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RBCtWtD f l3 VI V PB-239 110 PRELIMINARY ASSESSMENT OF THE ENVIRONMENTAL PROBLEMS ASSOCIATED WITH VINYL CHLORIDE AND POLYVINYL CHLORIDE Environmental Protection Agency September 1974 DISTRIBUTED BY: National Technical Information Seme U. S. DEPARTMENT OF COMMERCE SAL 000050U bibliographic data SHEET ' S-560/3-7,-00, !'' PB 239 HO 4, 1 :t u and i: le 5. Report D..tc Preliminary Assessment of the Environmental Problems Associatec September 1974 with VLnvl Chloride and Polyvinyl Chloride t. 7. A uclu'i i % See Title Pape of Report for Members of Task Force 9. IVrtortmnL' Orttat.i/.jtum Naim* and Adslfoss Environmental Protection Ae^ncy Office of Toxic Substances 401 "M" Street, S.W. Washington. D. C. 204o0 12. >yonsor.n*; O: pam/.uion Nairn.- and Address Same as if9 8. Fcrtorrniii.. '*:r.in. mon K< ;'t. No. 10. DroifCi "1 ask Ai_.it l,'nu No. 11. (.oruract want No, 13. Type in Keporr A: iVrtud CovorvJ Interim Report 14. 15. 'urrU'r.u-'m.ir;. Nmvs Report on the Activities and Findings of the Vinyl Chloride Task Force 16. Ab'.-.f.ici'i -mis Report summarizes the activities and findings of the Task Force established by the Administrator on February 14, 1974. to assess the character and extent of the problems associated with the production, dis tribution, use, and disposal of vinyl chloride and polyvinyl chloride. The Report is organized into dn Executive Summary, three Sections, and Appendices. Hie first Section discusses the nature and magnitude of the problems associated with vinyl chloride and polyvinyl chloride activities. The second Section discusses previous and planned activities within the Federal Government of particular significance and the role of industry. The Report concludes with a Section setting forth the specific recommendations of the Task Force. The Appendices present a considerable body of original data developed by the Task Force with the assistance _______ of a large number of_ EPA specialists._______________________________________________ 17. Key Vtcrds and Document Analysis. l7o. Descriptors Vinyl Chloride Poluvinyl Chloride Health Effects Ecological Effects Economics Producers Materials Balance Sampling and Analysis 17b. Idcmifiers/Opcn-KnJcd Turms 17c. COSATt Field (iroup fctpfidjttd by national technical INFUOSRSpMr.ftpAfiCTldI,OVcANl , SERVICE SAL 000050.188 PfliCES SUBJECT TO CHANGE 18. Availability ^tatemcnr Release Unlimited NT1&.3J IREV 10 731 i 1. t'XDURSI.O IIV A\.<l A\0 CM-.SCO. 19. Security Cbss (this Report' r\*a.A*MFH-D 20. Sec urity (.lass (This fJapc rvn.ASsil'itn THIS FORM MAV l>K RKI'KOPUCHO 2L -Nu. ot Faces 22, Frico uscoi-vt-OC tus-Pi* PRELIMINARY ASSESSMENT OF THE ENVIRONMENTAL PROBLEMS ASSOCIATED WITH VINYL CHLORIDE AND POLYVINYL CHLORIDE A Report on the Activities & Findings of the- Vinyl Chloride Task Force Compiled by the Office of Toxic Substances Environmental Protection Agency Washington, DC September 1974 With Contributions from the Following Task Force Members OFFICE OF WATER AND HAZARDOUS MATERIALS Mr. Glenn E. Schweitzer, Office of Toxic Substances (Chairman) Dr. Nancy Beach, Office of Toxic Substances ^Coordinator) Mr. John B. Ritch, Office of Pesticide Programs Mr. David Becker, Office of Water Quality Planning & Standards Mr. John Nardella, Office of Water Quality Planning & Standards Dr. Richard Rhoden, Office of Water Quality Planning 6, Standards Mr. William T. Musser, Office of Water Program Operations Mr. Benjamin 11. Pringle, Office of Water Program Operations OFFICE OF AIR AND WASTE MANAGEMENT Mr. Mike H. Jones, Office of Air Quality Planning & Standards Mr. Alessi D. Otte, Office of Solid Waste Management OFFICE OF ENFORCEMENT AND GENERAL COUNSEL Dr. William M. Reid, Office of Technical Analysis OFFICE OF PLANNING AND MANAGEMENT Dr. Joel Jacknow, Office cf Planning and Evaluation OFFICE OF RESEARCH AND DEVELOPMENT Dr. Lawrence A. Plumlee, Office of Program Integration Dr. Henry F. Enos, Office of Monitoring Systems Dr. Robert McGaughey, Office of Environmental Sciences Dr. Andrew J. McErlean, Office of Environmental Sciences Mr. Paul E. des Rosiers, Office of Environmental Engineering Dr. Dale A. Denny, NERC-Researc.h Triangle Park Mr. Frank P. Scaringelli, NERC-Research Triangle Park STAFF OFFICES Mr. George Marient'nal, Office of Regional Liaison Ms. Leslye Arsht, Office of Public Affairs Mr. Pope A. Lawrence, Office of Federal Activities Mr. Bryan F. LaPlante, Office of Legislation REGIONAL OFFICES Mr. George J. Moein, Region IV, Atlanta, Georgia Dr. Oscar Ramirez, Jr., Region V, Dallas, Texas t it 0000' -iW 1.89 sfti- PREFACE This Report summarizes tlie activities ami findings of the Task Force established by the Administrator oil February H, IL'T-l, to assess the character and extent of the problems assocdated with the production, dis tribution, use, and disposal of vinyl chloride and polyvinyl chloride. The discussion antt conclusions -presented in the Report should be considered preliminary since the Task Force has only scratched the surface of a complicated subject and analyst's within the Agency are continuing. The Report is not a statement of Agency policy even though many of the recommendations are already being implemented. During the lifetime of the Task Force the Agency took several regula tory steps concerning' vinyl chloride. These were directed to banning pcstieidal sprays containing vinyl chloride as a propellant and requesting information f 'om industry pursuant to Section 114 of the Clean Air Act concerning vinyl chloride air emissions and related control tech lologics. Since .those activities have been or are being documented in detail in other reports, they are mentioned only briefly in this Report. Similarly, in recent months the Occupational Safety and Health Ad ministration, the Food and Drug Administration, and the Consumer Product Safety Commission took a series of regulatory actions directed to vinyl chloride. While recognizing many of the problems facing other Government agencies and the implications for ERA of their regulatory steps, the Report dwells primarily on those activities of direct i esponsibility to EPA, and problems such as worker exposure to chemicals, use of polyvinyl chloride in food packaging, and consumer products containing vinyl chloride have not been a major concern. The Report is organized into an Executive Summary, three Sections, and Appendices. The first Section discusses the nature and magnitude of the problems associated with vinyl chloride and polyvinyl chloride activities. The second Section discusses previous and planned activities within the Federal Government of particular significance and the role of industry. The Report concludes with a Section setting forth the specific recommendations of the Task Force. The Appendices present a consider able body of original data developed by the Task Force with the assistance of a large number of EPA specialists. SAL 000050:1.90 iL TABLE OE CONTENTS FREEACE EXECUTIVE SUMMARY , Background EPA Concerns Further Steps CHARACTER AND SCOPE OF PROBLEMS BEYOND TIIE WORKPLACE Emergence of ihe VCProblem Exposure to YC ofSpecialImportance to EPA Pesticidal Sprays Discharges from YC/PVC Plants: Materials Balance and Monitoring Data Transportation Accidents Unreacted Monomer Entrapped in PVC Products Health Effects of Vinyl Chloride Persistence of VC Ecological Effects of VC Otiler Chemicals of Concern in PVC Activities Size and Character of the PVC Industry Lessons Learned from VC/PVC Experiences Relevant to Other Chemical Problems INTERESTS AND ACTIVITIES OF GOVERNMENT AGENCIES AND INDUSTRY EPA Regulatory Authorities Pesticide Registration Air Pollution Water Pollution Solid Waste Disposal Pngi i 1 1 2 3 4 4 5 8 10 10 11 12 13 16 16 ii ^ ' 0 0 0 0 5 0 :l. 9 ;j. Pape Ocean Dumping Drinking Water Proposed Toxic Substances Control Act Supporting Research Activities Regulatory Interests of Other Agencies 19 Aerosol Sprays Worker Protection Unreacted VC Monomer in PYC Products Transportation Handling Related Research Activities Role of Industry 22 Reducing Discharges of VC and Other Toxic Chemicals Medical Surveillance Fenceline Monitoring for Chemical Discharges Toxicological Testing of VC Testing for Persistence and Environmcntal Fate and Effects of VC and PVC Testing for Levels of Unreacted Monomer in PVC Resins and PVC Products t RECOMMENDATIONS 26 Regulatory and DirerMy Supportive Actions Ivy EPA 26 Steps by Industry 29 APPENDICES APPENDIX I - SELECTED ECONOMIC CONSIDERATIONS APPENDIX II - PRODUCERS OF VC AND PVC APPENDIX III - THE MATERIALS BALANCE AT VC AND PVC FACILITIES APPENDIX IV - INTERIM METHOD FOR SAMPLING AND ANALYSIS OF VC IN WASTE WATER EFFLUENTS AND AIR EMISSIONS APPENDIX V - SUMMARY OF REGIONAL ACTIVITIES iii SAL 000050:192 APPENDIX VI- PERSISTENCE OF VINYL CHLORIDE APPENDIX VII- HEALTH EFFECTS OF VINYL CHLORIDE APPENDIX VIII- DISPOSAL OF PRODFCTS CONTAINING POLYVINYL CHLORIDE APPENDIX LX - ACTIVITIES OF TASK FORCE iv SAL 000 050;!. 9 E XEC U TIV E SU M MARY Background EPA's recent concern over vinyl chloride (VC) and polvvinvl chloride (PVC) was triggered by reports in January 1074 of (a) deaths of four PVC workers believed to be attributable to exposure to VC, and (b) an estimated material loss of VC and PVC of six percent during the PVC polymerization process. The investigations of the Task Eorve confirm that in the United States substantial amounts of VC--probably exceeding 200 million pounds annually -- and large quantities of P\ C -- probably exceeding 50 million pounds -- arc being discharged info the environment during the PVC pro duction process. Meanwhile, additional epidemiological and toxicological evidence supports the linkage between worker deaths and VC exposure. The YC/PVC industry has experienced rapid growth at home and abroad in recent years with PVC products currently permeating our entire economy. This multi-billion dollar industry involves not only several dozen large manufacturers of VC and PVC resin but also thousands of fabricators producing a variety of products based on PVC and probably employing more ihan 300,000 workers. There are readily available sub stitutes for PVC in some of these products; more expensive substitutes for others; and no substitutes for still others. A principal constraint on near-term production increases has been availab lity of ethylene, a petroleum derivative. A new constraint is the uncertainty over Govern mental regulatory ac tions affecting YC'/PYC activities. VC has induced angiosarcoma of the liver in rats and mice exposed to concentrations of 50 ppm at intervals simulating occupational exposure,, and this same rare and fatal tumor has been identified in at least 15 former workers in U. S. PVC facilities. Cancers at other sites, non-malignant liver disease, and a unique occupational disease -acroosteolysis -- have also been attributed to VC exposure. There is no direct evidence that VC contributes to adverse health effects at the lower levels of exposure encountered outside the workplace; how ever, two recently reported cases of angiosarcoma of the liver in non-workers who had lived near PVC fabrication plants suggest the possibility of such a correlation. At the same time there has been little effort to search for adverse effects at these lower levels. Since carcinogens are generally considered not to have a "no effects-' threshold level, there should be concern with possible risks to health at even the lowest levels of exposure to VC which are encountered in the ambient air, and possibly in water. Preliminary monitoring results at seven industrial complexes involv ing 10 PVC resin and 2 VC plants indicate that the levels of VC in the ambient air near the plants fluctuate sharply, apparently due to the periodic opening of reactor ket+les in the PVC plants, accidental plant discharges, variations in the production process, and meteorological conditions. While almost all of the samples collected contained detectable levels of VC, more than 90 percent of the instantaneous observations and 97 percent of the 24-hour samples showed amounts less than 1 ppm. At 1 SAL 0000SOU.94 several of the chr'mical complexes, a number of individual air samples showed more than 1 ppm. At one PVC plant a high of 33 ppm was obtained ai .one.. site; however, remeoied sampling indicated that this level was an unusually high excursion with iln-> avt-pago at this site less than l _ppm~_ .Most of the air sampling was done within one-half mile of the property lines of the plants. In one case a level of 3.4 ppm was recorded at a distanc e of three miles from the plant, but the average of sevc ral readings at this site was approximately .0. 5 ppm. Water effluents were also monitored, and levels varied considerably depending on the in-plant handling of wastes and treatment of wastewater. The highest level for wastewater leaving the plant site was 20 ppm. More typically, levels of 2 to 13 ppm were found. Not unexpectedly, the levels of VC entrapped in sludge and other solid wastes from the reactor kettles ranged from 100 ppm to, in one ease, 3,000 ppm. EPA Concerns The principal near-term issues facing the Agency include (a) an assessment of the risks associated with exposure to VC, with such an assessment hampered by inadequate data concerning health effects at the levels likolv to be encountered in the environment and only very preliminary monitoring results, (b) the costs to industry to reduce the levels of VC entering the environment, keeping in mind that much of the cost will be passed on to society as a whole, and (c) regulatory and related steps which will contribute to reducing the risks at an appropriate cost. Two closely related areas of interest are (a) the amount of Agency resources to be directed to VC/PVC in the months and years ahead, and (b) lessons that have been learned in addressing VC /PVC that can save time and resources in addressing other chemicals. VC air emissions from PVC polymerization plants -- and to a lesser extent from VC plants and possibly PVC fabrication plants -- are the most immediate concern to the Agency. The earlier problems related to the use of VC as a propellant in pesticidal sprays have been largely resolved with the banning of such sprays. Other current concerns related to VC include the Agency's capability to provide sound advice in the event of transportation accidents involving the release of VC; the fate and effects, if any, of VC trapped in water effluents, and particularly VC that might thereby appear in drinking water; and the migration of unreacted VC from PVC products into drinking water or into the ambient air. There arc of course a host of other chemicals involved in VC/PVC activities that should be of concern. Impurities in the VC, PVC as inhaled or ingested particulate, additives introduced to alter the proper ties of PVC, copolymers used in conjunction with PVC, and chlorinated hydrocarbon wastes from VC production all need further investigation. The by-products associated with ^VC incineration and the leaching of additives, and particularly plasucizers an ; toxic metals, from PVC products which come into contact with the aquatic environment need additional study. SAL 0000501.95 2 Further Steps Development of an air emission standard for VC is currently under way, with additional monitoring activities being planned in the immediate future to improve the basis for the standard. While additional epidemio logical and toxicological data arc slowly becoming available, it is unlikely that there will be a good technical basis within the next few months or perhaps evenwituin several years for establishing an appropriate ambient level to protect public health. Therefore, a performance standard may be i'ar easier to develop and implement than a standard based upon achieving a specific air quality level. Initial estimates indicate that available control technology when installed can reduce VC emissions by about 75 percent from PVC resin plants and 90 percent from VC plants with a concomitant increase in the cost of PVC of about four percent. Currently available information indicates that such reductions should result in ambient air levels which present no established risk to healtii or welfare. Meanwhile, close liaison with the Department of Labor is important to insure that the regulatory approach to protect the worker is compatible with EPA regulatory activities. The Agency should monitor for VC in drinking water suppL.es. Monitoring is also needed in the ambient air -- indoors and outdoors -distant from chemical complexes to determine whether concentrations of PVC products release quantities of unreacted VC that should be of concern. Further refinement of monitoring methodologies is needed in support of these efforts. The limited toxicological and epidemiological studies that are planned should be fully supported. The Agency should continue its leadership role in bringing together other Agencies to exchange views on regulatory actions, supporting acti vities, and research projects related to VC and PVC. Industry should be strongly encouraged to accelerate its efforts to reduce VC discharges and its very limited research, testing, and monitoring activities to clarify further the problems associated with VC and PVC. Finally, we have been alerted in a rather dramatic fashion to the need for greater attention to an important segment of our industrial base which will surely continue to expand in the years ahead. Many of the considerations and uncertainties that have punctuated the VC/PVC deliberations undoubtedly characterize a far broader swath of concerns over high volume industrial chemicals in general, and plastics in particular. Hopefully, we can extrapolate from current experiences with VC and PVC in identifying problems with other potentially important commercial chemicals early in their embryonic stage and thus minimize health and environmental hazards and also the economic dislocations attendant to corrective actions. In this regard the Agency should continue its efforts to seek early enactment of the Toxic Substances Control Act which can provide a much needed broader bisis for addressing these types of problems. 3 SAL 000050:1.96 CHARACTER iV\:D SCOPE OP PROBLEMS BEYOND THE WORKPLACE Emergence of the YC Problem On January 22, 1974, the B. E. Goodrich Company, the largest U. S. producer of PVC resin, notified the National Institute of Occupational Safety and Health (NTOSII) that four workers from its PVC polymerization plant in Louisville, Kentucky, apparently had died from a rare cancer, angiosarcoma of the liver. All four workers had been closely associated for many years with the production of PVC resins. The rarity of the tumor and the clustering of deaths at a single plant raised suspicions that an occupational discus" related to VC- exposure had been found. Since that time, 10 additional cases of this tumor, which developed in U.S. PVC polymerization workers since 1961, have been confirmed. This tumor has also been reported in seven workers at European polymerization plants, one worker at a U. S. PVC fabrication plant, two workers at EuroI can fabrication plants, one worker at a European VC plant, and two resi dent.; in the general population near U. S. fabrication plants. Concurrently, toxicological data from animal studies became available which further strengthened the suspicion of VC as the etiological agent in the formation of the liver cancer. A broad spectrum of cancers was reported by Professor Cesare Maltoni of Italy in different animal species at various exposure levels. His inhalation studies of rats exposed to 50 ppm at repeated intervals approximating occupational exposures have produced angiosarcomas of the liver, and abdomen as well as tumors of the kidney and skin. In mice exposed to VC the same tumors have been observed, widi the addition of lung tumors. Animal studies sponsored by U. S. industry have confirmed Maltoni1 s observations at 50 ppm. Recent epidemiological studies also suggest the possibility ? multiple cancers attributable to VC exposure. Meanwhile, statements by industry and Government officials indicated that the material loss to the environment during the PVC polymerization process may be about six percent, with more than 75 percent of the losses being VC air emissions. Also, it soon came to light that VC was being used as a propellant in pesticidal sprays, and the EPA Regional Offices were becoming more aware of railroad accidents involving VC tank cars. Until this series of events the Agency had not been particularly con cerned with VC rs an urgent problem. PVC plants had been on the list of industries to be examined as candidates for new source perform ance standards to limit air emissions. Also, limited studies of PVC disposal were underway, and VC and PVC resin manufacturing activities have been addressed in the Effluent Guidelines promulgated under the Federal Water Pollution Control Act. However, only since January have VC/PVC activities been elevated to the lev^l of priority Agency attention. * Vinyl chloride (CH^CHCl) is a colorless, faintly sweet smelling gas at room temperature. As a gas it is readily flammable a -d explosive but is usually handled industrially as a liquid under pressure. Polyvinyl chloride resin is a fine powder which is produced by polymerizing vinyl chloride. The re sin is the base ingredient for a wide variety of plastics. Exposure to VC of Special Importance to EPA Pesticidal Spravs Spurred bv the active interest of a consumer protection organiza aon, the Health ilcsearch Group, one of the earliest L'PA concerns this year was the use of VC as a propellant in a large number of pcsticida'1 sprays. After the searching of EPA pesticide registration files more than 50 different sprays containing VC -- including a large number used indoors -- were identified. It lias been estimated that in addition to the cans in the possession of consumers, up to 100,000 cans .verc in the channels of trade. Preliminary tests at EPA research facilities showed that 'a 30 second release of an aerosol containing VC could result in a concentration as high as 400 ppm in the air. Related tests showed that in closed rooms VC will persist for many hours, and even when diluted by cntilation, will probably result in some VC exposure within the household for at least several hours. (See Appendix VI). Discharges from VC/PVC Plants: Materials Balance and Monitoring Data----- --------------------------------------------------------------------------------------------------------- Industrial reports and analytical studies (see Appendix III) confirm that generally the material loss during the PVC polymerization process ranges from 4.5 to 7.5 percent. During geccnt months industry has taken a variety of steps to reduce the losses, and these losses may be now declining. The losses will vary with the type of process, the age of the plant, the level of technology that is employed, and manufacturing practices. However there is no doubt that in the United States substantial amounts of VC -- probably exceeding 200 million pounds annually -- and large quantities of PVC -- probably exceeding 50 million pounds -- are being discharged into the environment during the PVC polymerization process. Most of the VC escapes directly into the atmosphere, with lesser amounts dissolved in water effluent streams and entrapped in sludge and solid wastes. PVC losses occur as particulate in air emissions, sus pended solids in water effluents, and components of solid wastes. A principal area of VC leakage is associated with the operation of the polymerization kettles, including losses when they are opened or when they are recharged or sampled. Other 'osses occur during the transfer of VC from tank cars to storage, during the PVC drying process, and from leaks at a variety of valves, flanges, and pump seals Throughout the process. Polymer losses are similarly distributed among a variety of activities including dust collector losses, disposal of oversize particles, and sampling losses. In this regard two aspects are particularly signifi cant: there are- a variety of PVC processes with differing problems and control possibilities, and in every case the number of potential leakage points is very large. 5 SAV- oooo 501^ Losses at VC plants occur during the loading process, as the result of venting of gases, from leaks in pumps, and at other points. These losses are considerably less than one percent but still may be environmentally significant. As in the case of PYC polymerization activities, current industrial efforts should reduce these losses. No mass balance data arc available concerring losses at P\ C compounding and fabrication plants. However, the only source of VC at these facilities is the .unreacted monomer in the PVC resin which suggests that environmental discharges are less than at the VC and PVC polymerization plants. To obtain more direct evidence on VC discharges from VC/PVC acti vities, ambient air, waste water effluents, and solid wastes from seven chemical complexes were monitored during May. The 2 VC and 10 PVC production facilities located at these seven complexes are listed in the table below: Vinyl Chloride and Polyvinyl Cliloride Manufacturing Complexes Monitored by ZPA Regional Offices Louisville, Ky. Leominster, Mass. Plaquemine, La. Long Beach, Calif. Painesville, Ohio Delaware City, Del. Flemington, N. J. PVC Plant PYC Plant PVC-Plant VC Plant PVC Plant PVC Plant VC Plant PYC Plant PVC Plant PVC Plant PVC Plant PVC Plant The B. F. Goodrich Co. B. F. Goodrich Chemical Co. Borden, Inc. Borden Chemical Division The Goodyear Tire & Rubber Co. Chemical Division Dow Chemical, U.S.A. The B. F. Goodrich Co. B. F. Goodrich Chemical Co. Amei'ican Chemical Corporation American Chemical Corporation Uniroyal, Inc.. Uniroyal Chemical Division Robintech, Inc. Stauffer Chemical Co, Plastics Division Diamond Shamrock Corporation Diamond Snamrock Chem. Co, Tenneco, Inc. Tenneco Chemicals, Inc. The preliminary monitoring results indicate that the levels of VC in the ambient air near plants fluctuate sharply, apparently due to the periodic opening of polyvinyl chloride reactor kettles, accidental plant discharges, variations in the production process, and meteorological conditions. A summary of the monitoring results at each complex can be found in Appendix V. The monitoring method developed for this activity, and subsequently refined, is presented in Appendix JV. Since the samples were limited in number, time, and duration, additional monitoring is in order to obtain a more definitive assessment of VC discharges. SAL 000050.1.99 6 Most of the air sampling was done up to three miles beyond the prop erty lines of the olants although in two regions the EPA sampling teams were able to conduct part of the study v. ithin the plant property. Almost all air samples contained detectable levels of VC. However, more than 90 percent of the instantaneous samples and 97 percent of the 24-hour samples showed less than 1 ppm. In one case a level of 3.4 ppm was recorded at a distance-of three miles from the plant.' The average of several readings at this site was about 0.5 ppm. A high value of 33 ppm was observed around one complex ata distance of 0.3 miles from the fence line although the average at this site was less than 1 ppm. The levels of VC in water effluents varied considerably depending on the in-plant handling of wastes and treatment of wastewater. The highest level for wastewater leaving the plant site was 20 ppm. More typically, levels of 2 to 3 ppm were found. Not unexpectedly, the levels of VC entrapped in sludge and other solid wastes from the reactor kettles ranged from 100 ppm to 3,000 ppm. Transportation Accidents It is estimated that more than two-thirds of the produced VC is transported from the production site to another location, frequently located hundreds of miles away. More than 95 percent of the ship ments travel by rail tank car, with a small amount being shipped by water. During the past three >years there have been 16 reported rail accidents involving VC tank cars. The immediate concern has been pre vention of fire and explosion and only recently lias attention been directed to the long-term effects, if any, that might be associated with a one-time massive exposure to VC. Jj Unreacted Monomer Entrapped in PVC Products Industry has reported to EPA that PVC resin contains in very unusual cases .as high as 8,000 ppm of unreacted VC monomer although the levels are usually between 50 and 1,000 ppm. Presumably these levels are substantially reduced as the resin is processed further, with much lower levels (e.g. 5 to 20 ppm) present in finished products containing PVC. Nevertheless, the eventual fate of the unreacted monomer in PVC products is of concern. Conceivably, it could be contributing to a general environmental background level of VC, and detectable levels of VC may be present where there is a heavy concentration of products containing PVC, and particularly new products. In view of EPA's responsibilities concerning drinking water, a prob lem of special significance is the possible migration of unreacted monomer into the water from PVC pipe or liners used in drinking water systems. At present little is known about such migration. SAL 000050200 7 Health Effects of Ymvl Chloride There is no direct evidence about the liealdt effects on man of VC at the levels of exposure that have been or are likely to be encoun tered outside the workplace; however, the two recently reported nonoeeupational eases of angiosarcoma of the liver in neighborhoods near PVC fabrication plants suggest the possibility that there may be a correlation between tlie incidence of angiosarcoma and low levels of exposure. There arc also recent reports of angiosarcoma among workers at fabrication and VC plants who presumably were exposed to relatively low levels of VC. At the same time epidemiological and toxicological studies have clearly linked VC to angiosarcoma of the liver and other adverse effects at the higher levels of exposure that have been encoun tered in the workplace. Given the previous lack of effort to search for effects at low doses, it seems prudent to assume that there probably is not a no-effects threshold for VC, and there should be concern about the possible health effects at any level of exposure. Extrapolation of effects from animals to man, from intermittent to sustained or peak exposures, and from high to low dose levels is fraught with uncertainty'. Nevertheless, such extrapolations can be useful in helping set the basis for the necessarily subjective judgements that must be made as to health risks. With regard to the toxicological data, studies are currently underway at the National Cancer Institute and with in EPA using statistical methods to extrapolate from the effects at 50 ppm to likely effects at 1 ppm and lower. Such statistical techniques must be viewed with caution but can be helpful in providing a sense of perspective in assessing risk. The relative sensitivites of rats, mice, and men to VC are not known, nor is there good information on the relative sensitivities within a human population. Another difficulty is interjected in attempting to deal with the extrapolation from worker exposure (i.e. 40 hours per week) to neighborhood exposure (i.e. up to 168 hours per week), even assuming that time weighted averages arc* the determinant in ambient air rather than peak levels. The risks, if any, associated with ingestion of VC, via drinking water, food, or other routes arc totally unknown. It is prudent to assume that ingestion is no less worrisome than inhalation although the likelihood of sustained ingestion at even low levels seems remote. Summarized below are some of the most important known health effects of VC. A more detailed presentation of health data is set forth in Appendix VII, recognizing that additional information is continuously becoming available. Ongoing Agency studies are tailing this information into account. Anesth'Jtie Effects of Acute Ezposui'es: These effects have occurred in PVC workers exposed to high concentrations of VC as the result of acci dents or inadequately ventilated reactor vessels. A dizziness, nausea. SAL 000050201 8 and loss of consciousness occur which ace reversible upon exposure to fresh ajr. Human volunteers have reacted in j. similar way to high levels of VC inhaled for brief periods. Those subjects reported feeling dizzy or ineb- iated, experienced loss of certain reflexes, and on< ouniered feelings of impending unconsciousness. The effects were proportional io concentrations and duration of exposure. Acvoosieol'jpiv: A small proportion (from 1 to 3 percent) of workers involved in "manual cleaning of PVC reactor vessels have experienced a combination of symptoms known as acroostcolvsis. This is character ized by a soreness and thickening of the skin at the fingertips, a gradual dissolution of bone calcium at fingertips and toes, skin sores, and fre quently heightened sensitivity of the hands to cold (blanching of the ski~ and pain). Those symptoms were first described in 1067, and apparently occur only after several years of high levels of exposure. Liven Function Abnomnlili-'c: Changes in blood chemistry attributed to alterations in liver function have been observed in PVC workers whose 8-hour exposures to VC averaged 300 ppm. At levels below 300 ppm, the noted functional changes were minimal, suggesting a dose-response relationship with respect to liver function. There has been no overt liver disease noted. From Europe, there are reports that liver damage was found in Russian workers, and disease of the liver, skin, and other organs lias been discovered in workers in Rumania and France. Other chemicals arc invariably present in-the occupational setting, and may have interfered with the effect often attributed to VC alone. Live Aniiosnraoma: A fourtli effect related to occupational exposure is angiosarcoma of the liver, a rare form of liver cancer which is a pro gressive and invariably fatal disease. It has recently been reporred in 15 workers in PVC facilities in the United States. The exposure time of these workers in the factory setting has ranged from 11 to 30 years. Many of these workers were engaged in cleaning polymerization reactor vessels in an area where exposure levels were the highest. The etiological role of VC in the induction of liver angiosarcoma is not certain because of possible confounding factors. The occupational expo sure of the workers to other chemicals precludes identifying this substance as the sole cause for cancer. However, taking into account the effect of VC on animals in the absence of other chemicals, the implication of VC as the possible etiological agent is very strong, and unless another carcino genic agent is identified, VC must clearly remain the prime suspect. The reported eases of angiosarcoma of the liver have in the past been extraordinarily rare. For example, in the Third National Cancer Survey (1969-1D71), a population of 21 million persons residing in nine geographic areas was sampled for incidence and type of cancer. In this period, only eight cases ol' liver angiosarcoma had been newly diagnosed among that ten percent of the U.S. population. SAL 000050202 9 C.T-r.i'L'LL J. r'.rt"7.1:u<.r ?/ <o VC: On laboratory mammals VC con centrations of 5 to -0 percent have narcotic effects which are not unlike the human anesthetic effects noted above. The acroosteolysis syndrome has never be- ,, produced m animals, although disturbances in peripheral blood civ' ..iafion, abnormal cartilage formation in the toes, and abnormal skin im tons have occurred in rats. Liver enlargement in rats lias been seen with inhalation exposure as low as 100 ppm Tor 6 mohths, but little is known about frank liver disease caused by YC exposure. Among the several animal inhalation experiments employing repeated exposures of over six months duration, two have disclosed liver angio sarcoma at 50 ppm and higher in mice and rats. It remains to be deter mined whether the liver angiosarcoma observed in animals are precisely / the same as those reported for occupationally exposed workers and for non workers. Nevertheless, the similarities observed between the animals and man strongly suggest that the animal carcinogenic reaction is like that reported for PYC workers. Persistence of VC As discussed in Appendix VI, very preliminary investigations at EPA laboratories suggest that in the ambient air near the emission source YC can be considered as a stable pollutant whereas YC rather quickly escapes from agitated or aerated water. i The available results indicate a rate of reaction of about 8 to 10 per cent per hour for VC in air. The direct and indirect reaction products identified include ozone, nitrogen dioxide, carbon monoxide, formaldehyde, formic acid, and formyl chloride. High eye irritation levels found with human exposure levels are consistent with these products. Although YC would disappear significantly over longer travel distances, the conversions anticipated within a few miles downwind of YC emission sources indicate that "'C can be considered a stable pollutant near omission sources. The usual meterologioal dispersion equations l'or gases could be applied to approximate concentrations. Because of strong inversions at night during the fall and winter period, buildup of YC near emission sources might be of particular concern during such periods. Ecological Effects of YC As indicated above, preliminary studies concerning the volatility of VC from aqueous solutions as well as analyses of hydrolysis and photolysis suggest that the impact of YC in the aquatic environment may not bo significant. However, if there is a continued input of VC into water, it is possible that a steady state concentration of YC could be reached. Bioaccumulation and/or biotransformation might then become of con siderable concern. Potential terrestrial ecosystem effects, as well as transport pathways from source to plant or animal receptors, of VC arc unknown. How ever, the suspected volatilit\ YC t esuit in a large dilution factor which might reduce the toxicological or bioaccumulation hazard tc an insignificant level. 10 sal Mo 0502 03 Given the lack of past attention to the ecological effects of VC, some inferences drawn from the behavior of other low molecular weight chlorinated hydrocarbons may be helpful in anticipating the fate and effects of VC. In particular, 1, 1, 2 trichloroethane and 1, 2 dichloroethane comprise a portion of the waste products -- often referred to as tars --from the production of VC and are of conrern in themselves as well as possibly suggesting VC behavioral patterns. Other' potentially hazardous compounds, such as hexachlorobenzene and hexachlorobutadienc, are also found in these tars. Therefore, tars are discussed below. Other Chemicals of Concern in PVC Activities Immediately following the January report of worker deaths related to VC exposure, questions arose as to whether oiher chemicals, such as vinyiidene chloride, might also contribute to angiosarcoma either indepen dently or in conjunction with VC. Little work has been done to date to clarify this concern. Also, the toxicity of PVC particulate has become a significant interest. There have been some inhalation tojdcology studies conducted on PVC. However, there are no readily available data to indi cate whether any substantial risk is involved at the levels of exposure that might be encountered via inhalation or ingestion of PVC outside the work place. 2/ As pointed out in Appendix VIII, a large number of chemicals are used in PVC products as antioxidants, antistatics, colorants, iillers, plasti cizers, and stabilizers, and man\ ol' ihem can reach man through a variety of routes. The health effects of some of these chemicals are reasonably well known; the effects of others have yet to be explored. Several of them are particularly good candidates for further investigation, e.g. cadmium, barium. However, the Task Force has not attempted to assess in any detail vhe known health risks nor sort out the priorities for further investi gation. A special concern of the Task Force has been disposal of products con taining PVC and disposal of the by-products of PVC/VC plants. As discussed in Appendix VIII incineration of PVC produces HC1 and possibly metallic vapors. As the volume of PVC and other plastic products enter ing municipal waste systems continues to grow, the possibility of problems resulting from incineration and land disposal -- particularly leachates -will increase. In addition, toxic leachates from PVC used in the lining of fish tanks are known to have caused damage to aquatic organisms. 3/ The adverse effect of the tars from VC plants on aquatic organisms has been of special concern since they are known to affect at least some marine species at concentrations of 2.5 ppm. Worms and barnacles are also affected at levels below 5 ppm. Bioaccumulation of the tars appears possible through the food chain, and these materials also adhere to particles in water. However, relatively short biological half lives and rapid excretion rates may prevent serious accumulation of the tars. 4/ Size and Character ef the CYC Industry During 1973 YC production in the Uniicd States was at tlie 5.35 bil lion pound level with PYC and its eopolvmcrs at the -1.56 billion pound level. The industry ha- been opera tiny tor about forty years, and over the n..st five years has shown an annually compounded growth rate of 14 percent -- a rate of growth that is expected to taper off only moderately in the next few years. A few of the most significant characteristics of the industry are summarized below with additional details presented in Appen dices I and II. 5/ PYC has become ; very important polymer as evidenced by the broad dependence of nearly tvery branch of industrial and commercial activity upon products and components fabricated front this plastic. Markets include die apparel, building, construction, electrical, home packaging, recreation, and transportation industries. The wholesale value of the annual output of fabricated products is at least several billion dollars. The synthesis of YC is conducted in fifteen l'. S. plants, and thirtyseven plan*s are engaged in polymerization with almost all of these plants currently operating at or near capacity, rive new PVC resin plants are under construction and together with expansions at five others will yield an additional annual rapacity of 1.376 billion pounds. Additional plants are in volved in manufacturing copolymers using YC. Approximately 7500 plants arc en jged in lubricating products from PYC. It is estimated that 1000 to 1500 workers arc employed in monomer synthesis, an additional 5000 are engaged in PYC polymerization operations, and approximately 350,000 arc associated with the 7500 PYC fabrication plants. More than 97% of the monomer is used Mr the manufacture of homopoly mcr and copolymer resins, with the remainder utilized primarily for (a) the production of methyl chloroform, (b) additives in specialty coatings, and (c) until recently, aerosol propellants. Over 90% of the VC produced in the United States is manufactured by ethylene-based processes; the remaining 10% is synthesized by the acetylene-based process. In both processes VC is made by a continuous rather than a batch process. PVC resins are manufactured by four polymerization processes: suspen sion - 79% of total; emulsion - 13%; bulk - 6%; and solution - 2%, These are all batch processes. The number of PYC fabrication plants is at least several thousand but no complete compilation by company, location, and capacity is known to exist. For example, the B. F. Goodrich Company alone supplies finished resins and compounds to about 2200 U. S. customer plants. Some of the more important products are sot forth in Appendix II. / SAl- 000050205 12 Appendix I discusses the opportunities for PYC substitutes at com parable and at higher price. In many cases there are substitutes; in some cases there are no substitutes. At the present time worldwide shortages of ethylene and the uncertainty of regulatory actions concerning YC arc creating more intensive searches for alternatives to P\ C resins in a variety of applications. Lessons Learned from YC/PYC Experiences Relevant to Other Chemical Problems Except for continuing concern over spills and accidents. Government and industry have been rattier complacent with regard to the potential environmental threat from the high volume industrial chemicals (c.g. the top fifty in terms of production levels). This complacency is in large measure attributable to tlie idative absence of visible and uncontrolled dangers from exposure to the chemicals during their long histories. In addition, since cacti of these chemicals is manufactured by a number of companies, firms may lack incentive to invest, individual company resources to clarify the safety aspects of their usage. Clearly, the experience with YC -- the twenty-second leading chemical in terms of production -- underscores the problems that can result from such com placency. Despite the continuing commercial importance of these high volume chemicals, it cannot be assumed that adequate research, testing, and related safety measures will be taken by industry, and vigorous governmental leadership in this area seems essential. The Agency's experience in addressing YC discharges from PVC plants has highlighted the need for three key types of information for decision making and the difficulty of such decisions in the absence of adequate information: -- The levels of exposure to populations beyond the fenceline, with monitoring data being the key ingredient in estimating such levels. -- The health and environmental effects of the levels of exposure that are encountered, drawing on available epidemiological, toxi cological, and ecological data from all sources. -- The feasibility --in terms of technology, cost, and time --of introducing controls to reduce discharges. In all of these areas, concerted short-range efforts enhanced signicantly the existing data base and provided critical inp lis into the decision-ma ing process. Reliable techniques for sampling and analysis of VC were not available and had to be developed in a short period of time. Similarly, monitoring personnel gained their experience during the actual operations. While each chemical problem that arises will undoubtedly have unique charac teristics, EPA should be able to improve its anticipatory monitoring capability by such steps as limited stockpiling of equipment (e.g. Tedlar bags), clarification of organizational and funding responsibilities, and development of immediately available contractor support services. 13 In the pesticides area, the use of VC in aerosol propellants has emphasized the need for greater attention to the many inert ingredients in pesticides. With regard to water pollution and to drinking water con tamination, EPA must extend its emphasis beyond the traditional con cerns with gross pollution effects and with toxic metals and pesticide contaminants to include a wide range of other organic chemicals. Simi larly, in the area of air pollution, VC lias awakened the entire environmental community to the broad problem of uncontrolled and unmonitohed chemical discharges reaching neighborhoods adjacent to chemical complexes. Also, the potential problems associated with the incineration and burial of PVC products may be common to a variety of plastics. Even at this late date all the commercial products using VC have pro bably not been identified by EPA and other Government agencies, pointing out the need for a better means of acquiring information concerning the uses of toxic chemicals. Finally, the problem of unrcacted monomer in PVC products has opened a broad vista of possible new concerns associ ated with contaminants in polymers in general. -> A L 00^S0207 14 REFERENCES The material presented in this Section is based largely on original investigations and analyses conducted within the Agency. Most of these activities are elaborated in the Appendices which also cite many of the relevant scientific public ations. However, tile Appendices do not cover the entire range of the activities of the Task Force, and a few additional references concerning this Section are set forth below. 1. Estimates based inter alia on informal communications with the Department of Transportation and Manufacturing Chemists Associ ation. 2. A small sampling of the available literature on the effects cf PYC inhalation follows: Cylwik, B. , 1 Histological and Ilistoehemicai Changes of the Liver in Experimental Polyvinyl Cliloride Pncumonoconiosis," Rocz. Akad. Med. im. J. Marchlewskiego w Bialymstoku 17; 93-111, 1972. (Translation). Popow, J. , "Influence of Polyvinyl Chloride (PVC) Dust on the Respiratory System in the Rat,' Roczniki Akanemii Med. im, Juliana Marchlewskiego w Bialymstoku 24: 5-48, 1969 (Trans lation). Szende B. et al, "Pneumoconiosis Developing after Inhalation of Polyvinylchloride," Orv. Hetil. 112: 85-6, January 10, 1971. Wooley, W. D., "Toxic Products from Plastics Materials in Fires." Plastics & Polymers 41 (No. 156). 280-286, December 1973. 3. Bernhard, M. and A. Zattera, "The Importance of Avoiding Chemical Contamination for Successful Cultivation of Marine Organisms," 1970. Helgolander Wiss. Meeresunters. 20:655675. Also, informal communications with Bureau oT Sport Fish and Wildlife, Department of Interior. 4. Jernelov, A., R. Rosenberg, and S. Jensen, "Biological Effects and Physical Properties in the Marine Environment of Aliphatic Chlorinated By-products from Vinyl Chloride Production," Water Research 6: 1181-1191. 5. See also: Frey, H. E., "Polyvinyl Cliloride Resins," Chemical Economics Handbook, Stanford Research Institute, September 1973T Modern Plastics, May 1974, pp. 44-46. SAL 000050208 15 INTERESTS AND ACTIVITIES OE GOVERNMENT AGENCIES AND INDUSTE EPA Regulatory Authorities Pesticide Registration On April 26, 1974, the Agency determined that the potential risk associated with continued use of VC in pesticidal spray.' was unjustified, given the acceptable substitutes which were available. Therefore, on that date Notice was given of the emergency suspension, and intent to cancel the registrations, of all spray products containing VC for use in the home, food handling establishments, hospitals, or other enclosed areas. At the same time EPA requested that all existent stocks of such products be recalled by the manufacturers (39 ER 14753). In addition, EPA will no longer register pesticides containing VC for indoor or outdoor uses, and all existing registrations have now been withdrawn or amended to substitute another propellant. At present a few implementing details of this determination remain. Perhaps the most important action is to insure prompt removal of the cans containing VC from commercial channels and environmentally sound disposal of these products, i.e. proper land disposal. EPA Regional Offices have been actively pursuing this problem and should complete their efforts within severrl months. Air Pollution The results of the initial monitoring efforts clearly document the fact that neighborhoods adjacent to PVC resin manufacturing complexes are being exposed to some level of VC air emissions. At present there is no scientific evidence to indicate that these emissions pose an imminent hazard to people living near these plants. However, because of the severe health effects associated with occupational exposure to VC and the lack of data regarding the levels at which effects begin to occur, prudence dictates that steps should be promptly taken to reduce the emissions to the lowest practical level. Indeed, . EPA, together with state and local air pollution authorities, has an immediate responsibility to insure that these levels are reduced. The key questions revolve around (a) the levels of VC concentration that should be achieved outside the plant area, and (b) the regulatory approach that is most appropriate, e.g. ambient air standard, per formance standard for new sources, or emission standard for hazardous air pollutants. Several factors bear on such determinations in addition to the uncertainties inherent in the health risks involved, namely: the effect of regulations which are to be promulgated in early October by the Department of Labor on VC levels in the workplace; the technical feasi bility, costs, and timing of control technologies and other approaches to reducing emissions; and compliance schedules for the industry as a whole and for individual plants. jjsTke FR citations identify the Volume and rape of the appropriate Federal Register announcement. 16 SAL 000050209 Depending on the air emission level and/or the level of technology to be achieved, the costs of compliance could have several effects: The price of PYC could increase, thus opening the way for substitutes in some products. Some of the older plants might find it more attractive economically to close or to replace the old technology with new. New plants presumably would emphasize even more than at present larger reactors with fewer requirements for entry and other innovations to re ducing leakage rates. On May 31, EPA requested the manufacturers of VC and PVC resin to provide detailed technical and economic information concerning steps that have been and could be taken to reduce VC emissions. The in formation was sought under Section 114 of the Clean Air Act. The Task Force believes that a standard based upon achieving a specific air quality level will be very difficult to develop using currently available data. On the other hand a performance or emission standard, which is designed to drive down the emissions as low as practical, and in the longer run drive technology toward more envi ronmentally acceptable approaches, would see.n consistent with the desirability of reducing risks from carcinogens to the minimum possible level. Present preliminary estimates are that emissions can be reduced by 75 nercent in PVC plants and 90 percent in VC plants. Such reductions can be achieved by employing best available control technology which includes a variety of control measures that could be in place from with in several months to two years after promulgation of regulations. Each plant would likely use different combinations of such measures to achieve the necessary reductions. Currently available information indicates that such reductions should result in ambient air levels which present no established risk to health or welfare. The cumulative costs of the control technology are estimated to increase the cost of PVC resin by about four percent. An expanded monitoring program to gain additional data at selected plants to assist in setting an air standard is needed. Twenty-four hour integrated samples taken during a period of several days or longer at a number of sites around representative complexes are desirable. To the extent possible in-plant activities should be correlated with external readings. Since no previous monitoring was done at fabrication or co polymer plants, they should also be included. Water Pollution In view of its low solubility and volatility from water, VC is not currently a candidate for the hazardous substances list under Section 311 (spills) of the Federal Water Pollution Control Act. Similarly, VC in water has not been shown to present a threat to aquatic life, and there fore there is no basis at present to develop water quality criteria under Section 304(a) or to consider designating VC as a toxic effluent. At the same time, in view of the monitoring data indicating discharges up to a level of 20 ppm of VC from at least two PVC resin plants, farther investigations of its effect, if .any, on the aquatic environment seem in order, 17 SAL 000050 Tile Elfiucnt Guidelines for the Plasties Industry promulgated by EPA cover only PVC polymerization activities and not compounding or fabrica tion activities. However, some of the potentially most troublesome water effluent problems relate to the toxic materials used in the com pounding process. Also, as previously mentioned, the possibility of toxic additives in PYC pr viucts leaching into the aquatic environment is of concern. Further clarification of these problems is needed prior to considering regulatory action. Solid \taste Disposal Problems associated with disposal of PVC products through incinera tion and burial are discussed in detail in Appendix VIII. The emission of IlCl is the only clearly identified incineration problem at present although there are many uncertainties concerning the fate of PVC addi tives during the incineration process. There are well accepted environ mentally sound landfill techniques that should adequately contain PVC products. At the same time there are sufficient uncertainties -- par ticularly with regard to additives --in both of these areas to warrant more detailed investigations in the months ahead. There is no evidence at present that PVC will revert to VC during incineration or as the result of biological or chemical activity during environmental exposure. Disposal of the solid and semi-solid wastes from VC/PVC plants poses many problems encountered with hazardous wastes in general. One particular concern is the disposal of tars --a concern that was height ened last year when a large number of cattle were contaminated due to poor handling ant: disposal practices involving hcxachlorobenzene wastes. iy Another problem is the possible exposure of personnel at landfills to sludges containing up to 3000 ppm of entrapped VC which might be escaping. Given the widespread concern at the local level over VC/PVC activities, EPA guidance on handling such hazardous wastes would be welcomed. In the longer term the steps called for in the proposed Hazardous Waste Management Act might be particularly appropriate. Ocean Dumping The October 1073 criteria for evaluating ocean dumping permit ap plications prohibit dumping of organohalogcn compounds, except for narrowly defined trace amounts, and compounds which may combine with other substances to form organohalogens in the marine environment. These criteria cover the principal earlier concerns over ocean disposal of the by-products of VC/PVC manufacturing activities which were triggered by reports of fish kills in the North Sea from disposal of tars and oi the b .ildup of organohalogen compounds near Puerto Rico. Unfortunately, earlier ocean disposal practices for tars in the Car ibbean also have had adverse effects on marine life. 2/ 18 SAL 0000502:1:1. Drinking Water Currentlv (here arc no data <m VO c om e :itrations in community water supplies, primarily ljei an.se.' no one lias ever look -d for VC. Conceivably, it could bo present in drinking water. Possible sources are PVC poly merization plants just upstream from water intakes and from PYC prod ucts used in the distribution system such as t'YC pipe and storage tank liners. Monitoring a few selected water supplies should provide a basis for assessing VC concentrations that may be found in water supplies from both industrial pollution and product contamination. Adequate sampling and analytical procedures will of course be required to insure the soundness of the results. The results should be used to determine ihe need for additional sampling anrl possible research requirements. Proposed Toxic Substances Control Act An important authority which is currently missing is the Toxic Sub stances Control Act. The requirements for reporting of industrial pro duction data evisaged in the Act would enhance knowledge of the types and extent of different uses of VC, The testing provision would be the basis to obtain much nee-dec data -- and particularly data on toxicity and persistence -- for assessing the risks associated with low concentration levels of VC, including those levels that are likely to persist beyond the workplace. The proposed regulatory provisions would provide a mechanism ! ;r addressing those products using YC not. now subject to regulation under other laws. Also, if considered appropriate, steps might be tal en to limit the amount of unreaded YC in certain PVC products which could eventually migrate out of `hose products to pose an unnecessary risk. Supporting Research Activities As a component of the national effort to clarify the health risks associated with YC, the Agency plans to support a toxicological effort at the University of Cincinnati. These studies arc designed to determine the effects of YC on the developing ictus, to determine changes of YC toxicity caused by nutritional imbalance and interactions with other common chemicals, and to develop cell culture techniques for rapid screening of the oncogenic potential ` of YC and related compounds. Also, epidemiological studies of neighborhoods near PYC activities are scheduled to complement related efforts of other Government agen cies. Regulatory Interests of Other Agencies Aerosol Sprays Early this year evidence indicated lha' some supplies of hair sprays containing VC were still on the market, and the Pood and Drug Adminis tration (EDA) requested that all known manufacturers recall these 19 SAL 000050 supplies. In early April, throe manufacturers initiated recalls for hair spray and other drug and cosmetic? aerosol products. On April 22, FDA published a notice of proposed amendments to the Federal Food, Drug and Cosmetic Act concerning the use of VC as an ingredient, including propellant, of (a) aerosol drug products, and (b) cosmetic aerosol prod ucts (39 FR 14215). At the same time, but in a separate notice, FDA requested a list of all marketed drug products containing VC as an ingre dient or packaged in containers of or lined with PVC (39 FR 14238). On August 26, FDA published regulations which (a) banned the use of VC in cosmetic aerosol products, and (b) required a new drug application as a condition for marketing drug aerosol products when VC is used as an ingredient (39 FR 30830). The Consumer Product Safety Commission has undertaken two steps. An information gathering process was initiated in May to determine the specific aerosol products containing VC which are being or have been used (39 FR 16511). The Commission has identified more than 25 aerosol products containing VC ar.d is currently continuing its analyses. On August 21, the Commission promulgated a regulation, effective from October 7, banning as hazardous substances "self-pressurized products intended or suitable for household use that contain VCM as an ingredient or in the propellant" (39 FR 30114). Worker Protection i The Occupational Safety and Health Administration (OSHA) of the De partment of Labor, responsible for worker safety, determined that VC levels exceeding 50 ppm in the workplace present a hazard and on April 5 set an emergency temporary standard at that level (39 FR 12342). To initiate the process for setting a permanent standard, on May 10, OSHA proposed lowering the standard to the level of detection, defined at 1 ppm plus or minus 0.5 ppm (39 FR 16896). Public hearings to gather infor mation for a permanent standard and to assist OSHA in making a final judgement as to the adverse effects of VC and the appropriate levels of exposure to workers were held in June and July. The final standard is to be set by October 5, 1974. Much of the information being developed by OSHA is of direct rele vance to EPA concerns, and particularly concerns over an air standard. Even more importantly the regulatory action taken by OSHA within the next several months can have a profound effect on the need for and character of action by EPA. If OSHA uses health data as the basis for its standard, it is important that the interpretation of the data not be inconsistent among agencies. Also, OSHA should be encouraged to recommend control techniques which will not simply vent VC to the environment external to the workplace. Unreacted VC Monomer in PVC Products Early last year reports were received of possible migration of VC to distilled spirits and wines packaged in PVC bottles under an experimental program authorized by the Department of Treasury. Subsequent inves tigations by FDA confirmed that residual VC had migrated from the PVC 20 SAL 000050213 into vai ions distiller! spirits and wines. Since there were no available toxicological studies supporting a safe level of VC in food, I'D A published a proposal which in essence would preclude the use of PVC te_.in in con tact with alcoholic food (09 1;1{ 12931). At the same time, the Department of Treasury withdrew the approval of the experimental use of PVC bottles to contain distilled spirits. Since there was no indication, at that time, that VC migration occurred from PVC in contact with non-alcoholic foods, FDA proposed a regulati >n which identified criteria for safe use under tne prior sanction (38 FH 12931). Recently, however, FDA has received data confirming VC migration from PVC packaging into a variety of foods and currently is considering limitations on the use of PVC in food packag ing. The Consumer Product Safety Commission has not taken a position on unrcacted monomer in consumer products. Transportation Handling The problems associated with VC have heightened the concern of the Department of Transportation (DOT) as to whether any changes in its regulations are warranted since some commercially important chemicals have been identified as carcinogens. A major question is whether a single exposure to these chemicals can cause cancer. At present, DOT is con sidering the desirability of changes in labeling requirements and/or packaging requirements for carcinogens but lias not yet reached a con clusion. In July 1974, DOT published (a) proposals to amend tne bulk dan gerous cargoes regulations for the carriage of VC (39 FR 26752), and (b) a requirement for protective head shields on uninsulated tank cars carry ing liquefied flammable compressed gases such as VC (39 FR 27572). In a related action in August, DOT proposed amending the requirements for handling freight cars carrying hazardous materials to include those pla cards as "Dangerous" (39 FR 29197). Related Research Activities The Center for Disease Control (CDC) and the National Institute of Occupational Safety and Health (NIOSII) are maintaining a nationwide surveillance network of all cases of angiosarcoma of the liver which have been reported since 1965. For each case identified, the health history of the individual will be reviewed and analyzed to determine if there was any connection with VC or PVC plants. CDC/NIOSH are also conducting studies to determine if other cancers and other mortality causes are associated with exposure to VC. In these studies, pathological informa tion will be obtained from hospitals. A CDC survey among meat wrappers in Houston, Texas, should determine if chemicals produced upon combus tion of PVC film may be implicated in "meat wrappers asthma. " CDC/NTOSII are conducting a comprehensive epidemiological survey of workers from 11 polymeriv.ation and fabricating plants. Employee medical records are beitur subjected to intense sc reening to determine.' die seope and magnitude ol' VC effects. Hospital data obtained in this study are being sent to the angiosarcoma network. NIOSH is also planning studios to determine the levels of exposure at fabricating plants and to determine if cosmeticians exposed to -VC from aerosol hair sprays have had any eases of liver angiosarcoma. The Consumer Product Safety Commission plans to support rodent experiments to determine the effects over a lifetime of single dose and/or intermittent exposures of VC at several dose levels. Reproductive, mutagenic, and teratogenic effects may be considered. The National Institute of Environmental Health Sciences (NIEIIS) has taken an active role in bringing together interested Government agencies, industry, and the academic- community to begin to assess the public health implications of a broad range of chemicals used in the plastics mdustry. An initial meeting in Pinchurst, North Carolina, from July 29 to 31 was designed to set the stage for a continuing effort to sort out research pri orities within Government and industry, as well as to highlight the types of considerations that should surround regulatory actions in this field. The National Cancer Institute is providing pathology services (human and experimental animal) an! in collaboration with the Armed Forces Institute of Pathology is establishing a case registry for VC associated diseases. The National Bureau of Standards (NPS) is conducting research on -he development of calibration methods for EPA. This includes preparation of standard VC air mixtures in the ppm range and of charcoal sampling tubes with known VC loadings. NBS is also doing research to develop more sensitive techniques for the detection of VC in the atmosphere. Role of Industry During the past several months industry has cooperated extensively with the Task Force and with individual Agency offices in the assessment ot problems associated with VC/PVC activities. Summarized below arc some oi the areas of greatest concern involving major industrial commit ments. Reducing Disharges of VC and Other Toxic Chemicals There is no doubt that industry has taken and can continue to take a variety of immediate steps at relatively little cost to reduce the VC losses at VC and PVC polymerization facilities. During the part few months many plants have already started to tighten maintenance and operating procedures; other plants are installing improved pumps, seals, 22 SAL 000050315 and disconnect devices; while still other plants are introducing more significant process changes. One company is reportedly spending S3 million to tighten the processes at a single PYC facility; another company reports that it has 100 engineers working to introduce modifications that will dramatically cut VC losses at several plants. In the longer run significantly different approaches to'the polymerization process may be in order. Clearly, the opening of the reactor kettles is a major source of discharges, and a continuous rather than batch process should be considered as an example of a design change to reduce VC losses. In the batch process the trend toward larger ket tles will probably accelerate. At the same time some companies may elect to mark time with regard to major modifications or significant new departures until the initial OSILA and EPA regulatory approaches become clearer. A number of other toxic chemicals are also associated with VC/PYC activities. As previously mentioned the disposal of tars and the dis charges of toxic metals at PVC compounding plants are of particular concern, A number of the troublesome chemicals may be better known to industry than Government, and industry should not delay in taking correc tive actions even though these chemicals have not yet been designated for control by the Government. Medical Surveillance Clearly, VC concerns have triggered extensive medical surveillance programs of VC and PVC workers throughout the industry. These pro grams should become routine to cover a far broader swath of chemicals at VC/PVC and other chemical complexes. Published analyses of the results of such programs would be very valuable to EPA and other agencies. In addition, industry has a responsibility to support medical surveil lance programs for residents in neighborhoods adjacent to VC /PVC complexes and other types of plants releasing chemicals into these neigh borhoods. The character of such surveillance will obviously depend on the type of chemicals involved and the arrangements that can be worked out by industry with local health authorities. Fenceline Monitoring for Chemical Discharges Traditionally, the chemical industry has conducted very little fenceline monitoring not required by Federal, state, or local agencies to de termine the chemical discharges leaving ulant property. During the past several months, however, monitoring for VC has become a concern, and hopefully this concern will rapidly spread to other chemicals. Clearly, a plant manager should know the chemical mix of the air emissions SAL 0000502:1.6 23 drifting over the plant fence into nearby neighborhoods. Similarly, he should be fully aware of the chemical cross section of his liquid and solid waste streams. Thus, a far more intensive physical monitoring effort on the part of industry is needed - -monitoring not only for gross pollution (e.g. , biological oxygen demand, chemical oxygen demand, total suspend ed solids) but lor individual chemicals as well, including VC and related chlorinated hydrocarbons. Toxicological Testing of VC Until the recent revelations concerning the relationship of VC to angiosarcoma of the liver, the efforts of U.S. industry to clarify the chronic toxicity of VC wore nearly negligible, despite the commercial importance of VC. The industrial studies of the early sixties and the recent Manufacturing Chemists Association ( MCA) toxicological study on behalf of a number of companies have not been adequate, in terms of direction, scope, or quality. Even the additional toxicological studies which have been proposed by MCA calling for animal exposures down to 1 ppm of VC may not be sufficient if the objective is to understand in some detail the biological effects from the types of dose levels likely to be found in the workplace and beyond. This proposed effort, while important, is but a small step toward a very complicated problem. Also, a number of experts have expressed concern over the design and statis tical significance of the studies as cur rent'.y planned. Testing for Persistence and 'Environmental Fate and Effects of VC and PVC A related area is industry's responsibility to clarify the environmental fate and effects of the chemicals it manufactures, and in this case the behavior of VC in water and air (including degradation products) and the fate and effects of products containing PVC in soil and water. This is a new area which has not attracted sufficient attention from industry but which is of crucial importance in assessing environmental impacts of chemical activities. Governmental leadership will probably be essen tial in helping to point the way as to :he types of tests and analyses that are the most appropriate. Testing for Levels of Unrcactcd Monomer in PVC Rosins and PVC Products In view of t'r. likelihood that PDA will limit the levels of unreacted VC allowed in PVC food packaging, industry has recently accelerated efforts to analyze the levels of VC that are present in PVC resin used for food packaging and in the packaging itself. This relatively inexpensive pro cedure should be extended to other types of products as well. It is par ticularly important that the manufacturers of resin, who in general are well equipped to carry out the necessary sampling and analysis, advise their customers (i.c., the fabricators) of the quality of the resin in terms of unrcactcd monomer in addition to the usual quality criteria. The fabricators in turn have a responsibility to be aware of the levels of unreacted monomer that persist in the products that eventually reach the marketplace. 24 SAL 000050217 references The- technical information presented in this Section is based princi pally on informal communications with the concerned EPA offices, other Federal agencies, and industrial representatives. Two relevant publications not cited in the Appendices arc identified below: 1. Environmental Contarr?nation from Ilcxachlorohenzcnc, Office of Toxic Substances, Environmental Protection Agency, July 20, 10 <3. 2, Aubcrt, M., "Effect on the Marine Environment of the Combustion at Sea of Some Industrial Waste", Center of Biological Studies and Research and of Oceanographic Medicine (C. E. R. B.O.M. ), Nice, France, January 1974. S-U 0000302:1 25 1t IfCO ,\ IM E X DAT IO X S This Section sets l'orili the recommendations of the Task hon e concerning stops that should he taken by the Agency and steps that the Agency should encomai,c industry to take in the near term to (a) help clarify and reduce the risks associated with VC/PVC activities, and (b) take full advantage' of our experiences with these chemicals in ad dressing other chemicals. Regulatoyv and Directly Supportive Actions by EPA Recommendation HU An air standard for VC should be establivoed as soon as practical under the Clean Air Act for VC and PVC polymerization plants and, if warranted by further investigations, for PVC fabrication plants. The Agency should determine the ambient levels that are likely to be achieved and, to the extent possible, the health risks associated with such levels Recommendation H2: Additional ambient air monitoring should be carried cut to support regulatory action under the Clean Air Act. Those efforts should include sampling at a numbpr of carefully selected sites around a few VC, PVC polymerization, and PVC fabrication plants. The moni toring measurements made at these facilities should be correlated with specific in-plant activities such as reactor venting. Recommendation /'3: More detailed material balance studies should be conducted, in cooperation with industry, at a f.w VC and PVC polymerization plants. Specific VC leakage points should be more clearly identified, and attempts should be made to correlate the magnitude and timing of the estimated losses with the levels of VC detected in a monitoring program. Recommendation M: A program should be initiated to determine whether and to what extent background levels of VC are present in the ambient air -indoors, and outdoors--due to the presence of PVC products. Recommendation Ho: A limited VC monitoring program should be undertaken of drinking water supplies which might be contaminated from VC discharges from nearby PVC plants. Prior to undertaking the program sampling and analysis procedures should be carefully reviewed and refined as necessary. 26' SAL 0000502:1.9 Recommendation #6: A study should be conducted to determine the amount of VC migra ting out of PYC products used in water distribution systems--such as PVC pipe or storage tank liners. Prior to undertaking the pro gram sampling and analysis procedures should be carefully reviewed and refined as necessary. Recommendation #7; To insure comparability of results between laboratories EPA should further develop its interim method into a standardized method for monitoring levels of VC. Concurrently, the Agency should also investigate the feasibility of developing continuous air monitoring devices. Recommendation #8: Monitoring and bench-scale studies should be conducted around industrial storage and disposal sites and municipal disposal sites to determine the types and quantities of toxic substances leached or discharged out of (a) semi-solid and solid wastes generated by YC/PVC facilities, or (b) PVC products discarded by consumers. If these studies indicate that there could be a health or environ mental hazard, guidelines should be developed to control the storage and disposal of these wastes. Recommendation #9: The responsible Office should continue to support currently planned VC toxicological studies. Recommendation #10: The responsible Office should continue to support currently planned VC epidemiological studies. Recommendation #11: More intensive studies should be conducted on the behavior of VC in the atmosphere and in the aquatic environment, and particularly on its degradation products and related chemical reactions. These studies should be supported by both industry and Government. Recommendation #12: The industries covered by the Effluent Guidelines for the Plastics Industry promulgated under the Federal Water Pollution Control Act should be expanded beyond the production of resins to include the compounding and directly associated activities that result in discharges into the water of toxic metals and other chemicals of par ticular concern. 27 SAI... 000050220 / Recommendation sl3: Enforcement efforts, includin'! spot checks of manufacturers, distributors, and retail outlets, should continue to be pursued vigorously to insure that pcstieidal sprays containing VC as a propellant are removed from the channels of trade as rapidly as possible. Recommendation =1-1; Regional, State, and local authorities should be kept fully informed of Agency efforts under the Clean Air Act and other authorities. As the Federal approach becomes clearer, they should be encouraged to undertake supportive actions as appro priate. Recomn.enda ion *15: The Agency should build on the experience gained in respond ing to the problems associated with VC in strengthening its organizational, manpower, and contractor resources to anticipate and respond to similar situations involving other chemicals. Read'ly available information on the handling of VC should be made available to the Regional Offices to assist them in respond ing to rail or barge accidents resulting in the release of VC. i Recommendation 16: Laboratory procedures lor safe handling of \ C should be developed and distributed to all EPA laboratories. Consideration should be promptly given to how such procedures can most effectively be developed for a number of carcinogens that are likely to be of con cern to the Agency. Recommendation #17: Should the Toxic Substances Control Act be enacted, prompt consideration should be given to the need for and feasibility of (a) requirements for industrial testing of the toxicity of VC at low ambient levels and the persistence of VC in different media, and (b) limitations on the levels ol unreaeted VC monomer in selected PVC products. Recommendation #18: The Agency should continue its leadership role in bringing together the interested Federal agencies to exchange views on regulatory actions, supporting activities, and research projects directed to pi oblems associated with VC and PVC. In addition, an appropriate interagency mechanism should be developed to address a broader spectrum of potential problems associated with the plastics industry. 28 SAL 000050 Recommendation "ID: EPA should exercise leadership in stimulating Governmental and industrial elf arts to analyze in depth the other high volume chemicals (c.g., top 50 ir. terms of pounds of production) to identify those which deserve additional testing or controls to clarify or reduce potential environmental problems. Steps bv Industry Recommendation #20: All possible steps to tighten up operating and maintenance pro cedures to reduce VC and PYC losses at VC, PVC polymeri zation, and PYC fabrication facilities should be taken promptly, without waiting for further Governmental regulatory actions. R&D efforts should be expanded to develop new approaches to reduce losses during polymerization, such as continuous flow systems. Recommendation "21: Each VC and PVC resin facility, and indeed chemical complexes in general, should have up-to-date information on the character and extent of the chemical pollutants that are leaving the plant property as air, water, or solid \yaste discharges or degradation products. A systematic monitoring program operated by industry at the fence line and beyond will in many eases be essential to ascertain the nature of the pollutants reaching nearby neighbor hoods. Recommendation if 22: The levels of unrcacted VC monomer in all grades of PVC resin should be routinely ascertained and purchasers of the resin should be advised accordingly. Also, analyses of the rates of release of VC monomer from PVC products should be expanded. Recommendation #23: The Manufacturing Chemists Association should, in consultation with interested Government agencies, carefully reevaluate its planned VC toxicological experiments at low doses to insure that the design is (a) statistically reliable, and (b) relevant to the ambient air concerns of EPA. SAL 000050 29 PRELIMINARY ASSESSMENT OF THE ENVIRONMENTAL PROBLEMS ASSOCIATED WITH VINYL CHLORIDE AND POLYVINYL CHLORIDE (Appendices) i Report on the Activities and Findings of the Vinyl Chloride Task Force Environmental Protection Agency Washington, DC September 1974 30< SAL 0000 TABLE OF CONTENTS APPENDICES I. Selected Economic Considerations Production Levels Competitive Substitution International Aspects Control Technology II. Producers of Vinyl Chloride and Polyvinyl Chloride VC Producers PVC Producers PVC Copolymer Producers III. The Materials Balance at Vinyl Chloride and Polyvinyl Chloride Facilities Vinyl Chloride Production Facilities Polyvinyl Chloride Polymerization Facilities IV. Interim Method for Sampling and Analysis of Vinyl Chloride in Waste Water Effluents and Air Emissions Scope and Application Summary of Analytical Procedures Interferences Apparatus and Materials Reagents, Solvents, and Standards Sampling Calibration Procedure Quality Control V.Summary of Regional Activities Region I: Region II: Region III: Region IV: Region V: Region VI: Region IX: Leominster, Massachusetts Flemington, New Jersey Delaware City, Delaware S. Charleston, W. Virginia Louisville, Kentucky Painesville, Ohio Plaquemine, Louisiana Long Beach, California 1 1 1 4 4 6 6 6 8 10 10 11 17 17 17 17 18 19 20 23 25 25 26 26 27 27 28 28 29 29 SAL 000050 VI. VII. VIII. DC. Persistence of Vinyl Chloride Behavior of Vinyl Chloride in Air Behavior of Vinyl Chloride in Water ` Behavior of Vinyl Chloride in Closed Rooms Health Effects of Vinyl Chloride Occupational Cates of Liver Angiosarcoma Cases of Hepatic Angiosarcoma, Connecticut, 1935-1973 Observed Deaths /Expected Deaths in VC Workers Summary of Toxicological and Epidemiological Studies on Vinyl Chloride Disposal of Products Containing Polyvinyl Chloride Incineration Landfilling Resource Recovery Activities of Task Force 31 31 31 32 34 38 40 44 63 g3 64 65 67 32< a SAL 000050 APPENDIX I SELECTED ECONOxMIC CONSIDERATIONS Production Levels During 1973, VC production was at the 5.3 billion pcund level with PVC and its copolymers at the 4.6 billion pound level. PVC has become a very important polymer as evidenced by the broad dependence of nearly every branch of industrial and commercial activity upon products and components fabricated from this plastic. In Table 1, major PVC products manufactured during 1973 are iden tified. TheU.S. VC/PVC industry has been operating for more than forty years, ana over the past five years has shown an average annual growth rate of 14 percent --a rate of growth that had been expected to taper off only moderately in the next few years. The size of this industry can be appreciated bv considering that the synthesis of the monomer is conducted in fifteen U. S. plants, and forty-three facilities are engaged in polymerization of PVC (including its use as a copolymer) with almost all of these plants currently operating at or near capacity. At least >7, 500 plants are engaged in fabricating products from PVC. About 1,500 workers are employed in monomer synthesis and an additional 5,000 in polymerization operations. Estimates have suggested that up to 350, 000 workers may be associated with the fabrication plants. The wholesale value of the annual output of fabricated products based on PVC is at least several billion dollars. Competitive Substitution Should requirements for worker safety or environmental controls drive the price of PVC resin upward, it seems likely that some PVC products would be displaced by products using other plastics or other materials. Other products dependent on PVC might disappear alto gether from the marketplace. Probably one-fourth to one-third of current PVC products by value are marginally competitive with other plastic products. At significantly higher prices a lesser number probably would find substitutes in other materials at higher costs. Identified in Table 2 are a few of the substitute materials that might be considered. For some uses, there are no apparent substitutes. *7 *7< i s SAL 000050226 1 Mark c>t Category I. Apparel II. Building and Construction III. Electrical IV. Home V. Packaging VI. Recreation VII. Transportation VIII. Miscellaneous Table 1 MAJOR PYC PRODUCTS Products Baby pants footwear Outerwear Extruded foam moldings Flooring Lighting Panels and siding Pipe and conduit Pipe fittings Rainwater systems, soffits. facias Swimming pool liners Weatherstripping Windows Wire and cable Applia.-.ces Furniture Garden hose Housewares Wall coverings and wood surfacing films Blow molded bottles Closure liners and gaskets Coatings Film Sheet Phonograph records Sporting goods Toys Auto mats Auto tops Upholstery and seat covers Agriculture (incl. pipe) Credit cards Laminates Medical tubing Novelties Stationery supplies Tools and hardware Other 1973 1000 mel 12 66 31 26 211 5 39 525 44 16 13 16 26 194 20 145 18 51 54 36 9 9 59 35 66 25 88 18 15 83 66 8 23 23 7 18 8 45 Total 34 < 2158 2 SAL 000050227 Table 2 SUBSTITUTE MATERIALS FOR PVC PRODUCTS PVC PRODUCT Pipe & Tubing Flooring Electrical Insulation L ecords Film & Sheet Products Coatings Household Goods Packaging SUBSTITUTES Polyethylene Polypropylene Metals ABS resins Asphalt Wood ABS resins SAME PRICE RANGE X X X Polyethylene Polypropylene EPDM rubbers SBR rubbers TFE plastics X X ABS resins Acrylics Polyvinylidene chloride Polyethylene Polypropylene Cellulosics X X Acrylics Polyurethanes Cellulosics Styrene Polyethylene Polypropylene Wood Metals Acrylics X X X Polyethylene Polypropylene Polyvinylidene chloride Cellulosics Acrylics Polyurethanes Glass X X XXXXX XXX XXX X X XX XXX XX XX HIGHER PRICE 35< 3 SAL 000050223 International Aspects U. S. based manufacturers currently produce about one-third of the western world's supply of resins, with ihe U. S. market also consuming about one-third of the total, in l`J73, 3. 7 percent of PYC and 7.8 percent of VC manufactured in the United States were exported. Prior to the recent U. S, concern over worker and environmental controls at VC and PVC facilities, there was no reason to anticipate a major change in the U. S. share of production or market during the next few years. Recent increases in demand for PVC resins -- and concurrently for VC --at attractive prices have been of worldwide dimensions with expansion plans for PVC manufacturing being considered by a number of companies at home and abroad. There is presently an import duty on PVC resin from countries with status as Most Favored Nations of 1 1/4 cents per pound plus six percent ad valorem and from other nations of four cents per pound plus 30 per cent ad valorem. Given the current U. S. market price of 18 to 24 cents per pound for the general purpose uncompounded resin, there has been little incentive to import PVC resin. Also, there currently is little export incentive because of short U. S. supply and unattractive foreign prices. However, higher prices as a result of more stringent worker or environmental controls in PVC resin plants in the United States than abroad might well stimulate significantly increased imports. Control Technology While there appear to be a number of general approaches for reducing the discharge of VC into the environment at VC and PVC resin plants and the discharge of PVC at resin plants, in many respects the approaches must be tailored to the individual plants. All VC plants and some PVC resin plants are outdoors while other PVC plants are at least partially enclosed. A variety of production processes are used, and different kinds of technology are employed. However, there are some common measures that would reduce VC emissions. FOR VC PLANTS: 1. Reducing the escape into the atmosphere of VC when venting the tank car gauge tube, disconnecting the feeding line, and closing the valves during rail tank car loading. Mechanical disconnect de vices and double block and bleed piping are available to ease this problem. 2. Improving the quality of pumps to reduce the possibility of leakage due to failure of seals. Pumps are available today which could minimize this problem. 5. Venting unintentional leaks and spills into a system which is flared and, preferably, scrubbed. FOR PVC RESIN PLANTS: 1. Collection and destruction of purge gases from the reaction kettles prior to opening for cleaning, sampling, or recharging. 2. Centralized collection and filtering of VC vapor discharges from dryers and centrifuges. With regard to PVC particulate in air and water discharges, improved housekeeping and relatively simple ventilation filtering systems are usu ally technically feasible and effective. Laboratory data have shown that VC can be adsorbed on activated carbon. Concentrated VC vapor streams have produced a recovery work ing capacity on carbon equivalent to about ten percent of the carbon weight. Ambient air con' '"ninated with low levels of VC produces significantly lower adsorbent .rking capacities. Control of dilute VC is therefore possible but may not be practical using activated carbon. Carbon regene ration using steam or pressure swing appears possible, with recovery of desorbed VC for recycle. Clearly, these approaches will not eliminate losses but should mate rially reduce them. In the longer run, the development of continuous flow processes, the use of larger kettles, better housekeeping, and/or reductions in the number of feed lines might result in more dramatic reductions of VC leakage. REFERENCES T. Modern Plastics, Jan 1974, p. 43 2. The 1972 Census of Manufacturers shows 7, 574 plants manufacturing miscellaneous plastics products (SIC 3079), a substantial number of which use PVC. SIC 3079 probably covers most, but not all, PVC fabricators. 3. Discussions with representatives of the Department of Commerce, Manufacturing Chemists Association, and Society of Plastics Industry. 37* 5 SAL 000050230 APPENDIX II PRODUCERS OF VINYL CHLORIDE AND POLYVINYL CHLORIDE The major producers of VC, PVC, and PVC copolymers are listed in this st i non with the plant location and available capacity data. VC Producers Location Annual Capacity (Millions of Pounds) Allied Chemical Corporation American Chemical Corporation Continental Oil Company Dow Chemical, L'.S. A. Ethyl Corporation 13. F. Goodrich Chemical Company Monochem, Inc. PFG Industries, Inc. Shell Chemical Company Tcnneco, Inc. Baton Rouge, La. Long Beach, Calif. Westlake, La. Freeport, Tex. Oyster Creek, Tex. Plaquemine, La. Baton Rouge, La. Pasadena, Tex. Calvert City, Ky. Geismar, La. Lake Charles, La. Guayanilla, P. R. Deer Park, Tex. Norco, Tex. Houston, Tex. 300 175 650 200 700 390 300 150 1000 300 400 500 840 700 225 PVC Producers Air Products and Chemicals, Inc. American Chemical Corporation Borden, Inc. Continental Oil Company 38< Calvert City, Ky. Pensacola, Fla. Long Beach, Calif. Illiopolis, 111. Leominster, Mass. Aberdeen, Miss. Oklahoma City, Okla. 150 50 150 140 180 285 240 6 S Al- OO 005 02 3.1. Company Locations Annual Capacity (Millions of Pounds) Diamond Shamrock Chemical Company Deer Park, Tex. Delaware City, Del. 270 100 Ethyl Corporation Baton Rouge, La. 130 The* Firestone Tire & Rubber Company Perryvillo, Md. Poitstown, Pa. . 230 270 The General Tire & Rubber Company Ashtabula, Ohio Pleasants County, W. Va. 125 50 B. F. Goodrich Chemical Company Avon Lake, Ohio Henry, 111. Long Beach, Calif. Louisville, Ky. Pedricktown, N.J. 140 140 140 340 170 The Goodyear Tire & Rubber Company Niagara Falls, N.Y. Plaquemine, La. 100 100 Great American Chemical Corporation Fitchburg, Mass. 40 Hooker Chemical Corporation Key so r-Century Corporation Burlington, N.J. i Ilicksville, N.Y. Saugus, Calif. Delaware City, Del. 180 15 35 35 Monsanto Company Springfield, Mass. 70 National Starch & Chemical Corporation Meredcsia, 111. 10 Olin Corporation Assonet, Mass. 150 The Pantasote Co. of New York, Inc. Passiac, N.J. Point Pleasant, W.Va. SO 90 Robintech, Inc. Painesville, Ohio 250 Stauffer Chemical Company Delaware City, Del. 175 Tenneco Chemicals, Inc. Burlington, N.J. Flemington, N.J. 165 70 Union Carbide Corporation South Charleston, W. Va. Texas City, Tex. 160 240 Uniroyal, Inc. Painesville, Ohio 140 7 0000502,^ SAL PVC Copolymer Producers C omnan y Locations A. Polyvinyl Chloride-Propylene Copolymer Resins Air Products and Chemicals, Inc. Calvert City, Ky. B. PolvMnvl Chloride-Vinyl Acetate Copolymer Resins Air Products and Chemicals, Inc. Calvert City, Ky. American Chemical Corporation Long Beach, Calif. Atlantic Tubing & Rubber Company Cranston, R. I. Borden, Inc. Bainbridge, N.Y. Compton, Calif. Dcmopolis, Ala. Illiopolis, 111. Leominster, Mass. The Firestone Tire & Rubber Comany B. F. Goodrich Chemical Company Pottstown, Pa. Avon Lake, Ohio Louisville, Ky. Hooker Chemical Corporation Keysor-Century Corporation National Starch and Chemical Corporation Olin Corporation The Pantasote Company of New York, Inc. Hicksville, N.Y. Saugus, Calif. Meredosia, 111. Assonet, Mass. Passaic, N.J. Point Pleasant, W. Ya. C, Polyvinyl Chloride-Vinylidene Chloride Copolymer Resins BASF Wyandotte Corporation South Kearny, N.J. Borden, Inc. Bainbridge, N. Y. Compton, Calif. Demopolis, Ala. Illiopolis, 111. Leominster, Mass. 40< 88 00<>050233 Dow Chemical, U.S. A. B.F. Goodrich Chemical Company W. E. Grace & Company Morton-Norwich Products, Inc. National Starch and Chemical Corporation SCM Corporation Tenneco, Inc. Union Carbide Corporation Midland, Mich. Louisville, Ky. Owensboro, Ky. South Acton, Mass. Ringwood, 111. Meredosia, 111. Huron, Ohio Burlington, N. J. Flemington, N.J. Institute and South Charleston, W. Va. Texas City, Texas REFERENCES 1. 1974 Directory of Chemical Producers, USA, Chemical Information Services, Stan/ord Research Institute, Menlo Park, California, 1974. 2. Chemical Marketing Reporter, May 20, 1974. 4i< 9 000030234 APPENDIX III THE MATERIALS BALANCE AT VINYL CHLORIDE AND POLYVINYL CHLORIDE FACILITIES Vinyl Chloride Production Facilities Detailed, reliable data for estimating material losses at VC facilities with precision are not readily available. Therefore, only generalized estimates have been attempted. A simplified block diagram for production of VC from ethylene and chlorine is shown in Figure 1. Some VC complexes utilize oxychlorination units; others produce ethyl chloride from the by-product hydrogen chloride (IIC1) and ethylene. However, the production of dichloroethane (EDC) allows for many aoproaches to recycling of light and heavy materials such that the losses of VC are reduced. Even vent streams of inerts can be scrubbed with EDC for maximum removal of VC before venting. Light ends such as methane are usually flared and VC is converted to water and small amounts of HC1. VC losses have come primarily from vent streams, the storage and transportation loading systems, and seepages from pumps. If vent streams are not scrubbed or flared, the amount of VC reaching the atmosphere increases considerably. This in turn is influenced by the purity of the ethylene and the chlorine being fed' into the units. Usually, these inerts come out in the EDC unit but may be carried on depending upon the pro ducer1 s philosophy regarding the purity of the EDC to be fed to the cracker. Experience has been that the higher the purity of EDC both with regard to light and heavy material, the greater the efficiency of the cracking. It is frequently difficult to pinpoint the areas and quantities of VC losses. However, some generalizations can be made for, as an example, a plant producing 500 million pounds per year' of VC. (The industry is heading toward plants of this size and larger.) Tank car loading losses may be several hundred pounds per day. Vent stream losses could reach another 100 pounds per a y while losses of VC entrapped in the water effluent might be a few pounds per day. m addition to these very small operating losses, there are undoubtedly unintentional losses from leaking pumps, flanges, and containment vessels, with total plant losses probably less than 0.1% or less than 500,000 pounds per year. From an environment il standpoint, the disposal of the heavy chlori nated hydrocarbons may also present a problem. Some are sold to solvent scrap dealers for salvage. In the past much of the material has been dumped at sea or put into landfills or deep wells. More recently, incin eration has b2en used, which is known to produce HC1 emissions. 42- 10 SAL 000050235 Polvvinvl Chloride Polymerization Facilities Reasonably reliable data are available for estimating material losses at PVC facilities. However, generalizations applicable to the entire industry must be surrounded with many caveats. It must be emphasized that there are a number of PVC processes, and each plant has its own idiosyncrasies. VC losses will fluctuate depending on the care exercised in operating the PVC plant, types of products produced, trequency of product change, method of PVC shipment, and emergency situations. Estimates of losses have varied widely in the industry, indicating the complexity of establish ing precise losses for a given facility and overall losses on a nationwide basis. In general, older PVC plants are smaller than those being built today and are equipped with smaller sized reactors. With small reactors, the number of batches required to produce a given amount of PVC is greater, and tlius the number of process steps are increased with a greater poten tial for loss of both VC and PVC. Further, a small plant has the disadvan tage of having to make frequent resin changes to meet customer demands. During these changeovers a certain amount of off-grade resin is produced. In addition, older plants have the added burden of higher maintenance than new plants, but this tends to stabilize after a few years. The handl ing of VC and the production of the high quality resins which are demanded by the marketplace require a reasonable maintenance program. Mainte nance consists primarily of the care of agitator seals, pump seals, and valves and the removal of polymer which slowly builds up in VC lines -primarily in the recovery system. Although many older facilities have beei. in operation for years, they are usually not the same as when first installed. Some of the operators have continur.lly ndated the plants for many reasons including labor savings systems, new product requiremen-.fi, i ^placement of wornout equipment, addition of new product lines, ard safety. When VC was cheap and there was little concern about its toxicity, the emphasis was almost exclusively on productivity. Often this resulted in high losses of VC to the environment as recovery cycles were reduced. Today, the picture is changing. Not only are thv. producers trying to reduce the direct VC losses, but they are also trying to minimize PVC losses by scheduling longer production runs between product changes. As an example, the newer large plants are setup with multiple production lines. This allows the dedication of one line to a given product which results in very low resin loss due to product change. 43< 11 SAL 000050236 The traditional method of stating yield ot VC in PVC plants has been based upon pounds of prime resin in the bag as compared to VC invoiced. This often has led to a misunderstanding about VC losses with the interpretation that a 94% vield means 6% VC loss to the envi ronment. In fact some VC may never actually be received because of the inability to measure the weight of tank cars accurately, some of the losses are in the form of PVC scrap, and some losses escape as PVC particles. A properly run and maintained suspension plant using technology that, is ten years old should be capable of obtaining a 95% or higher yield unless some especially esoteric resin is being produced along with large amounts of scrap or off-grade resin. For the older plants, the losses will probably be significantly higher. Other than overall sloppy operation, the recovery system is the single most important part of the plant govern ing VC losses. If insufficient time is allowed or vacuum is not applied, then the VC content in the PVC/watcr slurry will be greater than neces sary. As a result, VC losses will occur in the centrifuge effluent water, drier/ product collector ventair, the venting of the reactor, and the slurry tank. The magnitude of VC and PVC losses in a typical PVC plant is described in Figure 'i. These losses are expressed as a range of losses depending on the feed rate, reactor size, reactor cleaning procedures, batch sizes, level of technology, and general housekeeping and operating procedures. The following comments on manufacturing practices may help put these losses into perspective: 1. VC Feed - This is shipped as virtually 100% VC and does not normally contain an inhibitor. 2. VC Unloading - Considering normal losses in disconnecting the piping, sampling, tank gauging, pump and compressor seals to the tank cars, losses to the atmosphere should not be greater than 100 pounds per car. 3. VC Charging - A 0.05% loss between storage and polymerization should cover losses from flanges and seals throughout all VC handling equipment. 4. Polymerization - The loss from build-up of PVC on the walls of the reactor is split between reactor wash-out and the slurry strainer. 5. Reactor Venting - Before the reactor can be cleaned, residual VC is ventc'cT After recovery and emptying the PVC resin, the reactor is full of a mixture of air, moisture, and VC at ambient conditions. 44 < 12 SAL 000050 6. Recovery - Processing schemes will vary, but one of the most widely used is the direct recovery of unreacted VC from the reactor. While the reaction can be carried out further, economically it is essen tially complete at 90% conversion or even less depending on the type of resin. At this point the residual VC is recovered by means of compres sors which evacuate VC from the reactor. The recovered VC is con densed and distilled before recycling to the reactor. 7. Drying - Unreacted VC is collected in the recovery system but there are losses of polymer in the drier due to coalescence of the resin and periodic clean-out. This is almost entirely scrap, 8. Product Collector - Most plants use bag collectors so that the loss of resin is less than one pound per hour, but there are losses due to product changes which raise the total. 9. Screening - Oversize resin is removed from the final product. This material Consists of scrap and off-grade resin. With the current PVC shortage much of this off-grade resin is used as prime resin by special customers. 10. Miscellaneous - In addition to the above losses, others occur as scrap or off-grade polymer and as quality control samples. a. Bad Batches - Most plants experience batches which are off specification. These range from "just slightly off" to solid batches, with losses at 2 to 3 batches per month or about 0.4% or 40 pounds per hour average1. Salvage value depends upon the degree of "off-grade" and market conditions. 0. Samples - Probably about 0.05% or 5 pounds per hour and is usually destroyed in testing. c. Polymer Build-up - VC slowly polymerizes in the pipe lines, particularly the recovery system, and must be removed peri odically. No quantitative value is available for this loss. d. Spillage - Some of the product is shipped in bulk and some is bagged. While some spillage occurs in bulk handling, more occurs in bag filling and in bag breakage. e. Centrifuge Effluent - Some PVC enters the effluent water. 11. Product Change-Over - As indicated previously there are losses in the drier and collector due to cleaning for changes from one product to another. In addition one must segregate the first product that comes through this system. The amount can vary widely depending upon the number of changes and the sensitivity of the product to contamination from the previous product. 4S< 13 ) 00050 S At The foregoing analysis, together with estimates provided by industry, suggests that the losses of VC at PVC polymerization facilities currently range from about 3.0 to 6.3% while PVC losses are on the order of 1. 3%. 46< 14 SAL 000050239 PRODUCTION OF VC FROM ETHYLENE AND CHLORINE SIMPLIFIED BLOCK DIAGRAM Chlorine^ Ethylene dichloroethane reactor A Purifi~}j cation Crack Quench Recycle dichloroethane ,, \ & Heavies To Wa^te or Pyrolysis Dry di< hioroethane KC1 removal VC purifi cation JUL * . Recycle HC1 dichloroethane drying Alternate system L-----> F.thylene ethyl chloride reactor -- -- ----> Ethyl chloride Cf-D Wa ter 'ji / l"Ml! <!. \f - 1 \/ ( .. \ i. ft PRELIMINARY EST1.MV C CE LOSSE' Pvcif: :us.'Cks;o:; polymc.*i,,;,c,.j typical ruc-ctsii /. j> (O APPENDIX IV INTERIM METHOD FOR SAMPLING AND ANALYSIS OF VINYL CHLORIDE IN WASTE WATER EFFLUENTS AND AIR EMISSIONS Scope and Application The initial basis for this method was developed during the moni toring program carried out by EPA Region IV in Ma.rch and April. The techniques used by Region IV provided guidance for the monitoring activities of other Regions, and the experiences of all Regions were then incorporated into this refined version of the original Region IV approach. This method is applicable to VC determinations in water effluents, sludges and scums, and atmospheric emissions. The limit of detection is approximately 0.06 mg/1 in water and 0.06 ppm (v/v) in air samples. Summary of Analytical Procedures Water composite samples, air continuous composite bag samples, and air and water grab samples are analyzed without cleanup by gas chromatography (GC). Separations are effected by selection of one of two types of columns depending upon the nature of the sample. Detection is by means of the flame ionization detector (FID). Tetrahydrofuran extracts of sludges and scums are used for injection into the GC. Aid continuous samples on activated carbon are extracted with carbon disulfide, and the extract is analyzed by direct injection into the GC. Calibration curves are developed using gravimctricallv prepared calibration solutions, or by using known dilutions of VC in carrier gas. VC confirmation should be made by mass spectrometric analysis of the GC eluent if possible. Independent confirmation may also be made in the event of extraordinarily high VC concentration sam ples by using long path Fourier transform IR spectrophotometry. This IR technique requires special equipment and about 20 cubic feet of air samples. Interferences Certain volatile hydrocarbons such as neopentane, butadiene, and freon 12 have elution characteristics similar to VC. However, on the GC column substrates specified in these procedures, these have not usually presented problems of resolution of the VC peak. When column substrates other than those specified have been useu, impurities from solvents and carbon adsorbents have been 49< 17 00005034 SAL- found to interfere with the VC elution peak. Under certain condi tions a peak is associated with the injection and subsequent with drawal of the microsyringe into and from the GC septum. These peaks can also give interferences with the VC peak. Withdrawal should be timed to avoid overlap of this peak with the VC peak. Apparatus and ?>laterials Gas Chromatograph Flame Ionization Detector Recorder - any potentiometric strip chart recorder which is compatible with the detector system. An integrator is also desirable to estimate peak areas. Column Materials for Waste Water, Sludge, or Scum Samples Borosilicate glass tube or stainless steel tube - 6' x 2. 5 mm ID preferred. When GC configuration requires columns of other dimensions, these should he used. Solid support - 60 to 80 mesh Gas Chrom Q Liquid Phase - 4To FFAP on specified solid support (weight percent). Liquid phase on solid support can be purchased directly from commercial distributors. i Column Materials for Air Samples Borosilicate glass tubing or stainless steel tubing - 8' x 2. 5 mm ID preferred. When GC configuration requires columns of ot'.^r dimensions, these should be used. Soil. pport - Carbopak A Liquk; phase - 0,4% Carbowax 1500 on solid support (weight percent). Liquid support on solid phase can be purchased directly from commercial distributors. Continuous Air Monitoring Materials - Carbon Adsorption Option Adsorption Tube - pyrex glass, 18" x 3/8" OD Activated coconut charcoal, 8-16 mesh. Any good commer cial grade, e.g. Fischer Scientific Company can be used, Becton-Dickson 27 gage 3/8" hypodermic needle flow control Vacuum pump Air flow meter 50 < 18 SAL 00005024 Continuous Air Monitoring Materials anti equipment - Bag Sampling Option Environmental Measurements, Inc. , Programmable Bag Sampler Tedlar bags (or equivalent) Gas Pressure Regulator (0-5 PSIG) Microsyringes - 10, 25, 50, and 100 microliter (graduated) Gas-tight sample syringes - 1 and 50 ml (graduated) Vacuum Sampling Cans - 370 ml steel Yacu-Samplers, or glass sampling bottles. Cans and bottles should be flushed with clean air or nitrogen and evacuated prior to use. Evacuated containers should be protected from rough handling to prevent implosion or collapse. Samplitg Bags (Tedlar or equivalent) - 12" x 12", 36" x 36", equipped with sampling valves and speta for GC sample withdrawal Automatic water sampler - compositor (manual sampling is optional) equipped with sample refrigeration capabilities, and a a means to prevent loss of vinyl chloride from open bottles Glass sampling bottles with teflon lined screw type caps - 50 ml capacity or other sizes depending upon sampler requirements Septum-sealed vials - 1 to 10 ml capacity Volumetric Flask, Glass stoppered. 25 ml Medicine droppers Dedicated GC/M.S. for confirmatory tests (preferable) Barometer Thermometer Anemometer Reagents. Solvents, and Standards Carrier gases - zero nitrogen or helium FID gases - zero hydrogen, oxygen Tetrahydrofuran, reagent grade, peroxide-free 5i< 19 SAL 000050244 Carbon tetrachloride (reagent grade) Carbon disulfide (reagent grade) Standards VC in zero air, 50 ppm (+ 2"'o) v/v VC, analyzed reagent grade (lecture bottle) Sampling A. Water Samples All waste water discharge points identified in NPDES permits should be sampled for VC. A minimum of three successive - 24-hour composite samples of each site should betaken. Com positing interval should be one hour (manual or automatic sampling is optional). Compositing interval of 20 minutes may be used if the automatic sampler has this capability. Samples should be taken at waste treatment units such as clarifiers and scum and sludge separators. Two 8-hour composites should be taken from the effluents from each of these points, and one 8-hour composite should betaken of scum and sludge from each separatt r unit. Compositing interval should be one hour. Three grab samples of clean process water `(city or private well) should be taken as blanks. Samples should betaken in 50 ml bottles with gas-tight, teflonsealed, screw cap closures, or in equivalent containers re quired by the characteristics of automatic samplers. All water, sludge, and scum samples should be refrigerated dur ing collection and storage. Compositing volumes should be selected to assure head space above the sample is absent or minimized to avoid loss of VC by its partitioning into the gas phase when samples are sealed. Provisions should be made to avoid such losses during continuous monitoring operations. Estimates of discharge flows should be made using any appro priate measuring device (venturi, weir, magnetic meter, etc. ). Samples should be preserved by refrigeration and protected from sunlight until they are ready for analysis. B. Air Samples Sampling sites should be selected which are downwind and in the plume of the atmospheric emissions from the plant. Samples should be collected only in areas where local residents or neighboring industries would be exposed. At a minimum, 52< 20 0000502.4 G Jini.'liiiL' .''!ui.ilil In- eeridmted, r.er a |n -rl >[ five davs. Sites siioiilo :-i selected in Uii- l>.>11-1>\ 11ni >ni site immediate!'.' up i*. l;i I t.Al and mu- immediat. dv i ;< wuwm'i (ii) T fi plant silt; ' m -- -h ,di..ul (l. 1 ;iil.-.-; i m i!- plain sue, "in; 1 uterallv 1 :'< (( > ..mi mil i.iiiTjllv right ii>> of tin- til.tn; .>iti- mi a tine round. ;) -rpctioirula c t" tin ;. '-.v i.! ini' wind ill; ection ami \v:<< ([., t 1 : a aw mil tr"m tin plant itc; 'w > samplm. sms (Ci, I!) apor- i\i::i,it.-lv 0. :i mi les d. r.i a wind; single sumnlmg sites. i-m h at 11s'.ja, cs approximately 0, 6 (I), n. H U ). 1.0 Ik I, and '.`O ( L) miles 11 wind from tin- olam site. II wind is fish-tailing Severely, move slmpllnr sltcsliund II approximately 0,5 mile upwind of tin1 fish-tailing wind <....... .... from the plant. Tim sites specified arc minimum. Add;1 imial sites may he selected contingent ml overrirliuL' m lcrnmete, c-ological considerations. These should he determined in consultation with <ho Regional mo too roll gist. These may be at ground or some elevated level, as deterr tilled hv the plume survev or as estimated bv release of me'enrologicnl balloons, anemometer, and wind direction indicators, etc. Prevailing Wind Ditei tion SAMH.iNti S1TKS .Miiiinuini S.imrdine Schedule .Miles t rorn ! I.i.r, sin- St: i Siinbol 1`ime Mon Wed 0. 0 A n. ; C * TTaiTT 1) * n.'.ot) A, A, 15 A, 15, B A, A, B 0.0 n ! 000 C, l>. ! e.n C.D.D 0. ; k I- I L'OC A, i: A, G, Ci a, t: 0. .1 ci II H00 B, B, K B, II B, B, G 0.6 1 1000 c.g K,K 1.1 0,3 .1 liJUO B.l - k, L 1.0 k J000 * II. L. I. - ;j.o k (Note: All tune.: are i ,n : .'.mutes for manual grab samples, or 4 Tminutes for automatic, programmable I lag's ant piers). Grab samples should be taken in .">0 ml gas-tight scringes, 50 to 100 ml glass sampling bottles, :i70 ml \ aeu-Snmp!er'" metal i ans, or It!" x It!" .apacilv i "dlar-type bags. Both the Vsn u-Samplers and the glass sampling bottles should be evacuated prior to use. (('.rtu ri: 'I hose max implode or coll ipse .vhen under vai unrn. I s>- due care in their handling). The pence; gas laws should he as-nnied t*i estimate gas vol umes. (ias-tiglit s\ ranees are flushed several times with am bient air before a sample is taken, Aitcr tlu- sample is taken, the gas-tight syringe is locked and scaled until it is ready for analysis. 53- sal 00005024 The Tedlar-typc bag samplers may be filled by pulling the walls of the bag apart manually, or better, by placing tne bag in an enclosure and pulling a vacuum on the outside sur faces of the bag. The bag is sealed until u is ready to be analyzed. Tedlar-typc bags are preferred for grab sampling. All samples should be protected from sunlight. Continuous Sampling - Carbon Adsorption Option: Continuous samples are taken in pyrex tubes (approximately 3/S'' O. D. x 18 * long) packed with a good gt ide of activated coconut shell charcoal. The charcoal is added to the tube in three segments, each 3-inches long, and each separated by a glass wool plug. The two ends of the tube are also plugged with glass wool. Both ends of the pack adsorption tube are plugged with serum caps during transport and for storage pur poses. How rate through the tube is controlled by inserting a BectonDickson 27 gage, 3/3" Hypodermic needle through one of the scrum caps into the end glass wool plug. Air is sucked through the tube by connecting it to a conventional vacuum pump. The arrangement is similar to that used in the National Air Surveillance Network. Flow rate should be about 200 ml per minute. For each adsorption tube, the flow rate should be calibrated in the laboratory before the sample is taken and should be verified again in the laboratory after the sample is taken. Clean needles frequently to prevent plugging. The adsorption effic icncy of the carbon in tiie adsorption tube should be verified in the laboratory by preparing a 5 ppm v/v VC mixture in the 36" x 36" Tedlar-type bag and drawing this through the adsorption tube. Flow rates should be verified before and after the experiment. It is important to note that all collections should be made with the adsorption tubes held in an upright position to minimize channeling. Adsorption tubes should be protected from sunlight cither by wrapping with foil or by enclosing them in a box. Each segmentof the adsorption tube is worked up separately by etching the tube in the middle of a 3" section with a file, successively breaking each segment and spilling its contents into measured volumes of carbon disulfide in glass stoppered test tubes. The additions should be effected cautiously and with cooling in an ice bath since the interaction of activated carbon with carbon disulfide is quite exothermic. A 2 microlitcr aliquot of the supernatant solution should be injected on the carbowax 1500 column for estimation of the adsorped VC. Suc cessive analysis of the three adsorption tube segments will indicate the amount of break-through of VC through the adsorb ent. 54< 22 53 A l- 0 0 00 vi 0 4 / ft The same procedure should be used fer taking samples in the field. Continuous Sampling - Programmable Bag Sampler Option: The sampler is programmed to take twentv-four consecutive one-hour composite samples. Bach one-hour sample is analyzed separately for VC content. Sampling rate of the individual pumps should be verified before and after use of the sampling device, Uc-cord the temperature and atmospheric pressure at which the samples are taken. All gas volumes and concentrations should be corrected to 25:>C and one atmosphere (760 mm Hg). At a minimum, con tinuous samples should be taker, at sites A, B, C. and D at ground level, unless otherwise indicated by micrometeorological conditions. Calibration A. Gas Analysis - Gas Dilution Option: Record ambient temperature and atmospheric pressure. Evaluate the 36" x 36" Tedlar-typc bag. Add 1 liter of the standard VC gas mixture (60 ppm, v/v) to the bag. This addi tion maybe made with a flow meter or with a gas-tight syringe. Dilute with nine liters of zero nitrogen or helium carrier gas. This gives a concentration of 5.0ppm (v/v) of VC. (13 ng/ml at 25C and one atmosphere.)` Evacuate a 12" x 12" Tedlar-type bag and add 0.5 1 of tile 5,0 ppm (v/v) concentration mixture. Dilute with 2 liters of zero nitrogen or helium oarrier gas. This gives a concentration of 1. 0 ppm (v/v) VC, (2.6 ng/ml at 25C and one atmosphere). Evaucatc a 12" x 12" Tedlar-typc bag and add 0. 5 1 of the 1.0 ppm (v/v) VC calibration mixture. Dilute with 2 liters of zero nitrogen or helium carrier gas. This gives a concentration of 0.2 ppm (v/v) VC (about 0.52 ng/ml at 23C and one atmosphere). Evacuate a 12"x 12" Tedlar-type bag and add 0.75 1 of the 0.2 ppm (v/v) VC calibration mixture. Dilute with 1.75 liters of zero nitrogen or helium carrier gas. This gives a concentra tion of 0.06 ppm (v/v) VC (about 0.16 ng/ml at 25C and one atmosphere). This is about the limit if detection for direct injection into the GC. With a gas-tight syringe, inject 1 ml aliquots of the 5,0, 1.0, 0.20 and 0.06 ppm (v/v) VC c alibration mixtures into a CC equipped with a Carbowax 1500 or Carbopak column and an FID detector. Use zero nitrogen or helium as carrier gas at a flow rate of 60 ml/min. Operate the inlet and the column isothermally at room temperature. 23 SAL 000050248 Prepare a calibration curve. Repeat until the calibration curve is reproducible, B. Gas or Water Analysis - Gravimetric option: Stock solution of VC. Pipet 40.0 ml of carbon tetrachloride into a larect 50 ml glass stoppered volumetric flask and accurately wmgh to 0.1 mg. Attach a tygon delivery tube to the VC lecture bo*Tc valve. Attach tlie end of the delivery tube to a piece of gl; - Wbing which has been constricted at one end, flush oi ' tube with VC, and slowly bubble VC into the CCl^ c,,i.lainmg volumetric flask until about 5.0 mg of VC has een added. Precautions should be exercised to prevent loss of carbon tetrachloride during this operation. Reweigh the volumetric flask to determine the weight of added VC. Fill the volume tric flask to the 50 ml mark (approximately 100 ppm wt/vol). (These operations should be carried out in a hood). Transfer 1 ml of the stock solution of VC to a 25 ml volume tric flask and dilute to the 25 ml mark with carbon tetrachlo ride (approximately 4 ppm w/v). Transfer 5 ml of the 4 ppm VC solution to a 10 ml volume tric flask and dilute to the 10 ml mark (approximately 2 ppm, w/v). Repeat dilution for a solution approximately 1 ppm, and 0. 2 ppm. Transfer the stock solution to a teflon-lined screw capped bottle. This solution can be kept for extended periods of time Transfer the diluted solutions to serum vials and cap them with teflon-lined serum cap septa. Inject 1 ml aliquots of the calibration solutions in the GC equipped with Carbowax 1500 on Carbopak A packed columns and an FID detector. Use Zero nitrogen or helium carrier gas at a flow rate of GO rrl/min. Operate the inlet at 150C and the column at 60 C. After the \ C peak has been eluted, program the column temperature to 150 C to elute solvent. Cool column back to 60C lor follow-on concentrations. Repeat procedure using a GC equipped with a 4% FFAP on Gas Chrom Q packed column and FID detector. Operate under the same conditions. Prepare a calibration curve to be used be used with water samples. 24 Procedure Water Sample Analysis Untreated w^ter samples (1-5 microli'.er aliquots) arc injected directly into the GC. A 4% 1- FAP on "Gas Chrom Q" packed column is used. Nitro gen zero gas or helium is used as the carrier gas*at a flow rate of 60 ml/min. Inlet temperature is set at 150C. The column is operated isothermaliy at 6 2C. Detection is by FID, Report concentration of VC in sample in mg/1. Sludge and Scum Samples Extract 5 grams of sludge or scum sample with 100 ml of tetrahydrofuran (THF). Analyze THF extract in the same manner used for water samples. If YC concentrations are too high, make appropriate dilutions of the THF extracts. Report concentration of VC in sample in mg Ig of sample. Air Sample Analysis Grab samples. Use a 0.4'fo Carbowaxl500 on Carbopak A packed column. Use nitrogen 2ero gas or helium as the carrier gas with a flow rate of 60 ml/min. Operate the column and inlet at room temperature. Use a flame ionization detector. Untreated air samples (1 ml) are injected directly into the GC. VC contamination of syringes requires attention. Report concentration of VC in gas samples in ppm (v/v). Continuous Samples Use same procedure as previously discussed for calibration of adsorption tube efficiency. Quality Control Duplicate sample analyses are recommended as a quality con trol check. *r.J:m4 < 25 (SAL 00005 APPENDIX V .^I'MMARV OF REGIONAL ACTIVITIES This Appendix briefly summarizes the results of the preliminary VC monitoring activities conducted bv EPA Regional Offices during the Spring of 197-1 at the i (-quest of the Task Force. More detailed reports are available from the Regional Of:ices. The sampling and analyses were carried out in a -'cry short pciiod of lime using new methods, based on the Agency's best scientific judge ment. They represent, in the Agency's opinion, the best methods then available. In large measure, the sampling and analysis methods were based on previous analytical studies in which similar chemicals were evaluated. However, they had not been thoroughly tested for accuracy and precision under field conditions. Prior to and during the sampling and measurement only limited qualitv control and standardization of procedures could be applied in the time available. The methods utilized were interim procedures which have already been subjected to further mouification. The nature of the PYC manufacturing process results in the escape of VC pulses which could lead to v.idelv fluctuating levels of YC in the ambient air. bo, too, changes in air movement may intluence concen trations at a given station at any one time. Therefore, the VC data reported are preliminary in nature and are subject to change as addi tional monitoring is performed. Individual measurements probably underestimate the YC levels cue to the possibility of YC leakages and other inaccuracies in the monitoring system. Region I: Leominster, Massachusetts: Borden Chemical Company (PYC); May 9, 10, 19. 1. One hundred and fifty-seven discrete (grab) ambient air sam ples were collected on plant property and within a 3. 0 mile radius of the plant. The YC concentrations ranged from less than the detectable limit of 0.06 ppm to C.O ppm. The samples exceeding 1 ppm were obtained on plant property near the fenceliue, 2. Twelve 24-h ,ur integrated ambient air samples were collected at tne fencelinc on pl.-nt property. The YC values ranged from less than the detectable limit cf 0.06 ppm ti 1 ppm. 3. YC concentrations in three 24-hour composite waste water samples taken from the iagoor. effluent ranged from 0.15 to 0.29 ppm. 4. YC concentrations in two sludge samples taken from the lagoon near the outlet measured at the 0.05 - 0.06 ppm level on a wet basis. 58< 26 ^AL 00005025'i 5. The plant is located jn a residenijal/industrial area on the edge of Leominster with residential developments adjacent to plant pro perty. 6. Shifting meteorological conditions ar.d rain hampered the sam pling program. Region II: Flemmgton, New Jersey: Tenneco Chemicals, Inc. (PVC); May 20-31. 1. Forty-three discrete ambient air samples v ere collected on plant property and within a 2. 0 mile radius of the plant. The VC con centrations outside the plant property ranged from less than detecta ble (0.01 ppm) to 0.05 ppm. On plant property a single sample collected on the dryer building roof contained 5.6 ppm. At ground elevation, the VC concentrations on plant property ranged up to 0. 30 ppm. 2. Twenty-three integrated ambient air samples were collected for 24-hour periods on plant property and within 2.0 miles of the plant. The VC values ranged from 0.005 to 0.038 ppm on plant property and from less than detectable to 0. 031 ppm outside the plant area. 3. Two integrated one-hour ambient air samples collected within 0.1 mile of the plant showed VC at levels of 0.32 ppm and 0.18 ppm. 4. A maximum level of 20 ppm was detected in three 24-hour composite samples taken from the water effluent discharge into the Bushkill Brook, which immediately flows into the Raritan River. This amounts to approximately 400 lbs/day. 5. VC concentrations in sludge samples taken from the lageon areas on plant property ranged from less than detectable to 1,000 ppm in wet weight concentrations; however, the concentrate i at the sludge disposal area was 54 ppm. 6. The plant is located in an area in which manufacturing facili ties are interspersed with farmland and relatively large acreage residential oroperties. There are a number of small communities within a few ; i les of the plant. Region III: Delaware City, Delaware: Stauffer Chemical Company (PVC) and Diamond Shamrock Chemical Company (PVC); May 20-22. S. Charleston, West Virginia: Union Car bide Corporation (PVC); May 24. 1. The air sampling and analysis activity was organized around a mobile laboratory equipped with a gas chroraatngraph using a flame ionization detector. VC levels were later confirmed by mass spectro meter. 2. A single discrete ambient air sample at the fenceline of the Diamond Shamrock plant showed 0. 2 ppm VC. 27 SAL 000050252 3. Four discrete ambient air samples taken near the .Stauffer Chemical plant ranged tro:nC,3 to 0.7 ppm VC. The highest level was recorded 0.5 miles from the plant and the lower levels at 0. 25 miles from the plant. -1. The area immediately adjacent to the Delaware Cif. < omplex is light ly populated residential areas for several miles. 5. Water samples collected at the Union Car-hide plant gave VC values of 1.1 and 0.8 ur.in for grab samples at several out.talls and 0.35 for a 24-hour composite. Samples obtained from the Kanawha Jliver did not have a detectable level of VC. 6. Sampling was attempted but was not feasible due to limited time and equipment difficulties at the PYC plants of the Firestone Plastics Corn pa ;y in Perryville, Maryland, and Pottstown, Pennsylvania. Region IV: Louisville, Kentuckv: B.F. Goodrich Chemical Company (PYC); March 19-21 and May 8-16. 1. The initial air monitoring program conducted in March was pre liminary to the more extensive program in May which showed significant ly higher levels. 2. In May there were 39 discrete ambient air samples colic"'ted in the area designated industrial (within 0.8 miles trom the nlant center). The VC concentrations ranged from less than 0.05 -o 5.6 ppm, with 10 samples exceedi: g 1 ppm. In the area designated residential/ industrial, 149 samples were collected within 0.8 miles of the plant with VC f-oncentrations ranging from less than 0. 05 to 33 ppm. The average concentra tions at the site registering .3-3 ppm were between 0.5 and 1 ppm. out 18 samples had concentrations greater than o.O ppm. f our samples were obtained in strictly residential areas with VC values of 0.05 to 1.6 being observed. The 1.6 value was 0.8 miles from the plant. 3. Five sampling sites were established within 0.6 miles of the plant for integrated air sampling over 24 hours. VC values ranged from less than 0.001 to 0.53 ppm. The highest value was obtained from a sampling site 0.2 miles from the plant center. 4. Wastewater from the clarifier discharge was measured in March at 2 to 3 mg/1 in 24-hour composite samples. 5. Dewatered clarifier sludge and clarifier scum contained 193 and 1G2 ppm of VC, respectively. Region V: Painesville, Ohio; Uniroyal, Inc. (PVC) and Robintech, Inc.* 1 Inc. (PVC); May 9-14. 1. Four of 137 ambient air samples taken at distances up to 3.0 miles from the plant showed levels exceeding 1 ppm of VC with the highest level being 2.26 ppm. Many oi the samples were less than C.l ppm. 60< 28 SAL 000050 2. Xinc 21-lunir integrated ambient air samples taken at various dis tant rs from the plant show* d levels up to 0.2 ppm of \'C. 3. VC' levels in 11 of 17 water "ffiuenl samples were less dian 0.2 ppin, wi'h three samples on * 1 ji1 p,,m, m> ludie^ a hich of 3.7 ppm. i. \ C hIs in nine 'bulge ampFas tin.- sludge would leave the il'.un |irnpe,,!.. ranged 11 "in d to 3520 ppm. 5, The complex is surrounded bv residential areas. Herein \1; Platim-minc, Louisiana: 'I'he Goodvear 'J'ire and Hubber Company (l'VC) and Dow Chemical Company (VC); April 7-0. 1. Then* were .'(1 discrete ambient air samples collected within 3.0 miles of tin; complex with VC concentrations ranging from less than detec table (.001 ppm) to 7.01 ppm. Most of the readings were less than 1 ppm, with tic highest value at the property lino. 2. VC concentrations in wastewater effluent measured by 24-hour com pus'tes were all below .05 ppm. 3. VO concentrations in residual reactor scrapings at the Goodyear plant ranged from 23 to 21 ppm. 4. The siimM cimiinueities of i -rrisonville and Ldiza are located less than l mile north and northwest respectively of the Goodyear plant. A few Irunes frin \hoo monvilie eytend almost to the north property line of th" *5'x>dvep y i.'lant. 5. Very limited air sampling was conducted in the Houston area in the vjeinitv of the pl aits list' d below. However, in view ot the inadc-quacv of this urinate, tie- .vimnlin,.; cH'ort '> this area is being continued. Deer Park, Tex., PW Plant - Diamond Sham rock C'orp., Diamond Sham rock Chemical Co. Deer Park, ley., VC Plant - Shell Ch'-miral Co., Industrial Chemicals Division Houston. Tc'-. , VC riant - Temiero, Inc., Ternero Chemicals, Inc. Pasadena. Tex., VC Plant - Lthyl Corporation Heuion i\: Long P.each, California; 13. F. Goodrich Chemical Company (l'VC); AnicH' an Cherni'-al Corporation (VC); American Chem ical Coipot-ati m (P\ C); M ;.v 7-10. 1. One hundred uid "igh*v JO-rninme integrated ambient air samples v/i-i a c"l haded within 3.1 inilir of di" < omipb--.. About 11 percent of the 61< SAL 000050254 .4 --f-\ readings exceeded 0.5 ppm, whale 5 percent exceeded 1,0 ppm. The maximum value measured was d. 4 rpm in a sample taken 3.1 miles from the plant; however, the average level measured at this point was about 0. 5 ppm. 3. Samples of wastewater effluents were composited for 3 to 24 hours and yielded values :rom , .5 to 3.0 ppm, with individual samples reacting up to 22 ppm. 3, Sludge samoles showed values ranging from 290 to 4200 micro grams of VC per gram of dry sludge. 4. The complex is surrounded by residential areas. Within the three mile radius of the plants t.tere are eleven schools. APPENDIX VI PERSISTENCE OP VINYL CHLORIDE 'I ho available information on the stability and persistence o: VC in the environment is currently verv limited. Some literature and laboratory studies have recently been initiated bv ir.dustrv and bv EPA. This discus sion summarizes the findings of EPA m date and particularly the results cf research efforts at EPA research facilities undertaken in'response to the needs of the Tank Force for at least preliminary data on environmental fate. Results of related experiments reported by industry seem to be consistent with the discussion. Behavior of Vinvl Chloride in Air The peas absorption of VC in the ultraviolet region is very far below the solar cutoff of about 2'J00 A, indicating that VC would not undergo reaction in sunlight in the absence of other reactive chemicals. When irradiated with simulated solar radiation in the presence of nitrogen oxides (nitric oxide and nitrogen dioxide). VC reacts to form a variety of products. The available laboratory results indicate a rate of reaction of about 8 to 10% per hour for VC, recognizing that reaction rates may vary with concentrations. The direct and indirect reaction products identified included ozone, nitrogen dioxide, carbon monoxide, formalde hyde, formic acid, and formyl chloride. High eye irritation levels were found with human exposure panels which is consistent with the products identified. The low reaction rate of VC, including reactions in the presence of nitrogen oxides, indicates that within a few miles cownwind of VC emission sources \C will persist and can be considered a stable pollutant. The usual meteorological dispersion equations for gases could be apr'.iedto approximate concentrations. Because of temperature inversions and the absence of sunlight at night during ;he fall and winter, buildup of VC might be of particular concern during such periods. Clearly at greater distances from emission sources, VC will have greater opportunity to disperse and degrade. The noxious gases which arc products of VC reactions should not be ignored. In air quality regions with large industrial activities involving large volume production of these chemicals, such products may contribute appreciably on particularly sunny days to eye, nose, throat, and lung irri tation. Behavior of Vinyl Chloride in Water The loss of VC from water at constant temperature and pressure de pends on the rate of agitation or aeration. DtstiLed water in a beaker spiked with 16 ppm VC, when rapidly stirred at 22C with a magnetic stirrer, lost 1)6% of VC in two hours, while quiescent water at the same concentration lost only 25% VC. There was no significant difference in the rale of VC losses from distilled water, river water, or effluent from a VC plant stirred at the same rate, indicating negligible adsorption effects with particulate matter. Plots of log water concentration versus time give straight lines, indicating volatility to be me only important loss 1 mechanism. 63< )i Al- 00 0 0 b 0 E o 6 Hydrolysis over a pH range of 4.3 to 9.4 does not appear to be an im portant pathway for loss of VC from water. Chemical reaction of VC in the clarifier effluent from a VC plant was followed at 5(fiC for 57 hours at pH 4.3, 8.0, and 9.4 in sealed septum vials. Concentrations indicated that VC at these three pH values decreased at the same rate. This lack of pH dependence suggests that the loss of VC occurred by volatilization rather than hydrolysis, or at least there is a very slow hydrolysis rate. This experiment should be repeated in leak-proof reaction vials. Very preliminary experiments do not show photolysis a*s an impor tant pathway for loss of VC in water. However, there are many uncertain ties in the experimental techniques, and additional studies are needed in this area. Earlier theoretical studies are consistent with these experimental re sults. One study on the transfer of small non-reactive molecules across the air-water interface (as in stream aeration) used a kinetic approach to predict that VC will be rapidly lost from an aqueous solution, with the rate of loss being a function of water turbulence, mixing efficiency, and molecular diameter. Another study, using a thermodynamic approach, predicted a rapid rate of evaporation of low solubility chlorinated hydro carbons, including compounds of low vapor pressure. Despite the foregoing efforts there is a general absence of data con cerning VC in aquatic systems. It is conceivable that as the result of poor or erratic mixing in lakes or ponds, together with slow but con tinuous release of VC from sediments and sludges, VC could persist long enough to accumulate biologically, via direct absorption or via the food chain, or to cause other ecological effects. Behavior of Vinvl Chloride in Closed Rooms Tables 1 and 2 present data concerning concentrations of VC in a typical room following release of a pestmidal spray containing VC. TABLE l One Hundred and Twenty Second Release of Insect Spray in 133, 000 Liter Room SAMPLE TIME COLUMN I VC FREON-12 COLUMN II VC mrON 12 No. 1 Collected at breathing zone during spray 41.64 ppm 8.15 ppm 41.!) p pm 7,94 pj: No. 2 15 minutes 16.91 3.13 17. 1 3, 111) No. 3 30 minutes 1.38 0. 27 1. 32 0.25 No. 4 60 minutes 0.08 0.018 0.061 0.018 No. 5 120 minutes 0.012 4. 0.010 - 52 SAL 000050257 TABLE II Thirty Second Release of Insect Spray in 21,-100 Liter Room SAMPt E TIME COM MN ! VC I 'RLON-12 ecu MN II Vf FREON-12 No. 1 No. 2 t alR-cted one minim- alter spray 30 minutes later 380. 1 ppm 84. " ppm 3S3.5 ppm 38. 2 o[im 52. 1 9.9 -t8, * 10. 3 No. 3 No. 4 GO minutes 150 minutes 2d. G 10. 3 4.8 2. 1 21. 5 Q 1. 7 2. 2 No, 5 Collected in adjacent hall 151 minutes 0.83 0. 17 o. 7 0. 15 ; Frcon-12 eoncentrations were determined using l.ydrooarbon t espouse factors to compare dilution effects; the actual concentration is Inciter bv a fa-uxr of 5.3. referent es 1. t npublished results ot experiments and analvses conducted at EPA lab'ra' mucs in Research Triangle Park, N. C. , and A'hens, Georgia, during April and Mav 197-1. 2. I tiimhhshed results of experiments on persistence of VC in water - -n.lui ted by Dot <'!i*-mical Company. '!. rsii-oi.'loii, E. C. and .1. R. Wallace. "Charm. tenzation of Stream lii-aerati <ri Cara'it, , '' El'A Eioh.ciial Research Sc-ies Report EPA113-73-012 (l> tuber. 1972). I. M u K-iv, Donald un i Aaron \V. Wolkoff, "Rate of Evaporation of LowSoluhilitv Contaminants Irmi Water Bodies to Atmosphere," I'.nvironmi-:it il h H' < c. 11 hnulogv, 7 (7):6 1 1 -6 11 (duly, 1972). (>5y 33 SAl. 0000502158 HEALTH EFFECTS OF VC APPENDIX \ It This Appendix presents much of the epidemiological and toxi cological data available as of August 197-}, on the health effects associated with exposure to VC, together with a few interpretive com ments supplementing information presented in the body of the report. However, the Appendix docs not present an exhaustive review or evaluation of available information. Table 1 summarizes the data, collected bv CDC/NIOSII, on the confirmed cases of angiosarcomi of the liver in VC/PVC workers in the United States and abroad. A total of 15 occupational cases have been discovered in the United States and confirmed as angiosarcoma of the liver. Of the 15 cases, 2 are still alive and undergoing treat ment. Fourteen of the 15 w ere employed in PVC production plants and the remaining one in a PVC fabrication plant. The average age at death for the U.S. PVC production workers was -18.5 years (with a range from 3G to 61 years; which is about seven years younger than the average age of death from liver cancer in the l!. S. male population. Based on the data available for the workers, the latent period for this disease appears to be on the order of twenty years, a period consistent with latencies observed for other occupational, chemically induced cancers. In the U.S. PVC production worker cases, all of the men were at one time "pot cleaners", required to enter the reactors in order to chip the residue of the chemical reaction from the sides of the 'pots." Since the residue often contained pockets of trapped gases that were literally released in the cleaner's face when they we: e ruptured by his chipping operation, the potential for exposure to high levels of VC while cleaning these tanks was particularly great during the early years of this operation. Ten cases of worker-related angiosarcoma of the liver have been reported from five foreign countries to date. Table 2 summarizes the epidemiological data, collected by CDC from the Connecticut Tumor Itcgistry, on five confirmed cases of angiosarcoma of the liver, including one accountant in a PVC fabrication plant and two residents near PVC fabrication plants. The case of occupational exposure occurred in a man who had been employed for 10 years as an accountant in a factory which pro duces vinyl sheets ar- processes PVC resins; it is reported that he frequently visited tne produc'.ion area of the plant. Of the two cases who had no occupational exposure to VC or PVC, one was a 73 year-old man who lived his entire life within two miles of a PVC wire insulation plant. The other was an 83 year-old woman, a housewife and retired cook, who had lived for 35 years "within one-half mile of the vinyl products plant at which the accountant had been employed. 6G< 34 SAL 000050259 While those findings establish no causal connection between exposure to FVC and aniriosarcoma oi ti'.e liver, they do raise the possibility of such a relationship. l ime will Bo needed to define the possible risR factors in persons who have worked with PVC since the latency period appears to be so long. Because of the rarity of this tumor, the additional finding in this study of angiosarcoma of tile liver in persons who had no occupational exposure to VC, but who may have had community exposure, is also worrisome but again establishes no causal connection. Epidemiologic investigation of additional cases of hepatic angiosarcoma that may be found to have had possible community exposure to VC will be necessary to clarify the significance of these eases. Tables 3A - 3D present the findings of the MCA-funded mortality study of VC/PVC workers, conducted by Tabershaw/Cooper Asso ciates. In calculating the risk of death, the usual method is to express the number of deaths which actually occurred as a percentage of the number which would have been expected in a tompaiablc population observed over the same ago and time intervals. This statistic is called the Standardized Mortality Ratio (SMR), Using the U.S. male population as the standard population of comparison, the SMRs were calculated, for each of the 35 cases of death for which detailed mortaility rates are published on a national basis. In the standard population each SMR would be equal to 100. The statistical signifi cance of the deviation of eac h S\IR in the study population from the eynpctcd value of 100 was tested. A single asterisk indicates these SMRs which differed significantly from 100 at the 5 percent level, "that is, which had a probability of . 05 or less cf occurring by chance. A double asterisk indicates those which were significant at the 1 percent level. SMRs based on fewer than 5 observed cases were not tested for significance. The overall mortality of the study population is statistically significantly lower than that of the U.S. male population. There were 352 observed deaths compared with 467 expected, for an SMR of 75. For each job, an exposure score was estimated by industrial hy giene and safety personnel in each plant, A score of 1 was given for low exposure, 2 for medium, and 3 for high. The number of months each worker spent on a given job was multiplied by the appro priate exposure score. The total for each worker was then divided by the total number of months of exposure to give an Exposure Index (El) for that worker. Table 3A shows the SMRs for workers with an El below 1.5 versus those at 1.5 or above. The dividing point of 1.5 represents a level halfway between low and medium exposure. Table 3B shown similar results for workers with less than 5 years exposure versus those with 5 years or more. In order to examine the possible interaction between duration and level of exposure, the study population was divided into 4 croups on the basis of both El (low vs. high) and duration of exposure (short vs. 7< 35 SAL 000030260 long) using the same dirhoto.v.i'a'ion ax l.n.lcs and 3I>, .iC shows the results lor short \ . rs.ts long i.-iev in the low t~! group, and Table 3A sltows the sane comparison the Iiig ! 1 la! group. Winn the Study population is divid. 1 uci oiaiing t > length and duration of exposure (Tabhs 8A and 311) and eombinnti ms of tlie.se measurements (Tables 3C and 31)), direr :uaior n.itlcrn.-; emerge. For malignant neoplasms as a whole. the .''.`.111 im rcaso.-. i;h men'.using eXootn.ro, whether measured by level, duration, >-r l. r.li. In :ue high exposure group with a years or more exposure (Tabl.- MIH there u`re 36 observed cases and 26. 11 expected. I or eardiova.-. ular renal diseases as a group, there arc also increases u. the hdi; with inrroasir.u exportin', but the number of observed eases remain less than expended, the differences being stai'stieallv sit nifieunt in .ill croups cxeept tin- high exposure, long duration group, f or all other > nuses, there are no con sistent relationships with exposure. Within the malignant neoplasms, the la test (.although not statisti cally significant) SMlt is in atu ers t-t the b.i.a til eavitv and pharvnx, with 5 observed, 2. 84 expert.: i, and an SMil -.f However, Tables 3A and 31) show that all tiles.- eases have ar. 1.1 beiow l,f>, atid -1 out of 5 have less than 5 vears t Cancer of the dige stivp s'- stt m shows le. s s m the s tilde p 'p'J- lation as a whole. How V`\ IT, . ' 11 ese V. orl.e rS :w il j Ids > u 1.5 ' il' hi giur. there are 12 observer! r uses wi. rC' 1-1 ,,1-e ported (T d. 1 e .`1 A). In die subgroup of the above v.htH`i;r*rs \ ;th .".'.'ears oi :. so i`: c nj . -sure,, t iif-i e are 11 observed eases and 7 * -17 (;> ' l'i ted, l Respiratory roncei j=!lOu > j slight i.'XCeS: ? in U-i* t`j ta 1 rj i Hip, atui a similar pattern fr>r dud rem >.p >sm e careen ies, with 13 observed versus 10.23 expected hen tr.e 1.1 is t. "> or higher, and 12 observed versus 8.50 expected when, tr. addition, the duration of exposure is 5 years or more. Malignant neoplasms of other .md unspec itied sites sliow an excess in the total group, and an iner.-ase with both level and duration of exposure (Tables 3A and 30). The relationship with exposure is more pronounced, since those with exposures of less than 5 ''ears have fewer cases than expected. The lymphosarcomas, altnough on erring at about the exported rate when the whole group is considered, are concentrated almost entirely in the high exposert long duration group, in that category there are 4 eases observed and 1.84 expected. The Tabersliaw/Cooper St : iv is based examination of 328 death certificates. The uu!h<>.s a. know!, d: three arcus where bias might have entered: (a) chore the l . m.ile population as the GS*- 5G 00005026:!. SA1. standard, (b) absence of 15% oi the stvdy population (untraceable', and (c) discovery, as the study ended, of a group of 1500 workers whose exposures occurred up to 35 years ago and who are not includec in the study group. Since the latency period fo r angiosarcoma of the liver is averaging 18 years at least, it would appear desirable to examine the data for these 1500 workers. In addition to the Tabershaw/Cooper study several other epidemio logical studies presented during the recent OSIIA hearings -suggest ihe possibility of a multiple cancer risk. Table 4 summarizes many of the published and unpublished toxi cological and epidemiological studies of human and animal exposures to VC. A list of the references cited in Table 4 completes this Appendix. 69- 37 00005026 3 Ai- 1. VC TCjn.'rK'r I'roJm t |i>n 2. PVC Po lysK-r I*' it i.'ti C A t It ,,. I,.unit ry SvcJcn Un 11 St .It l-H Un L1 vii St .It I'M L'ulti/d Sticks Vnltvil St lulled St -it i I'nl ted Slsile* I'n [ t i^l St.It l'M United St.ltl'N UnllvJ St It i'M i'n J t i*J St ite* United St.il v* tnil.vl Sl -ll t*M L'n Itvd St .It l'S k*\ ilfrtiinv U`. (Ictninv Cr*>.it Hr 11 i in N>rw.iy Jiwv Ji*n C/iach<^lnv.4H 1 i Ceci-hits 1 MVsik. 1 ) t a I U-iI St .i Ln Unlti-.l st.iti-s i.n- ii i. r i t i: m t.iU>- I IKi ITA I IONA! I AMS ur | | VIM ASi.lt' ..\^r (VIA C.i.u- * ... (U 01 Of 07 JUS Ofi 07 Oh JV 10 11 li 1) Oi 02 m Ul U.' 0} o: u n o,* h ] is 4 it ha 11 ud-no-; i 1 '.1 T\l tH -it ,\ /. fill ,'t Anni iT i .mil ........................... ro , ; NO-']., - ,S iio-osj- .'2 M OC)>tin-.** 0M> i- U 1 mo- oniin-On 12 no - uo-2v US-0 1- 22 OS-Us - .'0 O'j-'H - U os-in-1 i [)w;-i w li -i ;-ih 07-/ i- n (Jfl-Oi- to oo-ihi-ii] 12-2 l~l mo-00-21 12-0'*-.* 1 11-is- V* M ; ..#i ti/--till - S/ in -is-;; n 1 -1 ? U2 oh-oti-;; 10-0 7-.'.!* OS 2,1--.S Ilis-Oif 'll u;-; *-.*.* OV-I 1-- f Oh-iv-.,; 10-u- S7 10-01 -W no- [in...... tl i-tio-Sti un-no- si n J- (10-3 i us-oo- ;o , 1 `Ml- ' 1 OH Dll I|7 owm-*.; (12-00-?; H'i-Mi# (iS o.s- no- m 01-01 ' 7 4 O'i- OC- Ml U i-ii.j- ?u 0S-:M-1,V o s-no-74 uu-Ou-- 7l un ou-iiv 12-00-/2 12-20-11 00-00-70 ih S'* ;i S2 ;s ;s -i , V iii so >7 ;o 11 n Mi V1 Vrs, J-.t 1 t -i 1 Sr. vr/rvi w.uk Vl /VVV l.i 111 * K --U-|'"su 11- 2? 21 r 1 in j; 1 1 JH 2H LS IS 211 J 12 12 ?; lh Is IS 4 17 | / 1? 23 2 1 2tJ :s ? 2 10 U i; 11 M 2n 2U 22 21 J`> 1 H H.it i- O.-.i 1, *" * * ` '" 00-00-72 oj-tn-n nv-.'h-J! 12-10-77 it| -0 ?-u o.-av-u; Al lv*` OJ-27-6H fl.**-2,#-61 A l 1V* ns-m-Mt in-it.-/u 0S-U2-t> 07-04-7; 12-14-71 tjJ -2S-<iV 17-iJu- 72 01 -04-72 flo-0(J- 70 li it... fKJ . HO- 1 11 -ii- .1 tin.n'i. , ............. ,|l> ~. . ' . ................ |; i; - no -; 'ff ,V* i; I.. 11 si j-. 7-t t I 1 '-tri-?r' OOk'T Vt! Kxf!iN4ir>* W Oi*cn*m S\jtr: fOO' ImJ'i.itiM unfcn.it'n ii.it c* in 1 SOCKi \ ; S i>:*H li L7 Case So. Age ln t.im : CASKS OF KEPA1TC A*:MSAkCO.A. CON'JM rUVT, mS-19?) NCI Plainestw Date of Original PI agnosia [Ulr of Pcath 1 * Plsrurj.^_____ ______________ 0.-rup.it Ion Place el Hi1 Jen. t_ _ Hvp.it lc 11-25-67 Angiosarcoma 12-3-67 2 months history of durrlita, , anorexia, .mil 20 16 weight loss. Intermittent .Cnlomlnil p.itn. Nun-tender, firm epigastric mass. Hied after 4 day* with s|p<mt.mi--'us ruptured liver leading to shock. Fast Mstorv a1<nhol In take. Fireman 1917-42 Aluminum worker 194I--4 Cor set Hitter 1945-41 ket i red L 9M -0 7 Bridgeport - vntIre life 2 47 M Alcoholic 1-15-7) 2-15-7) Initial symptom* Id oNl-<ntlu.il polii with Cl rrh tN I i von King. l>c.ll volvulus f. >011.1, K* > eti'l'esv. A.*, ."out mt - Vlnvl l'o., til IdgepoTt - VIM-M I'JV -1 over nest 6 weeks* pain i-nr iron-4 with ve.jV- At i <iiir .mt - Plant Je Ptev hut'll y Bursv Portal neiSi Hl'O tenderness with l Kll liver. 3il.tpilosed lleit Co., 1954-6) 1m. .it lens Fibrosis by nvedle hlnpsy on 1-15-7). Deteriorated slowly Previous!v acroui.tant- until dealt* 31 d.i'n latir. etSi-r states !> O O nj K A 5 50 M Hepallr 12-19-73 Any,U>s,ir^oaa llep.ir |r* Ang 1 us.it i imi.i 1-12-50 llep.ittc AngloH.ircon.i 1-22-74 Admitted 12-2*7 1 with short hi*.tore oj KC0 abdominal pain r idiot ing to K shoulder. Had KlYj tenderneis. t>pe-i tlu-r blopr.y l^-19-7 1 shoved large tumor. So resection. i'elcriurjteu until death 14 l.ifer. 1 loo sew 11 .* Ki".t.)nrint cook 15 yrn 3-19-50 1 month history of a with .ihih'cnIn.i 1 pain and hark Firm eplgast rK ni-.s. Hied 6 days after udn Li's foil with < .ire inomat us 1 s am) pulmonary eiaha 11. u sew 11 e 5-4-7) Admitted for abiooln..lp.iln -mJ Jaundice 5-27-73. 4 i S liver. Pisebarged. .admitted 4-29-73 with abd dlntcnslrn, geiier.il edema, Icterus, fevi r, shaking chills. Rapid down hill course with death due to r ii- l and hepa tic failure, Past 11f t.:ry of alcolml Intake. Fisherman and c a ren ter before 1959 Pia-t*ri-r 1^59-60. t'nem ployed "96 1-73. f.tr .ll..rd i5 >e.iri* WI ii>hi' r 1 >. h Puerto KUo 1973-59 ?h w York City 1959-73 Br j.Jgeport 1971 T *b I * JA Ofl^tJlVtD tt;ATH:/tXfTCrtO Jfc./pH .WD *>TAKO .HUI/.EO HMtTAHTf rfATIO. XV VINYt CIU)K1DE WiUltMt*., , 8 ESTJKAnfi LYL Of UJCWMJJtit Cause of death with 1 .C.0.+number r.i <i. 3 s>t>i/rxp SH6 1 hl\. 3 obs/vsp swt! All causes 186/270.1i n** 137/193.66 80** ot- fo A Tuherculotte (001-019) Tuberculosis ciC respiratory system (0.31*006) Hillgnant nsoplnsi (Ufl-301) Malignant neoplasms, buccal cavity and pharynx (140*146) Malignant neoplasms, digestive organs and peritoneum (1)0-l)9) Malignant neoplasms, respiratory ays tea (loO*l64) Malignant nroplesat, grnltil organs (170*179) Malignant neoplasms, urinary organa (IA0-181) Malignant neoplasms, other and unspecified sites (140-199) Leukemia and aleukemia (704) LyaphosarroaM, lymphatic and hevsatopoiei li- 1 Issues (700-701, 70)) Diabetes metlitu* (760) Major cardiovascular and renal diseases (310-114, 400-460, 397*344) Vascv.sr lesions a Fleeting. CHS (33")-334) AheiaaatlC (ever 4 chronic rheu/tavlc heart dla. (4I30-60J, 410-416) Arteriosclerotic heart disease (6703 Konrheumat1C endocarditis (4J1, 47?) Ityp^rtenaivt heart disease (440*643) Other hyperlenslva disease (444*447) Oironlc 6 unspecified nephritis 4 rena? srletoM* (347-394) Ini lumas and pneumonia (400-44 1) Ulcer o( alumach and duodenum (360, yl) Appendicitis (3)1**331) Hernia and Intestinal obstruction (360, Shi, 370) Castrltli, duodenitis, enteritis and colitis (341, 331, 37?) Cirrhosis o( liver (361) Hyprtplasla of proslate (hill) Symptom*, senility and lll-dellned conditions (700-/93) All other dlseaaea (residual) Motor vehicle accidents (010-0)3) Other accidents (6*30*407, 640*962) Suicide (961, 970-979) Homicide (964, 960*983) Number of workers Person-years 0*\. 18 0/ 1.th 17/46.76 3/1.6? 7/17.30 ll/n.36 7/7.10 1/7.07 4/6.37 i/;. id 1/3.66 j/ 3.6) 04/l/O.tl 7/14.4/ 1/1.96 66/76.94 0/4.70 1/3.46 l/l.37 0/7.30 3/3.60 0/O. 39 o/o.t:6 0/0.Jh 7/A.uO 0*0,?3 0/4.7? 14/71.90 6/19.06 M/17-0) 9/9.73 0/6.96 0 0 90 )10 60* 66 93 31 166 69 31 146 /)* 37** 60 47 0 19 70 0 97 66 n 0 0 tI n 0 66* 41** 66* 96 0 4017 43)34 o/?. n 0/7.18 61/ J7.67 0/1.71 17/4.14 13/10./R i/i.j 0/1.37 6/4.32 7/1.37 3/7.36 7/7.6) 69/06.49 h/10.06 7/7.83 31/38.0) 1/7.89 Jl l.Sh 7/1.07 n/i.?; 0/4.11 1/l.60 0/'. 77 1/0.63 1/0.33 1 fb. 64 0/0.14 1/1.09 * /I3.B9 9/13.4b 6/17.67 V7.07 1/4.94 30)7 1710ft 0 n 134 0 141 l 33 /) 0 140 t It. i 17 61 ,* 64 ?> 93 18 3t, 701 0 0 -ft 0 l 71 I'th 16 o 34 41** 72 10** 107 11 ^SW'i Adjusted (or death* with cause unknown. *S(Knlti(<flt at II level. O **j| gnl Meant it 1% lrvl, o Mutern.it lonal CM*:* H 1 oil Ion of [11mim*h*u SWRCR; Tatirrufidiw UmpiT Aiiwi'r futon, fne., vl * "l! l?r * tly_ ^LrAL,,w Klo_.il hVj^rt Tahir 19 09SUVID KATK/Urtcru DCAT Its aND ST. J(D.JIDIID KINTAL ITT AATIOS IN VINYL CKUXltt wotms IT DONATION OF UntlS NftNLOTHEHT f death tfltb I.C.9, siMfcrr All Ctuill Tubarcalatlt (001-011) TuMrnloili e( respiratory systen (001-D01) KtUfBUt neoplasna (140*20}) Hit IfMot MofUiM, huccal cavltjp and pharyna, (U0*U1) HalLgnant HOflsat Ni^ntWt organs and peritcmrua (110-319) Malignant r^flaiai, respiratory sjritra (tbO'lM) Mall|Hu oeoplasns, genital organa (170-179) Malignant neoftam, urinary organa (100-lSl) Kalignaot iwopliM*, other and unspecified a (tea (190-199) Leukenta and eleukrwla (704) LjrvphoMrrou, IjnatiitH and hesutopoietic tissues (700-203, 70S) Dlcbid, nallitua (260) (ia)or cardiovascular and renal dlaaaata (3)0-334, 400*466, 192-594) Vascular leaiona affecting QIS ())0-334) Khtuwtlc fever 4 chronic rhrunatlc heart die. (400-402, 410-416) Arterloiclcrotle heart disease (470) (tonrheunatfe endorardttls (421, 427) Hypertensive heart disease (440-44)) Other hypertensive disease (444*447) Qironle 6 unspecified nephritis 4 renal sclerosis (592-194) Influent* and poeweela (4g0*49)) Olcer of ttonech and duodenua (140,141) AppendIcit Is (110*513) Hernia and Intestinal obstruction (560, 161, 170) GastMtIs. duodenitis, enteritis snd colitis (143, 571. HI) Cl n. bos is of liver (SOI) Hyperplasia of prostate (610) Synptoas, senility end ill-defined conditions (700-791) .ill other diseases (residual) Motor vehicla accidents (610*031) Other accidents (600-002, 640*962) SuUIJ. (W5. H'alcide (964, 960*961) Hunber of workers forson-years ^SM'i iljvital far fdtht with cau.a wilaoHn. #Slgnt(lc*iLt at 51 lvl. "Sl*ntfleant at 11 toval. 460 nemfh* ohk/np Sl >60 nenifcs obs/sxp SJ*^ 04/140.13 t/** 751/171.10 75" 0/7.1) 0/2.07 11/19.96 4/0.70 2/1.76 1/5.if 0/0.99 0/0.6) 2/3.40 1/1.21 1/2.01 7/t.00 76/11.41 4/1.97 7/2. )9 21/32.14 0/ 1. 79 1/2,42 0/0.79 0/t.51 5/7.11 1/1.07 0/0.24 0/0 * 2 1/0.40 1/4.49 0/0.07 1/7. 7N 4/11.97 10/16.14 7/17,94 6*6.34 1/1.60 0 0 76 666 46 65 0 0 71 96 60 134 61** 61 lot /* 0 49 0 0 173 112 0 0 )01 76 0 51 40 71 M* m 29 2911 14701 0/3.51 0/3.31 61/17.61 1/7.16 17/16.16 71/16.51 3/2.76 1/7.79 15/6.21 7/7.:i 3/4.0 7 3/4.14 123/117.39 9/ia,7i 3/4.5) 96/101.19 1/5.)3 7/7.01 3/1.67 0/2.76 2/7.09 t/2.76 0/0.4) 1/1.10 0/0.9? 2/11.16 0/0.33 0/5.09 16/26.34 7/16.61 10/17.62 10/10.26 0/6.20 0 0 lit 47 10b 116 117 )7 167 61 126 in 61** 4" 66 96 20 30 170 0 29 17 0 9) 0 16 0 0 6 3* 43** u* too 0 4134 A1711 O O rn O O O i* rr f>-. Ni T.it.U* *)C OBSERVED DtATHS/r.XPECTE ) Ut JHi /NO 'iTANU,*KDIZKLe HURT J.MY K.TU>. IN VINYL CKl-OAft* v.<UtJCtR5 WITH LXPCSURr. INDICES BELUn I.), BY UIA.TtUN OF EXITED IMPl.OYHtNT Cause of death with t.C.D. mw'i'T All cause* Tuberculosis ('101-019) tuberculosis ot respiratory system (001-308) Hallxnant neoplasms (140-203) Malignant neoplasms, buccat cavity and ph.uynx (140-148) Malignant neoplasms, digestive organs end peritoneum (130-159) Malignant neoplasms, respiratory system (160-164) Malignant neoplasms, genital organs (170-179) Malignant neoplasms, urinary organs (183-lfll) Mtlignant neoplasms, other ind unspecified sites (190-199) Leukemia and aleukemia (704) Lvmphos arcoau, lymphatic and hematopoietic tissues (200-70 1, 703) Diabetes eveliitu* (?60) Major cardiovascular and renal diseases (130-114, 400-468, 597-jw) Vascular lesions allectlny Ci> (113-1)4) Rheumatic fever b chronic rl.rumatlc heart ills. (400-41)2, 410-416) Ar ter lose tr rot L. heart disease (471) Nunrheumatlc endue*rdit|s (4J1, 477) Hvpertenalve heart disease (440*441) Other Hypertensive disease (444*447) Chronic & unspecified nephritis b renal *slernsit ()9/.S94) InJ lurnra and pneumonia (480*49)) Ulcer o( stomach and duodenum ()40. 5h1) Appendicitis (330-MI) Hernia and intestinal obstruction (3.o, 3bl, 370) Gastritis, duodenitis, nterltla and rolltls (341, 371, 377) Cirrhosis of liver (381) Hyperplasia of prostate (blO) Symplons, senility and It l*de lined rundltlon* (780- 79)) All other diseases (residual) Motor vehicle accidents ($10-813) Other accidents (01X1-107, 640*962) bulclde (9b), 970-979) Homicide (944, 980-98)) Humber of workers person-years adjusted lor death* with cause unknown. *" i An i tleant it U level. ^Significant at It level. *t*0 month* e xpoiurr lii'l months exposure obs/eap bKR1 ubs/exp SMH1 36/89.71 * 132/161.26 71** 0/1.41 0/1. 11 8/17.86 4/11.4) :/3.43 7/ ). 38 0/0.68 0,0.35 1/0.97 0,0. 79 0/1.76 7/1.15 71/31.18 2/3.9 | 7/1.30 lb/71.14 0/1.18 1/1.38 0/0.50 0/0.S7 3/1.56 0/fl.b8 0/0.1) 0/0.77 0/0.26 i/7.80 0/0,03 0/1,4 1 4/7.43 1/9.87 3/7.98 1/4.08 0/3.33 0 0 7) 10 lb 14 6) 0 0 120 0 C 70) 39 IM 6ft 0 74 (5 0 195 ,) 0 0 0 42 0 o 61 15 44 ftb 0 "/1.97 0/1.8) 79/11.46 1/1.17 6/9.08 9/10.00 7/1.62 1/1.5) 6/4.4) l/l .43 r 7. 2 i 3/7.30 63*66.82 5/10 )l 1/7,49 32/5. 87 0/ 3.0. 0/1.90 1/1.07 0/ 1. 3 1 7/3.9) 1/1.)3 0/0.24 0/U.61 0/0.31 l/b.09 n/n.;o 11' J . 79 10/12,97 3/9.27 8/9.8) 6/5.66 0/1.4) 0 0 9) 86 6B 91 177 67 187 73 46 l ?i ** i-,* 4k 91 0 1 101 0 53 67 0 0 0 16 l 'U )6 81 109 0 1715 71418 7 El 7 :vt:n Table 3!> OBSERVED DEATHS/ EX PECTE9 DEATHS t ND STANDARDIZED MORTALITY RATIOS IN VINYL CHLORIDE WORKERS HUH EXPOSURE INDICTS 01 U OR CJLEnTEH, BY DURATION OF EXPOSED EMPLOYMENT Cinif At death with l,C.D* number Alt cum Tuberculosis (001-019) Tuberculosis of mpotatory system (001-008) Hiltiiml nropUici 040-203) Kitl|[fl4nt neopleiat, buccil cavity acid pharynx (140* KB) Malignant neoplaame, digest! organ* and peritoneum (ISO-15S) Malignant neoplasms, ropunorjr system (160*164) Malignant neoplasms, genital org mi (170*179) Malignant neoplasms, urinary organ* (IRQ-Ill) Malignant neoplasms, other and unspettiled Mle* (190-199) Leu Vml a and aleuhrmla (704) Lwr-phosan pj , lymphatic end hn etopcitet lc tlsauew (700*20). /05) 'I*abate* rellitu* (260) Me`or cardiovascular end renal disease* {M0-))6, 600*668, 592-39*) vascular lew ion* affecting O'* ()J0-n4) Rheumatic lever A chronic rheumatic heart dla. (400*402, 410-416) arteriosclerotic heart dlseese 70) hontheumat|c endorardlt1i (471, 4771 Hyper l entlve heart disease (440*44)) Other hypertensive disease (444-447) Chronic A unspecified nephritis A rennl sclerocl.s (392*394) Influents ana pneumonia (410-49)) Ulcer of stomach md duodenum (340r )4l) appendicitis (530*333) Hernia and intestinal obstruction (560. 3bl, 5*0) Castritl*. duodenitis, enteritis and colitis (34), 371, 572) Cirrhosis ol liver (311) Hyperplasia of pros! ite (Ml) Avnpt !*, senility .md sll-ileltned cnudl t it-ns (/80* 793) All other disease, (residual) fistor vehicle accidenta (810-8 13) Oi hr i tlJ.nl* (Itflft to:. NulclJ. (Vnl, Uil-gjv) femicide (9h4, 980.905) H-iber of workers Persnn-wears adjusted (or deaths *9tgliIrani *\ 't level. **blglItrant IX level. s*ue unkm>vii. <60 month* exposure (ti) month* exposure ob/exp sra1 uhs/rxp 6rtt` 38/47,91 0/0. Jb o/o. n 5/t>, 37 0/0.7) 1/1.67 1/1.19 0/0.29 0/0.76 I/I. IB 1W/00..4741 CiO.bl 7/K.34 2/1.87 0/0.87 5/10.41 0/0.57 0/0. 7(i 0/0.27 0/0 34 0/0.99 1/0.35 0/0.08 0/0.14 1/0.14 0/1.36 0/0.01 I/O. 80 0/4.07 7/6.05 4/4.71 3(2.40 1/7.18 1740 17878 79 00 96 0 76 71 0 n 107 288 178 304** 01)3 u* Q 0 00 0 0362 0 904 O 0 n138 14 b 107 138 38 119/147.81 m* 0/1.37 106//17.64.8U 0/0,99 11/7.47 1.Vll.il) l.'l.M 0/1.76 7/1.51 )l/l. I 4/1.84 2/2.04 62/70.46 4/8.19 7/2.04 46/47.63 1/7. 17 7/J. 10 7(0,81 0/1.73 0v/5; .1) 0/0.19 WO.49 0/n.4l 1/5.08 0/0.1 l 0(7. in fr, 11.88 J( /.43 7/7.96 4/4.62 0/7.76 n 0 14 1 0 151 144 7) 0 204 90 777 100 90 30 100 98 44 66 251 0 0 0 0 n709 701 a M* 78 26 88f) '181 K w* r \i \ o O a o Table 4 SUMMARY OF TOKI COI.OC I CAL AMI n'OV.Mlitt.l'ClC.U. STVDIKS Cti V1KVI. CHUHUnK Author\\<n Wt t lni;en Sp If* Hti&am Sfi_ No. expos r*F. Hr*. Jcr J>ev_________ iu vs ,\ r a Con*-. Total hose _____ irrvrtt tun' IJ.fXiO 10.000 2V,0QQ iMOKt-rimw Narcosis Vtoduied syupicta* of dlrrlncs*, dlsoTivntm ion* hir.id.-irEie and burning sensation on soles of feet. Cabur Mecca-fOdu Manta f1962) Clara. Abstract Otiun $2 Workers exposed to DPT, Benrone, Hexarhlorocyclo- besane, VC, PVC. HIcM>d: Ih* rease In rata l.is** l-icroase In pi-rcaidase, tnd'jnhrrsQln* and glut hath June Changes occurred during second year of work. {.enter tiret-nhcfrl Ail.'Sa (196 it Hunan T. A fijbur K.ulu 1'rc J.i Ahrif li'-ui -lu.ui-4 Ami a V,i 11 rlry inwj l lieto, AbMfai l Jluxen 3 Twice per dy C0 1/3 slightly dirty r 3 for 3 days. 4,000 61.2 0/6 hod any etlert* 5 s]n. nemelons 6,000 1*6. t 1/6 s 1 l/.ht 1 y rflxxy at 6 hour* In tervals 12,000 16,000 2 VO. *3 jn*7 2/6 definitely dttxy 3/6 dlrry, rui.mea, blurred vlblcn and heaving syiipiotts stopped alter erpnsure 20,000 416. 7 6/6 Intoxicated, one with persistent headaches VOX level of no el feet Is 1.15 Sii stat .'Bent shout rrpested exposures 76 PVC Workers hfcresse plasma albumin I nr reams! B eru) 8 globulin DeerIn 8/8 for ni-tui lipoproteins |jer ft/<> In m-run i h*1 Inesi 4>rase Un r v/inm In ')>*J liu'sr t* se N>om<>] L 1***1 r * I < I >*>11' Korr.flJ Hf MMS Jiyruvlf *< Jd Of iK'Ucmu Tuba (1966) Ch*a. Abstract JIunan Experimental: PVC Workers Control! Other clinically heal thy prop Ir Hrpulfcf-Hl : VC*H20>chloral f rhloracetlc acid fl). Result*. (1) was found In SOI of exp!1. people, lnil !n n<>nr ill (iintro)*. Hunt ol * finding* were In p<*op)e reposed ?-V years. 11 thru* Sara ,{.gli Uulth 1* high* r(^ g l*'t*i 11 a la lower th.Hi people with tui (1) In urine* * *"< tty to mi>1 b^| i/r; (1) *f* t i d sflf-r 7 wir*. Pathology Hone reported None reported None rejKirted None report ml ll.irtlA d.in* {Ob?> Wllit'n ^CuTSl,'* I .it cm Creech (19*7) L if < t.i St* v iff l*+j\ i SI i t tmvj o ^JlCtnlry .>( A Ah-.t M, t U'iUJi I'npuSj] 'j1. - li s lE'i*i i llwi.i il . ,,r *! llniMt: H r f . Ht%. T-'t.ii JH'T Ci'Ot . ihrMi- * D.tv iJiyn pjMH-ifivs Ohse rv.i t 11 >n'f Kilim logy One vi-rker 1i.nl knee rj> and .oe* [nvolvnl In iIn- m ro-ont **o 1 yt* 1 a, Other worker nnly linnJ*. M Sn i ims *>J .irri)-<t>ii>o1ys)s iM.t|',nost>J In 11)C*0 1J /1000 OX) vnrkneit itnsoc t.il wi VC i^lvUiMh< wlui handled t inislird renin tit uncd pulyaerl e.ii tmi Intends to have *cio- fer [il.ist (c {iTinlurt prndut 11 nn nsteolyulh. Are r.inye of . I t. r -il wutlrri 26-4 7. 1 nr(jli.it lon jn r!tnl f lluii l? BmntKs of pnlyi l.inln^ I-*| cl lilt. . 220) Af co-nsteolynl n anaor Jnted with Kl VTMljd Hll|ttllH. M l.\j Vt i'l II 500 /ft. I 1 ./ tf if h r* - - .< v t<ir*iri, o /(i hr*!, .if m r ** *ri* wi fi- an m.if. .t. \, y. ! | :> |.r- ii h if 4 hr* . I n S' ]Z. .Hu .nlvi fM i 1 l < < f-j fi<f ci|. Ah*4 the A-ini' net n( breath ill . -jy f irv . 1 (} |<'lwinit m i *n*u I c j>. u r ', H(.nr k* pi,f r.-d SCJ I. t'Lini',1 -< Jri fit,: rfipritHTi, i.tn* c. (*r I >a r I ,e.it Jon. Nniit' Reported. <. * 7 . 1 m re i ii- I n u y s t 1 l 11.it * . H-na.tn 18 58 15 50P* 1095 ia;> *1n never*] other (4r |nrii><i A fi1 - fir | Yfc t !, T* V KJ< T - *1'* r he Vit.luil ' H iyil>iri<iBc, aversion to t.its, enlarged lim-r Kaynaud * n n > nd mme Fnl-arne*! liver* aiuor liver I tisuff lr li*nrv. l l/'jO't h nt .n rn - ii .1 .-i.I > s I *i. lll.-1.ti Im I ttl ti ll*'111 ! It. il 1*1 If. ,\l lit I- III * Vi IIII -.yi.1^1 cf|1 tll'l OTil' rvltlrfi* when It In easily perreplIMr. Acfnt try: (VO tin f.nrory filler* -it air ill sf Ti.irfi- tine: 7 Olio ppa (VC) nt i'*li]t n' wrier entry: 2,000 ppa in pi tntn vlieri* ji-toOHli'idvnli Oi i ill I nl - I SO pp- finis) In ,-1 tnl will* mi dl'.ninc | V ! .i. j .n. "-.>/ :il other port it of plant: I 0 t o 1 5 |V<*' \/ i 1 -h>,si!-, Ja.it >-t.. . .. THt. ?.- ; iH'Js.'tl ii .'.m B l nr:.in \lt vIuhjhi N.isr Iti^nus in (mij i*' cc A * 1 m r.i-r *?ut. !il*-r < r* M / rfii*. in 0> tirs. : i.*\ p.*r ' 'll. . \ s-.'_Lj i;___ J ^y* .1"* : j'j.s-_ i t'sf r I\r'lt..1r/ 11 2]'iifj rtan-vi'^m H i ! - J i ! ::! Ji* *'n-! j:."+-pl | in-d w!M< band I i-.iriliiK til . i . 1 i 1 ... :*tt I tu bf fur relation bi-t m i-n rt'ji (nr i Msn ifrg*tii*l^'iIV*.lh. ] <> ..it.fc lt*d iv liJ<i.t!* A< rt>"i,*ii".lyil`i .>|ij., .in, to l<* 'j. mi; 1 in.- .(rt>| .n r.i'intmlyi.lh. HVhti-.tili rut her th.in l'-i ,i! .Itsva .. Vf/J.-*!! S11. rv.ii y ,t* it.ill*. Mi illy n-I.Uicl to ji n>- htioly- . j.ill.-tsih H *d wi rki I .is rvr ri--u-* nr-v'i s.si`l his. tu--'naiad's plia-nor., r,.'n ant cvded 1 I >. vi > ` v 1 ir Ivs Inns l'i .ill lour Ni-k,. <".i ,i.:d V "...1 ] .iti< i* Ln i-r.i* Nulijn t. I'li1'>i;.--n.'ijr.ijiM- ..Nnnrau 111 i vd uot presont In \ - i.n j nub Jo, t x. l*r Inti-: c.mu rorrvl.itvd with rwdti-y r.ijdili' | i-ijnm. Ki.'l-hi^f.il svitllStv k'icl.ln nora.il limit s. No liver a.-nl .irRVTavnt or lay;-><tliy-- 1 t .1. h 1 iu t ii *, -II*. d mxy l min 1 v Afi>t ic Arid tol.l l ira. a\ r.'t Mill nort.i I. AdditLnr1.1l snail or .MnuTC.il it ii-H tT .i(S<r ituSk-fM.H < 11 ni. .ii l.ii-or iiurv Invent ljc.it iunit found In ulnar si;. It. id, <Ph..i Ic is fit j it iVi" . and fi.it o 11 <i. * i1" , 1 ' > v Mi t j.-u. . l',-r',-r *.1 d st .it I < ortvlnt f<>n bet won xi'Vi-rnl 1 In I..11 i.,'.i Mir <-cr.viit h -uni tulul .tune .iml r lm<- ti .tvW.ifrfo V>' KifM'lltr.itl'if}. S<irh" fi-[.<*rt.d. *' liver fiin<Tl.ni Indlrvs stjuj .1 positive < ori vl.ai tun witS tut.11 d.;s; ` iNn>irr..iI 1 v It I |t.la > . ,1 j !< I vr . * 111 -Ia 9a 111 h:1 jdi.iU-1n J olli'f Imllie, .!>i:iv-rvl.r a d 1ml .1 r * 11.M nut h Id e ......Inotm.il ! nuli>: ,1 r '<vi.l>i|l .uid dl.ntiillr S j h tu. v 3 r.Mn ru-> ( tvv . ui*ri-lal t-.n. j t,i 1.1 prnl J u. t / / \ / aVut Ik.' r rl M if Htol U r Li'Lh Jch Mil li*r Jkilll* L.tn*c rolinvr W 11 k vn HIM) *1-- *.'< Hun.iti :<!* Sii. J 20 rir. ps-r :ujf Jii.-'i i" ii. . i-j- -i.. i. 1S to 21 v.ns. /It i *i: W't ilNpra f t- J i - ......... 1 - 1 y ; > i tj !. r - ri. 5 .f , V. t,j '* y*. m CC A 1a Mv. r r <1 : t !/'/' r.itr .-1 Vi. *1. t **- *-.i i !i /,/u. t11 < ' I 1 ['! r n 1 a li.i` t > > i <11 ly/niM <| h i U*.i ..t * ,-t *. yr.> r r* j . J / /'J. I I . S ! * h I :t - .f Y J IT J'rVj. I i'fl ( . Jf. ; IT 1, t Iwvs , . - tit. i* i - >' v.i.i.m-.I, r . I i ' ] J m . t , ,] / if ///',. b, .i Si", itt-i l itjfMOO ! : i 1 - * -,t,r rr.il ! n i J In Rr 1 - > i i .1 *1 I j r>*Ht w<4t .ihi'i't.;!! in (>'il rrtini lun df i <*f K'> m it , w.m rlt w* '*\ \u it//ft SfcFT van rl **v.t crt <\`t 0j in I4//Q. Alklllru* plfiSpS.lt .** * >48 ut./sl in 7^20 +i *i> .? -rt . ct a ** I *,i % It)' /nao 11 v ImuiuJ j */,'*/< l-yj/, n J/ ') |n i///t A f'ldiNl y.'i/yiit y;* s Hard ;n f, ft i VflTlii'M*' V* tnH *4 f-sfdpli.i,-, *>f In .' / ) |.v*r hi i*t a-in^.y . n rr.n,-;.t Mt II 1*1 kit u.i I lit ll] w- J rnin111 alit I FT V20. Y,u -i I .Ul.M'Mn.l vt In !"V/II. !..< il fatly luMIliall.ti in rilunvl'. nl m-| i .mil ,i|i .- I#- J nt r.i lol-ulnr .ttnf portal nj.a. t.i In it/7 0. I ,id<H t I'sn.i I ( par.iaw-t vr;+ wr<* n.ir- itil. 9 ]Rum>Lp^i(.il tt'Ma ilcuif .irn th't fi ;n ll i-J . Sr-WAXV nl !'> ii OM* I. Al 'Mr 4 PI |H wcu i-ai .n Mr. vis/1 < Astnvi.s (r So. KrHAi.iv lUy:* ............ __ IXiVM'kl !*: il !i.i JH'ti -1 \v; in.-.n v Veit Ur[ t i ityrn ur.sj (Ki*v1< w AlM . 1r) I It H r it r.n VI NU \,t V* *.'+ SO M) <i Nt> 1 1 X - AA 1 .11 *. i .it <* M) St) NIT M> i i -it a NU S.> VI 11 n IW=* s:> Ml. < SI) \;j | nin. Nil 1 o [ n. SSJ KD <4 , i 1 t t su k; lfii;,..'l to < I , .' -r. 1 ft. 'Hitt 1X0,00*1 < 10,oon /uti.lilril .VHT.OOtJ t Vi 1. (Hlft NI <i 1 .Ihl'l 11.1(1 i Ml. UllO 1 70. Of hi 1 IH V< }< ,r i.lr.l I, |n:, i * r * r i nil 11-i I k i 1 ]'. ` i. - ! V' t * i n i ti t j i" . i s r lt< i . > n. t til r -it i l*r. `r.itr. rril .i T i -i 1 t, f pi ill ;>j.m i i , ; 1 i; ! I .i. i tr< i * : i - 11 t t M . ................... - -i . .i -| i.1' i-. rlln ,i t i*' n I -i r . > liy it u l.t I.! !, fit HI to 1.0 |.i KS 121,0-W 100.0O0 < iff I .! >1; i e t. , >. i Tv.kh NIT Oct&s Hit.* NIJ r>. P(ic ND NU J / (or s.evrr ,i l wV s m5 7 f or Kl'VlT.it Wltl Si) 10 nin. t M> hc*t 1 iO.OUl i 'i 2 t)U,, 000 *>. V)0 74*..1UU to ?(Jr>.U0 2 Oil, IKK) t ti boo.rxm 1 . rOfi 1 <1 Sit *! n.i] it . ti.m.'-- : . . -r rr k ti.. . M it ln->l : -.m. . - - i !.:, : I : n : 111 l i i . 11 - . t ti 11 t 11 1 . . t 1. i r. i AH .ill.il US !? *~-r MU 'h-v ; H\iA \,.T. t . .'if', 'ki^'n 1! * ' K,-. . -- \Tl 1= Jv asi^!,; i.-H ** Ml u. nun SP {.. HU* NCI N - Hth/J i ." Ml o.w Mi 0*5-1 Sl> 0.5-1 [i.ivi i 1 nxrosi n: Coin . I.f| 11 3 . ?r .... .Pi1'-1' ' lOO.OuO 5,(Xn SI1 2,'Mr) 10.1 it...................... r . 11' t lh'!i. l lull i-M i i ;i t T i. n t I m;> I. r.i t * I . pi. i ' i]i !* r .*. !. x I* i: i : .t! - :l i ,1,1 r | .. i i... , Hi* tiMR.it t i`u Ftuher Uirlit { ll-in/U r U'W V f aIu* r cr t fir IM iv lianr Uar \w * <mt 7* ML*' SI* 5 ti.'i 1 fi.t h NH . . I'M* M* 'i 5 <).'* l>. - 1 l tti*n!i*r f .uil*a*iiK .uiil iTuritl<*n nf cNJuihiiri" A *rk` i* LUO, tk.1 2, i r.- 2ihl,i- M forkt-Ison ft Oven Rjiwf (mn Nunln-r iif .in I r.i I * .iml il >f.tt Icii uf oKpotutn* .in jIm'vi* li;'f,f}0l> * ,* N^ibSi'T til iinln.ila miJ duration of i*H|mtijri' RJOV a N Above Hits M 10 7 (VI/wit > 10 7 14. jMh) 40'J*0On 50l> rt, I tu u.oik; , i 1 *-. M ' . .U . . - wi-1, - l.n T ' U V i tl W*- l * Wk'li'.1.' inil 1-lf, 1-T HI...... I , SL| ` , wt-ff ii 'I r> u , i .1 l ->n! t I: ' t* ' . krI . M, i!> ............................... ... . ! k .- T r iii , . ii* !:. ii...- - I >i * . lul III I[ ' I . SAL 0000502 V*. ' .1 I'M \ Authors AM HAI.S Sj^'i les Sox 7*n ______ Hrs/djy Torkelson Oven Rove <mn coneInuvd ji i 7 F< J OC P* w A (2a) Rats w 12 F 12 C. Pi* i X 10 FF Rabblfk H 1 DuK" F1 i>r l r1 Hit fin'd t onl ri -1 ,, l>ntll exp iMod and 1vmexpe group*; 7 7 7 7 7 7 7 7 I*.tyw FXftisrKi O.ii* . lot.(I Nisf W3 _ 0G llrt i-xjMi-.nroH fn 20* </.** 200 ; -t 2'H Stint hs) :'*} hMvI -,i'V3 R. . i Cnul T..J -inla.il* All *r. nps w< r * n<*mi] in ,ipy. arri^t **, 3.>ti : !:v ami growth. K.':'i.i i (lies, globtn, h.-runvrlr, fl I - ' nora.11, I i i>'T it. loti ttt `JiltVT, St.^T, .i1. itltir <i -v i ujra.il. All t.'.*n/b. !j Wfiit1-.* r iti.> n mil w .m.t I' rats, ilv*r/hmly w> { k>>( r L.' w-ij. !;i- r.-iHo!, -J ;.* patf<;l> ity w.ih n- naal. .U. r .si <>plc p.i - w.i> noi- ft il In i I *pt* except liver ul H on I F rjM>t c >: Out ral lohul ir jtr*;i,i tr i* t Ion : 1 m'f t .is i n < (2b) Sane prrtoi'olx ICO ti t,, iitit All ,i; ir.ilrt w>n.- nnrm.il in appearance. iaiM! Kv .11.4} Crons and alcm- -5.1 [ .lion* (in w.t li.'mi 1. n, ht-iaii o*t It , . 11 *> iuplc appearance of tls6kien were Liver I ur*.t Ion (tlfJJ* SiaJT, SOPT, a I ki nornal. lim* pli. I'.jli.itast*) von* normal. Llver/body weight ratio ol **. aivi h ram were tarter Chan font rots* O s>* .VJlMX UAIA ANI.'IM-S KM'DSIKI- AulhoTN S peel ex Sex No. HrsAl.iy J.IVS Cum . Tot a t Hose ppn-J.iv* Oliserv.it tor.* Tor kelson ( > Nat* Oven hi*we mM ) mi; 1 To+e J M 54 MJi M5 i m 5 n. 5 H 5u M5 1 H5 i * 5 0.5 Of ..f AA Hi Hats M 24 / Pigs V H 24 12 7 7 F 12 7 Rabbits N l 7 J lh>* 1 1 F1 7 Hit r lied tont rojs. cXIMDi'lI ami iinexjioHed ,,k roups. VI tvV J i 6.5 wont In JH above 7 Oil 2(X1 21)0 20IJ loti too 100 ton 4, MW) ?, TWO 1 , ISO SM 2. itln 1 , 1 VI 5M 26't 1 10 exposure In l HS days 41l.lvei /1<dy/ weight ratio larger dun runt mis , not c.ml. ** M " M " *' l.lvet /body weight ratio * uae as rortrols 41 * i* * * * * t at 1st U-jiI ly n I K.n 11 " *< llvor/lo.lv weight ratio higher tli.io emit rots. not si .it Ini leal 1 y h tgn 1 f 1 * nnl . " *' '* " *' * '* SortLil lo all reapeets f >* < * All |> ira-i t-r . nnriTL.il In all Hpeelei. Lester Shorn.TM ND 2 0-2 1 Greenberg rats NO 2 0-2 1 Ad .ins (U ND 2 0-2 1 (1967) HD 2 0-2 1 ND 1 5 ntn. 1 42 lal l* 1 ND i 2 1 50.000 60.000 70.non 100.000 150.000 150,000 0-4,160 0-5,000 0-5,&)0 o-8. no 552 4, no 12,500 Moderate Irtox lf.it Ion . ri^htlnp, reflex lost. Mare InTisise Intnx leal Ion, r I v;li( Lrk reflrx present. More Intense (ntoxfeat Inn, righting, reflex lost. Cornual ref lex rl i '..i' Ill'll S. no gross pathology. Respiratory failure of sane .mfn.il. Deep a ri v t h es 1.1, e < wap l e t e r mov e t y after e* pomi re. Nit pat nology observed. a o o o Soec t e Sex No. exposure: Mrs, per Day Days l*imc. turn Total Oose nrre-O.ivs UI'-II liMA _--. -- _J W' h o rvji tj o^ _____ _____ Lester (2) Ureenberg Alans IHM) Cunt*d Sherman rats M F 9S 9A 2 then n 100.000 Vjrljl.il' 80,0.10 Same exposure* as above Aft or 1-cruj ] do.it hs, replacements wore made In chambers. Two male* survived .%t L IS expo sures. Kema Inlrg .-nil nulls .nvl replacement s survived an average of right exposures Ore dliuj .it i or two exposut cs .it tO(l,0ft0 jtvd evolve .it A0.O kJ. I'm* ill.1.1 after rr * rxpi'siirr* at 100,000 and twelve at 80,000. Six/nine survived nil l ift cor exposures. Pathology QC 01 A * a t* 9 ft 0 0 (3) Sherman 21 rats F IS a li s Waya/20,000 week 20,000 for 3 months 414,000 414,000 h IS 8 Same 0 F a Same 0 0 0 Cent r,*l .inliTuilv flint r>l animals Cinwth stopped during exposures an.I resided .11 TU^TEB/.l i ill* allot exposure*. Extorn.il appearance iiomjl. Liver color, appearance, consistency, degree of congestion was sine as control a. 1/JO died. External appearance of all animals normal. Liver l.ngci, spleen smaller than controls. Vhltc til'onl i'rllf lower, lymphocyte* higher, m-ulripMI* Iiiwi r than lontrnls* 6-vlv weight and hesuglohln were same as controls Control an Inals. It/ (] died. Lung* liad focal pneumonia which healed after two veeVs of rceovc^y from exposme. 0ne-lh*rd of animals had parasitic cysts In liver. Liver pathology sane as controls, hut more variation In amount of fntty Infiltration. Spleen h.il advatu'isl lyirphocytic hyperpl.ihJa. Kidney pathology same an con trols. All organs had normal gross ap pearance. Liver para* tic cysts In .ill animal. I.lver fat normal. No nhi.om.il hlsto'ngv. Congot fnu and swelling greatci tn liver than controls. Congestion and swelling lcma In kidney than controls. Conges tion and swelling s.inc In spleen as controls. SAL 000050278 f Authors Lester Greenberg Ailaan (1963) Cunt *d <x Cl A Snei'leH Sea So. U) She resin H rats F 5 j H5 f5 Mrs. per fMv EXPOSURE Cone. Uavs mi* j :<i 50,000 9 19 V).0<J0 ft 19 0 B 19 0 Total Dose "S i 'a 317.000 )I7,000 0 0 Ohj..*rv.n Ion So ttoru 111 v. On *1 tv* 1-4. .mJra.ilm lost weight, showed nruoiolon I i'.i I syaptoiaH. On days 4-IS, weight Rain was norul. SeruiB trnti'i-jctn.itie, henatorrlt, and prothroobfn t InifH WtTc nors.il. Wlii re and red cell counts were lower than cant rol ILilr: .ill *i (tales Inid rtiln hair ai'J scaly Calls; I mi U>ri .m.| loali'ls veie ti.iira.il . !)v. i/l.o.Iv weight r.iil.i v.ih higher than ronirols r out r 1 .ui t-i 11 s. Pallmloity Cross organ appearance was taste .is cent ruin. Liver pathology showed congested cella. Liver parasitic cysts seen Jn all anlaals. ;r; j> Kurhlet ()*<.!) Abstract \MT. ! si \ Kjt. Ml, * i,. ns. Mite tiD h. m> XI) Hr*. per EXPOSIRE Cone. -J!TJa_____ T^lrtl ill'll' __ Db-ervjr i.-n^ Nt> 1 ND 2 su ; ND 0.5 otnutei 100 LUO lOD 5,000 15, mm 5(MKKi DIM mice 4l,>fi(i l?5,0lvi 4tt..lK0 NIJ S> 'l!*'ki .it S.OilO n.! 150,000 ppm. At MI,0ili1, .mlnul* v>*rr l.; ;-er Ji t Ive, returned t* ni>r.l after ,itiirr* An 151.1 Js npr.ived wlili 1 i< -'`i.i-J but h 11 r |'i -iv ratholyAv No MHtulugJ<`<il dABU*K Sn chinc In long histo logy Vaxln f lekhova (1966*J Abstract Vmln Plokhova U9*b> Abstract Rabbits ND ND *Mironic 3.500 i,*no NO HahMl* NO *'* U.7 J,3il0 (5*5 to os.l 3.900 .V Vaxfn M.'VKuva (1V6VJ) Abstract -`1 cnllla rabbi ti' KD 6A L50 B in lJ to 300 ''itln riokhova (1969b,' Abstract ft.it a SI) NO 150 {5 dui<* hie} ttr.itn vi i i t r leal .icllvtty clungc*: Appearance nr h*,r-i waves /80 Hvrtz} I., .interior and pow- l^ri.pr hyo* jiujs a1 one yiin f. i i\ ulolorv cliun^i'S. tv heart r*jir. arrhythmia Oft rc.ihrJ IVtl vtilt.ljte Ji. i Tt .** *f ituT>t( (fti ttf KyAtt'ltr Vciiv*`vd bl^od l tow. Increased artefic.1 pressure* AUereJ f*waves in EEC ir**o posterior hvp.ithala mu*. Ivtenilal* fr-n# anterior and posterior hypothalamus tn r<'a***d bv 18-JU: and 70-851 respire lively. Alter 20 d.is, blood adrenaline rose from 3.5 tn h. # >7*7; at 40 and more Ais-m. It was b*b Avn9*.' I'> > leri**r hypoth.il a*>un electrical activity aluo chung/d. IMa is tlu direct cause of hypertension- disrupted cardiac work rhytlm, Bradycardia and rr`;ythaf.i. ReJuecd relative duration of 1-11 an 1 i`-I t interval*. Kfl.it ive duration of iJRS complex did not change. After 15 days recovery: cardiac activity rhythm return*- i to noro.il, but the duration of the sound interval remained below Initial level* for aaottu 15 J.iV'i. There tor**, max. pci aissilble Vt. rnneentrat Ion ta tiyuli (vant ly leu* than .Ob?*/! (lJppo), / Author* Spur In JSM exposure Kfi. per No. Por Doru AKIMS I. IMI\ t'nrtf. Total Ouse PP-pra-Pay5OWjuat.tongS2. Clapp Vat a Kaye Young n-69) Ablrarl NO VU>U (1970a) or oc A Ulster bats H N Nt> - 25 4 25 Viola (1970b) Kata Ulster mo g Vi 1 l Siib- NO ('ut a neons 260 10,000 (5day. 0 per wk for 12 months) 1,100x10 1 10,000 417 Viola Blgntt 1 Csputo (1971) Kata Histor M M 2b 4 260 Vlay/vh 25 1 260 .May/wk 10,000 0 l vmaio1 0 Urine contain* ul lylmervaptm If rtf Id tiHi! 1-h)'iJTixv(r<pvlcr*M(j|ir Jr acid, Ui**v cutnpouuj* .trine by tiie reactions ef allyl crwpiHifl ln with glut nchlonoH, Animal* slightly sleepy during exposure. Cross behavior deteriorated ifter 10 Most animals had pathological Involvesent of brain, liver, kidney, thyroid. tfcnilb&. 11/5*1 died of * ardl<*~ respiratory Severe proliferation of cart liege and r*n>pt\i nt |mhi . 0 uird o( In bon* abnormalities In small m^tatar- the peritoneal cavity* No mention of VLn tumors. nal bonea. Severe I Issue Jege.aera tion In brain and live.* anJ thyroid. Connective tissue Invaded small ar teries In fart. Enlarged, prolifera ting Aipfer cells In liver. Distribution of VC 1 n tissue! None observed. Kt\J ti-lJj* had snj.h Bore Vi* iluin serum- high var tut lu.i VC Ik In urine,'but auifor quvttliv lx lost via lung*. (VC) (aits rapidly In first boor In vxpireJ air, Mood, urine* ami brain, liver Alter l hr*, no Vi Is meuaui .ibl e Controls shoved no Almost Nil rxptl. animal* developed skill and lung tumors. Very few bone tumors; when seen they were In all 4 extre mities. 652-70X of tumors were skin tumor it near parotid and *ubmixl llary glands. Frequencies: SKIN LUNGS HONE 26/26 16/26 It-/26 Lung tumors were glandular. New cartilage and subsequent ossifica tion in 4 ex crenel lea. Hard nuuia first seen after 10 months exposure. .\ i. Author* .spec ir* Sen So. EXPOSURE Hr*. per Pay Pay* Cone. i-pa Vatin Kochetkov (1972} Abstract Rabbits Rate NO XI* NO NO NO NO 6 nos. 'UOto 1A0 Jays) 12-1* AM MAI. ii\[ \ Toiat Dose pr^~bay* Ob sorvitton h NO CUanne* In elect rival activity ut l.ypotha* * Hypei adreH.il Inemla. Card lo-v.ij.cul.ir fund Ion Impaired. Hone resorption and u<*( eoporosls* Theory: All syup'orns are caused by bvpat'i.f | ibijs disfunction and sub n emicr t 1*o rao iu* 1 n bo 1 a <w c. Pathology \\ All! MM iit\ fA A*jUiora Animal s Species Sex ____ _____ _______._............. OUsy rvat_lous .... ........ Pathology So, Hrs/Day Days cone r ppm Total dostppa-days. Survivors Total Liver Angiosarcomas Zyabal Surcniia* JJ^pbroBlastmaa Kjltoni 1974 Rats H 309 4 Sprague- F 268 Sda/vk Davley is CcO A Rats H 265 4 Sprague- F 280 5da/uk Dawley Rats SpragueDawley H F 30 4 30 5<Wwk 635 280 155 10,000 6,0C0 2,500 500 25*30 0 JO,000 6,000 2,500 500 250 50 0 30,000 11060X103 <635xio3 <26SX!03 v'./.'mo3 526.5X103 t S.3X103 0 41,6X101 20XIO3 167X103 2JXH)J 11.7X103 2.3X103 0 775X103 0/69 0/72 0'74 0/67 t/67 3/64 1/68 36/60 43/60 54/60 56/60 44/60 50/60 183/1V0 60/60 27 21 21 16 11 0 0 3 1 0 0 0 0 0 2 6 11 9 7 2 0 0 0 0 0 0 0 0 0 0 13 3 53 6 f3t 3 5 00 00 0 0 o0 0c 00 00 00 20 Rats H 36 breeders F 110 4 <wy 7 10,000 6,000 12-18 of preg.) 11667 7000 28/30 28/30 0 0 off spring O 10,000 6,000 11667 7000 30/34 (/) L (subcutrtoeous angles*rcona) 30/32 l (*.bcutaneoua ant 1osarcopa) Author* Industrial Bio - test Laboratories LwO" X K A Cn 3\ Anlm.il ii Specie* Sex mice rfiss CD-i nice M F rats Spra&ae Davicy outbred COBs M F turns ter Golden Syrian M Alt I UAL HA IA i'x|'iu>ur Obst-rvuL Jnn*1 No hrs/day d.iys cone. ppm Survivors 300 300 7 5da/wk 7 5Jj/wV 165 165 10/200 IW200 157/200 300 30U 7 5Jj/wk 7 Sda/wk 300 7 5da/wlt 300 7 5da/wk 165 165 165 165 2500 200 50 *00 SO 2500 200 50 2500 200 50 as of April 15, 1974 ?.itlioln;;v 1 Iver onxloH.m on.iK 17 4 2 REFERENCES Barctta, E. D,, I?. D. Stewart, and J.E. Mutchlcr. Monitoring Expo sures to Vinyl Chloride Vapor: Breath Analysis and Continuous Air Sampling. American Industrial Hygiene Association Journal, Volume 30, pp. 537-544. Basalaev, A, V. , A.N. Vazin and A.G. Kochetkov. Pathogenesis of Changes Developing Duo to Long-term Exposure to the Effect of Vinyl Chloride. GIG TR Prof Zabol 16 (2) : 24-27. 1972. Cla-p, J.J., C.M. Kaye, and L. Young. Metabolism of Alkyl Com pounds in'the Rat. Biochem. Journal 114(1), pp.`6-7. 1969. Dinman, B.D.. W.A., Cook, W. M. Whitohouse, II. J. Magnuson, and T. Ditcheck. Occupational Acroosteolysis: I. An Epidemiological Study. Archives of Environmental Health, Volume 22, pp. 61-73, January, 1971. Dodson, V. N., B.D. Dinman, W.M. Wbi.ehouse, A.N.M. Nasr, and H. J. Magnuson. Occupational Acroosieclysis: III. A Clinical Study. Archives of Environmental Health, Volume 22, pp. 83-91, January 1971. Gabor, S., VI. Lecca-Radu, and I. Manta, Certain Biochemical Indexes of the Blood in Workers Exposed to Toxic Substances (Benuene, Chloroben zene, Vinyl Chloride). Prom. Toksikol. i Klinika Prof. Zabolevanii Khim. Etiol. Sb. 221-223. 1962. Gabor, S., M, Radu, N. Preda, S. Abrudean, L. Ivanof, Z. Anea, and C. Valaezkay. Inst. Ilyg. Cluj., Romania. Bucharest 13 (5), 409-418. 1964. Grigorescu, I. and G. Tova. Vinyl Chloride; Industrial Toxicological As pects. Rev. Chim. 17(8): 499-501. 1966. Harris, D.K. and W.G.E. Adams, Acroosteolysis Occurring in Men En gaged in the Polymerization of Vinyl Chloride. Brit. Med. Journal, 5567, pp. 712-714. Ulus. 1967. Kramer, C.G., and J.E. Mutchler. The Correlation of Clinical and En vironmental Measurements for Workers Exposed to Vinyl Chloride. American Industrial Hvgicne Association Journal, Volume 33(1): 19-30. 1971. Kudryavtseva, O.F. Characteristics of Electrocardiographic Changes in Patients with Vinyl Chloride Poisoning. GIG TR Prof Zabol 14(8):54-56. Kuebler, H. The Physiological Properties of Aerosol Propellants. Aero sol Age 9(4), 44,47-48, 50, 90-91. 1964. Lange, C.E., S. Juhe, G. Stein, and G. Veltman. Uber die Sogenannte Vinylchlorid-Krankheit. Dtsch. med. Wschr. 98, pp. 2034-2037. (Ger man) 1973. 92< 60 SAL 000050285 Lester, O., L.A. Greenberg, and W, R. Adams. Effects of Single and Repeated Exposures of Humans and Rats to Vinyl Chloride. Amer ican Industrial Hygiene Association Journal, pp. 265-275, May-June, 1963. Maltoni, C. Preliminary Report on the Carcinogenicity Bio-assays of Vinyl Chloride. Presented at OSHA Vinyl Chloride Pact Finding Hearing, February 15, 107-1. Markowitz, S. S. , C.J. McDonald, W. Fetiiiere and M.g, Kcrzner. Occupational Aeroostcolysis. Arch Dermatol 106 (2):219-223. 1072. Marsteller, H.J. Ciironie Toxic Liver Damage in Workers Engaged in PVC Production. Deutsche Mcdizinisehe Wochcnschifi 98 2311-2314. 1073. Mastromatteo, E. , i\I. D., A.M. Fisher, II. Christie, and II. Danziger. Acute Inhalation Toxicity of Vinyl Chloride to Laboratory Ani mals. American Industrial Hygiene Association Journal, Volume 21, No. 5, October, 1960. Meyerson, L. B. and G.C. Meier. Cutaneous Lesions in Acroostcolysis. Arch Dermatol 106(2):224~227. 1972. Torkelson, T. R. , F. Oyen, and V.K. Rowe. The Toxicity of Vinyl Chloride as Determined by Repeated Exposure of Laboratory Animals. American Industrial Hygiene Association Journal, Volume 22, No. 5, pp. 354-361. 1961. i Vazin, A.N. and E.I. Plokhova. Creation of an Experimental Model of ' toxic angioncurosis" Developing from the Chronic Action of Vinyl Chloride Vapors on an Organism. GIG TR Prof Zabol 12(7):47-49. 1968a. Vazin, A.N., E.I. Plokhova. Pathogenic Effect of Chronic Exposure to Vinyl Chloride on Rabbits. Farmakol Toksikol, 31(3):369-372. 1968b. Vazin, A. N., and E.I. Plokhova. Dynamic Changes in Epinephrine like Substances in Rabbit Blood Following Chronic Exposures to Vinyl Chloride fumes. GIG TR Prof Zabol 13(6):46-47. 1969a. Vazin, A. N., E.I. Plokhova. Changes in the Cardiac Activity of Rats Chronically Exposed to Vinyl Chloride Vapors. Farmakol Toksikol, 32(2): 220-222. 1969b. Viola, P. L. Pathology of Vinyl Chloride. Mcdicina del Lavoro, Vol ume 61, No. 3 March, 1970. Translated from the Italian. 1970a. Viola, P. L. The Vinyl Chloride Disease, (unpublished translation) Sum mer, 1970. Viola, P. L., A. Bigotti, and A. Caputo. Oncogenic Response of Rat Skin, Lungs, and Bones to Vinyl Chloride. Cancer Research, Volume 31, pp. 516-522. S3< 61 Von Oettingen, \V. F., M. D. The Halogenated Aliphatic, Olefinic, Cyclic, Aromatic, and Aliphatic-aromatic Hydrocarbons including the Halogenated Insecticides,Their Toxicity and Potential Dangers. Public Health Service Publication No. 414, U.S. Department of Health, Edu cation, and Welfare, Washington, D.C. 1955. Wilson, R. II., W. E. McCormick, C. F. Tatum, andJ.L. Creech. Occupational Acroostcolysis, Report of 31 Cases. The Journal of the American Medical Association, Volume 201. No. 3, pp. 577-581. 1967. S4< 62 SAL 000050287 APPENDIX VIII DISPOSAL OF PRODUCTS CONTAINING POLYVINYL CHLORIDE This discussion on disposal of PVC emphasizes incineration and landfilling, the only presently used large-scale methods for the disposal of solid wastes. There is also a limited discussion of resource recovery possibilities. Incineration The two areas of concern related to PVC incineration are incinerator air pollution and incinerator and gas scrubber corrosion. Hydrogen chloride is the major toxic material released when PVC is burned. It has been shown that virtually all of the chlorine is released from PVC on combustion, resulting in HC1. It is estimated that 0. 2 per cent of solid waste is PVC, and 16 x lO6 tons per year of solid waste are incinerated in the United States. Thus, on the order of 32,000 tons of PVC are burned annually, releasing approximately 18, 500 tons per year of HC1 as air emissions. Other solid waste sources which can produce HC1 are chlorides in food waste, plants, grass clippings, and inorganic salts. The formation of compounds requires volatilization and reaction with incinerator flue gases, Achinger and Baker compiled data indicating an emission factor of six pounds of HC1 per ton of solid waste burned. Recent data on HC1 emissions obtained by Battelle show a factor of 5.1 pounds per ton. A value of five to six pounds per ton would be a reasonable emission factor to use for HC1 emissions from municipal incinerators. Using an emission factor of 5.5 pounds per ton gives 44,000 tons per year of HC1 produced by incineration of municipal solid waste. The amount of IIC1 produced from PVC using the above calculation is 4 2 percent of the total. Much more HC1 is probably now emitted to the atmosphere from the nation's coal-burning power plants than from our municipal incinerators. However, there still could be a hazard in the immediate vicinity of an incinerator as a direct result of its HC1 emissions. Of particular concern is the possible dispersal of the stack gases to cause the ambient concen trations of HC1 at ground level to exceed harmful concentrations. How ever, HC1 is not at the present time regulated by EPA. Other air pollutants could, be formed from the additives in PVC dur ing incineration. Several additives are usually incorporated into the poly mer to emphasize particular properties not inherent in the base polymer. The types of additives are antioxidants, antistatics, colorants, fillers, plasticizers, and stabilizers. Some of the additive agents used are: anti oxidants--phenols, amines, phosphates, and sulfur compounds; antistatics --amine derivatives, quaternary ammonium salts, phosphate esters, 5*5< 63 000050288 SAL polyethylene glycolesters; colorants--silts or oxides of metals, aluminum, copper and inorganic pigments; fillers--silica, glass, calcium carbonate, metallic oxides, carbon, cellulose fillers, asbestos; plasticizers--phthalates, organic phosphates; stabilizers--lead salts of acids, barium, cad mium, calcium, zinc, alkyl tin compounds. It is highly unlikely that large quantities of VC will be emitted during incineration of PYC. There is no evidence that PYC will chemically revert to YC. Some small amounts of entrapped monomer might conceivably survive incineration, but these quantities would be very low. The second area of conc ern with incineration of PYC is firebox corro sion and corrosion of pollution control equipment. HC1 can be a major factor related to corrosion of this equipment during incineration at certain temperatures. In the case of plastics, PYC is the major source of chlorine leading to UC1, but other plastics may also contain some chlorine. Incinerators with heat exchangers will have corrosion problems on the fire side of the exchange equipment when the combustion gases contact the outer metal surface. Other surfaces of concern are in the cooling area and in the gas scrubbers. Estimate,-, indicate that in incinerators with heat-recovery systems PYC in the refuse will increase tube maintenance costs by 15 to 20 perpercent over that to be expected if PYC-free refuse was used as fuel. About 05 percent of the incinerators in this country have some type of air pollution control equipment that is exposed to the high chloride envi ronment resulting from refuse combustion. Because of the high chlorine content of the combustion product;?, the cooling and precipitating water from the scrubbers that contacts the flue gas contains large quantities of chloride and is extremely corrosive to the structure. In summary, technology exists for controlling the IIC1 emissions that result from incineration of solid waste; however, the application of this technology will result in increased costs. If technology is not applied, then the contribution of PVC to the nation's air pollution problem will increase because of the projected increases in the usage and disposal. IIC1 scrubbing technology is available, but its application results in corro sion problems. Depending on construction materials, design, and opera tion, these problems can be either large or small. Landfilling PVC does not decompose significantly within the normal time frame of most other municipal solid wastes. It comprises only about 0.2 percent of the total municipal .solid waste being landfilled today, and the effect of PVC on the reuse of the landfill site, at least in the short run, should be negligi ble. !)6< 64 BAL 0000502,89 Since PYC degrades very slowly, in the landfill environment it should not add significantly to the production of leachate or decomposition gases as do other parts of the refuse. The additives of greatest concern are probably the plasticizers. However, if a sanitary landfill is designed and operated with today's technology, disposal of PYC products in a sanitary landfill should pose no special problems to the operation or to the ultimate use of the site. Resource Recovery Recycling of solid waste is a growing industry. Technology has been developed to recover some resources from many of the items in the municipal waste stream. However, the technology to separate plastics or PYC from the waste stream has not yet been commercially demonstrated. The solution to the separation of plastic waste from other components of the municipal waste stream is one deterrent to direct recycling and reuse of plastics, including PYC. However, gathering and centralizing the waste products are also major problems. Some typos of scrap PYC from the fabrication process are presently being recycled back into the manufacturing process. This reduces the solid waste from plastic fabrication plants and reduces the need for new raw materials. There is work underway to develop means for utilizing the benefits of recycling the total municipal waste stream. Examples of these recycling techniques are listed below. -- To recover heat given off during the incineration of solid waste containing PVC and other eomoustible materials as electricity or steam for heating. An example is EPA's research contract with the Combustion Power Company of Menlo Park, California, in which combustion gases are expanded through a turbine to produce power. -- To recover the products of a refuse pyrolysis operation either as a pipeline gas or as feed material for a nearby refinery. An example is EPA's research grant with West Virginia University in which refuse pyrolysis is being studied on a bench-scale. A second example is the Bureau of Mine's research effort to convert refuse to pipeline gas. Also, US and Japanese industrial firms are actively exploring this area. The recent charge in the world's supply of crude oil should speed up research and deveiopmenton new and existing ways to utilize more fully the resource of waste PVC. 37< 65 SAL 000050290 REFERENCES 1. E, A, Boettner, G.L. Bell, B. Weiss, "Combustion Products from the Incineration of Plastics, "Report No. EPA-670/2-73-049, July 1973. 2. "Compilation of Air Pollution Emission Factors," 2nd Edition, Publication No. AP-42, EPA, April 1973. 3. W.C. Achingerand R. L. Baker, "Environmental Assessment of Muni cipal-Scale Incinerators," Report No. SW-lll, EPA, 1973. 4. G.L. Huffman, "The Environmental Aspects of Plastics Waste Treat ment," Symposium on the Disposal and Utilization of Plastics, New Paltz, New York, June 25, 1973. 5. "Threshold Limit Values," American Conference of Governmental and Industrial Hygienists, 1972. 6. Fessler, R., H, Leib, II. Spahn, "Corrosion in Refuse Incineration Plants, " Mitt. Ver. Grosekesaelbets, 4J3 126 - 140, April 1973. 7. Vaughan, D.A., and P. D. Miller, "A Study of Corrosion in Municipal Incinerators, " Cincinnati, Research Grant, April 1973. 8. Miller, P.D. et al, "Corrosion Studies in Municipal Incinerators," SHWRL - NERC, Report SW - 72-3-3. 9. Baum, B. and C. H. Parker, '^Incinerator Corrosion in the Presence of Polyvinyl Chloride and Other Acid-Releasing Constituents," report by DeBell and Richardson, Inc. (No date) 10. George L. Huffman and Daniel J. Keller, "The Plastics Issue, "SHWRL NERC, Cincinnati, Ohio, August 28, 1972. 11. "Incinerator Gas Sampling at Harrisburg, Pennsylvania," EPA Con tract No. 68-02-0230, Office of Air Programs, September 1973. <)8< 66 SAL 000050291 APPENDIX IX ACTIVITIES OF TASK FORCE The principal activities undertaken or stimulated by the Task Force are set forth below MARCH - Recognition of problem of pesticidal sprays containing VC-Responsibility assigned to Office of Pesticide Programs MAPCII - Analysis of material losses during PVC polymerization pro cess MARCH 19-21 - Pilot monitoring effort at B. F. Goodrich Plant in Louisville MARCH - Preliminary evaluation of health effects data APRIL 2 - Meeting with representatives of PVC manufacturers organ ized by Manufacturing Chemists Association APRIL 4 - Meeting with representatives of interested environmental groups APRIL - Development of interim methodology for VC sampling and analysis APRIL/MAY - Visits to VC manufacturing facilities and to PVC polymeri zation, compounding, and fabrication facilities APRIL 12 - First of series of int'eragency meetings convened by EPA APRIL/MAY Monitoring at seven complexes involving 10 PVC and 2 VC plants APRIL/MAY Review of health effects data APRIL 30 Review of Industrial Biotest toxicological experiments MAY 27-31 MAY Preliminary VC water persistence studies Preliminary VC air persistence studies MAY/JUNE JUNE 3 Recognition of air emissions problem -- Responsibility assigned to Office of Air Quality Planning and Standards Technical review of monitoring activities JUNE 11 Administrator's meeting with senior executives of 29 com panies producing PVC and VC JULY Development of improved methodology for VC sampling and analysis 93< SAL 000050292 67