/w) silicone coolant. This was done to simulate organic fuel and soot conditions In a burning building fire and to provide condensation nuclei that could promote catalytic production of PCDF/PCOO. The fluids tested In this study were Introduced Into the combustor at a point where the temperature profiles were approximately 800C. The optimum temperature for PCDF (and PCOD) production Is believed to lie between 45Q and 65QC as a function of available oxygen. By Introducing the coolants Into the post flame region, the thermodynamic optimum temperatures were achieved without exposing the test liquids to flame conditions that would destroy product PCOF/PCDD. The materials burned In this study were silicone transformer coolants containing 1.5* (w/w) Union Carbide TF-1 transformer fluid (a material used to remove PCB from Inservice transformers). The five liquids tested are described In Table 1. A blank run was performed without a secondary Injection liquid to test the system background. A control series was performed with TF-1 In silicone coolant as the secondary Injection liquid. Three series were performed each Injecting a separate Aroclor doped at 50 ppm (w/w) in silicone coolant: 1260, 1254, and 1242. Each test condition was run In triplicate and the results reported In this paper are the average of three determinations. Table 1 COOLANT FLUIDS INJECTED INTO THE POST-FLAME REGION Run Fueld) 1 Kerosene 2 Kerosene 3 Kerosene 4 Kerosene 5 Kerosene Coolant Injected Silicone Silicone Silicone Silicone Silicone Dopant BC,o*nnktrol.(2..) Aroclor 1260(2,3) Aroclor 1254(2,3) Aroclor 1242(2,3) uT The combustion fuel was kerosene doped with IS (w/w) silicone. (2) TF-l at 1.51 (w/w) was doped Into the silicone coolant. 0) All Arolors were spiked Into the silicone test liquid at SD ppm (w/w) 7-13 HONS 019017 In a building fire not all the transformer coolant will be exposed to the optimum conditions for PCDD/PCDF formation. In the center of a fire, temperatures exceed several thousand degrees farenhelt, and PCOO/PCDF If formed, are probably destroyed Just as quickly. At distances away from the fire, temperature profiles decrease quickly until temperatures are Insufficient for conversion. Also, a fire Inside an enclosed area, will not burn evenly. Rather the fire will pulse as It varies between oxygen lean and oxygen rich conditions. How much transformer coolant will be exposed to favorable conditions for PCDD/PCDF formation will vary greatly between fires and cannot be predicted. In a shakedown test. It was noted that when less than the stoichiometric amount of oxygen was used, no dioxin and lowered PCDF conversion was observed. In setting the parameters for the burn tests, several volume percent excess oxygen was maintained. Therefore, the experimental conditions In this test protocol assumed that all dielectric coolant Is exposed to the flame region In a temperature profile necessary for optimum PCDD/PCDF formation, and under conditions of excess oxygen. Thus these conditions represent the worst case scenario. Stack gas samples were collected from the pilot plant combustor using a U.S. EPA Modified Method S (MMS) sampling train with each train collecting a nominal 2 standard cubic meters (SCM). This sampler was previously validated by Battelle for collection of PCDD In combustion sources for the U.S. EPA (2). The MM5 train consists of a primary particulate filter section, followed by a cold water-jacketed resin trap. The trap contains 22 g of XAO-2 resin. After combustion sampling, the filters and the XAD-2 resin modules from each train were spiked with Isotoplcally labelled Internal standards and Soxhlet extracted for 18 hours with benzene. The combined extracts were concentrated to approximately 6 ml and divided Into three equal portions. These separate aliquots were blind coded and sent to three laboratories for analyte enrichment and final analysis. The Battelle analyte enrichment consisted of partitioning the extracts through two liquid chromatography columns. The first column was multilayered silica containing alternate layers of sulfuric acid treated, and sodium hydroxide treated silica gel, separated by layers of activated silica gel. The second column contained approximately 3 g of activated basic alumina. The extracts from the alumina column containing the PCDD/PCDF analytes were concentrated and solvent exchanged Into ndecane. 7-14 HONS 019038 The extracts were analyzed Independently using two different gas chromatography/ mass spectrometry methods (GC/MS). 8attel1e and Oneida Research used capillary column GC/MS with high resolution mass spectrometry as the selective detection technique. The University of Umea used capillary GC/MS with negative chemical Ionization mass spectrometry to enhance analyte sensitivity and selectivity. Each laboratory was provided standard solutions of labelled PCDO/PCDF reference compounds which were analyzed to determine response factors for quantification. RESULTS In the Union Carbide servicing, residual PCB are extracted from transformers with a special coolant, TF-1. When removal Is complete, electrical grade silicone 1$ placed permanently In the transformer. The liquids combusted In this study simulated the permanent silicone with small amounts of TF-1 residuals from servicing, and 50 ppm (w/w) PCB. Tri/tetrachlorobenzenes and epoxide acid scavengers were also part of Askarel formulations and were Included in the silicone test liquids. Thus the materials tested In this study, duplicated the coolant from an Askarel transformer which had been serviced with TF-1 to remove PCD and subsequently retrofllled with silicone. The results of this study revealed no measurable PCDO production and only traces of PCDF. The PCOO results are given In Table 2. In all experiments PCM) reported as total tetra and penta congeners, along with the specific concentrations of 2,3,7,8tetrachlorodlbenzo-p-dloxln(TCOO), revealed concentrations either not detectable (NO), or below the detection limit (BDL). Furans were found at trace, but measurable levels. Results of the PCDF analyses are summarized In Table 3. It Is apparent from these data that Arochlor 1260 produces the highest relative levels of PCDF which Is expected due to the higher level of chlorination In Arochlor 1260 than 1254. Arochlor 1242 which has the lowest chlorine content also produced the lowest PCDF levels. In all cases the amounts of PCDF produced are below one ppb (w/w). The conversion of Aroclor to PCDF, as measured by the tetrachlorodlbenzofuran (TCDF) and pentachlorodlbenzofuran (PnCDF) congeners, were extremely low under conditions of a simulated building fire. Table 4 gives the conversion factor for PCDF (total TCOF and PnCDF) based on the mass of each Aroclor burned. 7-15 HONS 019019 Table 2 OIOXIN (PCDD) RESULTS FROM THE COOLANT FIRE STUDY (Results In ng/kg (pptr) of Coolant Burned) Dielectric Silicone Silicon Silicone Silicone Doom None Aroclor 1260(4) Aroclor 1254(> Aroclor 1242(4) Congener Tatra Renta Tetra Penta Tetra Penta Tetra Penta Battelle N0(1) (ND)U) NA(3) NO (ND) NA NO (NO) NA NO (ND) NA Oneida NO (NO) ND B0l(5) (ND) ND NO (NO) ND NO (NO) ND llnea NA (NA) NA ND (NO) NO ND (0) NO ND (NO) NO (1) ND Not detected at the limit of detection. In all cases, the limit of detection was below 15 pg/KG collant burned. (2) The 2, 3, 7, 8 isomer concentration Is given In parenthesis. (3) NA Not analyzed. (A) Aroclor dopants at 50 ppm (w/w) plus 1.51 TF-1. (5) BDL Below detection limit. 7-16 MQNS 019020 Table 3 FURAN (PCDF) RESULTS FROM THE COOLANT FIRE STUDY (Results In ug/Kg (ppb) of Coolant Burned) Dielectric Silicone Silicone Silicone Silicone Dopant None Aroclor 1260(*) Aroclor 1254(*) Aroclor 1242(1) Congener Tetra Penta Tetra Tetra Penta Tetra Penta Battalia 0.01, , MB/1' 0.86 (0.24) NA 0.54 (0.08) NA 0.13 (0.01) NA Oneida N0(?) (NO) NO 0.39 (0.20) o.so 0.19 (0.10) ND NO (NO) NO Umea NA(3) (NA) NA 0.35 (0.06) 0.24 0.42 (0.07) 0.27 0.12 (0.02) 0.06 (1) The 2, 3, 7, 8 Isomer concentration Is given In parenthesis below TCOF value. (2) NO Not detected at the llialt of detection. In all cases. the limit of detection was below 15 pg/Kg collant burned. (3) NA Not analyzed. (4) Aroclor dopants at 50 ppm (w/w) plus 1.51 TF-1. Table 4 PCS CONVERSION FACTORS TO PCDF TIMES 10- Aroclor 1260 Aroclor 1254 Aroclor 1242 Tetra 1 - 22 5 - 15 3-4 2.3.7.8 0.1 - 6 2-6 0.3 - 0.4 Penta 1 - 16 7 2 7-17 MONS 019021 CONCLUSIONS No PCDO or PCOF were produced by combustion of silicon transformer coolant alone. TF-1 (1.5X (w/w)) representing residuals from servicing operations, produced no detectable quantities of PCDD or PCOF during combustion tests. Silicone coolant doped with 50 ppm (w/w) Aroclor 1260, 1254, or 1242, produced no measurable PCDO, and only trace amounts of PCOF during combustion tests. The amount of PCOF produced In any test was less that 0.001 ppm (w/w), or less than 1 ppb (w/w), based on the mass of silicone Injected. The PCOF concentrations tended to decrease as the degree of chlorination of the doped PCB decreased; Aroclor 1242<Aroc1or 1254<Aroclor 1260. e The TCDF concentrations ranged from an average of 0.43 ppb (w/w) for Aroclor 1260, to less than 0.08 ppb (w/w) for Aroclor 1242. Likewise, PnCDF levels ranged from an average of 0.31 ppb (w/w) for Aroclor 1260 to less than 0.04 ppb (w/w) for Aroclor 1242. e For the case of retrofllled transformers, these data indicate that worst case conversion of residual PCB to PCOD Is negleglble, and to PCOF Is below parts-per-bllllon based on the mass of dielectric consumed. This Indicates that only trace amounts of PCOF would be formed during building fires that Involved retrofllled transformers, and most of the PCOF would be deposited near the fire source. 7-18 HONS 019022 REFERENCES 1. Chlttlm, B.G., et al. Chlorinated dlbenzofurans and dlbenzo-p-dioxlns; detection and quantitation In electrical equipment and their Formation during the Incineration of PCBs. Wellington Science Associates, Rockwood, Ontario, September, 1979. (Referenced In State-of-the-Art Review: PCOOs and PCOFs In Utility PCB Fluid, EPRI CS-3308, Project 1263-11, Final Report, November 1983, pp. 3-1811. 2. Cooke, M., OeRoos, F., and Rising, B. Hot flue gas spiking and recovery study for tetrachlorodlbenzodioxlns (TCOO) using Method S and SASS sampling with a simulated Incinerator, Final Report, U.S. Environmental Protection Agency, Industrial Environmental Research Laboratory, Research Triangle Park, NC 27711, EPA 600/2-84-159, August 1984, 24 pp. 7-19 MONS 019023 PYROLYSIS AND CCECUSTION OF PCB CCNTAM1NA31D TRANSFQffrER FLUIDS George Eadcn, Ph.D. NYS Department of Health Wadsworth Center for Laboratories and Research Division of Environmental Sciences Efcpire state Plaza Albany, New York 12201 Various laboratory-scale experiments have demonstrated that heating PCBs at high literatures can produce substantial concentrations of FCDFs. Real-world confirmation of this result has been produced in a variety of incidents in which PC&*containing transformers end capacitors have been involved in fires. However, much lees data is available on the proclivity of dilute solutions of PCBs to form PCDFs during pyrolysis and/or combustion. Naively, it might be predicted that dilution of PCBs would result in a constant percentage conversion to PCDFs, since the process is plausibly formulated as kinetically first-order in PCB concentration. However, other possibilities exist. The diluting fluid stay itself provide facile pathways for PCB decanposition into non-PCDF products, or it may be e much more effective competitor for the reactive species involved in FCDF formation, thus minimizing that process. Alternatively, it might be lugined that the diluting fluid generates a reactive species that accelerates PCOF formation, or, through a bulk solvent effort, stabilizes the transition state leading to PCOF formation. In view of these various possibilities and the potential econcmic Importance of the question, a study was initiated to assets the PCDF-forming potential of dilute (5,000-50 ppn) solutions of Aroclor 1254 in various solvents of potential interest to the utility industry (mineral oil, tatrachloroethylena, and silicone oil). Since transformer fires are highly ocmplex and variable events, no simple laboratory simulation will accurately predict their outcanea. two ratter different seta of experimental conditions were investigated here; nevertheless, these experiments do not assess all the variable parameters that might influence the couree of e real event. Pyrolysis, defined here as heating in the tfceence of a flmie, ms acotmyllehed by placing 100 ul of the solution of interest in open pyrex glees tube (tan OD x 50 cm length); the tube wee mounted vertically, and the lower 3 inches inserted into a tight fitting metal block pretested ml thermostatically maintained at a specific twperature (usually 450-650C). 7-20 HONS 01902* Gentrally, a contact tine of 15 minutes was used. The open end of the tube was packed in dry ice. As an additional precaution to avoid escape of any PCOFs, the end of the tube ms attached to an activated carbon filter. In an effort to minimise any 'potential exposures to toxic mixtures and to simplify analytical procedures, preliminary experiments were performed using individual PCB congeners expected to form biological Inert dibensofurans. Since only one or a sail lumber of dlbanxofuran products ms expected, it ms frequently possible to approximate the 'optimal conditions" (i.e., those resulting in maximux PCDP formation) using gas chromatography with electron capture or flame ionization detection rather than GC/MS. After theee range finding experiments were complete, 5000 ppn Aroclor 1254-containing mixtures were pyrolyzed to confirm optimal conditions. Finally, six amsples at each concentration (5000 ppm, 500 ppm (where appropriate] and 50 ppm) were pyrolyzed and randomly canblned to form two casposlte smnples at each concentration prior to QC/MS analyses. In addition, scanning GC/MS analysis was performed on the pyrolyzed 5000 ppm eolutiorm mxl on the 'blank* pyrolyzed solution to allow identification of the principal non-PCEF products formed. In consideration of results obtained from these experiments, it should be rwnmsbered that the tmapmraturs regimen actually experienced by a particular conganer ie not well-defined, since the liquid refluxes up the tifce and out of the heated region. Combustion, defined here as heating in the presence of a flaw, was conducted in an apparatus consisting of a blast burner, a combustion tube, a sample introduction unit and a sample collection unit. The quartz ambustion tibe (115 x 2.5 ae) has three independently heatable zones. The ample is introduced into the flaw of the blast burner via a syringe drive; residence time can be varied by the introduction of make-up gas. smplea are collected in an apparatus consisting of an iaplnger (connected to the canbustlon tube), end an XAD-2 packed absorption tube. The collection apparatus is, in turn, connected through an orifice to a vacuus line. Thus, wnpw of any FCEF froe the apparatus is unlikely. The apparatus permits determination of PCDF formation as a function of PCS concentration, residence time, wall temperature, oxygen concentration, ate. 7-21 HONS 019025 PCB ACCIDENT IN FRANCE C. Rappe, L.-O. Kjeller, S. Marklund, M. Nygren Department of Organic Chemistry University of Umei, S-901 87 Ume, Sweden R. Foumie Direction Oes Etudes et Recherches d'EDF 1, Avenue General Oe Gaulle, F-92141 Clamart, France In the evening of January 14, 1985, an explosion followed by a fire ruptu red a transformer in the basement of a residental building in Reims, France. Due to the low outdoor temperature the transformer was probably overloaded. The dielectric fluid in the transformer consisted of a mix ture of PCB (60*) and trichlorobenzene (TCB) (40*). Although the power was disconnected after the explosion, a "ball fire" apparently had initiated the combustion of flamnable material contaminated by PCB and TCB. Soot and smoke was distributed throughout the 6-story buil ding. Soot and wipe samples Two days after the accident dielectric fluid collected near the transformer and soot samples were analyzed. The results did not show the presence of polychlorinated dibenzofurans (PCOFs) or tetrachloro dioxins (TCOOs). How ever, other samples were collected in the building February 21 and April 2 and analyzed by us. Before extraction, the samples were fortified with 13c labelled PCOFs. A Supelco fused silica column was used for the HRGC sepa ration. The analyses were done on a Finnigan model 4500 NS Instrument, the quantitative values were corrected for recovery (60-100*). A series of PCDFs have been identified with total levels up to ug-mg/m?, see Table 1. In three of the samples we have also found polychlorinated biphenylenes (PCBPs) at about the same levels as PCDFs but no or very low amounts of PCDOs. Another series of samples were collected on March 15 and analyzed by a third laboratory. This laboratory could confirm the high levels of PCDFs but this laboratory did also report on a series of PCDDs at levels close to the levels of PCOFs. However, three other laboratories analyzing the same sample could not confirm the high levels of PCDDs, see Table 2. It seems to be essential to study the chlorine cluster and the M* ions for the PCOOs (m/z 320 , 354) to differentiate between this series and the PCBPs, which have one chlorine more and their M ions at m/z 322, 356, see Figure 1. 7-22 HONS 019026 Blood samples Blood samples from persons exposed in this fire have been analyzed. A few Clg and C1^ 2,3,7,8-substituted PCDFs have been identified at low ppt levels. Table 1 Levels of PCDFs and PCDDs in samples from Reims (Umel). 2 ug/nr Tetra-CDFs Penti-CDFs Hexa-CDFs HepU-COFs Octi-CDF > 30 960 760 530 290 2 ug/m 2 ug/m >8 590 570 490 220 -- 4.5 37 36 27 36 2 ug/m ug/m2 ug/m' 0.11 0.89 0.70 1.2 NA 0.2? 1.5 1.2 1.9 NA 0.38 1.40 1.90 3.3 NA Tetri-CDDs Pentl-CODs Hexi-CDDs Hepta-CDOs Octi-CDO NA <1 <i 35 16 NA <1 <1 32 14 NA NA < 0.005 < 0.005 < 0.005 < 0.005 < 0.005 0.11 < 0.005 0.18 NA < 0.005 < 0.005 0.14 3.45 NA < 0.005 < 0.005 0.33 0.33 The samples 1 and 2 were taken on the ceiling of the basement near the door of the transformer vault (February 21). The sample 3 Is a wipe sample collected externally on the door of the transformer vault (pebruary 21). Sample 4: Wipe sample on the second floor, near the door of an apartment (April 2). Simple 5: Wipe simple is i bathroom, second floor (April 2). , Simple 6: Wipe simple In i kitchen, second floor (April 2). Samples 4, 5 and 6 are collected after cleaning. NA Not Analyzed. 7-23 HONS 019027 Table 2. Results from the analysis of the same sample. Tetra-COFs Penta-COFs Hexa-CDF Hepta-CDFs Octa-COF Tetra-CDDs Penta-CDDs Hexa-COOs Htpta-CDDs Octa-CDO WATERLOO * ng/g CERCHAR ng/g 35.000 58.000 25.000 8.000 3.000 500 700 2.000 700 - 56.000 81.000 7.000 8.000 8.000 < 1.000 < 300 < 500 RADIAN Corporation ng/g RHONE- POULENC ng/g 490.0 820.0 190.0 3.7 14.0 220 420 25 110 160 NO** 550.0 45.0 NO NO 45 150 490 210 350 " Taking for the liquid 1.560 g/cm3, the results of sample are converted in ng/g. ** 2,3,7,8-TCDD not measured and for other TCDD, the detection limit is 1.0 - 5.0 ng/g. NO Not detected. 7-24 HONS 019028 Flgura 1. Pentnchlorblphnnylent Identified In Soot Staple Fro* Helm MOWS 019029 PCBa rirae: Preliminary Correlation of Qilorobenzera and PCB Contents of ths fluid with PCDP and PCDO Contants of Soot daanoaiarm, P.E.,* Wsstfall, B.T Csnpbsll, B. and Las, A.** PCBa, PCDOa, and PCDFa ara aubjact to raw ragulaticm promulgated undar tha Toxic substances Control Act and tha haeagos Ccnaarvatlcn and Baowary Act. lha finding of PCDOa and POTS In PCB* could raatrict dtapcawl option* for PCBa. A ravlaw of aa^or flza incidents In tra United stataa lndlcatas that PCDOa have baan found only in tha Binghamton, MY, transformer flra lncldant. Laboratory ccabuatlan studies furtbar support PCDPa formation froa PCS* and pass fit* chlorobaruanaa. No PCEC* wara found in analyaaa of flulda tarn txanafocaara involvad In transformer fix* incldanta. POPS do not appear to lncraaaa In PCBa aakarsl flulda ftoa normal usage In electrical aqulpaant. On July 9, .1985, tha Unitad Stataa Environmental Protection Agmey promulgated lta final rule on Polychlorinated Biphenyls in Electrical Trar*formers, tha culmination of a long fact-finding and rule-oaklng |M' n aaa that davalopad shortly aftar tha transformer flra at the State office Building in Binghamton, NY, on fateuary 5, 1981. In brief, this rule: M 1) Prohibita tha uaa of hicfmr secondary voltaga (480 volts and above] network PCB Transformers in or naar coaosrcial buildings aftar October i, 1990. 2) Baqulras, by October 1, 1990, the installation of anhancsd alactrleal protactian on lamer aaoordary voltaga natuork PCS Transformers and hl^Mr aaoondary voltaga radial fa Tranafanaar* in uaa in or naar riaaairlal buildings. *U.S. Environmental Protactian Agmcy, Office of Psaeitui-h and Davalnaanr. 401 K Street SM, Washington, DC 20460. ?U.S. mviroraental Protection Agency, HMEBL, 26 w. St. Clair Street, Cincinnati, CH 45268. **Tachnical taaouroas, Inc., 2202 Monroe Street, Rodwilla, MD 20S52. 7-26 M0NS 019030 3) Prohibits furthsr installation of PCB Transformers in or near ocsnarcial buildings aftar October 1, 1985. 4) Requires the registration, by Oerenber 1, 1985, of the exterior of all PCB. Transforeers with fire response personnel and building owners. 5) Requires the narking, by Deowber 1, 1985, of the exterior of all PCB Transformer locations. 6) Requires the renewal, by Darmmher 1, 1985, of stored ccsbustiblas located near PCB TTansfonaars. This rule does not spell the end of the issue surrounding PCS fluids in electrical equipment. Increased nedie attention, to the problra of ***** substances ganaration in electrical equipment fires has prompted Increased public awareness. In Washington, D.c., recently, fixes or leaks involving transformers in the Smithsonian Institution, the White House, and the Department of Health and keen Services were given front-page attention in the wehinerton Ba. Additionally, many utilities throughout the country have lanlrads of thousands of gallons of PCSs in storage awaiting pixpsi disposal. As acme utilities have discovered, irproper disposal can result in heavy penalties. In Ssteelier 1985, the Potcaac Electric rosier Cimpeny (KPOO) in Mahingtcn, D.C., signed a consent decree with the State of Muylard to dean >9 Pa contamination at a etorage ccapany to when COCO sold 75 transformers contaminated with PCBs. The cleanup Is saqpactad to cost TOCO from $1.5 to $3 Billion. Furthermore, the issue of PCBa-filled capacitors has not yst surfaced In the United States and it is not covered by the July 9 rule. However, capacitor fires in Swadan and Finland have certainly drawn attantlan to this area aa wall; aonewar, the recant transformer fire in Raima, Franca, has not diapallad this attantion. To complicate tha Issue further, under the Resource Conservation and Recovery Ace of 1976, Bit promulgated raw rules on January 14, 1983, with regard to dloodns-carctaminatad vestas streams. <2> This rule defines omrtain waste it lease as dioadns-oontaminatsd wastss and thus, narrows wssts treatment options to thoss approved for dioxins wests, arm part of the proposed rule is intended to oovar e broad variety of dicodne-contaminated vestas that arm identified as Bit implaasnts its Dioxin Strategy. In tha iaplraanhstlon of this strategy the Agency has established seven categories or tiers of 7-27 HONS 019031 investigation and study. Tiar 4 cows: cnbustien nuoi such as Knldpal and hazardous waste incinerators, PCS tnrsformsr/capacitcr flraa, reactivation fumacaa for apart granular actlvatad carbon, boliars using PCBs and PCP-treated' wood, ate. Thus, this rula eventually say oovar zaaldua satarlals ganaratad In a PCBs transformer firs If dloKlns-aaitasdratlon is amn, or, in situations where dioxins ara found with "PCBs wasta." A casa in point Is tha problaa anoountarad by a wasta nanagaaant company in niahasa It aocsptad 40,000 gallons of "PCB wasta" from tbs infamous Hyde Park Landfill in Niagara rails. Sines the wasta ccntainad >500 ppM PCBs, this wasta was legally a PCBs wasta. Unfortunately, Alabama Stats authorities wars not intoned via tha forwarder's bill of lading that tha nenaqusous phase laachata OWL) ccntainad 20.2 ppa 2,3,7,8-gen) along with hundreds of other haloganatad organic and pesticide! residues and sfestantlal guantltias (100 to 1000 ppm) of tOKle heavy metals. As a result, aavaral of the 41 storage tanka at tha wasta aanag--nt ooagany's tank farm tsci nmtaalnatad with dioxin and 1.2 aillion gallons of PCB wastes ara now tarsad "diodn wastes," with no short-tan solution in siqflt. Bagulatlona in tha United states to data have focused on tha piXOs and PCBs. No fadaral regulation has ban prosilgatad speciflcally for POPS. However, if PCCCa or PCDFs ara found in KBs, disposal options for PCBs ocuid be further restricted. Table 1 svanarizss tha analytical results of sobs of the major PCBs transformer and napscltrar fires identified in tha united States. This list represents only firs incidents where an effort was sada to aasanrs not only PCBs, but PCSOs and PCEtm as will. The list of reported pa transformer firs Incidents continues to grow in tha Unitad States and Buropa. PCEOa ware clearly identified only with tha Bln$amten, NY, tisnsformsr fire. Tha finding of PCOOs at Blii/aarrn, NY, is conelatent with labacatory findings of PCSOs trm pyrolysis of diiorcbanzsnss. The Blngiaadan, NY, tansfOcmar oontainsd <54 polychlorinated biphenyls (Aroclor 1254) and 15% tri end tatrschlorlnstad bananas, lbs Intense hast of the sln^imscon tin say have also created tha optimal conditions for bimolacular reactions of ehloro- banones, naoaseary for the forsaeicn of PCEOa. 7-28 HONS 019032 Table 1. Sene Major Fires Involving PCB's Transformers and Capacitors in the U.S. QJ m suu office ftitMim p-is-oi) (Traneforaer) MW Soot Ooplsa IMtl KXWi 7<s*3lH ug/g 2,3,7,0-Tcxrt 12-270 ug/g Cincinnati, (M BlwanUry IdlBOl (12-1-00) (Capacitor) Nips Maplaa MD Beaten, ** Office Building (1*02) Boot Baglas Total pcsrai 163 uyg 2,1,7,0-TCSri 3 ug/g ttimi, FL Vault (4-3-02) Soot Sallee OVUi loo-iooo ug/g and Flro Malone an Franciaoo, a Nips loplM (Ad) to M#r Moo) (5-15-03) (Tiaweforuer) law - 15.6 ug/g tat* Total rOGii 20 ug'g Tranefnraaa filled with (4,$) 2,3,7,0-TODi 0.6-2.0 ug'g ioo gala, af fynaial (660 KBS) (Arodor 1394) 0 M banatanaa. VNy hot flea, atgtloaloa 6 ngtin of tnrs- foraar with coloaea of ISO gala, of fluid. 0.000 0m cnly Ui Of KM () (Aroolor 1204) aa> IsmoIvoU in Oa capacitor But Um inatad at a iwi laud of 711 ug/10fea? ND Trmfnraar oantaining (7) Arodor 1294 umnywad vault <) 0.12,3,7,0-TCSDi appro*. of that datortort in Bliyadon 3 traneforaare with 1001 () Aradcr 1242. bo cMoco- ColxaWua, a Offioa Building P-04) (Capacitor Nipa l^ilaa Total BCOFbi ip to 10,000 iq Total RXDbi ip to 44 ng Capacitor with Areeicr (10,11) 2,3,7,0-TOTt to 1000 ng 2,3,7,0-OOWt to 3.0 ng 1242 cot taplH fatal room: lo.o ug/g Total races trace (tatra to octa). fxaoa snnt of chlenttnMM. (Detection Unit at u^g level.) MOWS 019033 Analysis of wipe smplae Cram the Galumlmis, OH, fir* also showed a vary snail amount of PCCOe, but the finding could not ba quantified In tha Boot aaspla. MO ehlorebansane was found In tha aoot sanple from Columns, OH. No analytical data is yet availabla cm tha capacitor oil itaalf, although it is known to contain Arador 1242; thus, it is not claar if pyrolysis of chloto* bantams was tha aouroa of tha sawll amount of PCEOa found. Ths tranaformar iiwolved in tha San Prancisco flra was also fillad with Aroclar 1242, hut containad no chlorobanzanaa. No PCDOs wars found in tha aoot. In tha San Francisco firs, SO gallcra of tha fluid won ralaaaad and allowad to older for S hours aftar tha firs waa dlsoowarad. T2k, through a contract with tha Kidwast Hasaarch Instituta, Kansas city, NO, has conduetad aavaral studias to waluata thamal dagradatian proctacta from dialactric fluid using a bsnedi seals thamal dastruetion systsn. (14> %s first part of tha study was to datarmins tha optima tasparatura, owygan, and rasidanoa-tlas oenditiona for PCOF formation. Tha faad into tha symtm waa mineral oil aplksd with thraa individual PCS oonganam (2,3,4,6- tatrachlorobiphanyl, 3,4,5,3',4',S'*haoachlorabiphanyl, and 2,4,6,2',4',*'- hmmchlorcblphanyl), which fuxa PCEFB by tha four raacticn machanima pcopuaad by Buaar and Sappa. Tha raaulta indicate that tha optima valuta am a taaparatura of 475% and an anraaa oxygen concantration of It. Uw raaidanca tisa, in tha range of 0.3 to 1.5 aaoends, did not significantly affect tha yield, although tha obsarmd yields of FCDFS wars lower at shorter raaidanca In tha moot part of ths study, dipilcata teat runs ware conduetad with mineral oil and ailiocna oil dialactric fluids containing PCBa (Aroclar 1254) at ccncantraticrm of 0, 5, 50, and 500 ppm. An salami fluid containing 70% Aroclor 1254/30% triehlorobanzanaa, and a ncn-PCS aakaxal fluid, containing mostly trlchlorobansanas with soma tatrachlorobanzanaa, warn tasted in duplicate. PCBfS warn found in all saaplaa. PCEOa warn found in tha aiaplaa frta tha triehlorobanzana rum and occasionally at low levels in sms of ths other samples. Op to 5,700 ng total PCDFs/al of spited faad oil or 4% conversion efficiency (PCBa to PCEFs) was observed for ths mineral oil and silicons oil rune. op to 19,000,000 ng total PCSfW/ml faad oil (19 ag/ml) or 7-30 HONS 019034 3% conversion efficiency was ctaaarvad for the oskarel fluid. Statistical analysis shoved a llnsar relationship for PCDFS formed versus the amount of peas. PCDFS and. to a leaser extant, PCTCe sere formed froe the trichlorobanzans dielectric fluid under the optimal Pa-to-PCDF conversion conditions, up to >110,000 ng total PCEFB/sl fasd oil (>0.004% yield) and 1,900 ng total PCDO/ml feed oil (0.0001% yield) sees observed for the trichlorobanrane runs. Tables 2 and 3 show the yields of the PCDF and FOX) hcmologuas froa the different runs. The results indicate that the optima conditions for FOX' foraetion fnoa FOe are near 675C for 0.8 seocni or longer, with 8% excess oxygen, under these conditions, PCDFs are formed from mineral oil or silicone oil contaminated with FOs at >5 ppa. Pars sere also fornad frta a trichlorobenrana dielectric fluid that oontainad no detectable FCBs. These results supportad earlier laboratory trark and analytical results of soot material from transformer and capacitor fires, tfilch determined that chlorobenzenes are regiirad for PCEOo formation. One problaa in evaluating data ganaratad frem the analysis of soot or wipe saaplas from a transformer or capedtnr fire incident is the lack of data an the oil itself. EPS has obtained aaaplas from transformers that ware involved in firs incidents at Mini, FL, Blnqfmmton, Nf, and Chicago, a. TPtal FOFa (Table 4) in the used fluids are within the range of the FCDFs values previously reported for stock seterial. It does not appear that the normal use in electrical equipment generates FCDFs to any extant. FCCDa and FCEFs appear to be formad only after FCBs and diluents are released from the transformar/capacitor housing. Tits FOs and diluents anheagiantly reset wear thermally stressful conditions in the presence of air or oxygon to form Faxs and FCEFS aa amldned by: (a) detection at ug/g levels in soot magpies tatan from vault walls; and (b) the relative absence of FCCDa and Peers from the PCS fluids thaaaelves. Further information has been provided from European sxpsrianoas(ls> ragsxding s process used to convert lindane asnutacturing vestas (o , s, a haxachlorocyclobascane, HCCH) to predominantly (70-75%) l,2,4-trl<hloro- 7-31 MONS 019035 table 2. POF'a Formed in Ccntxisticn Studios (14) tow tnanl Oil/ 1 |p HIM silicons oil/ ft pa *-12*4 tttmnl oil/ 10 |p ft-1254 llloom Oil/ SO n ft*1214 Maint oil/ too pa *~>214 <B) Silicons Oil/ 100 pa *-1254 (ft) 704 *-1254/20% (S) ddowftawaana Fluid (tri with ocas totem) m lab Parit - - not analyst* kM}>Mt yantititad 0 0 not datsotad HonoCXf1 Diet? (ng) (ng) Trior (ng) tatraCST (ng) hnucxr Haacsr apany octsrtr rare (ng) (ng) (ng) (ng) (ng) _ --- -- ---- - 1,700 - * 90 0.4 120 1,100 20 - 0 -- - - 1,200 0 1,100 7,000 1*0 - 2.000 29,000 -- 00 no 43 20 31 200 140 290 5K> 2,200 1,200 0 2.000 1,000 0 440,000 220,000 210 2,400 >12,000 11 0 49 22 0 0 90 9 110 110 39 12 21 72 02 040 3 090 43 *20 170 12 0 740 340 2,100 170 00 1,400,000 0,400,000 1,100,000 4,700,000 1,200 17,000 2,000 9,000 >19,000 >22,000 25 9 00 _ 0- 0- 0- a.i - 2.2 - 00 00 70 13 0 00 45 " 12 0 00 10,000 29,000 000,000 19,000 3,000 - 0- 1,200 0 0 - 0 - 0 0 0 0 0 - 0 0 3,400 1,200 - 0 - 100 00 110 190 390 290 420 1,300 4,700 2,100 13 3,100 0,000 0.4 9,200,000 0,700,010 22,000 9,000 >90,000 110 0 HONS 019036 Table 3. PCD's Formed in Ccnfcuetian Studies*14* Biliacm Oil/ 900 fqa Areelor 12M I 70% Areelor 1394/ 30% Trtdaoccfeemone OJcwtonoa Fluids (eeotly fcri with me totrs) Homaio Dicso Tticco Totnao Nnuao Hwecco mpteoD onterp rax* (ng) (ng) <ng) (ng) (ng) (nq) (ng) (mq) dm) -- 0 00 0 0 0 0 00 0 00 0 0 1,100 C30 0 0 00 00 00 0 72 3)0)7 230 91 7.7 1.7 Ct ' l i S ** HONS 019037 Table 4. Analysis of Fluids Involved in Transformer Fire Incidents (11) Miaai, FL1 (May 29, 1984) (u^g) Bincfratsn, NY3 (February 5, 1981) (ugfg) Oilcay). EL3 (Septnsbar 28, 1983) (u^g) pats ND* ND* ND* pars (Total) TttH-CDT pwti-ap Mm-a* Mpta-ar oct*-a* 6.0 0.31 0.78 2.2 1.3 1.4 16.2 0.48 1.1 u.o 3.2 0.41 3.0 <0.01 0.053 0.47 1.4 1.1 QilorolMrzvm (TWal) irlchlenbanxanss Tetrachlorobansanee Pantachlotdaarganaa HMKhlonbmnc 430,000 280,00<^ 140,000 29,000 90c4 390,000 230,000* 110,000 13,000 5<i 160,000 100,000* 51,0008 5,500 64c PCBi (Total) Mcnochlorcbiphanyls DichloK^iptoanyla Urichlorcbijfcanyls TatzachloKQblptMRyls Mntachlarobiphanyls Hwi-h) rrr*i1rhwyU Heptachlorcbljfcanyls ratacMecctolpharyls Mbnachlcrcbiphanyls DaoachlacObl^Mryl 410,000 320 1,100 2,800 2,000 31,000 180,000 170,000 32,000 14,000 <3,900 580,000 230 730= 3,500 88,000 300,000 160,000 24,000 <800 <1,200 0,800 no, ooo <100 <190 <200 <400 11,000 49,0008 49,000 7,300 <1,600 <4,700 * Detection Halts apgnadaataly o.Oi ug/g for PCEFs/KXOs. d Aeeults of analysis at a dilution of 0.1 ag of oil/ml of basane. Moults of analysis aft a dilution of 2.9 sg of oil/al of banana. nasults of analysis at a dilution of 0.23 sg of oil/al of basons. 1 Aakarel Type A: (04 pas with 804 chlorine (Arcelor 1280) with 404 triehlordMcwm i1xbisi< 1 Aakarel Type Di 704 POa containing 944 chlorine (Aroclar 1234) and 104 trldileRtaun 3 Mineral Oil with 234 POa (Aroclar 1280). 7-34 HONS 019038 benzene (TCB), which, after purification, was transform! to 1,2,4,5tatrachlorobanzana usad as ths feedstock far 2,4,5-trichlecuphanDl. The procass involvad ths low tssgjaratur* (200-240C) pyrolysis of ths llndans wastas with a caxbcn catalyst using indizact hasting of a doaad raacticn ssntla. Ths rasiduas frta both tha nantla and tha trichlorobanzana still wars analyzed by Buaar in Switzerland (saa Table 5). Needless to say, tha extraction procedure required for this rasidua was excruciatingly daa emailing and tedious. Table 5. Dioxin laczner Differentiaticn for Pyrolyzed HOCH Residues and TCB Stillbottcms U5) Dlcpdn Trwr Cbnoantration, zq/Toj (ppa) 2,3,7,8-TCEO TCCO 1,2,3,7,6-PCEO PCtxn 1,2,3,4,7,6-BCCO 1,2,3,6,7,8-HCCD 1,2,3,7,8,#-HCDD H^arn 1,2,3,4,6,?,-4KXD 1,2,3,4,6,7,8-HCOO ocro 0.3 12 7 200 45 150 65 660 1,400 3,000 7,600 Tha point hats is that axtraaa cars oust be taken whan pyrolyzing anchor distilling chlecinatad arcaatics to awrima air (oxygan) frtai the systaai. 7-35 HONS 019039 Finally, It ahould ba retail that EEA'a Dioxin Dispos&l advisory Sroqp has baan providing guidance igxn request to EPA regions regarding activVinactiva scrap natal reclaiming facilities, where PCS transformer and capacitor units ara prooaes'ad for thalr raspactiva ogpi valuaa. Ona such axaapla in tha Pittsburgh, PA, araa is a 1/2-acre sits in tha aidst of a residential calamity, with about 1000 parsons within a 1/4-sule radius, on this sits is a rcimsrrtal building containing a snail lnclnarator that was usad not only to ccsfeust PCBs, but also to provida hast to tha surrounding araa! In August 1962, NXOSH made an inspaction and datactad 8 ppa OCDO in a staple of soil talon at a dspth of 1 foot naar tha PCB liquid storaga araa. In April 1984, EPA Raglon III ataff removed and analyzad dust easplee tram Iraida tha building, tha results of whidi ara shown in Tabla 6. Table 6. Dioxin and Puran in Dust HcmoIooim TOX* 2,3,7,8-TCDO TCEF* 2,3,7,8-TCDr Ccneantration. ra/a 17-39 0.79-2.3 413-1232 74-241 As a rasult, an T--rllata Amaoval Action was initiatad on Hay 29, 1984. An axtanaion aurvay demonstrated that tha dicoein/furan oattaadnatlon taa lastristad to tha intarior of tha incinerator building. Hers than 5000 tone of PC-oontaadnatad soil, containing >50 pgn PCBa, wars ajcavatad, loadad, and transportad for ai^seei to tha CEQQS facility in Niagara Falla, NY, bafoce tha JOK Dioxin Listing Rile want into affact (on July 15, 1985). scraps eaaplas tram intarior building surfaces showed: TfXOa TCETS 10-94 rq/g 36-415 rg/<J 7-36 HONS 019040 Sixty transfonar casing* remain on aita today. Estimated coat for thm disposition of tha rswlnlng ocntaslnatad natarlals (1.*., PCBo, KXOs, and PCTTs) and ascurlty ot ths aita on a t^porary or Interim basis Is $2.aa5 Billion -- for a 1/2-aer# sltat No doubt the rssponslbls partlas will bs ldantlflsd but, In tbs lntaria, than main only two caortiflad/fully permitted facllitias for FO dastructlon: tha BA Moblla Incineration System, currantly ployad to destroy dioKlne-oentaaUnated wasta liquids and soils at tbs Camay Fan sits near McDouall, MD, and tha BA Office of Rasaarch and Davelopnant's cosbustion Rasaarch Facility In Jefferson, AR. In tha saantlaa, no new tadwelogy to rallsva tha capacity hnrtage Is attracted until rarmrtiai 19Sd. mamhile, tha confusion babusan tha applicability of tha TSCA PCS regulation or tha DCSR Dioxin listing Rila to a particular aita will main. In eoncluaion, tha following ralavant observations say ba sada: 1) Tha Rinspaatcn, OT, fira incddsnt is tha only cna tra ppa lavals of pccoa hava baan found and quantified; 2) Tha foraation of KEOa (ra ehlorobanaanaa is supported by various laboratory experiments and by tha Bln^saaten fin inddant; and 3) Nscsiss of thair potantlal for fening Pars and POP* under tbanal conditions, cblocebanzanas should ba used with can and dlfnaart of properly. 7-37 HONS 019041 BEnRENCES (I) Unit*! Statu of taarica (1985). Coda of Fadaral Regulation* 4fl:761 JUly. 9. <s> U.S. Fadaral Ragiatar. (1983). jfi(9): 1978-2004, January 14. (3) Unitad Stataa Environaantal Protacticn Aganey (1983). Oioadn Stzatagy, Newvfear 28. (4> Hutzirxjar, o., Onafiry, G.S., Chlttla, B.G., and Jchnacn, L.E. (1969). Fcraaticn of polychlorinatad dlbanzofuxana and dicodna during ccabuatlon, alactrical aquipaant flraa and PCS Inclnaraclan. BlBMD>l_UMUI> fggactlvaa 52=3-9. (5) Schachtar, A. and Tlaman, T. (1985). Occupational axpoaura to poly- chlorinatad dicodna, polychlorinatad furana, polyctilorinatad biphanyls, and blphanylanaa aftar an alactrical panal and tzanafcnaar aocldant In an offlca building In Blnghaaecn, MY. Biyircnaantai n~ifh '-='~ 52=305-313. (4) Moalnaky, J.R. and Flaach, J.p. (1981). Haalth hazard avaluatlon npcrtcur lady of Vlaitatlcn Elaantary School, clnciraiati, CH. MIOGH Dgort No. lira 61-237, JUly. (7> Maaorandua fro* G. Qioudhzy and J.C. Poanar to X. Mdfenua (Paginal Prograaa Conaultant) (1982). fdaulta of tha analyala of chlorlnatad diodna and dlbanzoturana in bulk aoot aaaplaa aaguanoa 13314, eapaitaait of Haalth and Huan Sarvlcaa, Octcbar 1. !*) Paraanal Qramin) ration (ta S.A. Sallabury (Maglonal Industrial Hygianiat) to R. Duffy (I.A.P.P.) (1982). Ikparoant of Haalth and Haan Sarvlcaa, Division of Pnwitlva Haalth Sarvloa. Dooanant 0409 g, ICIA 82-224, Octcbar 22. () lattar froa H.M. Hsua (Chlaf Enginaar, Pacific Gaa and Elactric Cagany) to C.A. Miita (Maglonal JKbdnistrator, California Daparcnant of Haalth Sarvlcaa), naraabai 9, 1983. (3) Paracnal nraiamlratlon froa J.R. Koainaky (NXOGH) to Paul E. daaRoalars (EEA), Ssptaabar 25, 1984. (II) HTinta treat S. auanacn and M. Erickson (Mldwaat naaaarrh Inatituta) to Dan Haggaa (EPA) (1965). Maaulta of analyala of oil and aoot aiawplaa froa Paul E. daataosiars. EPA Contract No. 68-02-3938, Jura 17. (32) Paraonal Coaaamlcatlon froa C. Mappa (Univarsity of tbaa, Svadan) to Pul E. daannalara (EPA), Octcbar 24, 1985. (13) Buaar, H.R. and Rappa, c. (1979). Formation of polychlorlnatad dibanzo- furana (PCSFa) tna tha pyrolyaia of Individual PCS iaaaara. StauKhan J(3)= 157-174. 7-38 HONS 019042 (M> Erickson, M.D., Cola, C.J., Flora, J.D., Jr., Goman, P.G., Haila, C.L., Hinahav, G.D., Hopkins, T.C., and Swanson, s.E. (1984). Thanal dagradation products Crot dialactric fluids, EPA-56C/5-81-009, Dacaafcar. (IS) pronal Communication from H. Jurgans (DEKONTA-Mainz) to Paul E. daaltasiars (EFA), Saptaafcar 23, 1985. 7-39 MONS 019093 PMT 8: IKTIMFILL AMD tEPLACEMENT FLUIDS HONS 019044 David Sllnn FORMEL -- A NEW, SAFER, NON-FLAMMABLE DIELECTRIC AND COOLANT FOR TRANSFORMERS ABSTRACT A test programme is outlined describing the search (or a dielectric fluid that is non-flammable under high energy arcing conditions and which, at the same time, gives an acceptable toxicity profile in the immediate vicinity of the test device during arcing. A number of fluids were studied using a combination of switching, destructive testing and analysis of fluid decomposition products as screening techniques. These studies, in conjunction with parallel examination of the fluid for other necessary properties, led to the selection of a blend of halocarbons as giving the best performance. Destructive testing of a 500 kVA transformer filled with this fluid showed that it passed the target safety criteria. The fluid has been shown to exhibit a satisfactory performance across the spectrum of properties necessary for a transformer fluid. In particular, the combination of its low viscosity, high density and high coefficient of expansion leads to outstanding coolant characteristics. Commercialisation has taken place and the trade name Forme! has been allocated. Each component of Forme! has been used widely by industry for many years and the toxicology has been studied extensively. It is considered, therefore, that the safety and environmental profile is acceptable throughout manufacture, use, maintenance and disposal scenarios. 8-1 HONS 019045 Section 1 RESUME Most of the work described in this report was conducted under the auspices of the Electricity Council in the U.K. Harwell Laboratories, Didcot, U.K. acted as independent consultants and I.S.C. Chemicals collaborated with regard to fluid supply and relevant technical advice. Emphasis in the early stages was centred on the need for a non-flammahle replacement for oil in switchgear. As this objective was not achieved and competitively priced alternatives, such as SFg equipment, were becoming available, the emphasis was changed to transformer studies and a target specification was drafted (Table 1). Most of the preliminary screening tests, under both switching and high energy arcing conditions, were conducted with typical substation switches containing about sixty litres of the fluid. During the course of this work, a variety of fluids were tested (Table 2), including commonly available "Iess-1 lammabIe" transformer fluids, such as esters, silicones and high-boiling oils. The latter fluids were found to give as large a conflagration as standard hydrocarbon oil, which was somewhat surprising in view of the fact that they are used on the basis of a substantially reduced fire risk. It quickly became apparent that any hydrogen containing fluid constituted a flammability risk under arcing conditions; for example, trichlorobenzene gave a small flame (Table 3). Exceptions to this finding were the cases where a highly volatile halocarbon, such as 1,1,2-trichlorotrifluoroethane mixed with a hydrocarbon (Table 3), gave a fire suppression effect. However, the vapour pressures of such mixtures were unacceptable and high concentrations of acid can be formed. After the flammable effect of hydrogen (even in small amounts) had been established, further work centred on fully halogenated materials. Also, because of increasingly stringent environmental considerations, it was considered that only those fluids could be used that had long established uses coupled with well documented and acceptable toxicity profiles. Furthermore, all such fluids should be already commercially available, at acceptable costs. When all the foregoing criteria were applied, the available candidate fluids narrowed to perchloroethylene and chlorofluorocarbons. Of the liquid HONS 019046 8-2 chlorofluorocarbon} available, only difluorotetraehloroethane (CFC 112) and trifluorotrichloroethane (CFC 113) were considered as suitable liquid candidates, from vapour pressure considerations in standard transformer designs. Both perchloroethylene and CFC 113 were already being marketed as transformer fluids. High energy arcing tests were thus conducted on those materials, separately and mixed, using sixty litre capacity switches u test vessels. In order to establish a safety target for the immediate environment during high energy arcing, the concept of the emergency exposure limit, EEL, was introduced (Table * and 9). This was defined as the maximum vapour concentration tenable by human beings, for a period of 9 minutes, without permanent harm. As thermal injuries from emerging hot liquid may also be a hazard, simultaneous measurement of temperature was made (Table 3). The high energy arcing tests invariably caused violent rupture of the 60 l test vessel, usually resulting in shearing of the bolts on the lid, followed by liquid being thrown in all directions. The most significant (actor emerging from tests on the remaining three candidate fluids was that the addition of chlorofluorocarbon* to perchloroethylene markedly reduced the small amounts of chlorine and phosgene produced by perchloroethylene alone (Table 6) so much so that phosgene traces were well within the safety limits. However, even in the case of the optimum mixture, chlorine levels were still marginally higher than the EEL. Having obtained the optimum mixture, and also taking the entire spectrum of properties into account (Table 1 and 17), the fluid was tested in a 900 WVA transformer, which resulted in phosgene being undetected and chlorine levels being well below the EEL (Table 7). Although the same order of energy was used for the previous switch tests, the transformer test was markedly less violent resulting in small bursts on two side welds followed by slow seepage of liquid during an hour or so. The improvement in the results obtained was considered to derive from the reduced mixing of fluid with air. At this stage, a toxicological and environmental review (1) covering the optimised mixture (Formal ) was conducted by the independent laboratory. This resulted in a recommendation that the fluid had an acceptable safety profile, based on a considerable history of use and extensive toxicological testing. A decision was then taken to firther test the electrical performance in full size transformers. This required compatibility testing in order to select suitable 8-3 HONS 0190*7 materials, which showed that most conventional types were satisfactory (Table 8). Physical properties were also measured and collated (Table 17). Two 500 kVA transformers were subsequently built and installed in the London Electricity Board distribution system and two 50 kVA transformers were built to study the relative properties of Formal and transformer oil (Table 9 to 12). In parallel with these studies* a standard 500 kVA oil-type transformer was fitted with about forty thermocouples to compare the cooling properties of various transformer fluids with Formel (Tables 13 and 14). These studies showed that the liquid had similar dielectric properties to oil and that the cooling properties were superior to other available fluids. A comparison of Formel properties with several other fluids is given in Tables IS and 19. Alter one year in operation, one of the LEB transformers was disconnected and the core and windings were subjected to close visual examination* which indicated that no deterioration had occurred. Accelerated laboratory tests were in agreement with these findings (Table 15L Following the commercial launch of Formel in February 1984, studies were made on the behaviour of Formel * if involved in a building (ire. These indicated that vapours arising from Formel did not add to the smoke hazard (Table 16). Recently, attention has been directed on the formation of soots during the pyrolysis of haiocarbons, following the detection of highly toxic dibenzoftrans and dibenzodioxins in building fires involving PCB filled transformers. Some initial studies on Formel (2) indicate a tendency to form fully halogenated ring compounds, including chtorofluorocarbons. These species have a relatively low toxicity. However* the detection limits were only about I ppm and firther Investigation is in progress at nano gram levels. Environmental authorities are concerned about the disposal of halogenated transformer fluids, especially in view of the problems currently being experienced with P.C.B.'s. Analysis of product from accelerated aging tests (Table 15), indicates that following its life in a transformer* the fluid can be reconstituted as Formel or can be separated into separate compounds for conventional solvent application. Current industrial requirements for the Formel-NF components are about 1.5 million tonnes in total, on a global basis. HONS 019048 8-4 Section 2 EXPERIMENTAL This section contains only a summary of the work done since a full description would be beyond the scope of this paper. HIGH ENERGY ARCINC TESTS (CATASTROPHIC FAILURE) These tests were conducted at the Switchgear Testing Company, Trafford Park, Manchester in the U.K. The majority of initial screening experiments were carried out in 60 1 distribution type switches at energies of about 8 kV, 6.3 kA for 300ms. After selecting the more promising fluids, the energy was raised to a more arduous level of 12 kV, 13 kA for 300 ms. Each test was monitored visually by high speed cine photography and thermally by an AGA Thermovision camera. After screening tests were completed, gas sampling devices were designed (Fig. 1) capable of collecting samples, from the time of arc inception to any required time afterwards. A typical arrangement of the test vessel and sampling devices is illustrated schematically in Fig. 2. Most of the analyses were conducted on site, immediately after each test, by personnel from the Physical Chemical Measuring Unit, Harwell Laboratories, Oidcot, U.K. Environmental and toxicological guidance, including emergency exposure levels, was also obtained from the same laboratories (Tables and 3). SWITCHING TRIALS in parallel with the high energy arcing test programme, switching tests were conducted both in distribution switches and in circuit breakers. Certain of the fluids exhibited promising switching properties, however, the work wes not completed following the successful introduction of sulphur hexafluoride switchgear. An overall summary of both switching and high energy arcing trials is given in Tables 2, 3, 6 and 7. 8-5 HONS 019049 MATERIAL COMPATIBILITY WITH FORMEL Before construction of a transformer, all cellulose and polymeric materials used were subjected to screening tests. Samples were immersed in Formel at a temperature of IQ(TC for a minimum period of 2 days. Assessment involved measuring dimensional change, weight change and amount of polymer extracted. Accelerated tests were conducted in the presence of metals, since certain metals such as aluminium, zinc, magnesium and their alloys have doubtful long term stability in the presence of halocarbons. Screening was conducted by heating Formel in sealed glass tubes at a temperature of 175*C for one week. These tests indicated that copper and steel are satisfactory. Following the selection of suitable constructional materials, two 500 kVA transformers were built and installed in the London Electricity Board. After operating for one year, one of the transformers was removed and the core and windings were inspected. Close visual examination revealed no corrosion or other compatibility problem. Chemical analysis of the Formel revealed no change. Measurement of the electrical resistance and breakdown voltage showed that the fluid was on-pade. The results from two 50 kVA transformers, respectively filled with oil and Formel (Tables 9 to 12), are an indication of acceptable compatibility, since small quantities of dissolved materials in Formel electrical properties, particularly tan ^ . can adversely affect the ELECTRICAL PROPERTIES The electrical resistance, tan ^ and dielectric constant of Formel are routinely measured on an Olman dielectric test instrument model No CB 78 using the cell specified in BS standard 198. The breakdown strength is measured using a Foster Oil Test 90 instrument with an electrode size and gap specified in BS198. Quality control values are given in Table 17. Capacitance, tan ^ , impulse voltage and partial discharge measurements were compared for oil and Formel using two identical 50 kVA transformers (Tables 9 to 12). The capacitance between the HV winding and the transformer tank together with the loss angle (tan cf ) of the total insulation was measured using a Hartman and Braun Capacitance / Tan J measuring bridge. Impulse voltages were measured according to British Standard 923 and comprised full and chopped wave impulse voltages at 75 kV followed by a repeat at 95 kV. Negative polarity 8-6 HONS 019050 was used throughout and the chopped wave terminated on the wave tail, 5p seconds after Inception. Partial discharge were measured with an ERA Discharge Detector Model 3 fitted with an Input Unit No. 3. Discharge inception voltage and extinction voltage were measured at 7 kV, chosen as the rounded-up voltage 10% above the nominal phase voltage of the transformer. COOLING CHARACTERISTICS The combined low viscosity, high density and high coefficient of expansion of Formel (Table 17) results in outstanding cooling characteristics. Hot-spot, winding gradient and overload measurements of Formel were compared with some other common transformer fluids (Tables 13 and 14). The 500 kVA transformer used was designed for use with oil and was fitted with about *0 thermocouples. Although a 30% overload performance is indicated, when Formel is compared to oil, this figure falls to about 20% in commercial Formel units, i.e. when the transformer size and number of radiators are reduced. The excellent cooling properties contribute significantly to competitively priced designs of transformers. FIRE TESTS WITH FORMEL In these tests Formel was compared with sulphur hexafluoride and trichlorotrifluoroethane (CFC 113) by spraying each fluid into a drum containing a blazing mixture of petrol and diesel fuel. The drum was 41 cms high, 36 cms in diameter and contained about $ litres of fuel during each test. Samples were taken at various points downwind. Concentrations of noxious gases taken at a point near the flame edge is shown in Table 16. It was impossible for personnel to stand at this position during the burning period. HONS 019051 8-7 Section 3 EFFECT OF FORMEL ON TRANSFORMER DESIGN A Formel transformer is very similar to a conventional oil design and a visual comparison is given in Fig. 3. However, the following differences apply?* I. The transformer is significantly smaller containing about half the fluid volume of an oiMype. 2. About 4036 less radiator surface is required. 3. The transformer is sealed under a partial vacuum at ambient temperature OK a. More stringent leak detection techniques are required during manufacture, because of viscosity and vacuum considerations. 5. Gasketing materials are limited to Viton and PTFE. HONS 019032 Section 4 ENVIRONMENTAL Only general remarks are given here, a more detailed report is available (I). Much is happening in the environmental field and many substances, including those that have been in use for many years, are coming under increasing scrutiny. Thus, common household substances such as white spirit, detergents, aerosols etc. have been found to have more associated toxicological hazards than was previously thought. However, the environmental disadvantages have to be balanced against the social inconvenience if such materials were unavailable. When authorities consider that usefulness prevails, pressure is quite rightly directed at improving modes of manufacture, handling and use. For example, products sold to domestic consumers now increasingly have detailed safety instructions prominently displayed on the package. The foregoing considerations apply equally to the component liquids of Formel , which have been used for many years in large tonnages for metal cleaning, dry cleaning, electronics cleaning and aerospace applications. They have been used In open top tanks, continuously, in close proximity to human beings. In the case ol the chlorofluorocarbon components, no rim ventilation has been considered necessary, because of their low toxicity. In recent years, for economy and environmental reasons, there has been a trend towards the use of partially or totally enclosed cleaning systems, in particular, dry cleaning machines using perchioroethylene have become totally enclosed and incorporate very efficient solvent recovery. Loosely controlled dumping of solvent residues, both from dry cleaning and industrial sources, hat led to perchioroethylene being found in water tables. Hence, this solvent is coming under increasing scrutiny and more controls are likely. However, there is no other non-flammable dry cleaning solvent likely to become available that can substitute for perchioroethylene and be free from environmental restrictions. Similar environmental disadvantages apply to chlorof luorocarbons, which are very widely used as refrigerants, solvents and aerosol propellants. Again, it is unlikely that suitable alternatives will be discovered. 8-9 MONS 019053 Recent studies conducted on behalf of the ERA have confirmed that perchloroethylene is a hepato carcinogen to the sensitive B3C6FI strain of moose. However, there is no present evidence, from a considerable amount available, that this applies to other animals or to human beings. Current official thinking, in the U.K., does not consider the evidence as significant with respect to human beings. To put this finding in its context, transformer oil can be carcinogenic to humans, particularly if the oil has been pyroivsed which results in the formation of polyaromatic compounds. Work conducted at the Mid West Research Institute, on behalf of the EPA (a), has Indicated that perchloroethylene forms traces of dioxins and dibenzofurans when pyrolysed in a laboratory tube furnace in the presence of air * oxygen. By contrast, unpublished results (2) during an initial study on the behaviour of Forme! pyrolysed in a tube furnace in the presence of air, indicated that the material behaved in a markedly different manner to perchloroethylene alone and, in fact, closely resembled the behaviour of chlorofluorocarbon 113. Minor concentrations of residues were formed (approx 0.1%) comprising fully halogenated ring compounds of the chioro and chlorofluoro types. These results parallel the comparative behaviour observed during high energy arcing tests, where free radicle reactions, taking place under high temperature conditions, are modified by the addition of chlorofluorocarbon* to perchloroethylene (Table 6). Further tube pyrolysis studies are in progress using the conditions specified in the EPA sponsored work. If one attempts to foresee the future in the light of current knowledge, it is likely that the long established solvent uses of the Forme! components will become subject to tighter restrictions leading to increased use of semi-enclosed or fully-enclosed cleaning systems. Solvent reclamation will also become of increasing importance. Formel transformers are hermetically sealed and therefore already comply with these requirements. The fluid can also be reclaimed by distillation methods. Pressing consumer needs for the component fluids, in present applications, will ensure their availability into the foreseeable future The safety requirements pertaining to Formel are almost identical to those required for refrigerants used in air-conditioning systems. Storage, transport and handling is simple and there are no problems in maintaining an excellent Standard of industrial hygiene during manufacture, use, maintenance and disposal procedures. HONS 019054 8-10 Section 5 CONCLUSIONS it is impossible to discover a transformer fluid with outstanding properties in aJI required aspects (Table t). Presently available "reduced flammability risk" fluids such as silicones, esters and paraffinic oils showed no reduced flammability advantage under arcing conditions. Extensive testing of a wide variety of fluids led to a blend of liquids being selected, (allocated the tradename of Formel ), that passed all of the target criteria and, in addition to being totally non flammable, exhibited outstanding coolant properties. Electrical characteristics of Forme! are similar to hydrocarbon oil and thermal stability is superior. The fluid is moderately volatile and account must be taken of this in the design of transformers, however these are not markedly different from standard oil designs. Formel is classified as a low-toxicity material and can be safety used by observing simple rules of industrial hygiene. It is unlikely that severe restrictive legislation will be applied to the components of Formel in the foreseeable future. 8-11 HONS 019055 Table 1 TARGET TRANSFORMER FLUID REQUIREMENTS Under high enertv arcs . Total non-flammability . Immediate environment must be tenable by human beings for 5 minutes after arc inception. Environmental . Toxicologically acceptable in manufacture, use, maintenance and disposal scenarios. . Capable of being recycled. Commercial . Acceptable cost of finished transformer containing fluid. . Raw materials must be readily available. . Preferably adaptable to conventional oil-type designs. General properties . Effective coolant . Thermally stable . Acid free . Maximum pour point of - 30*C . Acceptable compatibility . Good dielectric properties . Maximum vapour press 1 atmos. at 100*C 8-12 HONS 019056 Table 2 FAILURE MODE OF LIQUIDS TESTED UNDER BOTH SWITCHING . AND HIGH ENERGY ARC CONDITIONS Candidate Fluid 85l* oil FaiJure mode 2. 5, 6 HB oil HB ester 5 6, HO Silicone 5, 6, HO Candidate fluid Perc/CFC 112/ CFC 113 67:28:3 Perc/CFP 212 *0:20 Perc/CFD 213 80:20 Perc/CTB 80:20 BSlbS oil/Perc 50:50 Failure mode None 3, 6, 7 3, 6, 7 l. 3, SO 2, 3, 5, 6 Oz as u. Perc 1, 3, 6 8S148 oil/CFC 113 50:30 3. 6 CFC 113 6 BS148 oll/Halothane (due to volatility) 70:30 3, 6 TCB 4, 6, HO BDO/CTB W:0 2, 3, 4, 6 CP 4, 6, HO BDO/TC8 60:*0 2, 3, 4, 6 Fluorocarbon 3, 6 7 BDO/PE 60:40 CP/CFC 113 2. 3, , 6 L, 3, SO Perc/BDO *0:60 2. 3, 4, 6 CP/CFC 112 I, 3, SO Perc/CFC 112 70:JO 6, HO CP/HB Ester 4, 6, HO Notation . HB high boiling Perc s perchioroethylene CFC 113 * tiichiorotrifluoroethane CFC 112 tetraehloroditluoroethane CP chlorinated paraffin SPg a sulphur hexafluoride BCO a brominated diphenyl oxide TCB a trichlorobenzene CFP 212 * hexachlorodiiluoropropane CFP 213 a pentachlorotrifluoropropane CTB a triehlorobenxotrlfluoride PE a phosphate ester SO a switching tests only conducted HO a high energy arcing only conducted Failure mode number Switching TTToor electrical performance 2. Flammable gases 3. Unacceptable toxic/acidic products High energy arcing t. SmalJ i lame 3. Large conflagration 6. Unacceptable toxic/acidic products Coat 7, Unacceptable 8-13 MONS 019057 Table 3 FLAMMABILITY AND TEMPERATURE MEASUREMENT OF SOME OF THE FLUIDS TESTED UNDER HIGH ENERGY ARCING CONDITIONS FLuid Fireball Formal BS148; 1972 Insulating Oil B3148 oil 50% Perchloroethylene Trichlorobenzene (TCB) BS1* * 50% T riehlorotrifluoroethane Complex Ester Phosphate Ester DichJorobenzotri fluoride (DCBTF) Silicone * Paraffinic Oil * No Yes Yes Yes No Yes Yes Yes Yes Yes ^ Hj (by weight) in Molecule None 14.0 7.0 1.6 7.0 8.0 5.0 3.4 11.0 14.0 Temperature and duration of Vapour or Fireball < 300/0.5S > lOOITC/Ss > 1000"C/l0s 700*C/ls < 400*C/ls > 1000*C/7s > I000*c/5s 700^/1. > 1000-C/Ss > I000*c/*s NB (i) High energy arcing conditions - prospective energy 3-phase. ITkV, 13kA 500ms, Hi) Test equipment contained 60 litres ol fluid under test. (Hi) Energy level 1-phase, 7kV, 6.3kA, 300ms. 8-14 HONS 019058 Table k RECOMMENDEO EMERGENCY EXPOSURE LIMITS (EEL) FOR SOME OF THE FLUIDS TESTED Material Formel Halothane Trichlorotrifluoroethane (113) Tetrachlorodifluoroethane (112) Perchloroethylene Trichlorobenzene TLV ppm 50 10 1000 500 1000 50 5 Toxicity STEL ppm EEL (ppm) 150 1000 50 3000 1500 130 1000 50 * value not known ppm is given for w/w values (w weight) TLV * Threshold limit value STEL Short term exposure limit (15 minutes) It. IS) 8-1$ HOMS 019059 Table 5 recommended emergency EXPOSURE LIMITS (EEL) for POTENTIAL DECOMPOSITON PRODUCTS FROM SOME OF THE * FLUIDS TESTED* Parent Compound Potential Decomposition Products Sulphur hexalluoride ( Sulphur pentafluoride ( Sulphur tetrafluoride ( Thionyl fluoride ( Sulphuryl fluoride ( (Oxygen difluoride ( Sulphur dioxide Tetrachlorodifluoroethane Sulphur hexalluoride Trichlorotri- (luoroethane i < ( Fluorine ( Hydrogen fluoride (Carbonyl fluoride < Hilo thane < Cereclor (Chlorine Tetrachloro. < difluoroethane < Tetrachloro. (Hydrogen chloride ethylene ( Trichlorotri- < fluoroethane < Trichlorobenzene < ( Carbonyl chloride Brommated ( Bromine diphenyl oxide (Hydrogen bromide Halo thine (Carbonyl bromide Toxicitv TLV ppm very toxic very toxic moderately toxic very toxic toxic 0.025 0.1 * 5 0.05 2 toxic toxic toxic 1 3 2 toxic toxic I 5 very toxic very toxic toxic very toxic 0.1 0.1 3 - STEL ppm 0.075 0.3 too 0.13 2 * 0.3 10 - EEL ppm 10 1.0 100 50 100 80 30 200 5 10 20 - * values not available TLV Threshold limit value STEL Short term exposure limit 8.16 HONS 019060 Table 6 COMPARISON OF VAPOUR CONCENTRATIONS OF PRODUCTS FROM SEVERAL HALOCARBON FLUIDS TESTED UNDER HIGH ENERGY ' ARCING CONDITIONS IN 60 L. VESSELS Decomposition Products Sulphur tetralluoride (5F*> P ppm N/A Hydrogen fluoride (HF) Fluorine <F2) N/A N/A Carbonyl fluoride (COF2) N/A Hydrogen chloride (HCO Carbonyl chloride (COCl2> Chlorine (Cl2) Perchloroethylne (C2CI,)P 183 15 115 6000 T richlorotrifluoroethane (C2C13F3) (113) N/A Tetrachlorodif luoroethane (C2C1*F2) (112) N/A FLUIDS TESTED 113 Formal PPm PPm ppm N/A no N/A ND 1000 ND ND (u HF) ND ND ND ND EEL (for 5 mins (oom 10 100 J0 80 S3 N/A 43 200 5 N/A 2 2J N/A 90 N/A N/A 1300 3 J0 1000 20000 N/A 90 3000 ND N/A 480 1500 Not-- . . . . . ppm given in w/v (or instantaneous values Tests carried out in switches each holding 60 litres of fluid Test energy for each event was 3-phase, 12 kV, 13 kA for 300 ms N/A not applicable ND not detected 8-17 HONS 019061 Table 7 VAPOUR CONCENTRATIONS OF DECOMPOSITION PRODUCTS FROM A 500 kVA TRANSFORMER, FILLED WITH FORMEL, WHEN TESTED UNDER ' HIGH ENERGY ARCING CONDITIONS Chemical Compound T etrachloroethylene Tetrachlorodilluoroethane (112) Trichlorotrifluoroethane (l!3) Carbontetrafluorlde (14) Trichloromonofluoromethane (11) Monochlorotriiluoroethane (13) Chlorine Hydrogen chloride Carbonyl chloride * Carbon monoxide Concentration in ppm w/v Inst at l min 1100 270 130 65 80 20 5 5) 60 35) 20 20) 23 2J ND ND NO NO ND EEL for 5 min (000 1500 3000 > 4000 30 200 5 NO > non detected below I ppm w/v * > non detected below 0.5 ppm w/v . Inst a Instantaneous measurements - at point of emerging fluid EEL * Emergency exposure limits 8-18 MGNS 019062 Table 8 MATERIALS SUITABLE FOR USE WITH FORMEL Metals Insulation / Adhesive / Paints Gasket / Seals Copper Steels Brass Bronze Solders Paper Pressboard Polyvinylacetate Polyester Nomex PTFE SRBP Epoxy resins Polyurethane Adhesive Tapes - Gum arabic or Hydroxy cellulose Ftuorinated elastomer gaskets and "O" rings Polytetrafluoroethylene (PTFE rope and tape). All welded construction Notes Surface Coatings - Epoxy or Urethane, both of two-pot types (.Aluminium and Zinc should not be used. 2. Polymeric materials can vary because of formulation compounding techniques and the degree of polymerisation, etc. If in doubt, compatibility testing should be undertaken. Table 9 COMPARATIVE CAPACITANCE AND TAN FOR OIL AND FORMEL IN IDENTICAL SO kVA TRANSFORMERS, BEFORE IMPULSE TESTING Test Voltage kv .2 1.0 2.0 3.0 4.0 3.0 6.0 7.0 0.2 Oil Capacitance eL 80S 803 80S 803 803 803 803 803 803 Tan 0.00264 0.00264 0.00264 0.00264 0.00267 0.0027 0.0027 0.00268 0.00268 8-19 Formel-NF Capacitance Tan j' PF 886 0.003 883 0.0033 883 0.0033 883 0.0033 883 0.0053 883 0.0033 883 0.0033 883 0.0033 883 0.0033 HONS 019063 Table 10 COMPARATIVE FULL WAVE AND CHOPPED WAVE IMPULSE VOLTAGE TEST RESULTS FOR OIL AND FORMEL IN IDENTICAL 50 kVA TRANSFORMERS 75kV -ve Polarity Full-Wave Chopped-Wave Full-Wave TRANSFORMER Oil filled Serial No. C539ft9 Formal filled Serial No. C53950 Phase a2 m Phase B2 m Phase C2 III Phase A2 m Phase B2 III Phase c2 m m m III m III m m m III m III m 95kV -ve Polarity Full-Wave Chopped-Wave Full-Wave m mm m mm mmm mmm mmm ut in m Notation / s voltage withstand Table II COMPARATIVE PARTIAL DISCHARGE VALUES FOR OIL AND FORMEL IN IDENTICAL 50 kVA TRANSFORMERS BEFORE APPLICATION OIF IMPULSE VOLTAGE Voltaaes ' Vl V. Discharge at 7 kVI Oil ft kV < 5pc 3.ft kV 5pc Forme l-NF ft.S kV < 5pc ft.2 kV 9pc I > inception e a extinction 8-20 HONS 019064 Table 12 COMPARATIVE PARTIAL DISCHARGE VALUES FOR OIL AND FORMEL IN IPENTICAL 50 kVA TRANSFORMERS AFTER APPLICATION OF IMPULSE VOLTAGE AND AC VOLTAGE WITHSTAND TEST (21 kV FOR I MINUTE) Discharge at 10 kV Oil 9 kV < Jpc S kV 7pc Formel 8.5 kV < 3 pc 7.8 kV I2pc Table 13 COMPARATIVE TEMPERATURE RISE TEST RESULTS FOR A SELECTION OF TRANSFORMER FLUIDS Fluid Tested tt Tav <Tr thot Tav> SPOT Formel-NF *0.7 37.2 3.3 66.* Winding Rise HV LV (calc'd) *2.2 *0.7 Winding Gradients HV LV (calc'd) Estimated Viscosity (cst) at 7<rc io<rc 5.0 3.5 .89 .5* BS l.S Oil *7.2 39.5 7.7 86.0 50.7 5*.l 11.2 !*.3 20 2 Complex Esters *8.3 39.2 9.3 88.6 50.* 3*.8 18.6 21.3 90 6 SUlcone *8J 31.0 10.5 93.* 51.3 59.9 20e* 27.2 50 13 Paraffinic Oil 34.7 *0.5 1*.3 101.2 57.9 64.0 17.7 23.8 350 16 SL 1. All test conditions remained the same for each fluid. 2. The hottest spot for each fluid was at the top of the copper coil of the low voltage winding 3. Transformer used was designed for oil. 8-21 HONS 019065 Table 1* OVERLOAD PERFORMANCE OF FORMEL Ptrimeter Hot Spot Temp *C Top Fluid Temp "C Fluid Rise *C Ambient Mean *C Radiator (Tj-Tg) *C Winding Gradient *C HV Winding Gradient *C LV Winding Rise *C HV Winding Rise *C LV Pressure psig 10096 (8.3kW) 66.6 60 *1.5 22.5 7.5 *.9 *.5 *2.2 *1.8 -3.7 Non-Flammability 150% <17.2kW) 95.5 93.0 69.3 2*.0 12.5 5.6 1.6 68.8 6* .4 3.3 175% (23.3WW) 115.0 109.0 83.2 23.5 15.5 12.2 5.7 87.7 81.2 12.6 1. Before temperature rise tests were conducted, a partial vacuum of 125 mm was obtained within the headspace. 2. Transformer used was designed for oil. Table 15 TYPICAL ANALYSIS OF FORMEL BEFORE AND AFTER TREATMENT FOR ONE WEEK AT 175-C, IN A SEALED CLASS TUBE, IN THE PRESENCE OF UNCOATED COPPER AND P.V.A. COATED COPPER Component Subatmca Analysis, wt % by G.L.C. Before After Total chlorofluorocarbons 35.0 3*.8 Perchioroethylene 65.0 65.1 Other compounds - 0.1 Notes 1. Repeatability of analytical method 0.1 2. Identity of other compounds not determined. 8-22 HONS 019066 Table 16 FIRE TESTS WITH FORMEL, CFC 113 AND SULPHUR HEXAFLUORIDE Fluid under Test Fetd ra,e ,0 *urnln g./mm Gas concentration at 0.5 m. distance Irom flames ppm Chlorine Carbonyl Hydrogen Hydrogen Perchloro- Sulphur halides chloride fluoride ethylene dioxide Formel 810 Formel 890 CFC 113 390 Sulphur hexa fluoride 250 <0.2 9.3 <D.2 2 <0.2 2 - <0.3 53 39 L9 - 18 0.03 - - 0.02 - 9.3 - - 25 - 69 Emergency Exposure Limit IDLH Threshold 30 23 5 200 too 1000 ND 2 100 20 300 100 Note : Flow rates above those values given for Formel tended to extinguish the flames. and CFC 113 8-23 HONS 01906? Table 17 PROPERTIES OF FORMEL FLUID p^ifitation Electrical Strength * kV (2.5 mm gap) r of r 2 kV($) Volume Resistivity *-fi-/cm (500 V d.c.) Dielectric Dissipation Factor * (Tan J ) (2400 V a.c.) Relative Permitivity * Nj 1 (2400 V a.c.) Moisture Content * (p.p.m.) Total Acidity (p.p.m.) * Tests carried out at 20*C Value 50 kV min 10*^ min 0.01 max 2.36 20 max 1 max Other Properties Flammability in Air Flash Point *C Fire Point *C Auto-ignition Temperature *C Explosive Limits in Air per cent by Volume Toxicity OSHA TLV p.p.m. Thermal Conductivity m*m** Specific Heat U kg"1 Coefficient of Thermal Expansion per cent *C'* Density kg l'1 Average Molecular Weight Boiling Point *C at:- 1 Bar 10 Bar 20 Bar Pour Point *C Surlace Tension * Dynes cm'1 Dynamic Vlscoaity cP Latent Haat of Vaporisation: k3 kg'1 Solubility * of Ny mi I'1 Solubility of Oji ml l*1 Vapour Pressure Bar at: 20*C 40*C w*c 8oc ioo*c Value Non-flammable None None None None 50 824 0.895 0.107 1.63 178 L03 200 250 - 33 26 0.884 192 162 85 0.04 0.10 0.24 0.48 0.90 Values at 20*C 8-24 HONS 019060 Table IS HEAT TRANSFER PROPERTIES OF FORMEL COMPARED WITH OTHER COMMON TRANSFORMER FLUIDS Property Forme 1 Dynamic Viscosity at 20C 25*C 50*C 100*C Density g/ml 25*C IOO*C Coefficient of Expans ion/*C Specific heat at 25*C Cai/gm *C Thermal conductivity W/m *K (at 20*C) 48 .34 .47 1.64 1.48 1.07, xIO-* 0.21* 0.10 BSI48 oil (a) Silicone oil (a) Fluids Paraffinic Complex OH (a) Ester (a) PCB (il -23 30 7 30 2 16 48 .86 xlO'3 0.303 .96 - 1.0 xlO'3 0.306 . 330 85 16 48 . 45 xlO'3 0.46 100 _ . 15 _s 63 .98 4 xlO'3 1.31 1.44 xlO*3 0.3 0.263 0.14 0.10 0.16 0.10 Table 19 DIELECTRIC PROPERTIES OF FORMEL COMPARED' WITH OTHER COMMON TRANSFOMRER FLUIDS Property Formal Electrical strength 70 kV/2.5mm (2kV/Lriae) Volume rcstistlvlty cm at 23*C 10'J Relative permitivity 2.36 Tan at 25*C .001 Moisture content ppm 10 BSltS oil (a) 60 Fluids Silicone Paraffinic Complex PCB oil (a) Oil (a) Ester (a) (a). 55 43 50 50 10*5 10l* 1013 1013 10>* 2.2 .00003 20 2.7 .00002 30 2.38 .001 35 3.2 4.3 .001 .05 20 70 (a) figures obtained from published data 8-25 HONS 019069 Figure i. Schoattlc Dlagraa of Stapling Device Used During High Energy Arcing Teecs 8-26 HONS 019070 ALL DIMENSIONS IN CM Figure 2. Typical Or lent ion* of Taat Vaaaal and Sampling Davlcaa During High Energy Arcing Tcata 8-27 HONS 019071 Figura 3. Two 11/.433 kv, 3-PhJ... 500 kVA Hansstlcally Solid lEuilonui (right) Flllod with 240 Litres of FotMl-BF (loft) Filled with 470 Litree of Hydrocarbon Insulating Oil 8-28 HOftS 019072 REFERENCES l. Toxicity and Ecotoxicity of Formel Didcot, Berkshire, U.K. . C Stevens, Harwell Laboratories, 2. Private communication between 3 Butcher, Harwell Laboratories, Didcot, U.K. and H Lloyd, Electricity Council, 30, Millbank, London, U.K. 3. ESI Standard 33*14, available from the Electricity Council, address as for reference 2 above. a. Products of thermal degradation of transformer fluids, F. V. Kutz, D. T. Heggen et al, Interim report No 2, Work Assignment 23, Mid West Res. Inst., Kansas, Project No. 8201-A(23), under EPA Contract No. 68-02-393S. 8*29 HONS 019073 STATE-OF-THE-ART REVIEW OF COMBUSTION/PYROLVSIS BY-PAOOUCTS OF PCB SUBSTITUTES J. ROONEY MARSH SCS ENGINEERS Since 1976, the manufacture and commercial use of polychlorinated biphenyls (PCBs) have been restricted by law. Proposals have been made to remove existing PCB-contalnlng transformers and capacitors from service. A number of chemicals have been and are being considered for use as PCB substitutes In electrical applications. Although all have been tested for acceptable dielectric, heat transfer, and flaaaaablllty properties, few have been extensively analyzed for combustion by-products. PCBs were not restricted for problems with their dielectric properties or heat transfer capabilities, but rather for suspected toxicological properties that were not considered when PCBs were first commercially produced. These toxicolog ical properties art attributed not only to the PCBs themselves, but also to the presence of various toxic chlorinated aromatics (n the by-products of PCB/askare! fires. It Is thus necessary to examine the chemical behavior of proposed PCB substitutes to Identify the potential for similar problems. A state-of-the-art literature review was conducted to determine what Is known regarding the chemical and toxicological nature of the combustion by-products of various PCB substi tutes. DATA ASSESSMENT Until very recently, the major concern In any fire or explosion episode was fire fighter safety. As a reiult, tests have focused almost exclusively on major gaseous combustion products such as carbon monoxide, hydrogen cyanide, oxides of nitrogen and sulfur, hydrogen chloride, and so forth. These are the Immediate life-threatening combustion products with which one must deal, and they are gen erally the simplest to detect and measure. However, It has become evident In the aftermath of several PCB Incidents that the toxic trace combustion product problem Is concerned more about soot deposits than the vapors formed. Trace PICs are produced In such low levels that vapor malsslons dispersing In the atmosphere rapidly reach Inconsequential levels. These same PICs may concentrate In soot, however, and soot provides a reservoir for 8-30 HONS 019074 continued Missions or exposure long after a fire has been extinguished and the gases dispersed. Furthermore, analysis of soot or even gas samples for trace PICs at the levels typically produced requires very sophisticated analytical Instrumentation and highly trained specialists. Even then, complete Identification of PICs In a par. tlcular sample may take years of work. As the level of sensitivity of analytical Instruments Increases, even more toxic PICs may become evident. For Instance, continued research on PCS combustion by-products has Identified not only chlori nated dioxins and dlbenzofurans, but also polychlorinated chrysenes, pyrenes, xanthenes, terphenyls, queterphenyls, and others. This level of research has been directed at PCB because of Its negative publicity and the perceived crises In regards to several PCB Incidents. No such crises exist for the proposed PCB substitutes. As a result, with a very few exceptions, comparable research has not been conducted Into their PICs. As noted above, existing data tend to focus on the macro combustion products present In the vtpor state rather than trace PICs In the soot. Consequently, there Is relatively lit tle data on trace PICs coeipareble to that on dioxins or dlbenzofurans. These types of by-products simply have not been Identified and studied In most cases. PROPOSED PCB SUBSTITUTES: LIQUIDS Two types of esters, phthelete esters end benzylneocaprate, have been considered as PCB substitutes. In general, pyrolysis of esters will produce gases similar to and no more toxic than those obtained from hydrocarbons. One major decomposi tion product Is phthallc anhydride which can react further to form naphthalene and biphenyl. In the presence of chlorobenzenes, PCB and chlorinated naphthalene may be produced. Polydlmethyl slloxane has been widely used as a retroflll fluid. Ourlng thermal decomposition, amorphous silica, several cyclic slloxanes, and a variety of sim ple hydrocarbons are produced. Most of these compounds are not highly toxic, and animal Inhalation tests on pyrolyzed slloxanes have generally Indicated a low toxicity. Chlorobenzenes have generally not been considered PCB substitutes as much as additives to PCBs and other dielectrics. Decomposition of chlorobenzenes can produce a variety of highly toxic compounds. Pyrolysis of nonochlorobenzene can 8-31 HONS 019075 yield mono- end dlehloroblphenyls, chloronaphthalene, end vinyl chloride. In the pretence of elr, chlorobenzenes can produce chlorophenols which cen, In turn, dimerize to PCDFs end PCDDs. Meny of these combustion/pyrolysis products ere very highly toxic. Methylated dlphenylethene end phenylxylylethene ere used es components In dielec tric fluid mixtures. No Infometlon wts found on the coeibustlon/pyrolysls prod ucts of either compound, but pyrolysis of chemically similar diphenylmethane end 1,2-diphenyl ethane produces a number of polynuclear aromatic hydrocarbons. Few of these are considered to be highly toxic, but several are known or suspected carcinogens. There Is no Information available on the thermal decomposition products of butylated monochlorodlphenylether, another PCS substitute. However, both the unsub stituted dlphenylether and polychlorinated dlphenylethers have been studied. Dlphenylether can break down Into phenol, benzene, and dlbenzofuran. Polychlori nated dlphenylether can produce PCOFs and PCDDs. There Is also no Information available on the thermal decomposition products of the alkyl biphenyls, specifically Isopropyl biphenyl and j^-propylblphenyl. Paraffinic hydrocarbons, such as polyalphaolefln and RTEmp, tend to decompose Into a variety of short-, medium-, and long-chain saturated and unsaturated hydrocarbons. In the presence of air, organic acids, alcohols, and aldehydes are formed. Perchloroethylene Is being promoted as a transformer fluid neat, mixed with min eral oil, or mixed with fluorocarbons. Chlorine or hydrogen chloride are the principal decomposition products to be expected. Under certain conditions, phos gene or trichloroacetic acid may be produced. PROPOSED PCD SUBSTITUTES: DIELECTRIC GASES Chlorofluorocarbons are used as dielectrics both neat and mixed with perchloroethylene. Although generally thermally stable, at high temperatures or during arcing, decomposition Is possible. Chlorine, hydrogen chloride, hydrogen fluo ride. phosgene, and carbonyl fluoride are among the by-products which can be expected. Phosgene and carbonyl fluoride. In particular, are highly toxic. Sul fur hexafluoride can be used alone as a dielectric or in a mixture of gases. It 8-32 HONS 019076 produces number of long-lived by-products under fire and arcing conditions. The principal by-product Is thlonyl fluoride; other products Include sulfuryl fluor ide. thlonyl tetrafluorlde, and sulfur dioxide. Toxicity tests on sparking gases have yielded a higher toxicity than the above compounds would Indicate. Thus, there are one or more unidentified trace decomposition products which contribute significantly to the toxicity of the decomposition gases. PROPOSED PC* SUBSTITUTES: SOLIDS Two solids were reviewed: epoxy resins and polyvinyl chloride (PVC). Complicat ing an assessment of their decomposition Is the fact that neither Is a pure com pound or even a mixture of a few discrete compounds. Rather, each Is a mixture of resin, hardener, filler, and various other materials, many of which may have a variable composition. Thus, the decomposition products of these solids can vary extensively, depending on the nature of the additives. Pyrolysis of epoxy resins can produce a variety of organic compounds Including benzene, methyl chloride, ethyl chloride, acetone, propylene, ethane, pentane, toluene, cresol, phenol, and others. Several of these are known or suspected carcinogens. Decomposition of PVC can yield benzene, toluene, xylene, aliphatic hydrocar bons, _-methylnaphthalene, several chlorinated benzenes, and phosgene. Because of the production of chlorinated benzenes, the formation of PCOOs and PCDfs Is a distinct possibility, although none have been identified In PVC pyrolysis gases to date. 8-33 MONS 019077 DIFFUSION*!. MOOEUNG DURING TRANSFORMER RETROFIU C. R. Atwood, I. R. Moor*, P. R. Dillon INTRODUCTION The successful operation of t rotrofill typo process, juch as UNISON RECLASS 50**, for the removal of polychlorinated biphenyls (PCBs) from transformers depends upon a thorough understanding of the complex mechanisms Involved, along with a recognition of the spectrum of sites and shapes of the diversity of Internal aatarlals used. Experimental observations In the field and laboratory have been necessary for evaluating the basic concepts of the process, but mathematical modeling has been essential to develop and confirm the details of the mecha nisms, as well as provide a tool for process definition and predictive control. Field data for our modeling were obtained from several Union Carbide transfor mers at South Charleston, WV. These were supplemented by laboratory diffusion studies, and modeling has been carried out on both the detailed aspects and the overall RECLASS S0sa process. Two approaches have been used. A discrete ele ment type simulation was found valuable for understanding the phenomenological details, while a model based upon piecewise integration of Flck's second law (unsteady state diffusion) was found more useful for the overall process description. The algebraic details are too lengthy for discussion here. THE LEACHING PROBLEM A drained and rlnsad transformer retains Askerel In a variety of ways. There Is residual fluid held In gravitationally nondralnable pockets or In cravtces by surface tension. More Important, however. Is the Askarel absorbed within the celluloslc Insulation, which consists of craped paper, pressboard, adhesive laminates, and aven wood. There is a spectrum of depths and tightness of such structures. No amount of scrubbing with vapor or liquid can remove this absorbed Askarel, although elaborate means have been devised and even marketed with limited success. The residual PCS always subsequently leaches out of the Insulation and voids any atteaipt to reclassify the transformer as non-PCS. The 1985 UNION CARBIDE CORPORATION All rights reserved 8-34 MONS 019078 RECLASS 50" process ramovas this absorbed Askarel and rtplaces it with an acceptable fluid, eg, dimethyl silicons oil (1,2), DIFFUSION ' The Halting operation In the leaching of Askarel Is diffusion. In order to properly evaluate the results of laboratory and field leaching, It vas useful to develop a discrete elemental analysis model based upon Pick's law. The Insula tion matrix ms mathematically treated as a flat plate divided Into many layers. The Incremental diffusion across the layer boundaries ms simulated In a step wise manner for those sequential layers, and repeated over as many time periods as desired. It ms thus possible to determine the concentration profile changes In the matrix, as Mil as the rata of PCS elution from the matrix. Diffusion Is time dependent, and In transformer leaching m have no choice but to wait until the PC8s diffuse from the core of the transformer. It Is essen tial that the leaching solvent be an acceptable transformer coolant, for we do not wish to curtail electrical operations during this diffusion period. It would seem quite logical to choose silicone oil for this purpose, as has been frequently done, though that Is an unfortunate choice. There are many critical factors here, and we can discuss only a few within the scope of this paper. Miscibility. This Is crucial as ms pointed out by Morgan and Osthoff (3) of Beneral Electric Co. Even If the solubility for PCS Is substantial, the lack of miscibility leads to an Askarel/laachant Interface In the celluloslc matrix Itself, and consequently a barrier to diffusion Is set up. This barrier signi ficantly decreases the rate of diffusion, Increasing the time required to achieve reclassification. Miscibility, on the other hand removes this problem. Viscosity The diffusion rate Is an Inverse function of the viscosity of the medium. The shapes of the PCI/tlae leaching curves and matrix concentration grodlents depend upon the solute/solvent viscosity ratio. This Is lllustroted In Figure 1 for flat plate leaching. Viscosities of the sane relative magni tude result In convex curves for classical diffusion (dotted linos), uhoreas If the solute (Askarel) Is much more viscous, "S" shaped profiles result (solid linos), and the leach curve shows a flattened region, - misleading If not completely understood. The application of classical extraction equations would leod to extremely erroneous estlnetes of residual PCD. We have coined this phenoaonon "ablative' diffusion, since the Askarel Is effectively removed layer by layer, as the stoop concentration gradient moves back Into the matrix. 8-35 HONS 019079 Temperature. This ts significant principally by Its effect on vlscosltlas (saa discussion abova). Tha higher tha oparatlng temperature during diffusion, tha lower tha viscosity of tha diffusing medium. Tha affact of tamparatura on visco sity is vary pronounctd In tha casa of Askarels, and suggastlng that fastar ratas of diffusion occur at hlghar temperatures. In an oparatlng transformer, tam paratura will ba a function of alactrlcal load although ambient temperatures also can ba a factor. Lightly loaded transformers can ba heated, and tha desirability of doing so will depend upon Individual circumstances. Circulation. Bulk fluid circulation and tha bulk PCB concentration level are commonly thought to ba critical, - hence previous attempts at retroflll have emphasized these factors. Although relevant, they may not ba critical, prin cipally because tha rata of diffusion Is controlled by high concentration gra dients deep within tha celluloslc matrix, as In Figure I (b), and this rate is slow relative to the normal convective mixing of the bulk fluid. Only when the PCB removal Is nearly complete can Its concentration In the bulk fluid act to retard the process by "back diffusion". At this point one must act appropriately to maintain tha leeching in the kinetic regime. Silicone Oil as a leechant. Prtvlous attempts at retroflll have utilized sili cone ell as the leechant material throughout the leeching period. We have Iden tified the problems associated with silicone oil which made this an unfortunate choice. Silicone oil has a high viscosity and Is Immiscible with Askarel. Askarel Is slightly soluble In silicone oil, but the oil Is virtually Insoluble In Askarel or any chlorinated hydrocarbon. As a consequence, the Askarel must diffuse very slowly Into the oil, while the Askarel/oll Interface Is drawn Just as slowly Into the celluloslc matrix. While transformer reclassification can be chlcved by this approach, the time required to attain this ultimate goal has proved to be unacceptably long, on the order of 5-6 years or more, compered with a fraction of this time for the RECLASS 50s* process. Additional studies, discussed below shew 4iy this Is the case. Most Askarels are mixtures of highly viscous PCB's and thinning agents such as trl- or tttrechlorobenzenes. The latter are more soluble In silicone oil than PCBs (about 3/1), and diffusa out preferentially, leaving a highly viscous, possibly solid (4), PCB residua. Figure 2 is analogous to Flguro 1 (b), and profllos computed from tha non-discrete elemental modeling approach show how proforantlal latching loads rapidly to high PCB concantratlons at tho silicon* oil Interface, greater than the BOBS Initial concentration for type A Askarel, and thus much more viscous. (Tho upper curves are the PCB concentrations In the 8-36 ' HONS 019080 Askarel ph*jt, while tht lower curves ere the PCS concentrations In the silicone phese, the vertical lines representing the Interfaclal positions). After 1200 days, the residual Askarel Is nearly pure PCS (Arcelor* 1260), and possibly solid. As a result, diffusion of PCBs Into the silicone oil Is greatly retarded, although the rate is high enough to void any attempt at reclassifica tion. laboratory Studies, figures 1 and 2 are mathematical simulations, but Figure 3 shows comparetlve leaching studies of Askarel soaked pressboard with 1-30$ sili cone oil and UNISON'S proprietary transformer fluid, TF-1. The silicone leaches rapidly at first (though slower than TF-1), but soon slows to a crawl, due to the buildup of the highly viscous PCS layer at the Interface. Similar studies have been carried out for a variety of solvents and Insulating materials of dif ferent sizes. While such a study cannot disclose the actual PCS profiles as they exist In tht Interior of the matrix, the extraction curves themselves are consistent with those calculated from the discrete element model. Tht sharp reduction In the extraction rate with silicone oil, for example. Is consistent with the formation of the highly concentrated and viscous PCS layer at the interface. Figure 4 shows a device designed to study the Interfacial penetration rate In the absence of tht celluloslc matrix. The capillary Is loaded part way with Askarel (or other fluid) and the vessel filled with silicone oil. The Interfece gra dually falls, and the figure gives plots of the Interfacial level vs. time for type A Askarel and tht proprietary TF-1 as the bottom layer. The Askarel curve not only falls more slowly, but the rate continues to decrease as the con centration of residual PCS and the viscosity builds up. Tht curve for TF-1 Is steeper, because TF-1 Is less viscous and Is more soluble In silicone oil. These curves are even more linear than that In Figure 1 (a). Because of the sharp concentration gradient at the Interface, Interfacial diffusion can be con sidered an extrema form of tht ablative diffusion phenomenon exhibited by miscible fluids. RETMFlll STHATE6T The previous data Indicate that It Is Impractical to try to leach Askarel with silicone oil In any reasonable length of time. Hmever, It Is practical to leach with TF-1, and TF-1 can be readily leached with silicone oil. Accordingly, combined leaching by TF-1 and silicone Is a preferred strategy. It was first damonstratad to ba successful with our own South Charleston transformers. Four transformers were reclassified to non-PCS, and a fifth is presently undergoing 8-37 HONS 019081 the 90 day last, with rectification expected in the naar future. A tilth transformer was initially retrofilled with silicone oil instead of TF-1, and accordingly is still leaching, but the data from this, as well as the other five, has been helpful in the process design, model, and optimization. PROCESS MOOELING While the discrete element analysis type of model has been useful in elucidating the phenomena critical to leaching, it is rather unwieldy for field modeling. For this purpose a model based upon piecewise integration of Flch's second lew proved useful. This also entailed the conception of the transformer insulation as a flat plate, with the recognition that there are in reality a spectrum of depths and matrix tortuosities to be considered. For all practical purpose, there is a process controlling effective depth, or related time constant, for the system. This represents the bulk of those structures which contain signifi cant Askarel and are difficult to leach. The looser, shallower matrices are not controlling by virtue of being easily leached, while the very tight structures do not contain enough PCS to be significant. Pick's second law can be expressed by: where C is PC8 concentration, t the time, x the depth in the matrix, and 0 the dlffuslvlty. This equation cannot be directly Integrated but can be solved in terms of a Fourier series, to give an extremely complex description, C(x,t), of the concentration profiles, and allow computation of the bulk fluid composition, Cfc(t), as a function of time. Discussion of these expressions and the tech niques used in their derivation cannot be detailed here, but utilizing them In conjunction with actual transformer leach data has permitted optimization of the process in terms of total elapsed tine and fluids used. CONCLUSIONS Transformers differ, and the RECLASS 50s" model Itself Incorporates three adjustable parameters which can be estimated early In the process and reftnad as additional data are obtained from specific customer transformers. These parame ters are the fluid holdup of the Internal components, the nondrainable, though free, liquid residue, and the time constant for the system (i.e., the trans former type), which reflects the effecive dlffuslvlty and critical (i.e., pro cess controlling) diffusion depth. From the model one can estimate the resMial PCB left to leach, and hence the next optimal process step or sampling Interval. 8-38 HONS 019082 At result, on* can service the transformers in a safe, tlaMly, and cost effec tive manner, and can offer in the market place a service which guarantees the attainment of non-PCB status. REFERENCES 1. Robert A. Westin, "Assessment of the Use of Selected Replacement Fluids for PCBs in Electrical Equipment", EPA, NT1S, PB-296377, March 1, 1979. 2. J. Reason and V. Bloomqutst, "PCS Replacements: Where the Transformer Industry Stands Now", Power, October, 1979, p. 64-65. 3. L.A. Morgan and R.C. Osthoff, "Problems associated with the Retrofllltng of Askarel Transformers", paper A77, p. 120-9, IEEE PES winter meeting, NY, NY, Jan. 30 - Feb. 4, 1977. 4. 0. Hutlinger, S. State and V. Zltko, "Chemistry of PCB's", CRC Press (1980). 8-39 HONS 019083 Figure 1 Ablative vs. Classical (dotted) Diffusion. (Numbers are relative days of leach) Figure 2 Interfacial Leaching of Type A Askarel with Silicone Oil. k Figure 3 Laboratory Leaching Studies for Pressboard Saturated with Type A Askarel, 60C. Figure 4 Interfacial Motion Studies 8-40 HONS 019084 DECONTAMINATION OF PCB TRANSFORMERS USING ENSCO, INC.'S RETRO--1 PROCESS J. Lee Tlnney INTRODUCTION The electric utility Industry Is expected to function In sn efficient, relleble, end cost effective manner. At the sum time, they must sdhere to federal guidelines nd stste regulations, face material shortages, hold rates down, and conform to rigid federal and state environmental laws, one with the greatest Impact being the EPA's rules and regulations governing PCBs. PCBs were found harmful to the environment after more than fifty years of existence. Without delay, environmentalists pushed for an Immediate remedy, and consequently, the Environmental Protection Agency published rules and regulations prohibiting the manufacturing, processing, distribution In commerce, and certain other uses of PCBs. Electric utilities have been saddled with a tremendous economic burden as they Interpret the laws and formulate programs that ensure prompt and complete compliance, and as Is often the case, they are the leaders In recognizing their responsibilities and developing solutions. As compliance to the PCB rules and regulations are Implemented, many questions and problems have to be answered and solved. In all Instances a basic choice has to be made; that Is, to either leave the PCBs and adapt to the laws or find a method to remove the PCBs and not be restricted by compliance. This paper addresses the evaluations of one method to remove PCBs for the purpose of reclassification of transformers containing PCBs. MPIl'S PCB TRANSFORMER CONCERNS Mississippi Power 4 Light Company, like other utilities has serious PCB concerns and firm management objectives for a successful and economic solution to these PCB concerns. A primary concern of MPIL Is PCBs and PCB-contamlnoted transformers In public areas that are considered a high risk (or high liability) transformer. 8-41 MONS 019085 To resolve this PCB concern, MP&L faced three options: 1) Do nothing and continue to comply with present rules and regulations and any future, more stringent, regulations that might come along; such as, the new "transformer rules." The problem with doing nothing Is that It does not significantly reduce the liability and risk of having a transformer with PC8$. 2) Eliminate the PC8 liability and risk by replacing the PCB transformer with a non-PCB transformer. The PCBcontaminated transformers would then be relocated but the PC8s would not be eliminated; consequently, these transformers would require further handling and attention at a later date as PC8 regulations are tightened. 3) Leave the transformers In place and find a way to remove the PCBs. High risk transformers Ideally need AIL of the PCBs removed to reduce the liability and risks. Anything less leaves the possibility of some future liability from the remaining PCBs In the transformer. Thus the analogy--No PCBs equal little or no risk, and some PCBs equal high risk. For MP&L's PCB transformer concerns. Option 3 (Removal of the PCBs from the Transformers) seemed to be the best choice. Our objectives were simple--to find a system which could declassify a PCB transformer to extremely low PCB levels at an economical price; and the transformers must not leach back above a 2ppm PCB level to eliminate all liabilities or risk from the PCBs. THE ENSCO, INC. RETRO-1 SYSTEM In the spring of 1984, MP&L began talking with ENSCO, Inc. above its new transformer flushing system under development at Its White Bluff, Tennessee, PCBTransformer Decommissioning Plant. It was suspected that this system might accomplish our PCB transformer declassification objectives. After several months of talking and evaluating the development of the ENSCO system, MP&L entered Into an agreement to allow field testing on four (4) PCB-contamlnated mineral oil transformers. The pilot field project objectives were designed to: 1) Evaluate ENSCO's ability to accurately estimate their processing time and limits; 2) To effect changes (as necessary) In the Retro-1 equipment by field testing; 3) To accomplish MP&L's objectives of declassification of a PCS transformer to below 2ppm with only one processing of the transformer; and 4) The processing cost per transformer must be economically compatible with other options for totally eliminating PCBs at the transformer location. ENSCO called Its system "The Retro-1 Transformer Recycling Process." It was designed to accomplish a thorough Internal flushing of a drained transformer so that the residual PCBs remaining would be less than two-tenths of one percent (0.2*) of the original amount of PCBs In the transformer. 8-42 HONS 019086 The proprietary Retro-1 process utilizes heated florocarbon vapors which bathe the Interior of the drained transformer until the Internal parts achieve the temperature of the vapor. Then this process Is stopped and a refrigerated, liquid florocarbon bath Is begun and the transformer Is cooled down. This completes one "cycle* of processing with the florocarbon bath. These cycles are repeated for a calculated number of times according to an ENSCO formula based on the ppm level and size of transformer. The Interior components are alternately heated with hot vapor and chilled with the liquid bath. The Retro-1 process permeates and penetrates all Interior areas of the transformer case. Including the windings. Insulation, cloth, mica, bakellte, wood, and laminations. This repeated "deep cleansing* results In the maximum amount of residual PCBs being removed from the transformer. Before beginning this field test, one of MPtL's primary concerns was the public awareness of the project since It Involved PCBs. Public Involvement: The transformers chosen for this field project were sidewalk vault units located In a downtown Jackson network distribution system. Any work done on them would require blocking street vehicle traffic lanes, parking zones, and portions of sidewalks above each unit. The field work would be very obvious to the public and the local news media. For these reasons It was decided to hold an advance press briefing to announce plans for this project and answer any questions. The advance press briefing was a good Idea because there were no further press involvements. The general public seemed curious at times, but no complaints or concerns were ever expressed. The project was treated no differently than routine transformer maintenance work. RETRO-1'$ FIRST FIELD PROJECT Owe Alternative. In January of 1985, MPtL signed an agreement with ENSCO, Inc. for the purpose of field testing the Retro-1 system on four downtown network, vault type, transformers. The transformers were high liability PCB-contamlnated mineral oil units. The ppm levels were 1800ppm, 320ppm, 221 ppm, and 33ppm. This range of PCB contamination levels was chosen to help develop data and determine ENSCO's ability to accurately calculate the number of cycles needed to accomplish a final declassification level of 2ppm. If the Retro-1 system were able to accomplish MPtL's objectives, then this method would be the *onc alternative' we had been looking for. 8-43 MOMS 019087 field Implementation. ENSCO brought the Retro-1 system on-site at each location and set up on the sidewalk above the vault transformer. After MP&L de-energized and cleared the transformer, the ENSCO crew connected the Retro-1 equipment and began removal of the existing PCB oils. Next, the cycling process was started and the hot and cold flushing began cleansing the residual PCS from the Interior of the transformer case. After the calculated number of cycles was completed, the transformer was vacuum filled with new mineral oil Immediately following the heating cycle. ENSCO removed all PCS waste from each site as It was generated for proper disposal per EPA regulations. The transformers remained de-energized for 24 hours after the processing and then were energized without load for another 24 hours before being returned to service. In each case, the transformer was successfully re-energized and the on-going testing phase, for eventual declassification, was begun. The time required at each site varied from two to five days depending on the ppm level of PCBs in the transformers since that is what determined the number of cycles of processing. The whole project took less than three weeks. Testing Procedures. Each transformer was tested for PCBs before processing, Immediately after processing, at two weeks, and then once a month. The results are shown below: Before After Transformer Process Process 2wks. Imp. 2mo, 3mo. Amo. Smo, A 33ppm lBppm 2ppm 3ppm I <!ppm <1ppm <1ppm B 221 ppm 3 4K *1 -.1 C 320ppm <1 <i 3 i "1 .8.1 <.1 D 1BOOppm eel 19 10 0 19 17 20 Our test results shorn that the Retro-1 process can effectively remove all PCB PCB and PCB-contamlnated mineral oil transformers In the 2000ppm or less PCB range. RETRO-1'S SECOMO FIELO PROJECT In May of 198S, HP4L signed a second agreement with ENSCO, Inc. for the purpose of using the Retro-1 system on two "Askarel" PCB transformers. The transformers were power plant auxiliary switchgear type, 1500KVA and 285 gallons of askarel fluid. The PCB levels were 680,000ppm and 900,000ppm. The objectives of this project were: 1) To determine what level of reclassification or If declassification could be achieved by using the Retro-1 system on all-askarel transformers; 2) To determine what time frames were necessary to accomplish declassification; and 3) To evaluate the processing cost per askarel transformer. 8-44 MONS 019088 It was suspected that with a combination of the 1) "Deep cleansing" ability of the Retro-1 system. 2) Refilling with silicone fluid, and 3) Carbon filtration of the silicone fluid to remove any residual askarel--would accomplish very low levels of declassification of an askarel transformer. Before Trsnsfomer Process After Process* Owk Bwks A 680000ppm 2274ppm B 900000 2037 "Aveng# of 5 tests over 8 weeks 1st Filter 9wks Filter Filter 14wks 305ppm 512 16wks Filter Filter 19wks 12wks 17 Our tests results show that the objectives, for declassification, were obtained and In a relatively short time frame. Both transformers now have residual PCS levels of less than SOppm and we expect to declassify them as non-RCB. Notice that In Table 2 there are two 48-hour carbon filtration periods at 9 and 16 weeks. The savings for askarel transformers using the Retro-1 method versus replacement and disposal were approximately 40-601. ECONOMICS The final decision to use the Retro-1 process rests with the economic evaluation of this process. The only other alternative method to accomplish our objective would be the expensive replacement and disposal (per ERA PCS Transformer Disposal Regulations) of each transformer. The exact cost for the Retro-1 process Is dependent upon: 1) The PCS concentration level; 2) The size of the transformer; 3) The difficulty of the replacement work; and 4) The cost of the replacement non-PCB transformer. CONCLUSION The Retro-1 process results indicate that It should be considered as a viable alternative for declassification of PCB transformers. And depending on the Individual unit. It Is a cost effective method which can prevent replacement and disposal of many transformers. MP8L plans to begin a systematic evaluation of all downtown network vault transformers to determine which units qualify for Retro-1 processing. We expect a savings of approximately 60S over any other method of removing the RCBs from these high risk, high liability, locations. MP1L also plans to evaluate future uses of the Retro-1 process for all-askarel type transformers where we expect a savings of approximately 408. 8-45 HONS 019089 An additional benefit of the processing is that the transformers are completely cleaned of sludge that has built up from overheating and overloading. This sludge reduces the efficiency of the transformer and they have to be filtered at least once every five years in order to remove the sludge and contamination buildup. The Retro-1 process accomplished a more thorough interior cleaning of the sludge than 1$ possible In a normal maintenance filtering process and fulfilled a normal routine maintenance period. This Is not only an economical advantage but It also Improved the operating efficiency of the transformer. We think that the removal of the PCBs, the thorough cleaning process and the Improved efficiency of these transformers have extended the expected operating life of the transformers. These factors. In combination with the other economical considerations, help justify the decision to use the Retro-1 process on high risk, high liability, vault-type transformers and selected askarel transformers. 8-46 HONS 019090 WESTIMCHOUSE ELECTRIC CORPORATION MATERIALS ft MANUFACTURING TECHNOLOGY DEPARTMENT SHARON, PENNSYLVANIA 16146 RP-2028-U PRODUCTS OF PARTIAL COMBUSTION OF PCB ALTERNATIVE DIELECTRIC fWIDS BY DR. C. CLAIR CLAIBORNE INTRODUCTION Alternative dielectric fluids which My be used in pises of askarels in sloe* criesl transformers srs of relatively rsesne origin. In 1982. ehs EnvlronMneal Procsedon Agency concluded "that adequate substitutes existed for PCI's In Indoor transformer locations from cho perspective of firo ssfoty end sloe* trlcel efficacy- (1). Subsequent fir# incidants Involving PCB transformers focused attention on sll types of txsnsforMts snd their behavior In combustion aituaetone. As a result of thoso Incidents, EPA revised its planning end Issued s request for Informs* Cion as a firac aeap In promulgating a rule concerning transformer fires (2). Although that rule vas directed at transformers vhieh may contain PCB*a, at the seme doe, the EPA requested information on the partial and completa combustion products of ssvorsl alternative transformer Insulating fluids products. Al though soma information was available on the products of completa combustion (defined as occurring vhsn chore is an excess of oxygen preeenc), Heels was available on cho products of partial combustion (where insufficient oxygen is pressne for scolchlomoerle completion of the combustion) (3-5). It is gen erally accepted that in confined areas, such as vaults snd tunnels, cho nature of many fires is such that partial or incomplete combustion mey be eh# predom inant mode of combustion. This study was Initiated to investigate the partial cosfeustlon products of several of the insulating liquids used in transformers. The program wee res tricted te combustion situations only; decomposition products produced by an oloctrle arc wore not considerad. The primary objective of this program was to determine the chemical compounds formed during partial or incomplete combustion of liquid dielectric insulating materials used in power transformers. To attain this objective an experimental program vas carried out after en extensive literature search. The literature search indicated that the InforMtlon desired vas generally unavailable. The references found In this search wore transferred to SCS Engineers and are the subject of a soparato project (RP 2028-12) and report by thee organisation. 8-47 HONS 019091 gXPEftTMEMTAL STUDIES Thermodynamic Emilltbrlua Calculations In order Co establish eome Indication of tho typos and levels of potential combustion products fro* tho liquid dielectric materials, theoretical thermo* dynamic equilibrium calculations were conducted for various oxygen levels over a range of reaction temperatures from room temperature to 1500 K. Data was assembled from various sources, Including the JANAF (Joint Army*Navy*Alr Force) Thermochemieal Tables, and Input into a mainframe computer utilising a program named "CHEHEQ", in the Vestlnghouse R&D laboratories. This propria* tary program, similar to a computer program developed by NASA (6), but with a larger data base, has been used extensively to calculate: 1) Concentrations of chemical species in multicomponent polyphase mix* tures at any specified pressure(s) and temperatures(s). 2) Concentrations and adiabatic flame temperatures of chemical products formed In the combustion process. 3) Thermodynamic and transport properties of gas mixtures at equilibrium for specified pressure(s) and temperatures(s). action Eva1melon* Two separate sets of combustion experiments were conducted for each material. In one set, a thermogravlmetrie analyzer (TGA) was modified to conduct the combustion and reaction products mere trapped In cold traps and fed to a gas chromatograph with an electron capture detector for subsequent analysis. The samples were placed in a platinum boat and heated from ambient temperatures with the oxygen level being controlled by a flow meter into the chamber. Xn the other experiment set, a stainless steel reactor was employed for the combuselon, and the reaction products were fed to a gas ehronatograph/mase spectrometer for evaluation. The samples were injected with a syringe into the reactor and the asmunt of sample was varied to vary the oxygen level. In an alternative to this procedure, designed to handle viscous materials, the sample was sealed In a small aluminum capsule which was inserted into the chaafeer by e gas-tight piston. Xn both sets of experiments, an ultimate reaction temperature of 1000 C was employed. This temperature was chosen after consultation with Dr. Richard Gann of the National Bureau of Standards as the most probable temperature for partial combustion situations (7). Materials One fluid of each of five types of Insulating fluid was selected for this study: Chlorinated hydrocerbon**tetraehloroethylene (CC1.), VECOSOL*, Vest* Inghouse Klectrle Corporation, original supplier: Diamond Shamrock Corporation; Fluorocarbon*-trlfluorotrichloroethane (C.F-CIO, Freon 113*. supplier: E.l. DuFont de Nemours; Silicone fluid*polydimeEhylslloxane. Dow Corning 561 Sili cons Transformer Fluid, supplier: Dow Corning Company; Mineral oll**VEMC0 C*, Vestlnghouse Electric Corporation, original supplier: Gulf Oil Corporation; High temperature hydrocarbon*-RTEitp*, supplier: RTE Corporation. 8-48 HONS 019092 EXPERIMENTAL MILTS letiachloroachvlanx With teerachloroethylene In the chermogravimatric chamber, considerable pro blems were encountered when the combustion was carried out at on air level corresponding to 70% of theoretical total combustion. Dotoetabla amounts of chlorine vara generated and In addition, alnea tha chamber wee haatad from ambient temperature upward, tha praaanca of vatar on tha Intarlor valla of tha chamber cauaad tha production of aaall amounts of HC1. Thla In turn cauaad corroalon of some of tha natal parca In tha TCA measurement system auch aa tha aapla rafaranca thermocouple. Sinea thla component vaa not aaaantlal to tha operation of tha Instrument for ehaaa experiments, It waa omitted in eha next run. However, tha aacond run cauaad anough deterioration of tone of eha oehar coaponanea of tha apparatua, eg. 0-rings and balaneo parta, to require over haul of tha Instrument. Aa a reault, tha runa ae 30% air were poeeponed and indeed ware not completed during tha project. Compatible materials are avail able which could alleviate thaaa problem# In future Invaoeigaelona. Other than tha expected ehlortne and the normal conaeltuanea of air. only HC1 vaa noted in aaall aaounta In tha combuatlon products Aa waa pradlctad in eha thermodynamic equilibrium calculations, phosgene waa not detected In any af tha runa. Unreacted atartlng material waa recovered In algnifleant quantities. Tha stainless steal combuatlon reactor waa used eo conduct thrao analytical runa with tatrachlaroathylane. two direct Injection runa gave chlorine aa tha pri mary produce and a low level (approximately 0.1%) of dfcehloroacetylene waa seen In ana of tha dlract injection runa. Unraacted tetreehloroethylene waa else recovered In both af thaaa runa. An additional sample run with tha piston/capaula method gave essentially eh# same results with dlchloroecetylene again being found. No particulars wars detected on a glass flbor disk trap located at tha raaotar axle. Vleh eha sample quantities used tn tha experiment, this Indicated ehat <3 ppm of halogonatad or polycyclic partlculaeaa ware formed. Trlchlorotrlfluoroathane Trlchlorotrlfluoraathana gave similar raaulta to eatrachlorooehylano whan it was examined In cha chermogravlmetrle chamber, except that chlorlns waa not obaarvad. Again, eha praaanca of vatar on cha intarlor walla did causa produc tion of HF which In turn eauaed a minor amount of etching of tha chamber. In thla particular cats, however, not all peaks in tha chromatograph from the electron capture detector could bo identified. Certain of eheee peaks undoubt edly could have beam associated with various fluorocarbon compounds that vara net readily available for confirmation of the peak identities. It waa decided chat tha raaulta of the other experimental arrangement would be used to quali tatively identify thaaa other products. Two runa wars made in the atainlaaa scaal raaeeor using cha direct injection procedure. The first run, in which the withdrawal of products waa carried out after 10 seconds, showed chlorotrlfluoroethylene and dlchlorotetrefluoroethene. However, over M% of recovered gaseous material waa unraacted atartlng mat erial. A aacond Injection was made and tha gaa sample waa withdrawn after 10 minutes. A little ehlerlne waa detected but unraacted material vaa predom inant. CFj and CFC1 waa also found, which may indicate a trace of active 8-49 HONS 019093 fluorine. although that aaaaa unllkaly. Fluorina was outside eh* scanning rang# of tha GC/MS configuration for chasa axparlaants. Thla run did not datact tha other two aaterlals saan in cha first run. Four runs woke aada on trlehlorotrlfluoroathana with tha plston/capsula each* nlqua. Ulth this technique, products datactad included tatrafluoroaethane. dlehlorodlfluoroathylana, ehloroerlfluoroethylsno, trichlorofiuoroethylene, tatrafluoroathylana and fluorochloroathylana. Again, no particulates of lneerase ware datactad, even in the run with tha graacasc variety of products, with eha saae da esc t ion Halt as with C^Cl^, 3 ppa. Hany of thaaa products aay wall correspond to cha results of the coabustlon in tha TCA. Since it was not possible to acquire these aaterlals, confirmscion was 1 initad to tha observation chat sons of chess aaterlals vara pre dicted by cha tharaedynaalc calculations. Silicone Ulth sllleone, a relatively large variety of gaseous products wars datactad, Including CO., H., CO, aeehane, ethane, acetylene and othar hydrocarbons. Again In this case, a large aaount of unraaccad aacarlal was present In tha chaaber and in tha coabustlon boat at tha conpleclon of cho experiment. Above all, a significant aaount of solid material was found In all tubing leading froa cha quarts coabustlon chaaber. Thla aaterlal was white and fluffy in appearance and was aoat likely silicon dioxide which 1* known to result froa coabustlon of polydlaathylailoxana (4). In tha axparlaant sat utilising cha stainless steal reactor, two runs war# aada with tha direct injection aethod. Since no volatiles vara datactad and because of tha relative difficulty of transferring this rsthar viscous substsneo, tha piston aethod was developed. However, again no volatiles wars datactad. Tha steal reactor tuba contained a large aaount of black, fluffy aaterlal. When this aaterlal was rsaovad and heated In a auffla furnace with an 0. excess at 1000 C, cha substance left a white ash. This lad to tha conclusion that tha aaterlal was probably SlOg aixad with carbon. No ocher particulates of inter est vara datactad on tha > fiber collector. In this case, detectability would have bean on cho order of <15 ppa duo cha different aaaa of starting aacerlal. cmmii ou Transformer aineral oil generated significant quantities of coabuaclbla macerlals such as asthane and achana, which possibly resulted froa crocking of the starting aaterlal, whan cha aaount of air was Halted to 30%. This Indicated that cha coabustlon was quits decidedly not coupleee. A surprisingly low aaount of carbon dioxide was found with both tha 70% and 30% air levels. High Toaoarsture Hydrocarbon The quantities of coabuaclbla aaterlals prsasnt in tha products of cha high taaparatura hydrocarbon ware relatively less than for tha cransforaar aineral oil. However, there ware significant quantities of ethylene found. Again, aa In tha ease of eha silicone fluid, a large aaount of unroactod aaterlal waa present In cha coabustlon chaaber. 8-50 MONS 019094 In * run made with chi# material in the CC/MS setup, only two produce* were detected In eh# gaseous product analysis by mss apeetroseopy: benzene and toluono. In relative com* only a all proportion of cho starting sample, woo praaont aa thoao product#. No partleulata notarial woo datactod. DISCUSSION In summation, it la laportanc to noto that nona of tha coabuatlona produced datactabla chlorinated or polyeycllc oroaoelo hydrocarbon poreleuloeao. The production of ehlortne (and hydrogen chloride In the praaanca of atmospheric huaidlty) fro* tetraehloroethylene auat not be minimized, but rather ahould bo balanced agalnat the non-flammable nature of the material. Much the itae statenone say be Bade about trlchlorocrlfluoroethane and Ita production of hydrogen fluoride and the verloue fluorocarbon aacerlala. The abeence of phoagene in theae experlaenta la alao to be noted. For the other aaeerlela. the preeenee of coabuatlble aacerlala In the product treaa indicated that even In eventa with only partial combustion, a potent* tally dangerous altuatlon say reaaln even after eha heat eouree la removed. REFERENCES 1. Fadaral Register, August 25, 1982. 2. Fadaral Reglatar, March 23, 1984. 3. "Fire Safety Properties of Sosa Transformer Dielectric Liquids," J. Lipovles, "J. of Flro & Flammability", V. 15, 39*55 (1982). 4. "Investigation of eho Thermal Oxidation of Folydlaochylslloxanos*, V. S. Papkov at el., "Polymer Science USSR". V. 19, 962-974 (1977). 5. "Thermal Decomposition of Chlorinated Hydrocarbons", 8. SJoberg, "Svenak Kealsk Tldakrlft", V. 64, 63-79 (1952). 6. "Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rockae Performance, Incident and Reflected Shocks, and ChapmanJouquet Detonations*, S. Cordon and B. J. McBride, NASA SP273. 7. Personal communication with Dr. Richard Gann, National Bureau of Standards. 8-51 HONS 019095 PCB TRANSFORMER DECONTAMINATION RATHER THAN BURIAL Ted Topolski ETI of North America Until this year, PCB transformers required burial at a secure land fill. Since the Environmental Protection Agency is encouraging new technologies rather than burial at landfills, they have permitted a reclamation and recovery facilities for PCB transformer reclama tion in Kansas City. This pcb transformer facility is under EPA control. Transformers are received, cleaned to less than S00 ppm, opened, and the internal parts processed through an assembly line operation for PCB removal and extractions. This paper includes handling, processing procedures for reclamation, to primary metal recovery for smelt. 8-52 MQNS 019096 RETROFIllING ASKAREL TRANSFORMERS - WORDS OF CAUTION J. P. K1 nney General Electric Co. Retrof111 Ing transformers that ara originally constructed for uao ulth aakaral la an alternative to complete changeout and dlapoaal. In some cases where apace It critical, removal Is very expensive, or the Installation Is unique, retroflll la an approach to consider. This decision needs to be made with soma key points In mind. In 1977 several papers 1' 7. 3 *r( published advising the Industry of the potential problems Involved when askarel transformers were retrofllled. Askarel composition, materials of construction and transformer designs were changed many times In the forty years they were manufactured. No overall recommendation can be made concerning all of these transformers. In each case It would be wise to Include an Inquiry to the manufacturer before deciding to proceed with retrof111Ing. As pointed out by Morgan and Osthoff1. the leaching out of KB's from transformer Insulation systmas la a very slow process. Changing selective adsorbents or making multiple retrof11 la In order to maintain low PCS concentrations can become a significant factor In the economic evaluation of retroflllIng. When General Electric's Medina Transformer plant changed from building askarel filled transformers to the production of silicone filled transformers. It was necessary to make several changes In the design of the product from that previously used for askarel. Most of these changes If made today would raqulra teardown of an existing askarel transformer, which Is a violation of federal regulations^, If the cleanup and retroflll process followed by a minimal of three months back In service lowers the PCB content to less than 500 ppm. federal regulations would then allow teardown and modification. If the transformer Is Inaccessible for rework of this type, operation after retrofllllng should be modified as described In the conclusion of this paper. 8-53 MOMS 019097 Tht key differences In properties between askarel and silicon* fluid which rqglr# design changes are Inputs* creepage strength* heat transfer capability* thermal coefficient of expansion* material cosipatlbllIty and lubricity. Sene of the differences In properties are shown In Tsble I. This table compares silicone fluid* transformer oil end askarel. The problems and suggested modified operation are covered In the following paragraphs. Table 1 PROPERTIES OP SILICONE* MINERAL OIL* AND ASKAREL Viscosity, cs st 25C st aoc Flesh Point. Opon Cup. Min Fir* Point. Opon Cup. Min Oxygon InOox Specific Gravity, 25% Coefficient of Exptnslon. cc/ec/C Pour Point. C Bolling Range* C Olelectrfc Constant* 2SC, 60 Ik Dielectric Strength. KY Disk Electrode. 0.25 esi gsp Silicone 50 20 300 340 21.4 0.96 .00106 -55 Non* 2.7 35 MlMftl Oil 10 2.7 145 150 15.6 0.66 .0007 -55 260-370 2.2 35 Ailllftl 12.8 4.2 No true f.| Non* to b.| 37.6 1.5 .0001 -40 209-361 5.3 35 HONS 019090 8*54 Tabla II DIELECTRIC BREAKDOWN STRENGTH FOR VARIOUS CONFIGURATIONS WITH SILICONE, MINERAL OIL, AND ASKAREL Iapulaa Braakdoun, kV Uni fora Flald. 2.54 am (O.I In.) gap CASTM DISK Elactrodaa) Non-unlfora Flald, Rod-to-Plart# 12.7 im (0.5 In.) gap Nagatlva Polarity Poaltlva Polarity lapragnatad Kraft Papar Round Edga Elactroda, 51 ma (2.0 In.) dlaaatar 0.467 na thlcknaa* 2.34 aa thlcknaaa Iapulaa Craapaga on Kraft Praasboard (2) Elactrodaa, 25.4 an (1.0 In.) dfa. Edga-to-Edga Spacing, 76.2 n> (3,0 In.) Poaltlva Polarity 60 Hartz Braakdonn, kV Impragnatad Kraft Papar Roundad Edga Elactroda 51 na (2.0 In.) dlaaatar 0.467 na thlcknaaa 2.34 a* thlcknaaa * Baaad on 1laltad taat aaaplaa. SlIiCQm Mlnaral Oil Aihiral 136.4 142.0 153.3 205.6 99.6 107.0 90.9 119.0* 114.0* 30.4 134.6 43.0 182.9 49.0 163.0 69.6 152.3 130.6 19.5 64.3 22.1 77.0 28.7 65.5 8-55 HONS 019099 POSITIVE POLARITY IMPULSE CREEP STRENGTH4 The surface Impulse creepage dielectric strength of high density kraft pressboard whan taatad In sUlcona fluid Is Just undar 70S of that experienced In askarel. Sana of tha more comprehensive dlalactrlc breakdown propartlas ara shown In Tabla II. Whan GE's than standard askaral transformer design was filled with silicone fluid and given positive polarity Impulse tests* there were surface creepage breakdowns. An Internal redesign to compensate for the lower Impulse breakdown characteristics of the liquid achieved the full Insulation levels required In the new silicone fluid transformer. If an existing askaral transfonser could be satisfactorily cleaned and then retrofIliad with silicone fluid* the BIL rating should be reduced and suitable surge arrestors should be applied to protect the transformer frcm excessive transient voltages. HEAT TRANSFER Industry standards for 55 or 65 teaperature rise liquid filled transformers specify a guaranteed winding temperature rise over ambient. The guaranteed hot spot rises over ambient are 6SC and B0C respectively. Heat runs conducted on prototype transformers with thermocouples enbedded In the windings Indicated from 5 to 2SC greater temperatures when silicone fluid was the cooling liquid as compared to askarel. Approximately 30ft more surface area was added to the cooling package to meet the guaranteed winding rise of silicone fluid transformers. If an askarel transformer Is retrofllled with silicone fluid* derating Is required to prevent serious damage due to overheating. THERMAL COEFFICIENT OF EXPANSION The thermal coefficient of expansion of silicone fluid is some 40ft greater than askarel. This results In tank designs with a greater gas space above the 2SC liquid level and a greater distance frcm this liquid level down to the highest conductor. If a retrofllled transformer is located outdoors* low ambient temperatures may cause contraction of the liquid that would expose the bus bars* bushings or other conductor. This In turn could cause dielectric and/or thermal problams. Adding external heaters or possibly an external expansion tank Is recommended when a silicone fluid retrofllled transformer is located outdoors. 8-56 MOMS 019100 MATERIAL COMPATIBILITY The gasket autirlili uMd for askaral transformers were changed many times over the years. Silicon# rubber and than Vlton* vara found to ba rasfstant to askaral. Silicon# rubbar usatf for approximately tha last 20 yaars of askaral transformer aanufactura Is not sultabla for usa In silicon# fluid. It Is necessary to raplaea all gasksts whan an askaral transformer Is ratroflllad. Again* ovar th# yaars* aach daslgn changa usually introducad savaral now atarials of construction. Soma of tha materials usad In askaral transfonsars ara no longar commercially aval labia and no material coaipatlbtl Ity tasting has ever baan dona on them In silicon# fluid or In any othar transformer fluid. If a silicon# dapolymerization catalyst Is prasant In any of thasa materials* tha flra point of tha liquid aay ba affactad. Son# othar iaat#r1a1s may causa viscosity Incraasas. Fraquant tasting of liquid samples from ratroflllad transfonsars should ba schadulad and should Includa flra point and viscosity tasts along with PC8 concentration tasts. LUBRICITY ' Tha "no load" (deenergized operation) tap changar of most Industrial load cantar transformers Is saldem changed fro* tha position sat bafora Initial energization. Tha cap of tha tap changar can ba padlocked to prevent operation by unauthorized personnel. If an askaral transfonaer Is ratroflllad with silicons fluid you should label Its tap changar as Inoperative due to tha difference in lubricating properties between tha two fluids. Thera is a posslbll Ity of tha tap changar mechenlmn locking up. Tha drive shaft aay break and If tha tap ehanger Is not In th# correct position tha transfonaer aay fall electrically on energization. Whan tha aanufactura of new silicone filled transfonsars was started a coaplete redesign of tha tap changar was nacassary to achieve satisfactory operation. FLUSHING SCLVENTS Sosa retroflll contractors have usad strong solvents to attempt to rawova tha aekarel which hasn't dripped frea tha core and coll after draining. This practice can seriously danaga tha wlr# enaael and othar resinous atarlals In tha transformer. One flushing solvent which shouldn't hans tha Insulation 8-S7 HONS 019101 ystmo tn GE industrial 1 oad center transformers Is a mixture of tri- and tetrachlorobenzenes. Since this was on* of the Ingredients of ukar*l It should be compatible for short duration of flushing. This recommendation applies only to transformers manufactured at General Electric1a Msdlua Transformer Plant In Rom*. Georgia. Information Involving other GE products or products of other manufacturers should be obtained directly from th* manufacturing sit*. Again, askarel impregnated Insulation may not give up its PCB content easily In this process. RETROFILLING WITH OTHER FLUIDS Tuo other fluids used In cooling and as a dielectric in nev transformers today should definitely not be used for retrofllllng. Dielectric Grad* Freon R-II3 Is used as a vaporization cooling fluid and askarel transformers uer* not designed for this cooling technique. Perehlorethylen* is compatible with paper Insulation but the sire enamels used In many of GE's askarel transformers will not resist th* solvent action of perchloroethylen*. High molecular uelght hydrocarbons have not been studied frcm a compatibility standpoint. You should cheek with local building codes and your fir* Insurance firms before using any specific retroflll liquid. CONCLUSION Several years of experience have demonetrated that retrofllllng of askarel transformers Is still a somewhat controversial topic In th* Industry. If a decision Is mad* to retroflll any Rom* built G. E. transformer, th* following precautions should be followed! 1. Obtain up to date Federal. State and local regulations concerning PCB's and follow them. 2. Recognize that PCB will leach out of the core and Insulation with time, possibly requiring additional retrofllla and more disposal costs In order to maintain acceptably low concentrations of PCB's In th* fluid. 3 Chang* out all gaskets using appropriate replacement gaskets. 4. Set th* tap changer before retrofllllng. lock It. and label as Inoperative. 5. Examine th* load and If at or near full load - reduce It to prevent overheating. Th* nameplate should be modified to reflect derating and th* presence of the new fluid. 8-58 HONS 019102 6. Derate the BIL of the transformer and apply suitable surge arrestors In the proper 1oct1on to protect the trsnsformer froe transients. 7. If the transformer Is Installed outdoors take precautions such as heaters for lew ambients so contraction of the fluid won't expose the bus bar or other conductor. 0. Monitor the thermal behavior of the transformer during the derated full load operation over an extended period. 9. When monitoring liquid samples for PCS decontamination progress Include viscosity and fire point along with other critical properties. Continue this testing on a yearly basis. 10. Consult with your Insurance carrier on the suitability of any retroflll liquid from a fire safety standpoint. 11. The manufacturers calculations and Judgements on derating and material compatibility mads by examining the old design drawings will be helpful but will also be an additional expense which will not have the confirmation of factory testing. In other words If you retroflll you are on your own. No hope that the Information In this paper will be of value to tho owners of askaral transformers who are considering retrofllllng or othor alternatives that lower or eliminate PC8's. REFERENCES 1. L. A. torgan and R. C. Osthoff. "Problems Associated with the Retrofllllng of Askarel Transformers"* A-77 120-9. IEEE Vinter Power Meeting* 1977. 2. R. A. Nelson* "Silicone Liquid Filled Transformers". Proceedings of the American Power Conference* Vol. 39* page 1069-1073* 1977. 3. J. P. Kinney and J. C. Crouse. "Alternatives to PC8 Transformer Insulating Materials". Conference Record of 1977 Twenty Ninth Annual Conference of Electrical Engineering Problmas In the Rubber and Plastics Industries* 1977. 4. P. F. Art end J. C. Crouse. "Polydlmothylslloxane as a Liquid Dielectric for Transfoimerst Electrical Breakdown and Dielectric Properties of the Fluid and of Impregnated Celluloslc Insulating Materials" A-77 173-6. Piper presented at the IEEE Vinter Power Meeting. 1977. 5. 40 CFR* Cade of Federal Regulations. Part 761.31. June 7. 1976 8-59 MON$ 019103 DECONTAMINATION OF AN ASKAREL-FILtED NETWORK TRANSFORMER 0. T. Drew Dunlop This paper describes < pilot project undertaken to determine the feasibility and economics of decontaminating and retrofllllng askarel-fllled network transformers used In B. C. Hydro's underground distribution system In Victoria, B. C. The Victoria network system consists of multiple 12 kV feeders with each feeder supplying a number of 12 kV to 120/208 V 500 kVA network transformers. The secondaries of each transformer are busted together forming a secondary network at 120/208 V from which service leads are run to customers. The network system Is completely underground with the transformers placed In vaults under sidewalks with open grills covering the vaults. When the original network system was designed In the mld-1950's, askarel-fllled transformers were selected because the use of askarel-fllled transformers In such locations was the standard Industry practice at the time and because of the serious consequences a transformer fire could have In such close proximity to the public. There are a total of 94 transformers In the Victoria network system. Fifty-five of the transformers are askarel-fllled; the balance of the transformers were purchased subsequent to the ban on PCBs In new transformers and are filled with conventional hydrocarbon Insulating oil. The Victoria network transformers are the only askarel-fllled transformers exposed to the public In the B. C. Hydro system. The transformer was thoroughly drained prior to beginning the solvent decontamination. Approximately 760 of a nominal 865 litres (87.91) of askarel were removed from the transformer by draining. The decontamination procedure was modified a number of times In an attempt to achieve the most efficient method for promoting the release of askarel from within the transformer components. 8-60 HONS 019104 Initially, vapor phase degreasing was used to decontaminate the transformer. Twenty-seven vapor degreasing cycles were completed over a period of 38 days with the transformer In a vapor phase system autoclave. One degreasing cycle was completed each working day. Shell Sol LX 154, a hydrocarbon mineral spirits, was selected as the degreasing solvent. Shell Sol has a boiling point of approximately 185*C (STP); a typical askarel bolls at greater than 200*C (STP). By using a solvent with a lower boiling point than askarel. the transformer components were constantly washed with clean solvent since the dissolved askarel did not volatile at the solvent boiling point. The vapor degreasing process consisted of Introducing hot solvent vapors into the transformer; these vapors condensed on the transformer winding, core and supports resulting In a washing action. The cleaning action continued for approximately five hours until the transformer components reached the temperature of the solvent vapors. With each successive vapor degreasing cycle, the amount of askarel released from the transformer decreased. The 27 vapor degreasing cycles removed approximately 84.1 litres of askarel from the transformer. The decontamination process was then changed from vapor phase degreasing to hot solvent soaks. The transformer was left In the autoclave and was filled with solvent. During each hot solvent soak, heat was supplied to the solvent filled transformer by flooding the autoclave with hot solvent vapors for a period of three hours. During the hot solvent soaks, the transformer winding reached an average temperature of 83*C. The hot solvent soak cycle was repeated 56 times, once each working day, over a period of 87 days. The transformer was flushed and refilled with distilled solvent every two weeks. A decreasing amount of askarel was removed from the transformer with each successive hot solvent soak. Approximately 109.9 litres of askarel were removed from the transformer by the hot solvent soak cycles. The decontamination process was then modified from hot solvent soaks to cold solvent soaks. Each cold solvent soak consisted of filling the transformer with distilled solvent and allowing the transformer to soak for a number of days In a static situation at room temperature. The transformer was then drained and refilled with 8-61 HONS 019105 distilled solvent. This procedure was repeated ten times over a period of 57 days, with each soak lasting from three to eight days. The cold solvent soaks were found to be Ineffective In decontaminating the transformer. Essentially no askarel was removed from the transformer by the cold solvent soak method. It was decided, therefore, to terminate the solvent decontamination and retroflll the transformer. The vapor degreasing cycles removed 84.1 litres of askarel which corresponds to an average of 3.1 litres of askarel per vapor washing. The hot solvent soaks removed 109.9 litres of askarel which corresponds to an average of 1.95 litres per hot solvent soak. This Is In addition to the 780 litres of askarel removed by draining. The amount of askarel removed from the transformer may seem Inconsistent with the assumed total quantity of transformer fluid of 865 litres. However, the quantity of fluid removed by draining Is approximate and Is considered to be accurate only within flOt. In addition, the 865 litres Is a nominal quantity; the exact quantity of fluid within the transformer Is not knwn. It was intended that the transformer be retrofilled with an environmentally acceptable synthetic Insulating fluid with electrical Insulating and fire resistance properties similar to askarel. However, because of the expected release of askarel Into the retroflll fluid and the cost of suitable synthetic Insulating fluids. It was decided to first retroflll the transformer with reclaimed conventional hydrocarbon Insulating oil. Prior to filling the transformer, the reclaimed Insulating oil was tested and found to contain no measurable concentration of PCt. The next oil sample was taken one day after filling the transformer with Insulating oil. The PCB concentration was found to be 118 ppm. This Increased to 169 ppm with the transformer In a static situation at room temperature for 20 days. The transformer was then Insulated with fiberglass batting and energized from the low voltage side to accelerate the release of askarel Into the oil. The transformer remained energized for a period of 216 days. Over this time, the PCB concentration Increased to 2,063 ppm. When It became apparent that only a minimal additional amount of askarel would be released If the transformer remained Insulated and energized. It was decided to drain and then fill the transformer with a synthetic Insulating fluid. The 8-62 ,,ONS a*9106 transformer njs allowed to drain for a period of 14 days In an attempt to remove as much askarel-contaminated oil as possible. Based on synthetic Insulating fluid characteristics and replacement fluid costs and availability, a decision was made to use Gulf Less Flammable Dielectric Fluid PM* as the retrofill fluid for the decontamination project. Gulf PAO* is a polyalphaolefln based synthetic hydrocarbon, compatible with conventional hydrocarbon Insulating oil. An oil sample was taken one day after filling the transformer with Gulf PAO*. The PCS concentration was found to be 269 ppm. A high Initial concentration of PCB was not expected and no suitable explanation for this could be found. Because of the heat transfer characteristics of the Gulf PAO* dielectric fluid, It was expected that the transformer would have to be de-rated. To determine the new transformer rating, temperature rise tests were performed. Based on the results of these tests and a maximum winding temperature rise of B6*C above ambient. It was determined the transformer should be de-rated by 201 to 400 kVA. An Insulating fluid sample was taken following completion of the temperature rise tests. The PCB concentration was found to be 335 ppm. To date the transformer has not been returned to service and after 18 months In storage the PCB concentration In the retrofill fluid Is 830 ppm. This represents a 99.921 reduction In the amount of free PCB originally In the transformer. The decontamination project was carried out without adverse effects to personnel, plant or the environment. There was no significant Increase In blood PCB levels of employees Involved In the decontamination program and no Increase In PCB contamination levels within the shop facility was observed. The decision to retrofill a transformer versus replacing the transformer Involves several economic trade-offs. The cost of decontaminating and retrofllllng the transformer and the remaining life of the transformer must be balanced against the cost and expected life of a new transformer. When considering the cost of a new transformer, the cost of storing and ultimately disposing of the askarel-fllltd transformer must also be considered. 8-63 HONS 019107 PCB REMOVALS - OPTIONS AND IMPLEMENTATION Francis E. Silvia, Boston Edison Company INTRODUCTION In June of 1983 the Boston Edison Company established a voluntary program to elimi nate askarel filled secondary network and station equipment from Its system by year end 1988. This program Involves the disposal of some 800 pieces of equipment exclusive of EPA-mandated capacitor removals. Two years Into the five-year project, we are on schedule and underbudget for this projected S32.SM program. The success of the project to date Is due In large part to the research and planning efforts of project personnel prior to Its Implementation. This presentation Is a general description of some Issues, decisions and options that must be addressed by any company considering the method of disposing of Its askarel equipment. It Is our Intention only to suggest a framework for project setup, not to evaluate the options contained therein. Evaluation, we believe. Is best left to the Individual company, since It Is best aware of Its own particular needs. THE CORPORATE OBJECTIVE A primary consideration In preparing a project plan is the definition of the corpo rate objective. In this case, how does a particular company wish to deal with Its askarel equipment? Does the company wish to be PCB "free", will It maintain some existing PCB equipment, or Is some level of PCB concentration between 0 and BOO ppm satisfactory? Establishing the objective Is essential to providing an overall direction to the project and to keep It on track In Its ensuing stages. It should be based not only on dollar cost, but also on potential future liabilities. Other factors that may Influence the decision Include the company's social obligations and responsi bilities to the public, the business comnunlty and the municipalities in which It operates. 8-64 HONS 019108 The task of establishing the corporate objective generally lies with the company's officers, since It Is they who are specifically liable for compliance with existing regulations. Prerequisite to their decision Is an evaluation of the alternatives available. An'In-depth analysis of alternatives must be provided If an optimum decision Is to be made. OPTIONS The project personnel, l.e., managers, coordinators and engineers, are responsible for evaluating available options and submitting recommendations to company offi cers. These analyses are, however, subject to re-evaluation as changes In tech nology and regulations come about. Presently available options Include retroflll of existing equipment with substitute Insulating fluids, the addition of a filtering system to a retrofllled unit, direct replacement of askarel equipment with new equipment, and last, the "do nothing" approach which simply maintains existing equipment In accordance with applicable regulations. At first glance the above may look simple enough since there are only four options from which to choose. But consider also that each of the four carries with It underlying considerations. For example, what types of alternate Insulating media are available for retrofllls or replacements? How do you deal with PCB equipment carcasses? How effective are PCB filtration systems? More specific questions Include future changes In regulations, availability and lead time for services and equipment, adaptability of new equipment to existing Installations, experience and licensing of hazardous waste disposal contractors, availability of disposal sites, the fire, dielectric and toxicity ratings of substitute fluids, the age, electric loss and possible de-rating of existing equipment. There may also be other ways to deal with askarel removals. For example. It may be possible to retire equipment and not replace it by shifting load to other Installations, reconductorlng, etc. Finally, where do you get accurate and reliable information on the above, and what about the costs? It Is easy to see that the choice of an option may not be as simple a matter as It first appears. A considerable amount of time must be spent In researching Informa tion In order to optimize the choice. 8-65 MOWS 019109 IMPLEMENTATION After alternatives have beer evaluated, the corporate objective established and options chosen, an implementation plan must be designed and executed. This plan Is essentially a master schedule of when field work will be performed, but It carries with It the underlying considerations of how, who and where. For example, there will most likely be priority locations to be dealt with. Should priorities be based on type of establishment (hospital, school, residential, etc.), voltage level of the equipment, or some other criteria? Who will perform the work? Are there sufficient In-house personnel available or should outside contractors be used? What about timing and availability of equipment and services? Can the project be Interlaced and coordinated with already planned construction? Are special procedures or accounting needed to acconmodate the project or are normal channels adequate? As with the evaluation of options, a number of Items must be addressed In order to formulate and optimize a plan. SUMkWRY Clearly, the execution of an askarel replacement program Is not a simple task. The options are numerous and. In many cases, the time available to accomplish the task Is short. It Is essential that all Issues be addressed If a program is to be tail ored to a particular company's needs relative to the use or replacement of askarel filled equipment. 8-66 HONS 019110 FMT 9: SPILL NNWOEKT PMKL HONS 019111 AFTER A PCB FIRE - CLEANUP INSIDE BUILDINGS CONTAMINATED WITH OIOXINS AND FURANS Kirk Blackmon Fir* Involving PCB transformers at office buildings In San Francisco, California, and Binghamton, Now York, resulted in the buildings being closed due to the presence of dioxins and furans. This paper presents four aspects of the subsequent clean up of these buildings: approach, procedures, results, and costs. My coaipany was directly responsible for much of the decontamination In the San Francisco building (One Market Plata), and the Binghamton State Office Building. In all these cases, not only were the buildings contaminated with PCB's after the fires, but also either dioxins or furans, or both. This means that if one of your transformers is Involved in a fire, and if any of the PCB oil Is subjected to high temperatures, you are going to have a serious problem. The most serious exposure you must consider is your potential liability from health related litigation. Do not let people into the building until you have had it adequately tested. But what about getting the contaminated area back In service quickly and safely. What can you do? APPROACH The two largest PCB-fire decontamination projects to date. One Market Plata and Binghamton, show that decontaailnation can be successful and the buildings reoccupied. Our approach to both these projects was basically the same. We did not attempt to neutralize or destroy the contaminants. Instead, we cleaned all surfaces, transferring contaminants from the building and its contents to cleaning agents, cloths and sponges. The cleaning materials were then disposed of as hazardous waste. In some of our more recent projects, we have discovered that water-based cleaning agents have proven in many cases to be the most efficient methods of removing contaminantt. Using these methods, a tremendous amount of waste water is generated. To handle this, we now have transportable water purification systems that are capable of reducing the contaminant levels to one part per billion. HONS omu 9-1 In Host esses, this Is clean enough to be placed In a city sanitary sewer system. PROCEDURES In completing these jobs, many procedures, chemicals, and equipment have been designed, tested, and Improved upon. A few of these procedures are listed below: Medical Surveillance Decontamination projects require the medical monitoring of all personnel entering the building until It Is given a clean bill of health. This Is Important for the following reasons: e It Insures the exposed people are not becoming contaminated, e Psychologically, these people feel safer because they are being monitored, e The medical surveillance will enable you to better defend yourself If liability suits are filed. Health and Safety Plans The Health and Safety Plans related to these types of cleanup projects have been developed and Implemented on all these previously mentioned jobs. These plans Include entry and exit procedures, training procedures, protective equipment applications, respirator programs, etc. Decontamination Facilities Part of the health and safety plans require that all workers change clothes and shower whenever they leave a contaminated building. Our transportable decontami nation facilities are equipped with dressing areas, showers, laundry facilities, and respiratory equipment maintenance areas. All of the water generated from this facility must be recaptured and processed through the water treatment plant. Protective Gear In many of these projects. It was found that certain areas of the buildings were lightly contaminated, some areas were moderately contaminated, and others heavily contaminated. It became quite cost effective to Isolate these different areas and prescribe protective equipment specifically for each Individual area. The lightly contaminated areas might require only gloves, boots, head protection, and no respirators, while the heavily contaminated areas might require selfcontained breathing apparatus and Impervious type suits. HONS 019113 9-2 Exterior Restoration At One Market Plaza, the contaminated area Included portions or the outside of the building. We had to develop a new piece of equipment specifically for this exterior cleaning, because none of the cleaning solution could be allowed to fall on the street below. Interior Restoration The Insides of these buildings normally require everything to be cleaned. This includes elevator shafts, walls, ceilings, floors, and the entire heating and air conditioning systems. Most of the cleaning was very detailed and In many cases, special chemicals were developed to release the binders that held the contaminants to each Item. Some of the most difficult Interior decontamination Involved the ductwork that distributes air throughout the building. At first It appeared that the entire systems at the One Market Plaza Building would have to be replaced, but we developed a new cleaning technique that worked well In cleaning all sizes of air ducts. The technique Is very similar to swabbing a very large gun barrel. A machine sends a swab through the ductwork emitting the proper chemicals while mechanical agitation Is taking place. After the ducts are clean, they are sealed with a resin based sealer. This technique was also used In Binghamton, where It was even more Important, because In Binghamton the ductwork was sandwiched between layers of concrete. Removing the ductwork would have required extensive demolition. Contents In addition to decontaminating the structure elements, many times all contents must be decontaminated also. Some of the most challenging of these are computers, word processors, and other electronic equipment. Fortunately, techniques have already been developed and Improved upon for removing the contaminants from such equipment. Three of the methods used to accomplish this are air brushing, ultra sound cleaning, and vapor degreasing. RESULTS One Market Plaza reopened to employees In March of 1984, ten months after the fire. Floors two through eighteen of the Binghamton State Office Building were vented to the outside air for the first time In four years In February, 1985. In August, 1985, these same floors were given a clean bill of health by the expert panel and released to the construction trade for refurbishing. He expect to finish the basement floors and the first floor and have It reopened soon. HONS 01911b 9-3 COSTS The first two major PCS decontamination projects generated awesome property damage costs, twenty-one million dollars for One Market Plaza and thirty-eight million dollars for Binghamton. Such costs may seem slightly less forbidding when compared to the cost of abandoning and demolishing the buildings, which Is Indeed the only other option following contamination of this type. But the cost of some of our more recent decontamination projects Is significantly less. Two examples are Arnold Air Force Station In Tennessee and the' State Highway Department Building In Santa Fe, New Mexico. Both were similarly contaminated but restored at much lest cost. In holding cost down on these type projects. It Is very Important that those Involved not try and reinvent the wheel. All of the preliminary research, development, testing, and experimentation that made the first two losses so expensive will help reduce costs for those that follow. There are also services available now that did not exist at the time of the Binghamton fire. For example a process has been developed to save contaminated network protective switches when replacing PCB transformers. Many utilities are replacing these switches because they are found to be contaminated because of their proximity to the PCB transformers. The cost of replacing these switches Is approximately $2$,000.00 each, but because of all the research and development associated with PCB losses. It Is now possible to have these switches decontami nated and restored to Hke-new condition for about S2.000.00 each. 9-4 HONS 019115 PCB SPILL RESPONSE AND CLEANUP RESULTS Author - P. J. Elsele In mid-1982 the Detroit Edison Company was pursuing an ongoing program of gradual polychlorinated biphenyl (PCB) capacitor replacement based on equipment failure. When one distribution capacitor unit would fall, the whole bank (3-6 units) would be replaced with non-PCB equipment. In early 1983 this program was accelerated to remove some 19*000 PCB capacitors from the 7600 square miles of Company service area to meet a removal deadline of October 1, 1988 set by Toxic Substances Control Act (TSCA) regulations. The regional office of the US6PA, concerned that utilities were not moving quickly enough to beat the TSCA deadline and cognizant of general public concern about PCB spills in the Crest Lakts area, met with the Company to encourage more expeditious removal. Although the agency was not aware of the progress made to date, the Company established a management team to Investigate and improve corporate PCB activities. The Company management team was established under a group vice president, and Included s PCB Program Manager and individual Departmental PCB Program Directors. In addition, corporate officials In Legal, Public Affairs and Environmental Affairs set policy on which response groups acted. The response program focused on five areas: improved communication with affected citizens, employes, agencies and the media; revised written spill cleanup procedures; Improved training in spill clean up; revised equipment removal and replacement schedule; and escalated sampling and analysis. The implementation of the complete program, including scheduling of replacement activities, disposal, procedurs revision and training, took approximately two months. Ten thousand distribution system cspscltors were removed or replaced for 1900 locations from mld-1983 to mid-1984. The program cost about 10 million dollara, including new equipment, labor and disposal. HONS 019116 9-5 Company cleanup procedures were rewritten to automatically Include excavation of soils at least thirty cm deep, one-and-one-half meters beyond the visible spill area, and to triple-clean all solid surfaces. Afterwards, soil and wipe samples were taken using the predetermined grid found In the 1981 TSCA Inspection Manual to determine If the PCB cleanup waa adequate. Laboratory analysis of PCB was done within the Company using a twenty-four hour soli drying period, soil mixing, eighteen hour soxhlet extraction, and electron capture gas chromatography. Chromatograph peaks were compared to various arochlor standards by means of linkage to a Nelson Analog to Digital Computer Interface. Split samples were sent to other laboratories to be analyzed for quality control. The process from discovery of spill through Initial cleanup to soil analysis results was typically about ten days. During this time period the excavated site was fenced or roped off. If the sampling results Indicated the site did not meet Company standards, the process was repeated. Associated with the cleanup activity was removal and replacement of equipment with non-PCB equipment to eliminate future PCB spills. Specific line crews were dedicated to both the cleanup and replacement activities. A major part of the program was re-inspectlon of current PCB capacitor spills as well as past spills dating back to 1976 for which there were records. Tble represented more than 200 spill sites where cleanups bad been conducted based on visual extent of the spill. One of the problems In re-evaluatlng these sites Is the variable regulatory requirements for spill cleanup over this time period. Prior to 1978 there were no federal standards for PCB spill cleanup, although the State of Michigan required cleanup of visible traces of polluting substances under its Water Resources Commission regulations. TSCA regulations could be interpreted as setting a spill cleanup limit of 500 ppm PCB In 1978, a 50 ppm limit In 1979, and a "prevention of significant exposure" In 1982. The latter has been interpreted by some to imply any detectable level. In the Company re-lnspectlon process. 57 percent of the spill sites met the applicable criteria for the year In which the spill took 9-6 HONS 019117 place. This Implies that the cleanup of visible traces sas sufficient over half the time. Since the Company had embarked on a recheck program and the most recent criteria was somewhat nebulous, all sites were cleaned to a newly defined operational standard. The Company set the minimum acceptable operating standard that remaining soil could contain no more than an average of 10 ppm PCS with the highest single acceptable value of 25 ppm. The goal was to remove all spilled PCB, but the operating standard would Insure protection of public health. Approximately 13 percent of the sites met this operational criteria after cleanup of visible traces. The data are summarized in Table 1. Although the single highest value of the eleven soil samples taken Is used to evaluate acceptability, this may be inappropriate since many times only one or two of the samples was elevated much beyond background. These elevated levels occurred at the base of the pole holding the capacitor bank. For example, using the spill recheck results for 1981 as representative for all years and applying the criteria to mean soil PCB concentrations, all twenty-six sites would meet the 1978 criteria. Only eight would require a cleanup to achieve average soil concentrations lees than 50 ppm and again this would be primarily due to one or two locations with elevated levels. This Is not unreasonable recognizing that less than five liters of PCB material were probably spilled. Spills did occur, however, more than once at some sites. Documentation of spills Indicated that this occurred tan times thus making the actual number of spills 223. TABLE 1 Number of Re-Analyzed Spill Sites Meeting Various Criteria Prior to Recleaning Spill Year 1984 1983 1982 1981 1980 1979 1976 1977 1976 Company Criteria 2 8 2 3 5 5 4 3 2 EPA 1979 Criteria 1 3 4 6 7 6 3 9 5 EPA 1978 Criteria 4 8 3 12 10 14 7 6 5 EPA 1977 Criteria 1 9 5 5 8 12 13 8 7 Total 8 28 14 26 30 35 27 26 19 Total 213 9-7 HONS 019118 A problem associated with attempting to recheck and reclean over teo hundred spill sites in a rapid fashion is the number of times recleanlng is necessary. Generally two cleanups were sufficient on old sites, that Is. one beyond the original visible trace cleanup when the spill occurred (Table 2). Almost sixty percent were adequately cleaned even for eight year old spills. This is not unexpected as PCB migration is usually slow depending on soil type. One excavation was not sufficient In porous soils or industrial area* where background levels would be elevated due to non-Company activities. An additional spot excavation and cleanup resulted in 61 percent of the sites meeting the operating standard. In some cases as much as seven excavations were necessary, for example, In an Industrial site at an old Junkyard, the excavation went down about 3m and extended about 25m In each direction. It waa obvious In that case that other sources of PCB material were aleo being removed. Usually soil removals beyond the second excavation concentrated on one or two small areas or "hot spots". This strategy was therefore successful in meeting the goals of being effective with short term customer disruption. The time period from initial excavation through completion for 85 percent of the sites was less than one month. TABLE 2 Number of Soil Excavations at PCB Capacitor Spill Sites Necessary to Meet Company PCB Criteria spin Year 1964 1983 19(3 1991 1990 1979 1978 1977 1976 Number 123 250 699 28 1 3 14 3 3 18 6 2 15 11 2 12 7 3 13 4 266 4 >4 10 13 30 60 12 52 33 51 41 Total 8 28 14 26 30 35 27 26 19 9-8 MONS 019119 Managing a PCB Fire Decontamination by Chris Kwoka SOS Environmental Engineering A successful philosophy for decontaminating a building contaminated by a PCB transformer fire involves general knowledge of: 1.) the type of incident, 2.) how the contamination spread, 3.) unit operational tasks governing the clean-up. The first two elements are quickly ascertained. The type of transformer inci dent, generally either soot producing or pressure venting, can be visibly deter mined through a simple Inspection. Though it is often difficult to explain how the contamination was spread throughout the building. The source of the contami nation is easily identified by locating the transformer vault. The third element, unit operations, involves the individual tasks associated with the physical decon tamination of the building. This presentation focuses on these unit operational tasks specifically, tasks directly associated with decontaminating a building interior, their priority, end how they relate to an actual decontamination we discussed. The unit operations involved in decontaminating follow a logical pattern. It is the reverse of the transmission route of the contamination. The individual teaks according to priority are: - Removal of gross contamination - Control of the building Interior air flow petterns - Demolition and removal of contents that cannot be decontaminated - Decontamination of the transformer vault - Decontamination of the HVAC system including ductwork end sir 9-9 HONS 019120 handling units - Decontamination of structural surfaces, ductwork and piping exterior surfaces - Content decontamination and document restoration There are additional support tasks not directly related with the actual decon tamination such as supply administration, health and safety, and sampling and analysis that play an essential role. These support tasks will not be addressed here, as they will not be addressed in this paper. The first unit operational task is the removal of gross contamination. Standing oil or heavy soot deposits not removed during the emergency response phase should be isolated and contained as quickly as possible. This involves absorbing any oil spilled on the vault or adjacent rooms and placing the saturated absorbent or any heavy soot deposits into containers for disposal. The second and most Important operation is controlling the air flow patterns within the building. This is because significant redeposition of airborne conta minants can occur when the air within the building is not controlled. It was observed at the One Market Plaza incident that decontaminated surfaces could only be cleaned to a plateau level which was above the established criteria until the contaminated air flow patterns were controlled by evacuating air through an acti vated carbon exhaust system. Once the negative air system was in place, two noticeable results occurred - the levels of contamination in the air started to steadily decrease and surfaces could be successfully cleaned below the criteria without being recontaminated. This philosophy was applied to the Sants Fe decontamination project st the very start of the decontamination work. Approximately 40,000 cfm of air was eva cuated from the 700,00 ft^ Sants Fe highway Department bullldng through four separate vapo-phaaa activated carbon treatment systems, this provided approximately 9-10 HONS 019121 three air changes per hour through the entire structure. To accomplish this* the building was divided into 2ones with barriers placed in strategic locations to enhance the control of the air flow patterns. Once the systems were operational, the PCB air levels within the building were reduced from 8 to 42 ug/m3 PCfis to <0.1 to 0.4 ug/tn3 within about four weeks. Surface decontamination was achieved without redeposition or recontamination. The third task is removal of building contents which cannot be cleaned, for example, porous surfaces such as drop ceiling tile absorb PCB and Dloxin/Furan contamination. These surfaces must be physically removed and discarded. Items which are not coat affective to decontaminate such as, note pads, pencils, staplers, pencil holders, desk calendars, etc. should also be removed. The transformer vault must also be addressed. The surfaces in the transformer vault are the most contaminated because they are the closest to the source. Generally, the only successful way to decontaminate the vault is to remove the layer of material from the wall, celling and floor surfaces if they are porous, metal and non-porous surfaces can then be decontaminated by similar methods as described in decontaminating ductwork. Next, the building heating, ventilating and air-conditioning system can be divided Into separate tasks - cleaning the ductwork and cleaning the air handling units. If the ductweefcis large enough to physically allow a technician to enter it, the decontamination process involves initially vacuuming the ductwork followed by a detergent washing and rinsing and a detailed final cleaning. This final cleaning involves using rags on a one-wipe-throw-away basis for cleaning metal surfaces. For ductwork with dimensions too small for a technician to enter, another stra tegy for decontamination must be used. One method is to cut access holes about 9-11 HOHS 019122 every four feet - close enough together to allow a technician to clean all of the ductwork by hand. A second approach is to access the ductwork at strategic locations such' as elbows, turning vanes and slide dampers and running foam plugs or "pigs" repeatedly through the ductwork until it is clean. The foam plugs are used for both washing and rinsing. Once the interior of the ductwork is decontaminated, all of the exterior sur faces must be cleaned. Decontamination starts form the ceiling and proceeds downward with all surfaces wiped with detergent end thoroughly rinsed using clean rags with each rinse. Contents and personal effects can be inventoried and decontaminated simulta neously with the structural decontamination. Hard case items such as desks and filing cabinets are decontaminated in a manner similar to structural surfaces. Office equipment* paper, documents, end miscellaneous desk Items can be effectively deocntamlnated using freon based technology. The final unit operation is decontaminating the floors. Plastic that was ini tially laid la removed and the floors are cleaned according to their surface type. In summary, past experience has shown that there are a series of unit operations Involved in decontaminating the interior of a building. However, one of the moat Important aspects of decontaminating a builidng is the necessity to control eir flow petterna of contaminated air within the building. This can be done by evacuating air from the building from strategic locations and exhausting the sir through a vapor-phase activated carbon treatment system. This philosophy has s twofold benefit. The negative sir treatment system effectively decontaminates the sir within the building and permits the systematic decontamination of surfaces within the building without the fear of recontamlnating surfaces that have already been cleaned. 9-12 HONS 019123 Expanded Abstract for PCB Seminar MANAGING CLEANUP OF MAJOR PC0-CONTAMINATED SITES Authors: Nicholas A. Speed, uenny S. Parker, William t. Cllster Sites contaminated by major discharges of polychlorinated btphenyls (PCB) are usually distinguished by the magnitude of Investigation and cleanup efforts required and the nature of laws, regulations, and policies applicable to them. This paper, derived from our draft guidance manual as developed for EPKI In December 1984 for remedial action at such sites, provides an overview of PC8 concerns and regulatory policies applicable to major PC8-contam1nated sites. It also presents an approach for managing remedial actions necessary for their cleanup. Few classes of chemicals are subject to the degree of regulation accorded PCBs. because of the complexity of these regulations and the extent and nature of court review and Interpretation, the regulatory policies and standards applicable to PUB cleanups are uncertain and variable. Establishing acceptable criteria and cleanup levels for a specific site may Involve extensive work with several agencies (Including the Environmental Protection Agency (EPA)), each with differing requirements. Successfully resolving the critical question of "How clean is clean enough?" for any given project site Involves detailed consideration of sitespecific conditions and can be both difficult ana expensive. Managing the correction activities at a major PCB-contamlnated site Is discussed by addressing remedial activities as three dynamic and Interrelated phases:1 1. Site Investigation and Problem Definition 9-13 HONS 019124 2. Correction Planning for Problem Resolution 3. Implementation and Verification of Corrective work Site Investigation Is a dynamic process since new Information, generated as the work progresses, often alters the Initial assessments which were based on earlier data. Site Investigation begins with problem Identification based on eklstlng and available Information and moves progressively toward problem definition. This work progression should often be staged to ensure adequacy of the Information base while minimizing overall project costs. When the site problems and site conditions have been adequately defined, decisions must be made about the specific measures to be applied to problem resolution. Numerous options can be considered for technical application depending on the nature of the contamination problems and the objectives and requirements of the PCb cleanup. Screening or applicable measures occurs as the understanding of the problem progresses. The screening and evaluation of alternatives for correction of specific problems and the selection of corrective measures to be Implemented on a specific site Involve decisions which are critical to project success. The basic criterion for selection in accordance with current ERA and judicial Interpretations of the Toslc Substances Control Act (TSCA) is the achievement of the lowest level of cleanup practicably attainable through the normal use of available technology. In accordance with this criterion, the selected plan will represent a balancing of numerous costs and benefits. After selection of a plan which the user determines to represent 'bestpracticable" correction of his PCB contamination problem, the plan can then be developed In a format suitable for submission to the regulatory agency(s) as the 9-ia MOHS 019125 user's Recommended Plan ot Corrections for the site. This Plan is a proposal which should effect the following actions: 1. Summarize relevant site information. 2. Define existing PCS problems and site conditions. 3. Evaluate alternatives for resolving existing PCB problems. 4. Define recommended corrective actions and their impact, b. Provide a preliminary plan for Implementation. 6. Solicit regulatory agency acceptance of the Plan. In general, the user's Plan should not depend on reference to other reports. Since the main objective of this Plan Is obtaining regulatory concurrence with the user's proposed actions* all Information critical to decisions by agency personnel should be Included In summary form or appended. Submission of the user's recommended plan to Involved regulatory agencies can be considered the start of the Implementation phase. Acceptance of the corrective action plan by the lead agency* as well as all other agencies having significant regulatory Involvement In the project* is an essential milestone which must be achieved prior to any planned remedial work on the site. With few exceptions, regulatory acceptance of the correction plan will be limited to agreement-1nprlnclpel" and conditioned upon actual achievement of stated cleanup or correction objectives* which can be demonstrated by verification sampling and monitoring both during and following site remedial work. Consequently, all project risks remain with the user and must be mitigated by careful completion of Implementation planning, close management of construction work* and verification of results. Plan finalization in preparation for construction Involves completion of several elements outlined in the Recommended Plan of Corrections: 9-15 HONS 019126 1. Confirmation of chosen contracting strategies. 2. Development of contract documents for contracted work. 3. Identification and prequal1flcatlon of potential contractors. 4. Obtaining necessary permits and approvals. Because of the Inherent complexity or major site contamination problems and the usually similar complexity of the corrective measures applied to their resolution, careful management of construction activities Is crucial to successful project completion. The user retains general authority over the work and must commit appropriately qualified and designated personnel to ensure that the construction work is completed by the contractor In accordance with contractual requirements. Verification of the effectiveness of implemented corrective actions may represent the end of major construction activity on a site, but It may also extend long Into the future. Where long-term monitoring Is Involved, successful completion of the cleanup project may be judged over a period of time In terns of quarterly or more frequent data with these data being used to interpret the degree of success of the corrective actions. MQNS 019127 9-16 PCB CAPACITOR FIRE AT IRgQ'S HIGH VOLTAGE LABORATORY AND SUBSEQUENT DECONTAMINATION D. Train, A. Chanberland, D. Dupont, J. Cestonguay IHTIODUCTIOW On Novenbcr 20, 1984 a large power transformer vaa being taatad lnaldt tha Annas of IttQ'a High Voleaga Laboratory. Pare of tha taat circuit conalatad of a capacitor bank which vaa located on an uppar floor Inalda tha building. During tha taata, an explosion occurred lo eha capacitor bank. This Initial explosion started a firs and further explosions at fairly regular intervals within tha capacitor bank. Tha fire burned for about six hours before It vaa eventually extinguished, but not before it had destroyed two thirds of tha capacitor bank and eaueed tow damage to tha laboratory roof and part of tha building structure. For the first two hours tha smoke, which was vary black and dense, was contained within tha building but after thee It escaped to the outside by Beans of a hole which had burned through the roof. Tha capacitor bank comprised both mineral oil and aakaral insulated units. The estimated volumes of oil and aakaral which ware burned wars 2580 L and 670 L respectively. The day after tha fire, an Inspection of the Interior of the building showed that a fine deposit of soot had settled throughout In a oonunlform fashion. Typical analysts of soot staples Indicated approxlaately 2500 ug/g of PCB-1242, 0.6 ug/g of 2,5,7,6 TCDF and 0.1 ug/g of total TCDD. Water staples froa the baaeaent vert also analysed and tha aaxiaua concentration of PCBa found was 1250 ppb of aroclor 1242. Owing to the level* of PCDPs found, tha building, representing a total voluae of 500.000 a1, sad Its cooeanta were considered too contaalnated to peralt an laeadiste return to normal operation. A major elaan-up, repair and decontamination program was organised in order to resume normal activities in the shortest possible time. CHAlMJf AMD KEPAlt 0BCAMI2ATI0N Since no previous experience of building contamination on this seal# axletad anywhere in Canada, a dean~up and repair organisation vaa established by drawing upon eha expertise which already existed in Hydro-Qugbae in eha field of nuclear generating station construction. A mandate for the nanagenent and execution of the 9-17 HONS 019128 repair vork and decontamination of the building end contents wee given to the Engineering and Construction department of Hydro-Qutbee. The responsibilities of this group included: preparation of detailed vork schedules and cost estimates; engagement and co-ordination of activities of the various contractors; control of costs, time and materials; engineering and quality control including the measurements of contamination levela; establishing and supervlaing of safety practices; overall aupervlalon and inspection of all aspects of the work; and disposal of contaminated materials. A Coordinating Coaelttea was also set up with the following responsibilities: detsmlnatlon of priorities for the repair and decontamination work; establishment of suitable acceptance criteria for the contamination levels of surfaces and air; negotiations with unions, environmental agendas and governmental aafety and health authorities; communications with the media (press, television, ate.); establishing of medical examinations and periodic checks for the clean-up crew.This Committee worked in close liaison with the Engineering and Construction team. An Evaluation Committee was created to follow the progress of deconteminetlon by means of regular checks and interpretation of the results of the analysts with, whan nacaaaacy, racoemendatlona concerning acceptance or rejection. Stringent sampling procedures having detection limits 10 times lower than the acceptance criteria were set up. The sampling and subsequent enelyeee were performed by en independent laboratory, thereby avoiding conflicts with unions, environmental agendas and governmental safety and health organisations. Both ths Construction group and the Evaluation Colttee reported to the Coordinating Committee* There were regular meetings with the representatives of tho unions involved to Inform thorn of tho nmturs of the contamination, the medical aspects, the precautions required, etc* and all communications with tho media wore channelled through only one person The human and public relations aspects of the operation wore considered to bo of prime importance and contributed significantly to tho efficient progress of tho entire project. ACCEPTANCE CRITERIA Tho acceptance criteria for re-entry to the building are similar to those developed by Kim and Hawley (lj* They are baaed on a maximum dally intake of 2 pg/ kg-day of 2,3,7,g TC00 or equivalent and are 10 pg/m* and 25 ng/m2 for air and eurfaet contaminations respectively. In practice, both air and surface contamination levels vara measured and evaluated graphically. If eha points plotted lay within 9-18 HONS 019129 the combined acceptance Halts, re-entry without protsctlvc clothing wss permitted; otherwise, furthsr decontamination wss required. Th# so-called* "dioxin equivalent" level wee established as follows; Dioxin equivalent* (CDDs) (CDPs) (CPBs) where: CDDs - (2,3,7,8 - TCDD) + (total PeCDD)/5 CDfe (total (TCDP PsCDF HeCDD/10 CBPs - (2,3,6,7 - TCBP) (total PeCBP)/2 During tha Intermediate classing stages the dioxin equivalent level on eurfaees was evaluated approxlaately by measuring the level of PCB 1242 and dividing by the ratio R defined as PCB 1242 concentration on surfaces R " dlofcln equivalent concentration and a value of R 1000 was deteralned from the aany measurements aade on soot samples. MEDICAL CONSIDERATIONS Medical protocols were established to evaluate clinical manifestations of toxicity to PCBs and furans of personnel who either were exposed to smoke during the fire or participated In the decontamination afterwards. These protocols consisted of the determination of any previous exposure to PCBs end the extent of exposure during the fire, updating of personal clinical history and complete Individual medical examination. Including biological tests comprising complete blood count, liver function, cholesterol, triglycerides, blood, plasma protein electrophoresis and PCB plasma tests. No significant health problems have been attributed to workers or members of the clean-up crew exposed to PCBs and/or furans. METHODS OP CLEANING AND DECONTAMINATION Various cleaning methods were employed to decontaminate the building end the thousands of components sod pieces of equipment. Some of the methods were: highcapacity vacuum cleaners for the soot, solvent applied with compressed air nossle and rinsed with water, solvent alone on some electric penels, use of Preon TP for electronic instruments and documents, and removal of surface layers of porous materials such as fibreglass, gravel, etc. The effectiveness of the different techniques Is indicated in Table I. 9*19 HONS 019130 TABU X Contamination levels before and after cleaning for varloue decontamination techniques TECHNIQUE .. Vacuun High-pressure watar Jtt " Lot^preesure water Jet plus eolvenc Hand wipe with cloth plus solvent Freon TF layer removal (fibreglass) PCS 1242 contamination level "" Before cleaning After cleaning 51^.0 yg/i2 3.70 ug/a` 230.0 " 37.00 " 160.0 " 68.00 - 373T5 " "' 6.0 " 12 x 10.0* ' 33.00 " 108.0 " ------------------------- 37TB-- ---------------------------------- r0J.0g3--."---------------------- 56.0 " 7.90 " 68.0 " IJ3T5 " '.i u*/l 15.5 " 8.70 " ................................TT55--** -- 1.60 u/( 2.00 " ~ Items of protective clothing such aa hate, seeks, gloves, boots, etc. were decontaminated ec the end of each shift end refused. The cyclohexane used for this work wee purified by dletlllatlon end ra--cycled. All water used for cleaning was filtered and purified prior to dlsposel. Solvents In the water were recuperated by distillation. WASTE DISPOSAL. All contaminated residues collected froa filters and distillation aystems were stored In sealed druae. Other contaalnated materials were also stored in sealed druae which were then sent to a special storage site to await eventual destruction when such fsellltiss become available in Qutbec. RgmiHCW (lj Kin, N.K. and Hawley, J. "Re-entry Guldllnes Blngheapeon: State Office Building," Docoaent 0549P, Bureau of Toxic Subatance Aeaeseaent Oivlalon of Health Risk Control, Hew York State Department of Health, 1984. (2) Beilin, J.5, end Bernes, D. "Health Retard Aeeeeaaent for Chlorinated Dloxloe end Dlbantofurane other than 2,3,6,7 TCDD," SPA Raport No. JB02062, Septtaber 1984. 9-20 HONS 019131 GUIDELINES MO ALTERNATIVES FOR PCB SOIL-SAMPLING PROGRAMS Warren G. Hansen Thomas L. Johnson Karen A. Sahatjlan Tetra Tech, Inc., Bellevue, WA INTRODUCTION During the past several years, there has been growing concern snong utilities and other PCB users about the quantity of sampling that Is necessary for proper management of spills onto soils. This concern was generated. In part, by closer scrutiny by regulatory agencies, the tightening of cleanup requirements, and the high cost of sample collection and testing. For small spills onto soil froe single pieces of equipment, utility representatives have recommended a performance-based cleanup standard^). This approach encourages rapid response and eliminates the need to wait for sample analytical results (sometimes as long as 3 or 4 days). However, for larger, more complex spill episodes, soil sampling, as demonstrated by Industry practice, remains a significant part of the response effort. Examples of sampling Include old storage areas, spills to watercourses, and transformer salvage sites. Utility concern for these types of sites is focused on the extent and Intensity (and hence cost) of sample coverage, the sampling design (l.e., grid versus random grab samples), sampling methods and depth, and pre-cleanup versus post-cleanup (confirmation) sampling. The purpose of this paper Is to provide guidance to the utility representatives faced with the more complex cleanup situation. As a consultant to a group of public and private utilities Involved In a voluntary cleanup, Tetra Tech, Inc., recently completed a remedial Investigation and feasibility study at a transformer salvage yard In the Pacific Northwest, as called for by the utility group's consent agreement with the U.S. Environmental Protection Agency. This paper Is based on the experience gained during that effort and should be useful to others who desire to retain technical and budgetary control over the management of larger spills. Why Sample? The most obvious reason for sampling Is to determine the extent of contanlnatlon, thenby defining the general dimensions of the problem (area and depth) and permitting the proper location of barrlcadas, fencas, or other delimiters. Depending on the specific situation, discharge Into storm sewers, drains, or watercourses may 9-21 MQNS 019132 need to be determined. For larger spills, sampling Is valuable In defining the volume of soil that must be ultimately treated or removed. In certain Instances, sampling may also be useful In Identifying contaminants that may have been contributed by other sources or site users. DEFINING THE PROGRAM'S OBJECTIVES In addition to defining the extent of contamination, a sampling program may also Include these objectives: a Detection of related contaminants (dloxlns/furans and askarel carrier solvents) If the case warrants a Identification of "hot spots" (smaller areas of high concentration In the site's Interior) requiring Immediate attention or special removal/disposal procedures. DESIGNING THE PROGRAM The proper design of the sampling program Is critical to Its success and usefulness of Its results over the duration of the cleanup effort. Each plan should be sitespecific, and may also be Influenced by regulatory agency concerns. Although the general objective Is to design a program that 1$ sufficiently representative of the site, actual experience has shown that budgetary limitations will often be a controlling factor. A typical procedure Is as follows: e Estimate the limits (area) of the site through Inspection and accounts of spills and past operations e Select a sampling technique, or combination thereof (l.e., rectangular grid, triangular grief(2), or grab sample) Including sampling at depth. If necessary - t For stations on a grid systan, select a "starting point' grid size and calculate the number of samples for surface soil sampling as follows; --rectangular grid: ,, . Total Area (ft2) S2 (ft2) --triangular grid: N . x Total Area (ft2) T* (ft5) where: S Distance between stations for rectangular grid T Distance between stations for triangular grid. A program cost-estimate can then be developed based on a dally "production* rate and unit costs for labor, supplies, and sample analysis. An additional percentage may also be calculated for program managmeent costs. For a two-person crew (one 9-22 HONS 019133 sampling, one receiving and recording) surface-soil sampling dally production rates of 50-70 samples are typical. The cost of supplies should take Into account the rigid requirements for equipment cleanliness, decontamination, and personnel protection. . If there Is reason to suspect penetration by PCBs, sampling for PCBs at depth should be carried out. Usually, PCBs do not Infiltrate any significant distance Into soils, particularly If the soils have a high organic matter or clay content. At the case-study site, penetration was caused by regrading of contaminated surface soils (for erosion control) and by chronic spills of PCB fluids directly onto the soil under a storage tank valve. Air-driven split-spoon samplers proved extremely efficient for soil sampling up to a depth of 4-10 ft. A useful technique was to archive (store) the deeper samples and analyze them only when the shallower samples showed elevated PCB concentrations. Sample Testing Hand-in-hand with rigid quality control requirements for sampling Is the need for careful analysis. Mien dealing with a comnerclal laboratory, one must accurately communicate the desired analytical technique (total PCBs or specific Isomers), the necessary detection limits, and quality assurance measures (duplicate analysis, blanks, spikes). Guidelines regarding these measures have been developed by Tetra Tech(3). Data evaluation Upon receiving results from the laboratory, each value should be checked to be sure It was reported at the specified degree of accuracy. Extraneous or unrealistic results should be noted and checked against site conditions and visible characteristics of the sample. Results of analyses for test standards (samples of known PCB concen tration used for calibration), duplicates, blanks, and other quality-assurance samples should be assessed to determine the overall quality of the analytical effort. Program Costs The preparation of the feasibility study for cleanup of the salvage yard site highlighted the trade-off between sampling program costs and the actual cost of soil removal. For this large site, a rectangular grid system of surface soil sapling and subsurface borings was established with 35-ft spacing between stations. Because contaminants were discharged throughout the area and further mtxed In by constant regrading. It was assuaad that the result of each sample was representative of the contaminant level within the entire grid. Therefore, the goal was to structure 9-23 HONS 019134 a grid system that Minimized the required samplIng/teatlng costs, and at the same time condemned the smallest amount of uncontaminated soil within each grid. Within practical limits, the soil excavation process may proceed on a grid-by grid basis. The lower grid-size limit Is defined by the width of a bulldozer blade (approximately 12 ft). Assuming an upper limit of approximately Soft, an analysis of sampling coverage (and program costs) can be compared to the resulting amount of soil that must be removed. For the case-study site, one major goal was to accurately define the edge of contamination. The ability of a grid network to do this was based on the distance between stations and the entire area Involved. For perimeter stations, this edge may lie Immediately beyond the outer station showing elevated concentrations, or It may extend beyond the station's grid. In the former case, almost half the grid will be uncontaminated, yet still be condemned. This potential "worst-case" extra soil removal Is converted into a cost and compared to the costs of alternate grid size programs. The calculation for an Idealized (square) site using a rectangular grid system Is as follows: a sampling costs S/sample x -- Sz versus perimeter soil excavation and disposal costs $/yd3 x 0.074 iSi/tiP where: A site area (ft2) S distance between stations (ft) P - assumed removal depth (ft) Tetra Tech Is continuing to evaluate these cost relationships for actual sites as part of Its hazardous material management services. Since sampling at the case-study site, Tetra Tech has completed a cleanup feasibility study and design drawings/specifications for site work. REFERENCES 1. Memorandum on Spill Cleanup Policy to the USWAG Steering Committee. Weld, Harkrader A Ross. October S, 1984. 2. 0. F. Parkhurst. 1984. Optimal sampling geometry for hazardous waste sites. Environ. SCI. Techno!Vol. 18, No. 7. ' 3. Tetra Tech, Inc. Quality Assurance and Quality Control Guidance for 301(h) Monitoring Programs (Oraft). Prepared for U.S. EPA, Washington, DC. April. 1985. 9-24 HONS 019135 VERIFICATION OF PCB SPILL CLEANUP BY SAMPLING AND ANALYSIS Daniel T. HeqRCT. Richard A. Levy, and John H. Smltn U.S. Environmental Protection Agency 401 M Street, S.W. Washington, DC 20460 Bruce A. Booner, Mitchell 0. Erickson, Stephen E. Suenson, Gary L, Kelso, and J. Kay Turman Midwest Research Institute 426 Volker Boulevard Kansas City, Missouri 64110 Oavtd C. Cox and Bradley 0. Schultz Washington Consulting Group 1626 1 Street. N.W. Suite 214 Washington, DC 20UQ6 The U.S. Environmental Protection Agency (EPA) Older the authority of the Toxic Substance Control Act (TSCA) Section 6(c) and 40 CFR Section 761.60(d), has determined that polychlorinated Diphenyls (PCB) spills must be controlled and cleaned up whenever the spill Incident poses a substantial risk to hunan health or the environment. The Office of Toxic Substances (OTS) mas reguested by the Office of Compliance Monitoring (OCM) to provide written guidelines for a method to verify the cleanup of PCB spills. Bnphasis Mas placed on the sampling design and sampling and analysis methods to be used for the verification of the spill cleanup. Three reports have been prepared. The first consists of a review and technical evaluation of the available documentation on PCB spill cleanup. Contacts were made with EPA regional offices and Industry experts. This first document Included the preparation of preliminary guidelines for the cleanup of PCB spills. The document was aimed at providing guidance In all aspects of spill cleanup for those organizations which do not already have working PCB spill cleanup programs. The second report. Intended primarily for EPA enforcement personnel, outlines a specific saapllng design. It also makes recommendations for sampling and analysis methods to be used to determine compliance Mlth EPA policy on the cleanup of PCB spills. The sampling and analysis methods can be used to determine the residual levels of PCBs at a spill site following the completion of cleanup activities. ' 9-25 HONS 019136 Although the methodologies outlined In this docunent ere applicable to PCB spills In general, specific Indlcents may require special efforts beyond the scope of this report. Future changes In ERA policy may affect some of the Information presented In this docunent. The third report Is a field manual which provides detailed, step-by-step Instructions on how to complete the field sampling for cleanup verification. This manual addresses field sampling only, and does not provide Information on laboratory procedures. The types of field sampling situations covered In this manual are those typically found when a PCB spill results from a capacitor or transformer spill. The EPA has established requlronents for the sptlled PCBs and materials contaminated by the spill. Under TSCA regulations [40 CFR 761.60d], PCB spills are viewed as Improper disposal of PCBs. Although specific PCB cleanup requlranents are not yet established In the TSCA regulations, each regional administrator Is given authority by policy to enforce the adequate cleanup of PCB spills to protect human health and the environment. Due to regional variations In PCB spill policy and the present lack of a national PCB cleanup policy, PCB cleanup activities have not been standardized. Individual companies owing PCB equlpnent and contract cleanup companies have developed their own procedures and policies for PCB cleanup activities keyed to satisfying the requirements of the appropriate CPA Regional Office. In addition, the EPA Regional Offices typically have provided suggestions for companies unfamiliar with PCB cleanup. PCB spills are generally viewed as unique situations to be evaluated on a caseby-case basis by both the PCB equlpeent owter (or his cleanup contractor) and the EPA Regional Office. However, a general framework Is often used to approach the problem. Most cleanup activities Involve quick response, removal, and cleaning, of suspected contaalnated material, and post-cleanup sampling to docunent adequate cleanup. Major considerations Involved In the cleanup process include minimizing environmental dispersion, minimizing any present or future nuean exposure to PCBs, protecting the health and safety of the cleanup craw, and properly disposing contaminated materials. A sampling design Is proposed for use by EPA enfore ament staff In detecting residual PCB contaninatlon above an allowable limit after cleanup of a spill site Is completed. The proposed design Involves sampling on a hexagonal grid centered on the cleanup area and extending Just beyond Its boundaries. (Aildance Is 9-26 HONS 019137 provided In the field Manual for centering the design on the spill site and for staking out the sampling locations, taking possible obstacles Into account. Compositing strategies In which several samples are pooled and analyzed together, are recommended for each of the proposed designs. Since an enforcenent finding of noncompl lance must be legally defensible, the sampling design snphasizes Che control of the false positive rate, the probability of concluding that PCBs are present above the allowable limit when, in fact, they are not. Sampling and analysts techniques are recommended for PC8-contam1nated solids (soil, sediment, etc.), water, oils, surface wipes, and vegetation. A number of analytical methods are referenced; appropriate enforcanent methods were selected based on reliability. Since flC/ECO is a highly reliable, widely used method, and is Included in many standard methods, it is a primary recomnended method for most spill situations. Secondary methods may be useful for confirmatory analyses or for special situations when the primary method is not applicable. Quality assurance IQA) must be applied throughout the entire monitoring progrew. Quality control (QC) measures and sample QC should be stipulated in the QA plan. They may Include protocols, certification and perfonnance checks, procedural QC, sample QC, and sample custody as appropriate. The work was supported by the U.S. Environmental Protection Agency under Contract NO. 68-02-3938 (to MRI) and subcontract to Battelle Coluabus Laboratories, Subcontract No. FA138(8149)A3A, EPA Contract No. 68-01-6721. REFERENCES MRI Report. Cleanup of PCB Spills from Capacitors and Transfonaers. Draft Interim Report No. 1. Revision No. 1, EPA Prime Contract NO. 68-02-3938, January 9, 198b. MRI Report. Verification of PCB Spill Cleanup by Sampling and Analysis. Draft Interim Report No. 2. EPA Prime Contract No. 68-02-3938, May ), 1986. MRI Report. Verification of PCB Spill Cleanup by Sampling and Analysis. Draft Interim Report No. 2, Revision No. 1, EPA Prime Contract NO. 68-02-3938, June 6, 1986. HR1 Report. Verification of PCB Spill Cleanup by Sampling and Analysis. Interim Report No. 2, EPA Prime Contract No. 68-02-3938, August 9, 1986. MRI Report. Field Manual for Verification of PCB Spill Cleanup. Draft lNterim Report No. i, EPA Prime Contract No. 6&-02-MJ8, June 27, 1986. USEPA. Verification of PCB Spill Cleanup by Sampling and Analysis. EPA-560/586-028, August, 1986. 9-27 HONS 019138 Risk Assessment Developments for PC8/PC0F Decontamination Projects Richard l. Wade, Ph.D.* M.P.H. Oirector, Risk Management Services . IT Corporationl815 Arnold Orive Martinez, CA 94553 Increased recognition of the spread of PCB's and PCDF's from transformer rat lures has resulted in Industry and government attention to preventive measures as well ascloser attention to decontamination efforts. Two critical questions which continue to surface after each of these failures which sometimes result in the spread of PCB'S and sometimes PCOO's/PCDF's is the degree of exposure to individuals and the degree of contamination necessary to allow the facility to return to unrestricted use. Two quantitive methods are now being used to help address these questions: (1) Risk Assessment: To evaluate the degree of decontamination necessary for reoccupancy of a building or reuse of equipment. This technique can be used to generate "safe" reentry criteria. This technique has been used to set soil, air, water, surface reoccupancy guidelines by both State and Federal regulatory agencies as well as by several utilitiesand manufacturing corporations whoai have developed site specific guideline proposals for government approval. (2) Exposure Assessments:To quantatively evaluate potential exposures and resulting risk from people whom had opportunity for exposure to PCB's/PCDF's at the time of one of these events. This technique has been used to quantify the risk of individuals with "exposure" opportunity. This paper will explore the most recent applications of these techniques and the state of the art in there use. MOHS 019*39 9-28 USEPA has Issued generic proposed guidelines on the use of and format for both risk and exposure assessments (A), (8), (C). These guidelines are generic. Significant differences exit between assessments developed by various parties, for the purposes of discussion this paper will breakdown some of the critical assumpt'ons made In the derivation of acceptable risk related to (PC3-PCCF potency and exposure). Today there is no scientific agreement as to what constitutes an acceptable non-effect level of exposure. Using the formula: ?.g X g - potency X * exposure X has been determined to range from 2.0 pg/kg/day to 0.06 pg/kg/day. (see Table I). EPA uses the 0.06 pg/kg/day 2,3,7,8- TCD0 equivalents although several states have accepted 2.0 pg/kg/day. (A) Federal Register Friday, November 23, 1984, Proposed Guideline for Carcinogen Risk Assessment. (8) Federal Register Wednesday, January 9, 1985, Proposed Guideline for Health Risk Assessments of Chemical Mixtures. (C) Endangerment Assessments for Superfund Enforcement Actions, Hogan et al. Support Branch Office of Waste Programs Enforcement, vs EPA 1984. Address request for information to WH-527, 401 M Street, SW, Washington, O.C. 20460. There Is also no agreement by regulatory agencies on the acceptance of risk, although EPA has accepted 1 x ltr risk In several risk and exposure assessments. Toxicity Oata: There has been very little change In the last 3 years - most scientist, do however, agree that 2,3,7,8- TCOO Is most potent as evidenced by animal card nogenIcty testing, cell keratlnlzation, and a enzyme inhibition blsassa/s. As the ring structure becomes Increasingly saturated with cl atoms the acute toxicity appears to decrease. Likewise, the cl atom in the 2,3,7,8 positions appears to be a critical determinant In acute toxlclties (C), (0). The exact mechsn'sms of acute 2,3,7,8 toxicity are still largely unknown. The dlbenzcfurans are considered to be significantly less toxic than the dioxins (0.1 0.33) x 2,3,7.8- TCOO. The only two lsomes of TCOO's that have undergone complete bisassay are 2,3,7,8TCDO and two congeners of hexachlorlnated dlbenzo dioxins (1,2.3.6.7. and 1,2,3,7,8,9 HxCDO). These hexa Isomers were on subsequent analysis found to be contaminated with 0.031 TCOO. 9-29 HONS 019140 Inh*latIon Rates: In evaluating opportunity for exposures most risk and exposure assessments consider 23 r of air per 24 hour day on the average. This nueper can however vary slgnlfIcantly with changes In duration of exposure opportunity and with work practices. Environmental Decomposition Factors: Photodegradation of 2,3,7,8- TCDO In areas of Intense sunlight has been demonstrated to be significant (C). However, eost risk assessments done to date place a half life from 5-10 years on PCB-PCOO-PCOF's found Inside buildings or In areas on nondlrect sunlight. (C) R. J. Koclha et al - Comparative Toxicity and Biological activity of Chlorinated Olbeneo-P-Oloxlns and Chlorinated Dlbenao Furans Relative to 2.3.7,8- fttO. Chemosnhere Vol. 14. on. S49-8BO . lags. (D) Eve Roberts - The 4h Receptor and Dioxins Toxicity From Rodent to Human Tissues, themosphere Vol. 14, No. 6/7, pp. 661-674, 1985. 9-30 MONS 019141 Table 1 ENVIRONMENTAL LEVELS OF TOTAL PCDD's/PCDF's (1) Air Inside Levels NO - 10,000* pg/m3 Notes Inside building 30 days following PCB transfomwr fellure. Outside Water stream .09 - 1.3 fg/m3 1 ng/mJ - 3 ug/m Incinerator Emissions ND - 440 ng/n* After Sllvex spraying (35 days). (2) Water Groundwater Most studies report NO Surface Runoff 0.05-0.06 ppt 42 days after SIWex application1 (6) (3) Soil (A) Surfaces (NO (<.l ppb) - 1800*) PPb <01 rvg/m2 - > 2000 ng/m2 (5) Oust See Incinerator above (Some buildings dust and others vapor phase contamination predominate) () Oils PCB oils NO - 40 ppm (total PCOO/PCOF)4 (?) Plants NO - 40 ppb2 Most studies shows no plants uptake from contaminated with low leve's of 2,3,7,8- TCOO (Possible Stveso exception) soils (8) Solid Haste NO - 440 ng/m3 (totals PCOO/PCOF Incinerator Feed Stock 1. Ambient Water Quality Criteria for 2.3.7.8- TCDO - page C-2, fiSEM 440/5-W3S01 ----------------- ----------- 2. 1810 f2 3. Rappe C. et al Formation of Polychlorinated Oloxlns and Olbentofuran In Municipal and Hazardous Waste Incinerators. Presented at the 103 seminar of F&J Seri Isa, Oloxlne. . IT sampling of PCB oils. . Kleopher R., 2,3,7,8- TCDO Contamination In Missouri, Chemosphcre Vol 14, No. 6/7, pp. 739-744, 1989. 7. Toslne H.M., Levels of PCOO/PCOF and Other Chlortntated Organics 1r) Municipal Refuse. Chemosphere Vol 14. No. 6/7, pp. 821-827, 1985. 9-31 HONS 019142 Table 2 TISSUE LEVELS PCDD/PCDF's Cattle Bovine Milk Levels 4-40 ppt fet* <40 ppt to 7.9 ppb Human Milk NO (<1) to 805 ppt Notes Cattle grazing on contaminated soils. Seveso: Normal Sllvex application rates did not result In any significant Increase In milk 2,3,7,8TCOO levels. Fish NO - 695 ppt (Significant variation depending on location caught). Human Adipose 5-10 pet Tetra Dioxins (5) (10) Tissue 600-8CO ppt Octa Oloxln 17 ppt Penta Furans 17 ppt hexa 1} ppt hepta Mtce Residing on 2,3,7,8 contaminated site Sol! (Surface TCOO) <20-1929 ppt ) - Sum TCOO <10-5237 ppt<9) Soil (Subsurface TCOF) 1413-23,920 ppt) - Sum TCOF NO - 13,809 ppt 1. Water,Quality Criteria Document. 2. Nappe C. Source of Identification. Especially With Respect to Dioxins and Plbenzofurans Found In the Emissions of Incinerators. Presented to Who Consultation on Organhalogen Compounds In Human Milk and Related Hazards. Be Ithaven, Netherlands 9-11, Januray 1985. 5. Ryan J., et al. Chlorinated Olbenzo-P-Dloxlns and Chlorinated Olbenzo Furans In Canadian Adipose Tissue Chemosphere Vol 14, No. 6/7, pp. 697-706. 1985. 9. Herda H., TCOO and Chlorinated Dlbenzofuran In Top Soil and Biological Saaiples From a Contaminated Refuse Pump, Chemosphere Vol 14, No. 6/7, pp. 919-924, 1985. 10. Similar results have been obtained by Graham et al. Background Human Exposure to 2,3,7,8- TCOO, Chemosphere Vol 14 No. 6/7, pp. 925-928, 1985, and, Ryan John, et al. Tissue Distribution of Dioxins and Furans in Hppum. a9nsX-F3r3omJ, tIhMeSG.--e--n--e-r--a-l-'--P---o*p--u--la--t-i-o--n. Chromosphere Vol 14. No. 6/7. 9-32 MONS 019193 Table 3 NOEL'S USED IN RISK ANO EXPOSURE ASSESSMENTS USEPA State of Calif. Health Oept. .06 pg/kg/day 2 pg/kg State of Calif. .06 pg/kg/day Air Resource Oepartnent New York State State of New Mexico Canada Netherlands COC 2 pgAg .06 pg/kg/day 10 pg/kg/day A pg/kg/day .028-1.40 ng/kg/day 9-33 HONS 019144 GUIDELINES Used In Various Environmental Exposure Settings for PCDO/PCDF Fish New York Health Oept. Ontario FOA 10 ppt 20 ppt 25 ppt Soil Air I ppb - CDC 10 pg/m^ NYS Indoors (8 hrs exp.) 10 pg/nr Calif. Indoors (8 hrs exp. -?- Ambient air (24 hrs exp.) 3-28 ng/m` - Inside Buildings Water Mlchlgan/outfall to river 10 pp quadrillion USEPA 2 part per qulntrtlllon 9-34 MOWS 019145 Decont. Effort Standard Accepted for Decontamination Dose basis of Standard Development Assessment Binghamton PCOO/PCDF PCB'S San Francisco PCOO/PCDF PCB Columbus, OH PCOO/PCDF PCB Santa Fe PCOO/PCDF PC8 Tulsa, OK PCOD/PCOF PCB Surface Air 3.3-28 ng/m2 1.0 ug/100 cur 3 ng/*2 10 pg/*3 (above background) 1.0 u/100 cmJ 10 pg/m3 1.0 ug/r 1.0 ug/m3 20 ng/m2 * , 1.0 ug/100cnr 1.0 ng/m* _ 1.0 i*g/lOOcnr 10 pg/3 , 1.0 ug/nr 1.0 lag/m3 3.3-28 ng/m2 , 1.0 ug/lOOeur 10 pg/m3 , 1.0 ugV 2 pg/kg 2 pg/kg 2 pg/kg .06 pg/kg 2 pg/kg * High Contact Surfaces 9-35 HONS 019146 Conclusions: Development of site specific risk and exposure assessments can be expensive but the cost Is decreasing as these techniques become more routine. The commonly made assumptions for such assessments are becoming more standardized, yet considerable variations still occur In the potency factors applied to Individual congeners of PCOO'sfPCOF's. Likewise, significant variations exists as to the potency of 2,3,7,8- TCOO (0.06 2.0 pg/kg/day) as acceptable Intake levels. Increased reliance Is being made of the exiting risk assessment documents and the resulting standards that have been developed. Thus, future risk assessment for PCB's, PCDO's, and PCOF's likely be on hold until further toxicological evidence Is developed. Advances In such risk assessment methods will likely be done as the result of critiques of the existing risk assessments. Site specific exposure assessments, however, are powerful tools to be used to modify existing guidelines or to document quantatlvely evaluate risk of persons either occupationally or Incidentally exposed to PCB's, PCOF, PCOO's. 9-36 HONS 019147 A SYST8HAT 1C APPROACH TO PC8 CAPACITOR SPILL CLSANUP COMPLIAMCS SAMPLING Msrk J. Knight* Stmn K. Vlnshlp* Bohdsn i. Dwytsrko* Thoms l. Hsmlngsr* As ths rsgulrtmnts for ths clssnup of PCS fluid rsltssts fron pols-aounttd cspscitors hsvt bscoos Increasingly nor* strlngsnt, ths nssd for fUld mapling protocol accurst* onough to dsaonstrst* coapUancs tilth thoss clssnup rsgulrsasnts hos bscoas apparsnt. Rsgardlass of ths clssnup standards sppllsd, s systsaatlc, rsproduclblt stapling spprosch which charactsrlzss pcb lsvsls across s spill sits is ths Utility's industry's host dsfsnss sgslnst posslbls futurs civil or rsgulstory setIon. Vlth st on# tliss ovsr 40,000 PCS cspscltors In ssrvlcs. ths Co--cnusslth Id Ison Coapsny hss bssn long faailiar with Pcs rslsssss snd accoapanylng *1 tigsting setIons. By Ists 19S3, with Incrssslng rsgulstory sttsntlon snd public concsro bslng focussd on PCS spill clssnup, ths ntsd for s --rs sccurstt, rsproduclbls issthod to ds--nstrsts clssnup coapUancs bscs-- sppsrsnt. Thus, sn sffort wss usds to datsralo* how to structurs s PCS spill sits stapling protocol to tcceapllsh ths following gosls: 1, Obtsin dsts on PCS dlspsrssl frosi rslssss svsnts to fscilitsts rtsponss/clssnup activities. 2. Accurstsly characterise PCS lsvsls rsasinlng st s clssnsd spill sits. *Qoaaonweelth IdIson Coapsny, mvlron--ntsl Affsirs Depertaent, P.O. Bo* 767, Chlesgo. IL 606*0 9-37 HONS 019143 3. Provide tvldonco to rlgoroudy doaoewtrato that a spill alta has been adequately cleaned end Is In compliance with pproprlAtt cleanup standards. Tha development of this protocol began with study or a data set of wore than 3M soil samples collected from PCS capacitor spill events. When this data sat was plotted to show PCB concentration In each sample vs. the distance of each SMple collection point frosi the source of the release. It was obvious that PCSs were being randomly dispersed farther, and in greater concentration, than had been previously thought. Identification of soil PCS levels In excess of 100 ppm at distances over 7) feet from the source pole were not uncoaeon even though lower levels tare measured nearer to the pole. The Inadequacy of our previous low-level sampling protocol was very apparent, as was the fact that PCB dispersion could not be predicted with a high degree of certainty. The only course of action appeared to be to Increase greatly both the amount of sampling and the area sampled at each spill site. The same data set was then used to develop Information predicting the probability of encountering PCB concentrations of a given level at varying distances from the capacitor pole. It was hoped that such Information would allow us to develop a field sampling program of appropriate Intensity to ensure that an adequate cleanup would be conducted across the entire site. This probability distribution was then employed to generate a diagram depicting the distribution of discreet droplets of PCS fluid (>90 ppm) from 0 to 42 feet away from a utility pole release point. Orld sampling systems (centered on the utility pole on which the failed capacitor hung) with various spacing between sample points were then superimposed over the distribution diagram. Using this approach, it was determined that a sampling system In which samples are located 5 ft. apart could be used to adequately characterise PCB levels In lightly contaminated erees some distence from the utility pole (le.. where the PCB fluid droplets art widely scattered) as wall as In those mors heavily contaminatad araas naarar tha utility pola. Plaid trials of this approach have shown It to be effective. When this grid system is deployed at a capacitor spill slta. additional samplas art collactad from obviously*Impacted areas or structures that do not fall onto tha grid systam. and from placas where PCBs ere likely to accumulate, such as cracks in pavement. Sampling la conducted such that the grid will encompass all araas of known contamination (defined by visible traces), and at least five feet beyond that area on all sides. When samples ere being collected to confirm the effectiveness of a cleaning attempt* samples are collected at five-foot intervale within the cleaned tree end at least five feet beyond the boundary of this area. 9-38 HONS 019149 M each soil sampling point, toll Is collected over an approximately 12-lnch-by-12-Inch area to a depth of about ona-alghth Inch. Vegetation tamplas art collected at each grid point over a 1 square-foot area. For hard surfaces, wipe samples are collected using the same grid system. An artifact of this sampling approach has been to Increase the number of samples collected per sampling event (there are usually between two and Tour sMpllng events per spill event) to roughly one hundred. To date, the Coasnonweelth tdlson Company has collected nearly 20.000 environmental samples using this grid system at approximately 73 Individual spill Incidents. In summary, this sampling approach has as its foundation the concept that PCS dispersion, particularly at greater distances from the pole, is a non-predlctable process. Only with multiple sample collection, and the charecterlzatlon of the site through the interpretation of numerous pcs analyses, can the actual pcs contamination remaining be adequately characterized end appropriate remedial action steps be determined. Multiple sample collection increases the probability that a given area of residual PCS contamination will ba detected, it does not guarantee that subsequent Bailing will not find additional, previously undetected contamination. What it does do Is greatly reduce the probability that additional contamination will be found. This, short of actually sampling evary square foot of site surface, is an optimal approach in terms of being cost-effective, risk-minimising end field-practice!. 9-39 HONS 019150 COMMONWEALTH EDISON COMPANY'S PCS SPILL CLEANUP PROCEDURES Bohdan I. Dayterko* Mark J. Knight* St#van K. Vlnshlp* Thoaas K. Heaningsr* Consonwaalth Edison coapany has had txparlertce with tha cleanup of ovar ISO pcb ralaasas froa alactrlcal egulpatnt. Thasa range froa alnor capacitor laaks to larga transforaar spills assoclatad with flra. Pacad with tha prospact of having to taka coaplax raaadlal actions at PCB ralaasa events. Coaaonwaalth Edison coapany has davalopad claanup procaduras to aaat tha following corporate and anvlronaantal goals. 1. Prevent tha spraad of PCB contaaination. 2. Notify affected custoaers and tha public that a spill has occurred, and restrict their access to tha affected area. 3. Notify and cooperata with all regulatory agencies In whose jurisdiction tha release occurs. 4. Perfora tha actual physical PCB reaoval and site claanup in as rapid and as an affsctlva Banner as possible. 5. Conflra tha effectiveness of the cleanup through well-planned stapling and analysis. 6. Restore the site to Its previous condition. 7. Accoapllsh the above objectives in a cost-effective Banner. *Coaaonweelth Edison Coapany. Bnvlronaental Affairs Oepartaant. P.o. Box 767. Chicago. XL $0690 9-40 HONS 019151 While every (pill event le e unique experience. adherence to the procedure, dlecueeed here. and with the above goal, tIrmly in alnd, will provide effective raawdtal action with tha laaat haalth rlak and lnconvanlanca to tha public. The cleanup procedure* daicrlbad her* are applicable to ralaa*** froa all type* of FO-contalnlnp electrical aqulpaant. but art principally uaad for polt-aounttd capacitor and vault or pad-aountad tranaforaar aplll*. These type* of spill* rang* froa slaplt leaks to fault-producsd energetic rtlaasts. Ivan alnor capacitor leaks, If undiscovered for scale length of tlaa. can result In large areas of contaalnatlon because of wind, precipitation and tracking. Energetic releases, especially tdien ecccapenled by high winds, can easily affect areas In excess of IIS a2 (2000 ft2). Th* type* of Mterlals affseted by th* spill* ranges froa soil end pavtmant to homes, autos and animals. Departing on th* physical condition art th* cost of an Item, it may be nor* expeditious to rewovs and replace that item rather than to elaan It. Additionally, certain ltau art better cleaned off-slte rather than in place. Tha successful execution of * cleanup U dependent on the accurate esaesaiaant of the affected ere*, the containment of the contamination to that area, the proper Mthodology for removal of that contamination from the ere* end, of course, sufficient sampling to determine whether the area he* been adequately cleaned to ensure compliance with appropriate cleanup standards, in performing these steps there ere not only technical constraints, but also non-tachnical regulatory, legal and public perception constraints which must be taken Into consideration. For the purposes of discussion, w My divide the cleanup effort Into two parallel pert*. One eddreeses the physical removal of tha contamination; the other addreases the non-technlcel Issues. Physical removal Issues Include how to secure th* site, techniques for soil and sod removal, techniques to clean or remove herd surface Mterlals, how to reduce PCS dispersion during the cleanup, how to package removed Mterlals for ultlMt* disposal, personnel hygiene and how to restore tha site. Non-technical issues includes dealing with regulatory agency personnel, with custoMrs art with tha public. Since Coamonweelth SdIson's cleanup procedures have been implemented the nuaber of cleaning attempts required to adequately clean e site have been reduced by approxlMtely 25%. Furthermore, cleanup performance at massive PCS spills (1.*., effecting several properties) have been particularly improved. 9-41 MOMS 019152 To facllltats tha training of claanup craws in our approach to PCI spin rssponss wa hava producad a vldaotapa prssantatlon (ditch show how all tha stops of tha claanup procadura ara axacutad and which also peasants soaw background as to why thsy ara nacassary. k slallar vldaotapa prasantatlon for trsnsforaar spills Is balng praparad. 9-42 HONS 019153 OOfWOWBALTM BDISON COMPANY'S TRANSFORM* SPILL RBSPONSB PRSFARBDNSSS BoMin I. Dwyterfco* Mark J. Knight* Steven K. Vlnshlp* ThoMt B. He--lnger* MctN of public sensitivity. even a Minor spill from a pa-filled transformer can develop Into a aarlous situation if tha fluid contaninatas customer or public proparty. Although tha Co--omealth Bdlson Co--any has procaduras which minimize this potentiali ralaasas nay occur which result In tha spread of contaminatlon beyond a vault, either through human arror or as a result of an uncontrollable accident. Such a release My not present an 1--lnent danger to Ufa or health, but, if the response Is nls--naged, the tine and cost of cleanup will Increase. Prolonged cleanups coupled with existing public concerns regarding PCBs will Increase the anxiety of customers and regulatory agencies. Consequently, the Co--omwslth Bdlson company has determined that it Is necessary to Mlntaln a trained te-- of Company personnel to: 1. Respond as quickly as possible once a PCS release has occurred. 2. Provide on-the-scene direction to Company personnel responsible for spill containment and cleanup. 2. Collect sa--las to verify cleanup success and compliance with cleanup standards. 4. interface with custo--rs, property owners and regulatory agency personnel. *0o--ooweelth Bdlson Co--any. Bnvlro--ental Affairs Department, p.o. Box 767, Chicago. XL 60690 9-43 HONS 019154 5. Provide follow up control and coordination of pcb releese response activities. 6. Pastor* affected customer or public proparty to Its original condition and um as rapidly am possible. because of the critical nature of PCS releases, the length of time required for emergency response teas personnel to reach a spill sit# is an iieportant concern. A response time of 1 hour after regular working hours and 20 sinuses during regular hours is possible in the Chicago area. Pasponee Is Initiated by local Dlvlalon personnel who use a paging aystas to contact a Primary Response Person. The Prlaary Response Parson will determine, based on svallabl# information, whether an emergency response is required. If it Is. ha will request to ba put in direct contact with the person in charge at the actual release site end will make further inquiries. He will also lssua preliminary directions over the phone for containing the release end restricting access to the sit*. He will then dispatch one or more Technical Response Specialist# to take on-site control. The Primary Response Person remains et hla phone and acts as a communication center for the first few hour* of the response. The response teen is specifically designed to address Incidents Involving PCR releasee end PCS equipment failures. Because of the specialized nature of these types of environmental emergencies. It Is possible to train and equip response terns persome 1 such that each team member can fully assess a raltase situation and sustain rasponsa activltlas until additional support bacomts available, such immediate, independent response capability elds greatly in achieving an effective, timely cleanup. This type of rapid end direct response is possible because of two factors, rirst, end most, important, la that that Individuals art not only trained and experienced in response activities, but also have been selected for their personal qualities, skills end attitudes. All personnel selected for emergency response heve obtained considerable experience In PCS spill response by starting as an assistant In tha cleanup and sampling of PCS capacitor spills and have built upon that taper lance until they are judged capable of Independently directing an emergency response. in addition, approprlata training coursas ara provided and drills ara conducttd to Improws skill lavels and to davalop a rasponsa team "spirit". Proper attitudes are developed by encouraging end testing employee resourcefulness and initiative in all aspects of tha work. 9-44 HONS 019155 Second. the emergency response equipment, Although simple, is selected, periodically reviewed, end revised for maximum efficiency. Bach response tM member has a sat of protective clothing and stapling equipment kept at heme, additional protective clothing and sampling equipment Is kept packaged In a central location accessible to all team members. A team of two can bring to any spill site sufficient equipment, including sampling supplies and protective clothing, to sustain emergency response support and sampling efforts for 3* hours and, If necessary, provide some equipment to cleanup crews. This allows Unediete response without welting for the supplies to be delivered from a central storage locetion. Since spill cleanups ere conducted In highly visible locations, it is critical that the work progress In a professional, organized and timely manner. Usually the customer's, aa wall as the public's, knowledge of FC&s is limited, end best. IncompLtte. Therefore, It is necessary to first place the customer's concerns In proper perspective. This Is done by providing clear and complete Information about PCM. explaining the response and cleanup plan and. by conducting indoor air sampling for PCBs in any situation where a building may be involved. After the initial response to a PCS release, the work of the response teem Is far from over. It Is st this point that the "attrition" of a protracted cleanup period, often stretching a weak or mors, begins. During this period, the response teem is faced with having to keep the cleanup effort moving along steadily on a 24 hour a day basis, while at the seme time feeing Increasing outside pressures from the public end regulatory agencies. Communication end control become the dominant Issues In this envlronmsnt. If properly handled, particularly during the early response stage, pcb transformer release events can be handled -so that negative Impacts to the effected Utility ere minimised. nous 019156 9-45 Ml ANALYSIS OF PCB CAPACITOR SPILL CLEANUP EFFECTIVENESS nark J. Knight* Steven K. Vlnship* Bohdan l. Dmyterko* TImms K. He--linger in 1994. the Co--onwilth IdIson Company responded to approximately 90 mall volume (Is.. 1.9 to 11.4 L (0.5 to 3 gsl.)) PCB releases fro* pole-mounted electrical capacitors. Ovar 12*000 samples of materials (eg., soil, vagatatlon. graval) and wlpa samples of hard aurfacas (ag., concrete, asphalt* ahaat aatal) hava been collactad at thasa spill sltas to determine both tha ootar boundaries of tha araa affactad by tha spill and whether an adequate claanup had baan conducted within tha affactad araa. A detailed analysis of tha data generated at 30 of thasa spill Incidents has baan conducted to evaluate: (1) tha efficiency of tha procedures employed to clean various types of affactad Materials at Individual spill sltas* (2) tha else of tha araa affactad by tha PCS release (ie., anywhere detectable levels of PCBs could be Measured), (3) average PCB concentrations In Materials and on hard surfaces at various stages of tha cleanup process and, (4) tha anount of residual PCB reMalnlng on tha spill site at the tine of site restoration. In addition, estlMatas of tha overall efficiency of the cleanup prograM at each site were also Made. Tha results of this analysis are noteworthy for a number of reasons. First, the surface-scrubbing techniques and soil removal procedures developed by tha *Cemmonwealth Bdison Company, Environmental Affairs Department. P.O. Box 7(7. Chicago* 1L <0(90 9-46 MOftS 0X9157 I Co--unusslth tdison Co--my affsctlvaly ramova pcb* from lmpactad araas in a tlnaly mannar. Sacondly. It appaars that avan tha iaoat cursory Initial claanup of visibly ispactad araas (tha visibly Lmpactad arts Is typically lass than 50%, md oftan lass than 10%. of tha afftctsd araa) will ramova mora than 90% of tha * of PCts ralaasad. Subaaguant claanup afforts usually atta--t to ramova lass than 1 kp of rasldual PCS contamination. To ramova a proportion of this rasldual larpa anough to ansura ccnplianca with claanup standards of lass than 50 ppm, larpa araas havt to ba claanad. Tha avarapa slza of tha affactad araa at tha spill sltas cons Idarad was 133m3; tha Majority of this araa will hava to ba claanad to ansura coapllanca. Two to four cltanlnp attanpts ara usually raqulrad to naat claanup standards ovar tha antlra slta. Tha affactlvanass (la., tha amount of PCSa ranovad par claanlnp) of individual claanln9 attanpts conslstantly daersasas throughout tha claanlng program at a plvan alta. This loss In affactlvanass is dut to tha fact that ons Is sttsmptln9 to rsmova Incrtaalngly smsllsr amounts of rtsldual pcs from tha sits, ones coapllanca with tha approprlata claanup standards had baan achlavad, tha astlnatad total PCS rasldual at thast sltas rangad batwaan 0.2 and 10.0 f (f 4.9 9). If ona assumas that a typical capacitor fallurt ralaasas 3.0 L (2 pal.) of PC fluid walphlnp 10.5 kp, an ovarall claanup affldancy of batwaan 99.04 and 99.990% (T 99.95%) has baan achlavad at tha sltas consldsrtd In this analysis. I i ; 9-47 MONS 01919a PUT 10: MISCELLANEOUS HONS 019159 IN SITU VITRIFICATION OF PCB-CONTAMINATED SOILS Craig L. Tlrnnerman Battelle, Pacific Northwest Laboratories Richland, Washington 99352 In situ vitrification (1SV) Is a patented process U) developed at Pacific Northwest Laboratory for the U.S. Department of Energy as an In-place stabilization technique for radioactive contaminated soils. Recent large-scale operational tests have dem onstrated the vitrification of 300 NT (6500 ft3) per setting. In addition, the process 1$ being evaluated for potential application to soils contaminated with haz ardous wastes, such as polychlorinated biphenyls (PCBs). Building upon this tech nology, an engineering-scale In situ vitrification test with PCB-contamlnated soil has been successfully performed for the Electric Power Research Institute (EPRI) to determine the fate of PCBs and their by-products when the process Is applied. PROCESS DESCRIPTION The in situ vitrification process as applied to contaminated soil stabilization requires the Insertion of four electrodes Into soil in a square array. A path for electric current Is established by using a small amount of a graphite and glass frit mixture placed between the electrodes on the soil surface. Dissipation of power through the starter material creates temperatures high enough to melt a layer of soil, which establishes a molten, conductive path. This molten zone continues to grow downward encompassing the contaminated soil. At the high temperatures (>1700*0 created, organic materials pyrolyze, diffuse to the surface, and combust. Any off gases from the process are collected, monitored, and treated. Remaining ash, along with other noncombustible materials, dissolve or become encapsulated In the molten soil. Natural convective currents within the molten soil help distribute the stabilized materials uniformly. The molten soil cools to a durable glass and crystalline form resembling natural obsidian. TEST DESCRIPTION maintained under vacuum by a process off-gas system, the EPRI engineering-scale test was performed In a sealed metal container on a 20 cm (8 In.) diameter by 30 cm HONS 0X9160 10-1 (1 ft) deep ton* of loamy-clay type sod containing 500 ppm PCBs (8 9 of Arochlor 1260). The test utilized a 23 an (9 In.) square electrode separation with cylindri cal molybdenum electrodes extending to a depth of 61 cm (24 In.). The contaminated soil was centrally located between the electrodes beginning at the 25 cm (10 In.) depth. The test was performed over a 6-hr period, achieved a depth of Bl cm (32 In.), and produced a vitrified block of 220 kg and 0.14 m3 (480 lb and 5 ft3). Mo operational problems were encountered during the test, and on-line grab sampling for chlorine and hydrogen chloride revealed less than detectable quantities (<0.33 ppm and <0.2 ppm respectively). For safety and environmental control, a dual-stage activated carbon filter (see Figure 1) was used to contain any PCBs released to the off-gas system. Metsnng Water Air Impingers Dryer Desiccant Figure 1. Engineering-Scale In Situ Vitrification System and Sample Locations 10-2 MOWS 019161 TEST RESULTS AND PERFORMANCE ANALYSIS Staples collected to analyze ISV processing effects on PCB Included: II off-gas emissions, 2)-residues In off-gas lines and containment equipment, 3) migration to soil surrounding the block, and a) residual level In tne vitrified block. Data from off-gas release and soil container smears provided the most quantitative values on the release from the melt during and after processing. Information collected from the florlsll adsorption tubes and the smear sample extractions (see Figure 1) Indi cated a 4.2 mg total Off-gas emission. 1.1 mg of which was deposited on container surfaces. These off-gas releases account for 0.05 wtt of the Initial PCB quantity, correspondlng to a greater than 99.91 thermal destruction and removal efficiency (ORE) for the ISV process. Note: this does not Include the removal efficiency of the off-gas system; therefore, a system ORE cannot be calculated from the available data. Activated carbon filters (2) can effectively contain any of these off-gas emissions. .The analysis of florlsll also Indicated a small amount furan (PCOF) and dioxin (PCDO) generated In total quantities of 0.4 ug and 0.1 ug respectively. The PCOF was detected only In the tetri and penta Isomers, while the PCDO was detected only In the hepta and octa Isomers. However, these small quantities are less than the reported amounts typically generated from a PCB fire 12) and do not represent a haz ardous operational concern. Sampling of the vitrified mass showed no detectable residual level of PCB, which Is to be expected considering the high processing temperatures. Also, no PCB contami nation was detected In the majority of soil surrounding the vitrified block. Indi cating that migration outside the vitrification zone was not a significant problem. A few samples directly adjacent to the block contained measurable concentrations up to 0.7 ppm, which is lower than 40 CFR 761 EPA requirements for cleanup. This Ini tial test data Indicates that the vitrification rate must be higher than the dif fusion rate of volatilized PCBs In soil, thus overcoming migration away from the hot molten mass. ECONOMIC ANALYSIS The cost of using In situ vitrification as an in-place stabilization technique has been estimated (). The cost estimate Includes expenses from four categories: site preparation and closure activities, annual equipment charges, operational costs (labor), and consumable supplies Including electrical power and molybdenwe elec trodes. Evaluations M) established processing economics at between S150 to 1330/m3 10-3 HONS 0191.62 ($4 to 19/ft3) depending on electrical power rates and soil moisture content. Soil moisture content Increases the operating cost of the process by requiring more energy and time (labor) to vitrify a given volume of contaminated soil because the water In the soil must be evaporated. CONCLUSIONS The July 1985 In situ vitrification engineering-scale test Illustrated the cleanup capabilities of ISV on soils contaminated with PCBs to meet current and anticipated CPA requirements. In addition, the test provided the following conclusions regard ing performance of the In situ vitrification process: * The small release of PCBs to the off-gas system (0.051) can be effectively retained by appropriate design of a conventional treat ment system, which utilises a carbon filter or afterburner. * Limited amounts of PCBs (0 to 0.7 ppm) were detected In the sur rounding soil and none were found In the vitrified block. Indicating that the vitrification rate Is apparently greater than the PCB dlf- - fusion rate In loaaqr-clay soil and that migration away from the vit rification tone during processing may not be a significant concern. * Processing of PCB-contamlnated soil by In situ vitrification Illus trated a processing destruction and removal efficiency of >99.9% for the process Itself, exclusive of off-gas treatment. Initial testing Indicates the potential for In situ vitrification technology trans fer from the nuclear to the hazardous waste arena as a potential remedial action technique. It Is not a panacea, but the process holds promise for application at selected, contaminated soil sites. REFERENCES 1. R. A. Brouns, J. L. Buelt, and W. F. Bonner. "In Situ Vitrification of Soil.* U.S. Patent 4,376,498, March 1963. 2. Charcoal Services Corporation Bulletin No. 283A. "High Efficiency Has Adsorbers.* Bath, NC: Charcoal Services Corporation. 3. Private Coaaaunlcatlon. F. L. DeRoos. Battelle Columbus Laboratory, Columbus, OH to C. L. Tlsmmrman, Battalia, Pacific Northwest Laboratories, Richland, NA, August 1,1985. 4. K. H. Qaa, et. al. "In Situ Vitrification of Transuranlc Wastes: Systems Evalu ation and Applications Assessment.* Richland, WA: Pacific Northwest Laboratory, PNL-4800, September 1983. 10-4 HONS 019163 EPRI's WORK ON PCS HEALTH EFFECTS Walter W. Weyzen About two years ago, EPRI contracted with elements Associates to conduct a study of occupational risks associated with exposures to PCBs. It was felt that. In view of the current uncertainties about the magnitude and nature of the hazards posed by PCBs, an objective, systematic, and technically sound assessment of occupational risk, based on available toxicological evaluation, should be made. The study consists of three parts. 1. The collection and evaluation of toxicity Information. 2. Characterization of the utility work environment. Identification of potentially exposed populations, and magnitude of exposures. J. Estimation of the health risks associated with exposures. The first two parts of the study have now been completed. Completion of the third part Is expected later this year. Technical overview of the study Is In the hands of a Scientific Advisory Committee consisting of experts In epidemiology, occupational health. Industrial hygiene, toxicology and statistics, both from utilities and academia, chaired by Dr. Feeder of SCE. The results of the study will be available as a four part EPRI report In 1966. In reviewing and evaluating the literature on PCBs, and chlorinated dioxins and dlbenzofurens, approximately 3,000 titles and abstract were screened, and almost 1,600 titles were entered In the bibliography. For these, hard copies were obtained and the titles were evaluated for their relevance to risk assessment. From these, 82 papers were selected as the basis for 37 critical reviews that will form the basis for risk assessment. In addition to such factors as experimental design, significance of outcome, special attention was given to the reviews and assesment of 10-5 HONS 019164 methods and materials used for the chemical analysis of mixtures to which humans were exposed or the materials used In animal toxicity studies. In addition, a method for weighing the results of epidemiological studies of human population was developed. The second part of the study Is an assessment of the extent, frequency, and magni tude of occupational exposure to PCBs and related chemicals In the electric utility industry. It Includes a detailed review of the literature, the results of a ques tionnaire circulated to about 100 utilities, and site-visits and surveys of four representative utilities. Included are characterization of the PCB equipment past and present, streamflow of PCB within the utility, the workforce, and job categories with potential exposure. Sources of exposure, such as the repair and maintenance of equipment and cleanup of spills and leaks, and explosions and fires, were Identi fied. Assessment of occupational exposures Is based on the chemical composition of the fluids used, actual measurements of PCB levels In the workplaces, and measure ment of PCB levels In blood or tissues of utility workers. All this Information was (n turn linked to the number of workers potentially exposed In each of the Job categories, the frequence, magnitude and duration of exposure. Initial findings of the study will be highlighted In the presentation. 10-6 HONS 01916b HUMAN AND ENVIRONMENTAL BIODEGRADATION OF PCBs John F. Brown, Jr., Donno L. Bedord, Lawrence H. Bopp, James C. Carnahan, Richard W. Lowton, Ronald D. Untermon, end Robert E. Wagner General Electric Research and Development Center, Schenectady, NY PCB PERSISTENCE* THE ETERNAL QUESTION Daring the 1970's, public concern over the apparent environmental persistence of the PCBs, heightened by preliminary reports (later revised 0)) that they had produced severe humon poisoning in Japan, contributed to a bon on their use in the U.S. and the initiation of remedial action projects designed to stop their further movement into the biosphere. Now, however, proposals for the excavation, transport, and reburial of PC8s are being increas ingly questioned, both by local residents and national environmental organizations (2). At issue is the old question of persistence: will PCBs really remain in environmental deposits forever, or will they, like other organic chemicals, eventually biodegrode? THE ASSESSMENT OF PERSISTENCE Our procedures (3-5) for assessing PCB biodegradation exploit the foct that the commerci ally used PCB products (eg., Aroclors) are mixtures containing most of the 209 theoretically possible PCB congeners in fixed relative proportions. Eoch individuot PCB congener differs in molecular size and shape from all the others, and hence also in its susceptibility to enzymatic attack. Eoch individual type of biodegradation will therefore alter the congener distribution, and hence gas chromatogram, of the Aroclor originally present in a character istic manner. Thus, the pattern of chromatographic peak alteration can characterize the type of biotransformation that is occurring, and the degree of alteration its extent. The specific microorganism or metabolic enzyme that is responsible for an observed environ mental transformation pattern may then be identified via laboratory studies with purified cultures or enzymes. Thus far, significant degrees of biodegradation hove been observed for PCBs in three very different components of aquatic ecosystems, namely, in higher onimois, including man; in aerobic bacterial and In anoerobic sediments. The three corresponding types of PCB biodegradation will be described in turn. 10-7 HONS 019166 QIODECRADATION AND PERSISTENCE IN MAN In birds, mammals, end perbops some lower animals os well, PCBs are handled like other fotsoluble xenobiolics: smoll omoonts moy be eliminated unchanged via the bile or lactotion, but most elimination depends upon oxidation to more woter-soluble forms. Such oxidations occur mainly in the liver, ond are effected by mixed-function oxidase enzymes of the cytochrome P450 family. Rates of biodegrodation vary considerably from species to species, as do also the ranges of PCS congeners thot moy be thereby eliminated. Our studies of 1976-1983 clearance of PCSs from a population of heavily exposed capacitor workers (3) suggest thot the individual PCB congeners may be divided into three groups os regards persistence in man: (a) non-persistent congeners, which did not accumulate; (b) moderately persistent species, which disappeared with half-times of 2-5 years; and highly persistent forms, which generally showed no significant decline. The non-persistent group was found to include virtually all congeners lacking 4-substitution on either ring, along with some of the lower 4,4'-disubstituted congeners. This group constituted 88-90% of Aroclors 1242-1016. The remaining, moderately persistent, components of such Aroclors consisted of certain 4,4'~disubstituted lower PCBs, such os the 2,4,4'-, 2,4,S,4'-, 2,4,S,2',4'-, 2,4,5,3*,4', ond 2,3,4,3',4'- congeners. The persistent group included oil hexa-, hepta-, and octochioro's with 4,4'-substitution; such species constituted somewhot less than half of Aroclor 1254, but more than holf of Aroclor 1260. BIODEGRADATION AND PERSISTENCE IN AQUATIC ECOSYSTEMS In aerobic oquatic ecosystems, and soils as well, most metabolism of organic motter is effected by oerobic bacteria. The complex microbial populations found in such environ ments include species capable of metabolizing every one of the many chemical constituents of the organic matter naturally present, and also mony PCBs. To date, about two dozen pure stroins of PCB-degroding bacteria have been isolated from soils and sediments and characterized as to type and range of PCB congener-degrading ability. Most of the strains belong to the 2,3-dioxygenase type (4,5); thot is, they preferentially attack PCB species, such os the lower 4,4`-disub$tituted congeners, which have odjocent unsubstituted carbon atoms at positions 2,3 (or 5,6) on the ring. Within this group, however, there is still o considerable range of activities, with some organisms attacking only mono- and dichkxinofed PCBs and others attacking tetra's and some penta's. A few of the known strains, however, appear to belong to a 3,4-dioxygenase (4) or even monooxygenase type. These prefer to ottack rings with unsubstituted 3,4- positions, but can also slowly ottoek 4,4'disubstituted species, including 2t4,5^',4,,5'-hexochlorobiphenyl. 10-8 HONS 019167 In the upper Hudson, where the reported "Arocior 1016" level in fish hos been dropping with a hoif-time of about 2 years, the residual PCB resembles that of Arocior 1242 offer biodegrodation by 2,3-dioxygenose-type bacteria (5), which are readily isolated from The sediments. Evidently, this group of aerobes is ploying a major role in PCB removal from thot ecosystem. BIODEGRADATION AND PERSISTENCE IN ANAEROBIC SEDIMENTS In anoerobic oguatic ecosystems, metabolism of organic matter requires microbial fermen tation rather than oxidation, and hence also the concommitant formation of reduction products, for exomple, nitrogen (from nitrates), sulfur (from sulfates), or methane (from C02) Recently, we discovered thot PCBs could also be reduced (dechlorinated) in some anoerobic systems, notably the subsurfoce sediments of the upper Hudson River (5) and Silver Lake (Pittsfield, MA). At least six chromatographically distinguishable dechiorinoting agents, probably corresponding to six different strains of locally prominent anoerobic bocteria, are present in the sediments examined thus far. Those present in the upper Hudson can remove most or oil of the chlorines present on pgro (4-) positions of the biphenyl rings, and many of those in me to (3- or 5-) positions, but not those in ortho <2- or 6-) positions; their net effect has been to convert most of the Arocior 1242 in 20*25 year old deposits to ortho-substituted mono* ond dichlorobiphenyis. The Silver Lake dechlorination systems apparently remove ortho, meto, and poro chlorines from the more heavily chlorinated PCB congeners rather indiscriminontly, with only a modest preference for 4-chlorine removol, but leave many tri* and tetrochlorobiphenyls unattacked. Their net effect has been to convert the Arocior 1254 or 1260 deposits present to PCB congener mixtures having the average chlorine contents of Arocior 1242 or 1248, but with very different congener distributions (eg, the most prominent trichlorobiphenyls ore 2,5,3'- ond 2,4,3'*, rather fhon 2,5,4'- ond 2,4,4'-). It is noteworthy that the heavily chlorinated PCBs with 4,4'disubstitution, a group which includes all the congeners found to be either persistent in man or toxic In experimental animals, are the ones mast readily eliminated by dechiorination in anoerobic sediments- Thus, environmental dechlorination, while not eliminating the PCBs as legally-defined chlorinated biphenyls, can render them biodegradable in oerobic environ ments, and less persistent in birds, mammals, and man. NEW ISSUES Although PCBs are indeed undergoing both oxidative ond reductive biodegrodotion at certain major spill sites, nature is not cooperating everywhere. A determination of whether the PCBs at any given site are biodegrading or persisting will require careful ehromotogrophic analysis. MQHS 019168 10-9 Selection of the appropriote response to on environmental site found to contain a biodegrading PCB may also require careful examination of the distribution of congeners present. Animal studies (6) hove shown that only a few of the 209 possible PCB congeners exhibit significant toxicity. Ideally, it should be the projected levels of those suspect congeners, rather than the total level of oil PCBs present, thot determines the choice of response. REFERENCES 1. Kunita, Kashimoto, T., Miyoto, H., Fukushimo, S., Hori, S., and Obono, H. Cousol Agents of Yusho. Am. J. Ind. Med. 5:45*48 (1984). 2. Borelii, P. To Dredge Or Not To Dredge: A Hudson River Saga. Amicus J. 6:14*26 (1985). 3. Lawton, R.W., Brown, J.F. Jr., Ross, M.R., and Feingold, J. Comparability and Precision of Serum PCB Measurements. Arch. Environ. Health 40:29-37 (1985). 4. Bedard, D.L., Brennon, M.J., and Untermon, R.D. Bocteriol Degradation of PCBs: Evidence of Distinct Pathways in Corynebocterium sp. MB I and Akaligenes eufrophos H850. Proceedings: 1983 PCB Seminor. Palo Alto, CA: Electric Power Reseorch Institute, June lW5, pp. 5-151 to 4-118. 5. Brown, J.F. Jr., Wogner, R.E., Bedard, D.L., Brennan, M.J., Carnahan, J.C., May, R.J.. and Tofflemire, T.J. PCB Transformations in Upper Hudson Sediments. Northeast. Environ. Sci. 3:167-179 (1984). 6. Parkinson, A., Safe, SJH., Robertson, L.W., Thomas, P.E., Ryan, D.E., Reik, L.M., ond Levin, W. Immunochemical Quantitation of P-450 isozymes and Epoxide Hydrolose in Liver Microsomes from Polychiorinoted or Polybrominated Biphenyl-treated Rots. J. Biol. Chem. 258: 5967-5976 (1983). 10-10 HONS 019169 COMPUTER AID FOR COMPLIANCE WITH THE RECORDKEEPING AND REPORTING REQUIREMENTS OF THE PCS REGULATIONS Kent INTRODUCTION The body of information presented in this paper is directed to chose individuals who are responsible for compliance with the recordkeeping and reporting requirements of the PCB regulations (40CR761). Compliance with these regulator-, requirements has become more manageable for Kentucky Utilities Company since the in-house development and implementation of a computer-aided system for recordkeeping and reporting. The large volume of data that must be collected and manipulated necessitated the computerisation of the entire recordkeeping and reporting process. This type of computer application results in better data management and reporting while providing more efficient allocation of resources. The data handling system used by Kentucky Utilities Company has applicability to other utility companies who likewise have access to a mainframe computer. DATA COLLECTION An efficient system for data collection is necessary to obtain quality data and to assure the integrity of the reports produced. The data collection system established at Kentucky Utilities consists of two forms titled. "Drum Content Report" and the "Transformer Concent Report." These reports are illustrated in Figures 1 and 2. All PCB material generated for disposal is placed in drums at the site where the material is generated. The only exception is transformers. The Drum Content Report is filled out on every drum and accompanies the drum until it is transported to the Company's long-term PCB storage facility. This report is completed by the field personnel who generate the PCB waste. When the PCB item is received by the Long term storage facility, an inventory number is atsignad to the Environmental Engineer. Kentucky Utilities Company. Responsible for compliance with the PCB regulations and all environmentally related permitting. 10-11 MONS 019170 DRUM CONTENT REPORT This report is to accompany every drum brought to Che Annex III PCS Storage Facility: Plant or Oivilton Originating PCB Item Drum Mo, District Date________________ ___________ Description of Contents Weight Fill Materia I Casket Clamping Band Additional Information if Contents are Capacitors: Leaking Yes/No Dace Placed in Drum KVAR Serial Number Manufacturer Date Drum Moved to Annex III PCB Storage Facility Person Responsible DO NOT WRITE IN THIS SPACE; FOR GENERAL OFFICE USE ONLY. Drum Identification 0 assigned when received at Annex III PCB Storage Facility Remarks__________________________________________________________________________________________ Figure 1. 10-12 HONS 019171 TRANSFORMER CONTENT REPORT Plant or Oivltion District Location Total Quantity of Fluid in Transformer Total Weight of Transformer Dlmensicn of Transformer: Height Length ft. ft. Widthft. Oate Removed from Service Oate Placed Into Storage Gallons lbs. Test Data: Method Used Date Tested ______ Results ___ ________________________ __________________________________ DO NOT WRITE IN THIS SPACE; FOR CENERAl OFFICE USE ONLY. Identification 0 assigned when received at Annex III Storage Facility Remarks Figure 2. 10-13 HONS 019X72 drum and recorded on the report. The drum is placed in numeric order with ocher drums in storage. The report is then forwarded to the Environmental Section tor entry inco the computer data base. All data that is needed co comply with the -egulatorv requirements of an Annex III storage facility Is collected from this report. This includes the dace removed from service if the material is capacitors or the date the waste is generated if it is debris or similar material. Other pertinent regulatory information collected includes the date received for disposal, the facility (in our case the district) that generated the material, and the weight of the item. If capacitors are contained in the drum, additional information is collected co facilitate other internal uses of the data. This information includes the KVAR, the serial number and the manufacturer of each capacitor in the drum. The information on serial number and manufacturer is presently not used, however, it could have future usee such as an aid In identifying and tracking the disposition of Individual capacitors. The Transformer Content Report is used any time a PCB transformer requires disposal. It Is used to collect the same pertinent Information for regulatory compliance in addition to some additional data that is required by the disposal contractor. In setting up the data collection system, a critical factor in making the program successful was the cooperation of field personnel. This was neceeearv because field personnel are the source of the data requiring collection and the most resource intensive part of the entire recordkeeping and reporting process turned out co be data collection. In order to obtain this cooperation, data collection had to be as simple and straightforward as possible. Also, it was necessary co minimise additional manhour requirements. People inherently do not like co complete reports, to any meaaura that reduced the time necessary to complete th(* reports was instituted. These measures included minimal changes co the existing report that was being used and to require that the reports be completed by the personnel that generate the PCS waste. DATA ENTRY Once the data has been collected In report form, it mutt be transferred co the storage file In the computer. Because of the volume of information chat needed eo be transferred, the process of data entry had to be efficient and the time requirement had to be minimal. Also the system needed co be simple to use. Manual entry into the data file is possible, in fact, it was used In the old system of data entry. This type of system can be time consuming and result in an unacceptable amount of error in the data. A new system was developed to reduce the 10-14 MOMS 019173 time requirement end to minimize the number of errors co an acceptable level. The new system consists of a menu driven program that interacts with the user. The program asks the user to input specific information describing the amount of data co be entered and if the data is new information or updating previous entries. Once the program has this information, it displays the appropriate screen for the user co input the data. If the data is new, the program will check the data for completeness once the user indicates the data antry is complete. The required information for new entries consists of all the data contained on the Drum Content Report or the Transformer Content Report. The information pertaining co the actual shipment for disposal is entered after the shipment occurs as an update. The update is performed in a similar fashion. The program will ask the user to supply che number of items requiring updates. This is indicated by inpucing the starting Item number and the ending item number. The program will update all item numbers within che specified block. The data supplied in che update Includes the date the shipment occurred, che manifest number of the shipment, and the disposal facility. After the input is complete, the program then asks che user to check che information entered for accuracy by summarizing che data on another screen that is displayed co che user. The user must confirm the accuracy by responding whether the data is correct or not. If the information isn't correct, the update is voided and must be re-entered. If che information is corrcce, che program writes che update to the iteme in the storage file. Although this may sound quite involved, the program is user friendly because its menu driven and it interacts with the user. This helps che user to understand how che program works and to figure out what information is expected to be inpuc and in what order and form. This system of data entry forces the user to check the material being entered for accuracy and completeness, which would not always be done wish manual entry. The input, update and check screens are shown In Figures 3, 4 and 5 respectfully. DATA STORAGE The process of storing the data in the computer had to be efficient because of the volume of deta requiring storage. The previous system of recordkeeping and reporting kept both e date file and the actual report in storage. This required an enormous amount of storage space. The new system incorporated several means co reduce the necessary storage space. One method Chet was used was co code as much of ehe data at feaslbla. All of che districts within the Company were assigned s numeric code unique to chat district. 10-1S HONS 019174 PCB STORAGE INPUT ITEM NUMBER: _________ TOTAL WEIGHT: DISTRICT CODE: _____ DESCRIPTION CODE: lb*. DATES: ITEM REMOVED FROM SERVICE: ITEM RECEIVED: // // KVA/KVARj ______ S/N: MANUFACTURER COOE: IF ITEM IS A TRANSFORMER. ENTER INDICATED VALUE CALLONS: Remarks: ****** ************************************************************************* pri3" - INPUT IS COMPLETE "PF15" -- ABORT INPUT SESSION Figure 3. 10-16 HONS 019175 PCB STORAGE UPDATE IN ORDER TO IDENTIFY WHICH ITEMS IN STORAGE ARE TO BE UPDATED. YOU MUST INPUT ITEM NUMBERS. THE UPDATE WILL THEN BE PERFORMED ON ALL ITEMS B! TWEEN (AND INCLUDING) THE TWO ITEM NUMBERS INPUT. START UPDATE WITH ITEM NUMBER: CONCLUDE UPDATE WITH ITEM NUMBER? DATE TO BE SHIPPED: // MANIFEST NUMBER: ~~ DISPOSAL FACILITY CODE: A***********************************************#*************************#**v "m3" INDICATES YOU ENTERED THE INDICATED INFORMATION "PF15" -- INDICATES YOU DO NOT WISH TO DO THE UPDATE FUNCTION. Flfur* 4. 10-17 HONS 019176 PCB STORAGE UPDATE IN ORDER TO IDENTIFY WHICH ITEMS IN STORAGE ARE TO BE UPDATED. YOU MUST INPUT TWO ITEM NUMBERS. THE UPDATE WILL THEN BE PERFORMED ON ALL ITEMS BETWEEN (AND INCLUDING) THE TWO ITEM NUMBERS INPUT. START UPDATE WITH ITEM NUMBER: CONCLUDE UPDA* E WITH ITEM NUMBER? DATE TO BE SHIPPED: // MANIFEST NUMBER: _______________ DISPOSAL FACILITY CODE: _____ THE PROPOSED UPDATE WILL INVOLVE _______ ITEMS. ENTER AN 'X' IN FRONT OF THE APPROPRIATE RESPONSE TO THE FOLLOWING QUESTION: IS THE NUMBER OF UPDATES PROPOSED VALID? ______ yes ---- n0 IF YOUR RESPONSE IS 'NO' THEN THIS SESSION MUST BE TERMINATED. **********************************************************************V.-*v.-** ***:. "PF13" - INDICATES YOU ENTERED THE INDICATED INFORMATION. "Pri5H INDICATES YOU DO NOT WISH TO DO THE UPDATE FUNCTION. Fl|uc 5. 10-18 HONS 019177 All types of PC6 waste chat could be generated were also coded wtch a numeric code as were the equipment manufacturers and the PCB disposal facilities currently used by the Company. Another measure that was Incorporatad to reduce the amount of storage space was to only store the data and not the entire report. This was the most effective measure in reducing the required storage space. A report writing program had to be developed to read the data file, interpret all codes used, and wrice the rcporc all within the program itself. Once the report is complete, it is sent directly to the printer with none of the report stored in the computer, examples of the report arc shown in Figures 6 and 7. One problem this method creates is how to reproduce the report when necessary. This problem was overcome by having the program copy all the data used to write a particular report and create a separate file to temporarily store the data. Once this file is created, it Is transferred to tape for permanent storage. If a specific report needs to be reproduced, the dace is simply transferred back to the computer and the program is directed to write a report using this data. This method produces the same report because it uses the same data used in the Initial report. MULTIPLE USES OF DATA One of the most beneficial uses of the new data handling system is the use of the data for inventory control. The information contained in the data file provides the means to strictly control the PCS Items currently in storage at the Company's long-term PCS storage facility. A separate system was developed to keep track of the items in storage and to determine the makeup of shipments for disposal. The system can be accessed to determine the current number of items being stored and to sort tha items into categories (e.g. number of drums of capacitors, of debris, etc.). This system is also used to determine the items to be shipped for disposal, based on Che dates the items are received (l.e. first in, first out). The report produced by this program also provides information on the categories of matarial to be shipped, the data each item was received by the storage facility, and the estimated cost of the shipment. The report Is shown in Figure 8. The report produced is used to schedule the shipment with the disposal contractor, to prepare the purchase requisition, and to provide the personnel at the long-term storage facility with information on which items are to be shipped so the items can be labeled with the required ORM-E shipping label. 10-19 HONS 01917ft PCS UEH NUMBER: 1500 DESCRIPTION: CAPACITORS TOTAL UEICHT: ' 125.65 KCS. (277.00 lbs.) DATE ITEM RECEIVED: 11/06/BA PCB SOURCE: CARROLLTON DISTRICT DATE ITEM REMOVED FROM STORAGE: 12/17/84 DISPOSAL FACILITY: ENSCO MANIFEST NUMBER: AR-61805 NOTE: TOTAL WEICHT DOES NOT INCLUDE THE WEIGHT OF THE DRUM. ft******************************************************** **********#vf*#******** PCB ITEM NUMBER: 1501 DESCRIPTION: CAPACITORS TOTAL WEIGHT: 1A6.06 (CCS. 022.00 LBS.) DATE ITEM RECE1VE0: 11/05/84 PCB SOURCE: CARROLLTON DISTRICT DATE tTEM REMOVED FROM STORAGE: 12/17/84 OISPOSAL FACILITY: ENSCO MANIFEST NUMBER: AR-61805 NOTE: TOTAL WEICHT OOES NOT INCLUDE THE WEICHT OF THE DRUM. ******************************************************************************* PCB ITEM NUMBER: 1502 DESCRIPTION: CAPACITORS TOTAL WEICHT: 166.92 KCS. (368.00 LBS.) DATE ITEM RECEIVED: 11/09/84 PCB SOURCE: HARLAN DISTRICT DATE ITEM REMOVED FROM STORAGE: DISPOSAL FACILITY: **STILL IN STORACE - 12/31/84 ** MANIFEST NUMBER: N**O*T*E*: **T*O**T*A*L*W**E*IG*H**T**D*O*E*S**N*O*T**IN**C*L*U*D*E**T*H*E**W*E*I*C*H*T**O*F**T*H*E**D*R*U*M**. ******************* Figure 6. Annex III Annual Report on the Disposition of PCB Items. A sample page showing itemised listing of all Items handled by the PCB storage facility. 10-20 HONS 019179 SUMMARY OF PCB STORAGE FACILITY TRANSACTIONS BREAKDOWN OF PCB ITEMS FOR THE CALENDAR YEAR 1984. A. 832 WERE RECEIVED AT THE STORAGE FACILITY. TOTAL WEIGHT: 184,770.56 KGS. (407,356.00 LBS.) 1. 399 OF THESE ITEMS CONTAINED CAPACITORS TOTAL WEIGHT: 68,119.94 KGS. (150,179.00 LBS.) 2. 0 OF THESE ITEMS CONTAINED PCB OIL TOTAL WEIGHT: 0.00 KGS. (0.00 LBS.) 3. 46 Of THESE ITEMS CONTAINED PCB CONTAMINATED OIL TOTAL WEIGHT: 6,941.40 KCS. (15,303.00 LBS.) 4. 387 OF THESE CONTAINED DEBRIS TOTAL WEIGHT: 109,709.25 KCS. {241.874.00 LBS.) B. 577 WERE TRANSFERRED TO DISPOSAL FACILITIES. TOTAL WEIGHT: 116,538.37 KCS. (256,921.00 LBS.) 1. 344 OF THESE ITEMS CONTAINED CAPACITORS TOTAL WEIGHT: 57,919.98 KCS. (127.691.00 LBS.) 2. 0 OF THESE ITEMS CONTAINED PCB OIL TOTAL WEICHT: 0.00 KGS. (0.00 LBS.) 3. 46 OF THESE ITEMS CONTAINED PCB CONTAMINATED OIL TOTAL WEIGHT: 6,941.40 KCS. (15,303.00 LBS.) 4. 187 OF THESE ITEMS CONTAINED DEBRIS TOTAL WEIGHT: 51,677.01 KCS. (113,927.00 LBS.) C. 372 WERE RETAINED AT THE STORAGE FACILITY. TOTAL WEIGHT: 88,860.44 KGS. (195,902.00 LBS.) 1. 162 OF THESE ITEMS CONTAINED CAPACITORS TOTAL WEIGHT: 28,855.47 KCS. (63,615.00 LBS.) 2. 0 OF THESE ITEMS CONTAINED PCB OIL TOTAL WEIGHT: 0.00 KGS. (0.00 LBS.) 3. 0 OF THESE ITEMS CONTAINED PCB CONTAMINATED OIL TOTAL WEIGHT: 0.00 KCS. (0.00 LBS.) 4. 209 OF THESE ITEMS CONTAINED DEBRIS TOTAL WEIGHT: 60,005.01 KCS. (132,287.00 LBS.) Figure 7. Annex III Annuel Report on the Disposition of PCBs end PCB Items. A sample page showing summery informetlon on ell Items handled by the PCB storage facility. Note that subtracting the numbers in A end B do not yield the numbers In C. This is because of Items received in 1983, end shipped In 1984. 10-21 HONS 019X80 PCB ITEMS AWAITING SHIPMENT FOR DISPOSAL FROM ANNEX III PCB STORAGE FACILITY ID* BRIMS Of PCB OIL DATE RECEIVED 'r' ------ SHIPPED UNOER MANIFEST NO. UNASSIGNED -.V ******** ***** ft*******!'.****** * 2002 2365 2366 2367 2368 2369 TOTAL ITEMS TO BE SHIPPED * 6 subtotal * BASED ON SCHEDULE A 02/21/85 07/22/85 07/22/85 07/22/85 07/22/85 07/22/85 TOTAL WEICHT > 2405 LBS. WEIGHT* LBS) 300 380 435 435 435 420 DRUMS OF PCB CONTAMINATED OIL SHIPPED UNDER MANIFEST NO. UNASSIGNED ***************************** 1943 1944 1954 2301 2314 2331 TOTAL ITEMS TO BE SHIPPED 6 SUBTOTAL . BASED ON SCHEDULE A 01/18/85 01/18/85 01/24/85 07/01/85 07/03/85 07/09/85 TOTAL WEIGHT * 2351 LBS. 450 450 416 460 225 350 DRUMS OF FILTERS SHIPPED UNDER MANIFEST NO. UNASSICNED ***************************** 2312 2370 2371 2373 2374 2431 2482 TOTAL ITEMS TO BE SHIPPED * 7 SUBTOTAL - BASED ON SCHEDULE A 07/03/85 07/15/85 07/29/85 07/29/85 07/29/85 08/08/85 08/18/85 TOTAL WEIGHT 1563 LBS. 180 240 260 218 220 220 225 .) GRAND TOTALS: TOTAL ITEMS TO BE SHIPPED - 168 TOTAL WEIGHT - 91891 LBS TOTAL SHIPMENTS REQUIRED 2.1 TRUCK LOAD<S) TOTAL KVAR 0 KVAR TOTAL ESTIMATED COST * BASED ON SCHEDULE A Flgurt S. Inventory Control Report. This version shows druas awaiting shipment for disposal. 10-22 HONS 019101 Th data file is also uaed to prepare quarterly reports on the disposition of PCB capacitors that have been removed from service as part of the Company's PCB capacitor phase-out program. The report is segregated by district (i.e. facility) and includes both the number and the total KVAR of capacitors removed from service. The report also provides information on the number of capacitors that have been shipped for disposal and thoae remaining in storage. This report is illustrated in figures 9 and 10. This report has been very useful in following the progress of the phase-out program. The disposal of the capacitors is the final stage of the phase-out program and this report indicates the degree of process in this final stage. PROGRAM STRUCTURE Several Individual programs which Interact with each other make up the total computerised system of PCB recordkeeping and reporting. Each program has a specific function it perfocmt end does so either upon command of the user or another program. The following details how the system is set up to allow this Interaction to occur. The fundamental logic behind the system is to have a master or execution program that will control the other support programs. This execution program is accessed by the user and prompts the user to input the function desired (E.G. input data, etc.). Once the user has indicated the desired function, the program runs the appropriate support program. Tn certain cases, the support program accesses another program to perform a specific function. This interaction can be carrted out as much as netded to ultimately accomplished a desired function such as writing the annuel report on the disposition of PCB items. The execution program in this system is celled "Newator Exec". Newstor is simply the program name which is short for new storage. It wet named this because it is a new storage system. Exec is the program type. It ie en abbreviation for execution and is actually a programming language just at Fortran is. Its primary function ts to control the execution of the support programs as describe earlier. The program is accessed by the user by typing "Ntvscor" end entering it into the computer. This procedure causes the program to ba run. It contlnuaa to run for the entire session and ts undar the control of the user. The user has the ability to ancer new date, update xiating data and initiate the writing of che annual document for the Coa^any's Annex 111 PCB Storage Facility. VS Fortran is the source code used in the support programs which perform these functions. 10-23 HONS 019182 DISTRICT OF PINEVILLE NUMBER OF CAPACITORS TOTAL KVAR ID# CONTAINED IN DRUM CONTAINED IN DRUM 2429 2430 3 I 300 100 DATE RECEIVED FOR DISPOSAL 08/08/85 08/08/85 DATE: SHIPPED FOR OISPOSAL IN STORAGE IN STORACE SUMMARY INFORMATION FOR THE DISTRICT OF PINEVILLE TOTAL KVAR OF CAPACITORS RECEIVED FOR DISPOSAL LOO KVAR TOTAL KVAR OF CAPACITORS SHIPPED FOR DISPOSAL . 0 KVAR TOTAL KVAR OF CAPACITORS REMAINING IN STORAGE LOO KVAR 'PERCENT OF CAPACITORS RECEIVEO SHIPPED FOR DISPOSAL = OX (BASED ON KVAR) TOTAL NUMBER OF CAPACITORS RECEIVED FOR DISPOSAL * 4 TOTAL NUMBER OF CAPACITORS SKIPPED FOR DISPOSAL 0 TOTAL NUMBER OF CAPACITORS REMAINING IN STORAGE = 4 PERCENT OF CAPACITORS RECEIVED SHIPPED FOR DISPOSAL - OX (BASED ON NUMBER) FIGURE 9. PCB Capacitor Phaseout Quarterly Report. Saeiple page presenting Information indicating the progress of each District (i.e. 'Facility') for the Phaseout Program. 10-24 HONS 019183 SUMMARY INFORMATION FOR ALL DISTRICTS *> GRAND TOTALS-YEAR TO DATE: TOTAL KVaR OF CAPACITORS RECEIVED FOR DISPOSAL = 93050 KVAR TOTAL KVAR OF CAPACITORSSHIPPED FOR DISPOSAL * 82900 KVAR TOTAL KVAR OF CAPACITORS REMAININC IN STORAGE - 10150 KVAR PERCENT OF CAPACITORS RECEIVED SHIPPED FOR DISPOSAL * 69% (BASED ON KVaR) TOTAL NUMBER OF CAPACITORS RECEIVED FOR DISPOSAL 1325 *** NOTEi TWO OF THESE CAPACITORS ARE SECONDARY UNITS *** TOTAL NUMBER OF CAPACITORS SHIPPED FOR DISPOSAL 1189 TOTAL NUMBER OF CAPACITORS REMAININC IN STORAGE * 136 PERCENT Or CAPACITORS RECEIVED SHIPPED FOR DISPOSAL - 90% (BASED ON NUMBER) --) GRAND TOTALS-TOTAL PROGRAM: TOTAL KVAR OF CAPACITORS RECEIVED FOR DISPOSAL - 135465 KVAR TOTAL KVAR OF CAPACITORSSHIPPED FOR DISPOSAL -125315 KVAR TOTAL KVAR OF CAPACITORS REMAININC IN STORAGE * 10150 KVAR PERCENT OF CAPACITORS RECEIVED SHIPPED FOR DISPOSAL * 93% (BASED ON KVaR) TOTAL NUMBER OF CAPACITORS RECEIVED FOR DISPOSAL 1863 *** NOTE: TWO OF THESE CAPACITORS ARE SECONDARY UNITS *** TOTAL NUMBER OF CAPACITORS SHIPPED FOR DISPOSAL 1727 TOTAL NUMBER OF CAPACITORS REMAINING IN STORAGE 136 PERCENT OF CAPACITORS RECEIVEO FOR DISPOSAL > 93% (BASED ON NUMBER) FIGURE 10. PCB Capacitor Phaseout Quarterly Report. Sample pege presenting information indicating the progress of all Districts (i.e. 'Facilities') for the Phaseout Program. 10-25 MOMS 019184 The ocher program used tn this system are called "PCBSH1P SAS" and "PHASEOUT SaS". as before, PCBSH1P and PHASEOUT are simply the program names. SAS is the program type. SAS ts a programming software package and is used extensively throughout the Company `for load forcasting, statistical analysis, and data handling and reportwriting. The PCBSHIP SAS program is the inventory control program. It is used (or inventory control of the Company's Annex III PCB Storage Facility. This program can be used to write a report showing the current number and type of PCB items in storage or to write a report containing the items to be shipped for disposal. This program was described in more detail in the previous section entitled Multiple Uses of Data, The Phaacout SAS program is used to write the report on the Company's PCB Capacitor Phaseout Program. This program is also described in the previous section. These two SAS programs are run independently from the Che other programs. They are not controlled by the execution program discussed earlier, but they do utilise the same data set. A future modification to the system will allow access to these two programs from the execution program. An IBM 4381 VM/SP Rel.4 mainframe computer is the system used at Kentucky Utilities Company. The recordkeeping and reporting programs operate under a CMS environment and are dependent on the use of CMS EXEC2 and REXX procedures, and XEDIT macros. Tht software Chat is utilised are SAS and XMENU, and VS Fortran is the program product used. SAS Insdcute Inc., Cary N.C. 27311. 10-26 HONS 019185 RADIOACTIVE AttO NON-RADIOACTIVE POLYCHLORINATED BIPHENYL (PCB) MANAGEMENT AT HANFORD Wesley W. Leonard* Robert F. Gretzlnger* Gary R. Cox* RADIOACTIVE PCB'S Equipment containing PCB's exists In both radioactive and non-radloactlve areas at Hanford. For this reason, all oil samples to be shipped offsite from Hanford for PCB evaluation must be monitored for radioactivity. A scintillation count/ checkup procedure for these liquid organics has been developed to accomplish this task and Includes the following steps: 1. A one milliliter sample (from the sample) Is collected and placed in a liquid scintillation vial which contains a standard xylene cocktail. 2. It Is counted for 10 minutes, and the results are evaluated against background levels of radioactivity. 3. If the sample Is above background levels. 0.1 milliliter of the sample is dissolved in 10 milliliters of Iso-octalne which Is then washed in ample 16 molar sulfuric acid and allowed to phase separate. 4. The sulfuric acid phase is decanted removing with it the radionuclides. 5. Repeat Step 3 three times. 6. A one milliliter sample from the acid washed solution 1$ re-analyzed as outlined in Step 2 above, and released for PCB evaluation when levels of radioactivity are below background. RADIONUCLIOE/PCB SEPARATION A Sulfuric Acid Phase Separation Process has been developed, by Rockwell Hanford Operations (Rockwell), to remove the radionuclides from the liquid organic PCB. Basically, this process Involves the same principles outlined above. Figure 1 Illustrates a possible scaled up version of this laboratory process which might obtain a definite liter per hour throughput. ^Rockwell International, Rockwell Hanford Operations, P. 0. Box 800. Richland Washington, 99352. 10-27 HONS 019186 -1 OlOVf MM I7M 1 -U ji! DM r\ pI*i DM ft SIMPPtO - OACHWC ftAMfun V4 UJkE~ MIMMO AOUtOuS COMMUOUt to*oour SAMPlMG MVOt LOAOOUl AOUtOUS ioaoout PUMP figure l. Sulfuric Acid PH*s Septrtiion Process HONS OHUJ l Polychlorinated biphenyl Items that are found to be radioactive are sent to Rockwell's radioactive PC9 management facility. Special storage and disposal difficulties have resulted because there Is no Environmental Protection Agency (EPA) approved disposal site for radioactive PCD solid waste materials. Radio active PCB fluids aiay be burned In an EPA approved Incinerator at Los Alamos, and a request was made to the Department of Transportation (00T) for permission to ship these liquids. This option Is on hold awaiting the determination of the Hanford site's total Inventory. When this Inventory Is known. Incineration and transportation costs will be compared to the Sulfuric Acid Phase Separation process to determine the most cost effective method of disposal of the radio active PCB fluids. An exeeiptlon request has been submitted to the EPA asking for a waiver to allow us to bury the drained, radioactive, PCB carcasses In our solid, low level, radio active waste disposal area, which has been modified to allow for a 20-year retriev able storage. Rockwell Is awaiting EPA's clarification on this request. TESTIN6 Rockwell's PCS testing program has grown from a 10 percent sampling of oil-filled electrical equipment for dtsposal, to 100 percent sampling of all existing ollfilled equipment In our electrical, mechanical, hydraulic, and heat transfer systems on the Hanford Site. Attempts to determine the total extent of PCB contamination on the site have developed Into a major project. It has Increased even further since the State of Washington has decreed that any Item containing PCB's up to 50 parts per million (ppm) shall be regulated If It originates from transformers, capacitors, or the reclamation thereof. When PCB's were discovered In the mineral oil of transformers stored for disposal, a 10 percent sampling program began of all existing transformers. Twenty-five percent contained 50 ppm or greater PCI's. At that time the 100 percent testing program was Initiated for all oil-filled electrical equipment. Other oil-filled equipment In non-electrical systems was sampled, due to the extant of PCB contamination found In the electrical systems. Polychlorinated biphenyl contamination was again found, which resulted In the 100 percent testing program of these systems. It Is from these hydraulic systems which perform non contact radioactive processing that most of the radioactive PCB's were produced. The Clor-N-011 screen test was used to reduce testing costs until the State of Washington enacted new regulations.* Department of Ecology, Hatardous Waste Regulations, Washington Administration Cade (MAC) 173-303 10-29 HONS 019188 All samples ere now being sent to a lab for the determination of PCS concentration. Soaie false positive test results were observed in the screen tests, probably due to chlorine containing Inhibitors in some of our oils. Each piece of equip ment tested is'dated and tagged with the test results, so that the PCS concen tration is known to anyone handling It. STORAGE AND DISPOSAL Equipment removed from service is dlspositioned to the "Storage For Disposal* facility (212-P). This facility contains: 1. A 1,500 gallon storage tank for PCD liquid. 2. A 2,000 gallon storage tank for PCB contaminated liquids. 3. An area for drum storage. 4. A controlled area for the storage of radioactive PCB liquids. Past practices, prior to obtaining the storage tanks. Included storage and disposal of equipment with the liquids Inside their carcasses. The contracted disposal company would then drain the carcasses, bury them, and send the liquids to an approved disposal site for Incineration. A "Certificate Of Destruction* for the oil was obtained, but ascertaining where the carcasses were burled was difficult. Presently, we are draining the carcasses, shipping the PCB carcasses separately, and storing all PCI contaminated carcasses on wooden pallets. The liquids containing PCB's are shipped to an EPA approved site for Incineration. In the future. It may be possible to bury the carcasses on site, and operate an approved incinerator. SUMMARY Conformance to all state and federal regulations is the goal of Rockwell in the management of both radioactive and non-radloactlve PCI's at Hanford. A continuing effort (s being made to locate, remove, and properly dispose of all PCI's. As Improved methods of management are developed, consideration will be given to them for their adaptation Into the Hanford Site PCB Management Plan. 10-30 HONS 019189