Document Vg5n1JpGDq2D5ZdD2jQDy8xj

BOX -R. N. Wheeler, Jr. Vinyl Chloride No. 8 PVC MASTER FILE PFD llllg 6/25/86 FILE/TITLE - VC PVC Dust - Epidemiological Study of Respiratory Disease VC PVC Dust Study VC PVC Fabrication VC PVC Industry Survey VC PVC Particles VC PVC Toxicity r VC Recovery - Suspension Dispersion VC Research Inhalation Study VC Research 1980 VC Research 1977 VC Research 1976 VC Research 1974 VC Research 1972 VC Research Metabolism Study VC Resin Content / 3 K/'/ ucc 06795 BOX R. N. Wheeler, Jr. Acrylonitrile PVC MASTER FILE FILE/TITLE Acrylonitrile Acrylonitrile Customers' Letters Acrylonitrile - EPA Acrylonitrile - ETS Court Action Acrylonitrile Epidemiology Studies Acrylonitrile Exposure Acrylonitrile - EPA Franklin Institute Acrylonitrile - Method Analysis Acrylonitrile - Niosh Study Acrylonitrile - Originals Acrylonitrile OSHA California Acrylonitrile OSHA Emergency Temporary Standard Acrylonitrile Proposed Standard Acrylonitrile OSHA Post Hearing Comment Acrylonitrile OSHA Standard Comments #1 Acrylonitrile OSHA Standard Comments #2 -2- ucc 067953 f BOX R. N. Wheeler, Jr. Vinyl Chloride No. 5 PVC MASTER FILE FILE/TITLE VC FDA Solvent Vinyl Resins HI ' VC Feron, et al - Oral & Inhalation Toxicity Studies VC Foreign Countries Standards & Miscellaneous VC Filatova - Dynamics of Condition and Disease - Workers in PVC VC Filatova - Problems of Hygien and State of Health of Workers r. VC Fishbein - Halogenated Unsaturated Hydrocarbons, 1979 VC Fox - Manufacture of PVC in Great Britain VC Gamble Respiratory System Eff cts VC Gauvain - Section of Occupational Medicine VC Gay - Measurements of VC in Aerosol Sprays VC Gehring RisK of Angiosarcoma VC Gehring - Toxicity Data Metabolic Activated Chemicals VC General 1965 - 1977 VC General Adhesives & Chemical C . Genesco Division VC General Tire & Rubber Company Visit VC Georgia Duck and Cordage -3 - ucc 067954 f BOX PVC MASTER FILE FILE/TITLE VC Gilbert, et al Residual VC Monomer VC Greenberg - Exposure of VC to Humans and Rats VC Guenther - Plastics and Their Occupational Health Importance VC Harris - Health Problems in th Manufacture and Use of Plastics VC Heath, et al - Chromosomal Damage in Men Exposed to VC Monom r VC Heath & Falk - Angiosarcoma of Liver among VC Workers in U.S. VC Hefner, et al - Percutaneous Absorption of VCM in Rhesus Monk y VC Hill - The Environment and Disease: Association or Causation? VC Hutton Associates VC ICI (Imperial Chemicals Industries) VC Infante - Risks in Communities with PVC Plants VC Infante, P.F. - Genetic Risks of VC VC Information Resource - U.S. Dept, of Health, Educ. & Welfare VC - Institute of Occupational Medicine Study VC Johnson & Anderson Meat-Wrappers ASTMA: A Case Study 4- - ucc 067955 PVC MASTER FILE FILE/TITLE VC Kobayashi, Y. - The Problem of Vinyl Chloride as a Carcinogen VC Kubota, J. - Occup. Diseases in Synthetic Resin & Fibre Industri s VC Lambert - Chromosome Aberrations in Workers Exposed to Vinyl Chlorid VC Lange - Futher Results in Polyvinyl Chloride Production Workers VC Lange - On the So-called Vinyl Chloride Disease - 1973 VC Latexes (Jennat) VC Lelbach and Marsteller - vinyl Chloride - Associated Disease VC Lilis - Prevalence of Disease Among VC and PVC Workers VC Little - VC Monomer Emissions from the PVC Processing Industri s VC Mack - Epidemiologic Methods for Human Risk Assessment VC Matoni & Lefemine Carcinogenicity Bioassays of VC Current Results - 1975 -5- ucc 067956 BOX R. N. Wheeler, Jr. Acrylonitrile No. 3 PVC MASTER FILE FILE/TITLE Atkinson vs. UCC (3) 'Atkinson vs. UCC (2) Atkinson vs. UCC Acrylonitrile - Health Assessment EPA UCC History r -6- UCC 067957 BOX R. N. Wheeler Vinyl Chloride No. 1 PVC MASTER FILE FILE/TITLE VC Activated Carbon VC Analytical Methods for Air Exposure VC Acroosteolysis Study VC Analytical Methods 1969-1977 VC Antonyuzhenko - Occupational VC Intoxication - EPA (1968) VC Angiosarcoma r VC Aquatic Ecosystems VC Anderson, D. et al - Chromosomal Analysis in VC Exposed Workers VC ASTMA (Meat Wrap) VC Bahlman - Vinyl Halides Carcinogenicity VC Barr, J. T. - PVC Bibliography (1980) VC Banzer - Migration of VC Mono from Pipe into Water, 1979 VC Baxter - Angiosarcoma in Great Britain (1977) VC Beaumont & Breslow - Epidemiology VC Berens, A.R. (1975) - Analysis for VC in PVC VC Bernt - Testing of PVC Films VC Bertazzi, et al - Epidemiologies Study of Vinyl Chloride Exposed Workers in Italy (1979) -7 ucc 067958 BOX PVC MASTER FILE FILE/TITLE VC B. F. Goodrich Stripping VC Birth Defects Reports VC Boettner- Combustion Products VC Boettner - Incineration of Plastics VC Boyd - Respiratory System VC Brady, J. et al --Angiosarcoma of Liver -r VC Brain Tumors VC Brain Tumors - EPL Report VC Bridbord, K. et al - Exposur to Halogenated Hydrocarbons in the Indoor Environment VC Briner Paint Mfg. Co. VC Byren, D. - Angiosarcoma of Liver VC Buffler - Experience of Workers VCM Production Plant - 1979 VC Business (1975) - Struggle to Meet PVC Safety Standards VC California SCAQMD (South Coast Air Quality Management District) 1980 8- - ucc 067959 BOX R. N. Wheeler, Jr. Acrylonitrile No. 1 PVC MASTER FILE FILE/TITLE Acrylonitrile OSHA Standard Comment - Sohio - Monsanto Actrylonitrile OSHA Standard EIA Environmental Contracts (Latex UCC) (Flexible Polyols - UCC) Acrylonitrile Ran Polyols Acrylonitrile Res. Analysis Acrylonitrile - SPI Acrylonitrile - OSHA Standard Acrylonitrile - SPI Polymer Group Acrylonitrile - SPI Task Group Acrylonitrile Training Material Acrylonitrile UCC OSHA Comments Acrylonitrile Water Quality Crit ria Acrylonitrile OSHA Standard SPI Comments -9- UCC 067960 PVC MASTER FILE BOX FILE/TITLE R. N. Wheeler Vinyl Chloride No. 7 VC Pneumoconiosis ' VC Miscellaneous #2 VC Nlosh (Jones) - Worker Exposur During Prod. & Fabrication of VC/PVC VC Niosh - Permanent Standards VC Niosh - PVC Chronic Inhalation Toxicology Study VC Niosh - Visits .r. VC Norris - Critique of Study in Rats and Mice VC OSHA Environmental Impact Statement VC OSHA Hearing Statements VC OGHA Permanent Standards VC OSHA Request for Information 12/79 VC OSHA Standard Amendment VC OSHA standards - Foster D. Snell Report VC Oxidation VC Perry - The Case of Vinyl Chloride VC Personal Monitoring Data VC Monomer and Resin Dust VC Pharmacokinetics VC Pigott - In-Vitro Studies Formulations of PVC - 10 - ucc 067961 BOX PVC MASTER FILE FILE/TITLE VC Popow - Influence of PVC Dust on ' Rat Respiration System VC Popper & Selikoff - Comparison of Neoplastic Hepatic Lesions VC Popper - Hepatic Cancers in Man: Quantitative Perspectives VC Prodan, et al - Experimental Chronic Poisoning with VC VC Product r VC PVC Decomposition - 11 - ucc 067962 BOX R. N. Wheeler, Jr. Vinyl Chloride No. 2 PVC MASTER FILE FILE/TITLE VC California Air Quality 'VC California Standard VC Canada 1977 VC Carcinogenicity: An Experimental Kodel for Carcinogenesis Studies VC Carcinogenicity Study - Midwest Research VC Carr, C.J. et al - Anesthesia 1949 VC Chemical Engineering (1975) "Chementator" VC Chemical Safety Data Sheet SD-56 VC Chromatograph - Automatic VC Ghiazze, L., et al - Mortality Among Employees of PVC Fabricators - 1977 VC CPSC (Consumer Product Safety Commission) Study VC Creech & Johnson - Angiosarcoma of Liver (1980) VC Crider, et al - Diffusion of Vinyl Chloride Monomer from PVC under Various Conditions VC customer Letters VC Cytogenetics VC Del Val Ink & Color - 12 - ucc 067963 BOX PVC MASTER FILE FILE/TITLE VC Dessy, E., et al - Effects of VC ' on Rats Kept in Ind. Atmosphere VC Dispersion Modeling VC Distribution - 1970-1975 VC Distribution Activities Distribution - 1970-1972 - Vinyl Resins * VC Dow Contract r - 13 - ucc 067964 BOX PVC Hart & Goodyear PVC MASTER FILE FILE/TITLE Hart v. Goodyear (Material in Response to Production of Documents) Litigation Ross M. Hart v. Goodyear Chemical (inc. Union Carbide) Hart v. Goodyear (Request for Production of Documents by Plaintiff) Hart v. Goodyear (Miscellaneous Information Pertaining to Production of Documents) Back-Up File - Hassey v. Uniroyal (incl. UCC) Gordon Gerber Ross-Hart v. Goodyear (including Union Carbide) Material Pertaining to Request for Production of Documents Hart v. Goodyear (Material in Response to Production of Documents) - 14 - ucc 067965 BOX PVC Maliko PVC MASTER FILE FILE/TITLE Maliko ' Maliko Deposition Toxic Info Mikyska - Background Material Exhibit 1 Court Papers Interrogatory Work File Articles on PVC Correspondence and Motes Handwritten Notes Product Liability - Mikyska vs. UCC Interrogatories - 15 - UCC 067966 PVC MASTER FILE BOX FILE/TITLE R. N. Wheeler, Jr. Vinyl Chloride No. 11 VC Training VC Tribukh, S., et al - Working Conditions & Sanitation in PVC Prod. VC UCC - Position Papers VC Ungavary, G., et al - Study of Teratogenic and Embryotoxic Effects VC Veltman, G., et al - Clinical Manifestations/Course- of VC Diseas VC Vertkin, Y., et al Broncho-Respiratory Organs of PVC Workers VC Viola, P. - Chlorinated Organo-Compounds and Ecology VC Viola, P. - Pathology of vinyl Chloride VC Volkheimer, G. - Hematogenous Dissemination of Ingested PVC VC Von Oettingen - Halogenated Olefunic Hydrocarbons VC Wagoner & Infante - Laboratory Bioassay Regulatory Control VC Wagoner 6 Infante - Review of Carcinogenic & Toxicological Eff cts VC Wagoner & Lemon - Occupational Hazards - The Hidden Killers VC Waxweiler, R. - A Cross-Sectional Epidemiologic Survey of UC Workers - 16 - UCC 067967 BOX PVC MASTER FILE FILE/TITLE VC Waxweiler, R. - Epidemiologic Investigation Excess Lung Cancer Risk VC Waxweiler, R. - Liang Cancer at a PVC Polymerization Facility VC Waxweiler, R., et al - Plastics Toxicology of Synthetic Resins VC Wyatt, R., et al - Epidemiologic Study History of PVC Workers r Vinylidene Chloride Vinyl Chlorid Amiton/Ackerley VC Bell vs. UCC Dendinger vs. Chrysler Plastic Prod. Grimm vs. UCC Lee vs. UCC Vera Norris vs. Lockheed Sally Neff vs. Celanese Sireci vs. UCC Stillo vs. Rubbermaid & UCC ymalikaf,Vfev8GC. " >. Nv Wheeler Report - 17 - ucc 067968 BOX R. N. Wheeler, Jr. Vinyl Chloride No. 9 PVC MASTER FILE FILE/TITLE VC Resin Content 1975 ' VC Resin Content 1971-1974 VC Resins Dispersion, Solvent & Solutions VC Resin - Pechiney - St. Gobain VC Resins Processes VC Resin - PPI Defacto VCM Group VC Resins SuspensiBn VC Resins Type 'O' (Suspension) VC Resins (Vinyl) Competitive Respiratory Complications of Burns - W.A. Crosbie VC Richardson Ink Company VC Safety Data Sheet VC Safety Association VC Sakabe - Bone Lesions Among PVC Workers VC Shindell, et al - The Healthy Worker Effect - 1978 VC Shintech PVC Plant - Freeport, Texas VC Simonds - Handbook of Plastics 1949 -Chronic Oral TQxicihyv.t*'Safes of VC - VA Copolyater - - 18 - ucc 067969 PVC MASTER FILE BOX FILE/TITLE VC Solvent Resins 1940-1957 ' VC SPI Communications Committee #2 VC SPI Fire Safety - 19 - UCC 067970 BOX R. N. Wheeler, Jr. .Vinyl Chloride No. 4 PVC WASTER FILE FILE/TITLE VC Epidemiological German Study VC Epidemiological HEW Study VC Epidemiology VC Epidemiology - Swedish PVC Process VC Epidemiology - Chiazze VC - ORC (Organizational Resourc s Counselors, Inc.) * Epidemiology VC Epidemiological Study of Exc ss Lung Cancer - Waxweiler, 1978 VC Epidemiology - Chemical Carcinogenesis Club, 1979 VC Epidemiology - Dow VC Epidemiology - Dupont, et al VC Epidemiology - North Rhine/Westphalia 1978 Report VC Epidemiology Study - Workers VC" EpIdfemToiogy Study - Union Carbide VC Epidemiology - Uhiv. North Carolina - Firestone Pit. VC Epstein Book ve Exposure Data 1975-1976 vc Exposure Data 1974 VC Exposure Data 1973 - 20 - ucc 067971 PVC MASTER FILE FILE/TITLE VC Falk, H. - Hepatic Disease at VC ' Polymerization Plant VC Fedotova, I.V. - Tumors Manuf. of VC and PVC VC FDA - Food and Drug Admin. 1980-1984 VC FDA - Food and Drug Admin. 1977-1979 VC FDA - Food and f>rug Admin. 1975-1976 VC FDA - Food and Drug Admin. 1973-1974 VC FDA Solvent Vinyl Resins #2 - 21 - ucc 067972 PVC MASTER FILE BOX FILE/TITLE R. N. Wheeler -Vinyl Chloride No. 10 VC SPI Hazardous Waste VC SPI Health Subcommittee VC SPI Man Practices VC SPI PVC Safety Group #2 VC SPI PVC Safety Group #1 VC Spirtas, R. - Angiosarcoma of Liver in VC/PVC Workers v r VC Storage 6 Recovery VC Stripping VC Suciu, I., et al - Clinical Manifestations in VC Poisoning VC Suspension PVC Business VC Suspension PVC General Tire VC Suspension Resin - Aycliffe & Shatvell VC Suspension Resins Competitive Producers VC Suspension - R&D Other than Texas City VC Suspension Resins - R&D 1967-1972 VC Suspension Resins - R&D 1950-1966 VC Szende, et al - Pneumoconiosis Developing After Inhalation of PVC VC Tabershaw & Gaffey - Mortality Study of Workers - VC & Polymers - 22 - ucc 067973 11 : 1 BOX PVC MASTER FILE FILE/TITLE VC Tamburro, C. - Health Effects of ' Vinyl Chloride - 1978 VC Teratology VC Theriault, G. - Birth Defects Ambient VC Toxicity - Mellon Institute Vinyl Film Study VC Torkelson, T. - Toxicity of VC by Exposure of Lab''Animals VC Toxicity CPSC Study VC Toxicity NTIS Study VC Toxicity Study Toxicity - Plastics, etc. Toxicity - Plastics Eckardt Toxicology - Oakridge - 23 - ucc 067974 BOX R. N. Wheeler, Jr. Vinyl Chloride No. 3 PVC MASTER FILE FILE/TITLE VC Dow - UCC Long Term Mortality Study VC Dust VC Eckardt & Hindin - The Health Hazards of Plastics VC Edsall, J.T. - Scientific Freedom and Responsibility (1975) VC Emissions VC EPA Std. 1-9-85*" VC EPA Standard - December 24, 1975 VC EPA Assessment Report VC EPA Amendment, June 2, 1977 VC EPA Draft Standard April 24, 1975 VC EPA Emergency Relief VC EPA - Environmental Aspects of Vinyl/Polyvinyl Chloride 1974 VC EPA Environmental Protection Agency #1 VC EPA Radian Report, January, 1981 VC EPA S&T Report 1975 VC EPA Standard - October, 1976 VC EPA Standard Support Environmental Impact Document VC EPA Standard UCC Comments - 24 - UCC 067975 BOX PVC MASTER FILE FILE/TITLE VC Epidemiological (EEH) Equitable ' Environmental Health, Inc. VC Epidemiological (EHA) Environmental Health Assoc., Inc. r - 25 - ucc 067976 BOX R. N. Wheeler, Jr. Vinyl Chloride No. 6 PVC MASTER FILE FILE/TITLE VC Maltoni's Study VC Maltoni - VC Pathology - 1976 VC Maltoni's VCM Toxicity Studi s 1977 VC Makarov & Makarenko - The Effects of Methyl Methacrylate & VC VC Marsteller & Lebach - Splenomegalic Liver Disease PVC Workers ^ .m VC Mason - Cancer Mortality in U.S. Counties v/ Plastics & Related Industries VC Mastrangelo, et al - PVC Pneumoconiosis Epidemiological Study VC Metabolism VC Miller - Changes in Pulmonary Function in Workers Exposed to VC VC Monitoring (Automated) of Vinyl Chloride Operations VC Monitoring 1978-1979 VC Monitoring 1976-1977 VC Monitoring* 1975 vc Monitoring 1974 - *2 VC Monitoring 1974 - 81 VC Monitoring 1969-1973 VC Monitoring - Industrial Hygi n Survey of Fabrics Div. - 26 - ucc 007977 PVC MASTER FILE FILE/TITLE VC Monitoring - Monthly Personnel Summary - 1976 VC Monitoring - Other VC Monitoring - UCC Distribution VC Moore - The Vinyl VC Monson, et al - Mortality Among VC Workers VC Muratov, et al ? Max. Permissible Concentrations of VC in the Air VC Mutagenesis VC National Institute of Health Reports VC Nicholson, et al - Mortality Experience of Workers VC Nicholson, W.J. - Occupational Hazards VC M4osh'- Industrial Hygiene Surv y VC Niosh - Industrial Hygiene Report - 27 - UCC 067978 <miTH CHARLESTON PLANT * -: UNION CARBIDE CORPORATION CHEMICALS AND PLASTICS P.O. BOX *004, SOUTH CHARLESTON. W. VA. 25303 Re: Maliko, Mazanowski, Wilkinson and Schaffer vs Union Carbide m "POLYVINYL CHLORIDE - VINYL CHLORIDE MONOMER" Literature Survey and Engineering Opinions Prepared by R. N. Wheeler, Jr. April 10, 1978 ucc 069586 -OtrrM CHARLESTON hamt UNION CARBIDE CORPORATION CHEMICALS AND PLASTICS PJO. BOX 1004. SOUTH CHARLESTON, w. VA. XSSOS "POLYVINYL CHLORIDE - VINYL CHLORIDE MONOMER" Literature Survey and Engineering Opinions Prepared by R. N. Wheeler/ Jr. April 10/ 1978 ucc 069587 2- TABLE OF CONTENTS Page SUMMARY AND CONCLUSIONS 3 R. N. WHEELER, JR. - QUALIFICATIONS 6 LITERATURE SURVEY POLYVINYL CHLORIDE INDUSTRY AND PROCESSES 8 VINYL CHLORIDE TOXICOLOGY 16 POLYVINYL CHLORIDE TOXICOLOGY 24 UNION CARBIDE CORPORATION CHRONOLOGY OF PVC ACTIVITIES 27 ENGINEERING OPINION ODORS PNEUMOCONIOSIS ESTIMATES OF EXPOSURE TO VINYL CHLORIDE MONOMER LITERATURE CITED ATTACHMENTS 32 34 43 53 62 UCC 069588 -3- POLYVINYL CHLORIDE - VINYL CHLORIDE MONOMER LITERATURE SURVEY AND ENGINEERING OPINIONS SUMMARY AND CONCLUSIONS 'LITERATURE SURVEY / f Polyvinyl Chloride Industry and Processes 1. Union Carbide Corporation solution polymerized PVC resins which were all bagged had negligible potential for vinyl chloride emission. 2. Union Carbide Corporation process bulk resins which are generally sold in bags had little potential for vinyl chloride emission. 3. Union Carbide Corporation suspension homo- and co polymer PVC resins which are generally handled in bulk contained appreciable residual vinyl chloride monomer. The operations carried out by ATC or OTD were transferring from bulk shipboard containers to bulk hopper trucks, bulk hopper rail cars and to multi-wallpaper bags on pallets. Vinyl chloride emissions from PVC resins at ambient temperatures are very low. Resins were not heated in the ATC operations. Vinyl Chloride Toxicology 1. Based on the information available to it, the VC-PVC industry and Union Carbide Corporation acted in a responsible manner. In retrospect, speedier action might have expedited the report of the carcinogenic properties of vinyl chloride by no more than one year. 2. Vinyl chloride exposure has been connected with angio sarcoma in humans. No other type of neoplasm has been identified as specifically caused by human vinyl chloride exposure. UCC 069589 \ , -4- Vinyl Chloride Toxicology (continued) 3. Vinyl chloride exposure has been related to acroosteolysis in humans. Polyvinyl Chloride Toxicity 1. Polyvinyl chloride or its usual copolymers display a very low order of toxicity. 2. Polyvinyl chloride has caused no identified excessive mortalities in the PVC fabricating industry and by inference would show similar properties at ATC. 3. Polyvinyl chloride in the form of respirable dust has been related to pneumoconiosis in workers and laboratory animals. Union Carbide Corporation Chronology of PVC Activities 1. Union Carbide Corporation initiated or participated in actions to study and control the hazards related to vinyl chloride and polyvinyl chloride exposure as a responsible corporate citizen. 2. There is no evidence that Union Carbide Corporation failed to act upon knowledge it had or obtained, concealed its knowledge from others or acted in a negligent manner with regard to the hazards relating to vinyl chloride or polyvinyl chloride exposure. ENGINEERING OPINIONS Odors Based on the material data and the specific complaints regarding the vinyl chloride resins, the nasal and bronchial irritation noted by the plaintiffs was due to. trace amounts of vinyl acetate and acetic acid given off by resins. Additionally, hydrogen chloride could be emitted during maintenance operations or equipment failures. UCC 069590 Pneumoconiosis 1. Research has not clearly shown that there is a relationship between pneumoconiosis and PVC resin dust. .2 The ingestion of vinyl chloride monomer via inhalation of respirable PVC dusts is negligible since such dust contains less than one ppm by weight of vinyl chloride monomer. 3. The Union Carbide Corporation PVC resins handled and bagged by ATC contained very little, if any, respirable dust. 4. Local ventilation was provided at ATC for operations that were dusty. 5. Exposure to the PVC resin handled by ATC for Union Carbide Corporation is unlikely to cause chronic human disability via inhalation. mates of Exposure to Vinyl Chloride Monomer Based on the material analysis, of potential employee exposure and the work done by Gollob Analytical Service Corporation, the ATC employees at Perth Amboy were not exposed to toxic concentrations of vinyl chloride and were only rarely exposed in excess of the permissible exposure limits set by OSHA, October 21, 1974. ' RNWheeler, Jr./ws R. n. wneeier, jr UCC 069591 R. N. WHEELER, JR. Environmental Protection and Occupational Health, Project Manager Union Carbide Corporation P. 0. Box 8004 South Charleston, West Virginia 25303 Coordinator with Union Carbide Corporation on environmental protec tion, health problems, and regulations. Represents Union Carbide Corporation to OSHA, EPA and NIOSH on such problems. Graduate Chemical Engineer from Virginia Polytechnic Institute in 1943. Employed by Union Carbide Corporation in various capacities for thirty-five years. Experienced in manufacture of polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl alkyl ethers, polyethylene oxide and related monomers. ORGANIZATION ACTIVITIES I.Organization Resources Counselors Washington, D. C. 1. Vinyl Chloride Task Force 2. PVC Fabricating Industry, Epidemiology Steering Committee II. Society of Plastics Industries VC-PVC Producers Association New York, New York 1. VCM-PVC-EPA Technical Committee 2. Health Study Committee III. Manufacturing Chemists Association Washington, D. C. 1. Vinyl Chloride Technical Committee .* a. VCM Research Program Coordinator b. VCM Safety Data Sheet Subcommittee 2. Styren Toxicity Technical Panel UCC 069592 IV. Society of the Plastics Industry New York, New York 1. Acrylonitrile Copolymer Group 2. Toxicology Committee a. Vinyls Subcommittee b. Vinyl Acetate Study Task Force V. Organization Resources Counselors Washington, D. C. 1. Acrylonitrile Task Force 2. OSHA Generic Carcinogen Proposal Task Force Publications 1. Wheeler, R. N., Jr. and Sutherland, M. E.: "Control of Vinyl Chloride Emissions in Distribution Operations", American Institute of Chemical Engineers, Houston Meeting 1974. 2. Wheeler, R. N., Jr.: "Specialty Vinyl Chloride Resin Processes, Effects of Governmental Regulations", American Chemical Society, San Francisco Meeting - 1976. 3. Wheeler, R. N., Jr.: "Automatic Monitoring Systems for Vinyl Chloride", American Institute of Chemical Engineers, New York Meeting - 1977. 4. Wheeler, R. N., Jr., Barr, J. T., Laundrie, R. W. and Snyder, P. J.: "Chemical Safety Data Sheet SD-56 Vinyl Chloride", Manufacturing Chemists Association, Revised April 1, 1977 (in process of publication). ucc 069593 -8i POLYVINYL CHLORIDE INDUSTRY AND PROCESSES Polyv.inyl chloride is a ubiquitous part of our environment today in that it appears in clothing, upholstery, wire insulation, food containers, coatings, phonograph records, flooring and an infinite variety of other items; Despite this wide application, there is little public understanding of the size and the complexity of the industry. In order to discuss the health related problems of the industry, it is necessary to review the technology of the PVC industry and to identify the sources of problems and factors contributing to them. The polyvinyl chloride industry consists of five major functions: 61/ (1) Manufacture of vinyl chloride monomer. (2) Transport of the vinyl chloride monomer to the user. (3) Manufacture of synthetic resins from vinyl chloride and other monomers (PVC). (4) Transport of the resins (PVC) from the manufacturing plant to the user. (5) Manufacture of finished and semi-finished plastic articles for the ultimate use of the consumer. 1. Manufacture of vinyl chloride monomer is carried out in large chemica) plants with capacities of '200,000 tons or more per year where ethylene, a gas, is treated with chlorine, oxygen and hydrogen chloride yielding ethylene dichloride (1.2, dichloroethane), a liquid. This ethylene dichloride is cracked (dehydrochlorinated) in a furnace yielding vinyl chloride monomer and hydrogen chloride (both gases). These are collected, separated and purified. The hydrogen chloride is recycled. The vinyl chloride monomer`is liquified with pressure and refrigeration. Most of these plants in the United States are lo cated on the Gulf Coast where easy access to salt and to hydrocarbon feed stocks exists. The plants themselves are built in the open and all UCC 069594 -9- operations are carried out under pressure in closed equipment and pipelines thus employee exposure to vinyl chloride monomer is minimal. This, in turn, explains why there have been no reported health problems associated with the manufacture of vinyl chlorid . 2. Transport of the vinyl chloride monomer to the resin manu facturing facility is carried out via pipeline if the plant is nearby or via tankers, barges, rail tank cars or tank trucks if the plant is remote from the vinyl chloride manufacturing plant. The primary modes of transport are rail tank cars and pipelines carrying liquified vinyl chloride under pressure. Aside from fires and ex plosions due to rupture of the transport vessel and subsequent ignition of the vinyl chloride, there have been no health problems associated with this function. 3. Manufacture of synthetic resins from vinyl chloride and other monomers involves reacting these monomers in agitated pressure vessels in the presence of catalysts and converting these liquids and/or gases to solid resins. A considerable amount of heat is generated by the reaction and this is removed by cooling the vessel. As the monomer is consumed during the reaction, the rate of reaction slows down and the heat transfer surfaces of the vessel become coated with solid resin; thus, after some optimum reaction time, the unconverted monomer is removed from the reacting mass by heat and vacuum and the resin (PVC) is recovered as a dried white powder or as a liquid latex of solution. There are presently four main processes for the manufacture of PVC resins: (1) Suspension polymerization (2) Emulsion polymerization (3) Bulk polymerization (4) Solution polymerization These processes along with pertinent variations will be dis cussed later with particular reference to the resin properties obtained by each process. For the present, one should consider UCC 069595 -10- the facts that a solid is produced in the reactor and a consider able amount of heat is generated by the reaction. These facts / require that after one or more batches of resin are made in a r actor, the solid resin adhering to the walls and in the openings be removed manually by scraping, washing with high pressure water or by washing with a solvent to dissolve the resin scrap; i.e., reactor cleaning. It is in the reactor area of the process and more particularly, the cleaning operating with worker exposure to vinyl chloride concentrations of 1,000 ppm or more that workers have contracted acroosteolysis 82/, 9 4/ and angiosarcoma. 70/ 4. Transportation of the resins (PVC) to the manufacturer of finished and semi-finished plastic articles varies with the pro perties of the resin and the amount consumed by the plastic manu facturer. A plant manufacturing vinyl film and sheeting using millions of pounds per year of suspension or bulk process PVC resins would be shipped rail hopper cars or hopper trucks of raw material. A plant manufacturing vinyl coated cloth for furniture would be shipped PVC dispersion resins in 40-pound paper bags because dispersion resins are very difficult to handle in bulk. A coating manufacturer using costly specialty PVC resins would be shipped material in 50-pound paper bags. Resin delivery in bags is more costly than in hopper trucks. Hopper trucks are more costly than rail hopper cars and rail hopper cars are more costly than contain erized water transportation. As a result of transportation economics, large resin producers establish distribution centers such as the Perth Amboy facilities of ATC to minimize the cost of product delivery to the ultimate consumer. While there is some potential for exposure to vinyl chloride monomer given off by the PVC resin, there have been no health problems identified in this area. 5. The manufacture of finished and semi-finished plastic articl s from PVC resins is a relatively simple operation, but many different procedures are used depending upon the type of PVC resin used and the properties desired in the final product. Most of the suspension and bulk polymerized resins are mixed with plasticizers (low volatile UCC _ 11 organic esters such as dioctyl phthalate), stablizers (such as organic compounds of tin, lead, cadmium or calcium), antioxidants (such as complex phenols), pigments (such as carbon black or chrome yellow) and processing aids (such as soaps or fatty adds) and heated to form a compound which is molded, extruded or calendered. It is this mixing operation which drives off most of any contained re sidual vinyl chloride monomer. This is also the point where the employee is exposed to a wide variety of other potentially hazardous materials. Dispersion (emulsion) PVC resins are mixed with similar materials to make a thick liquid compound which needs only to be heated to form a plastic article. Solution polymerized resins are dissolved in solvents and applied as coatings. Work related health problems have occurred in plastic manufacturing plants, however, unless they are specifically identified with exposure to vinyl chloride monomer via bioassay they are probably the result of xposure to other materials since monitoring studies have shown very low vinyl chloride levels or none at all in the workspace air. 74/, 14/ The PVC resin processes and the PVC products from these pro cesses are reviewed as follows: 61/ (a) Suspension polymerization is the major process used for the manufacture of PVC resins. It involves the charging of two parts water and one part vinyl chloride monomer to an agitated reactor along with catalyst and suspending agents such as polyvinyl alcohol. The mass is reacted at 50 to 60C until about 90% of the contained monomer is converted to resin. The resin water mixture is heated and subjected to vacuum until the unconverted monomer is substantially removed. The resin is then removed from the water and dried in rotary or flash driers by exposure to heated air. Process costs are low and a wide range of products can be produced. The resin particle size can be varied from 50 to 150 microns with varying degrees of porosity and varying composition if other monomers are used. The residual unconv rted vinyl chloride (RVCM) is removed with difficulty due to the large ucc 069597 -12 particle size and the low degree porosity. Commercial PVC by this process contained approximately 1,000 ppm by weight RVCM prior to 1974. The resin is widely used in bulk for its low cost, ease of handling and freedom from dust. (b) Emulsion polymerization.is the second most widely used process as well as one of the oldest for manufacture of PVC resin. Again, about two parts water and one part monomer (VCM) are charged to an agitated reactor along with surfactant (soap) so that with agitation a monomer water emulsion is formed. Catalyst in the form of a water soluble salt or organic peroxide is added and the mass reacted at 40 to 60C. until 70 to 90% of the contained monomer is converted to resin. Resin particles formed are very small (0.2 to 2 microns) and a relatively stable synthetic latex is formed. The reacted latex is stripped of its uncoverted monomer to a level of 5,000 ppm by weight on a resin basis prior to 1974. The latex product could be directly formu lated into coating materials, could be coagulated and the resin recovered by dewatering and drying or could be spray dried directly to recover the resin. In Europe, the resin is used for all types of fabricating technics while in the United States the latex or the spray dried resin is used for coating or for fabrication via plastisol technics. The resin is characterized by its small particle size (1 to 10 microns), high content of soap (1 to 2%) and its very low residual unconverted vinyl chloride content. The very small particle size coupled with spray drying and grinding cause almost complete removal of the RVCM (<1 ppm by weight). Dustiness, surfactant odor and con tent, poor $>ulk handling properties and cost have limited the application of the resin from the process to manu facture of specialty items from resins in bags. IJCf' 069598 -13- (c) Bulk polymerization was developed by Union Carbide Corporation in 1937 as a continuous one stage reaction. Vinyl chloride polymer is insoluble in vinyl chloride monomer thus on partial polymerization of the monomer, a resin monomer slurry is formed. This resin monomer slurry is fed to a tank of hot water where the monomer is boil d out leaving a resin-water slurry. The contained resin is dewatered and dried in a flash drier. The resin produced by this process is free of suspending aids and surfactant, is very porous, has a particle size of 60 microns and con tains less than 10 ppm RVCM. With aeration, the RVCM con tent of the resin falls rapidly to zero. Manufacturing costs are high, limiting resin use to specialty items. Distribution entails both bulk and bag handling. In Europe, the bulk process developed by Pechiney St. Gobain, is a two-step high conversion batch process involving no water. The first polymerization stage con verts 10% of the monomer to polymer. This mixture is then charged to a second polymer!zer where the reaction is carried to 60 to 90% monomer conversion. Resin in the second reactor is subjected to heat and vacuum to remove unconverted monomer. Resin particles are 50 to 150 microns and very porous. Prior to 1974, this process resin was very high in RVCM (or 5,000 ppm). Costs are low and the bulk product is competitive with suspension resin. A number of United States producers use this process. Neither the UCC process nor the PSG process are amenable to producing resins containing appreciable quantities of comonomer. (d) Solution polymerization is a process unique to Union Carbide Corporation. It was commercialized in 1933. Vinyl chloride monomer, comonomer, solvent and catalyst are fed to a continuous reactor system. The UCC 069599 14- polymer formed is soluble in the reacting mass so that .the reactor product is a viscous resin-solvent solution. This solution is distilled to remove the unconverted vinyl' chloride monomer and the resin product recovered by treating the resin solution with water and drying the product. The resin particle is very porous, is always a copolymer, is free of soaps and suspending agents, has a particle size of 75 microns and contains less than 1 ppm RVCM. Manufacturing costs are relatively high and the product finds its greatest use as a coating material; i.e., paints and lacquers where it is used in bag quantities The emission of unconverted vinyl chloride from PVC resins during the course of normal mechanical handling and storage is an important consideration in view of the chronic toxicity of vinyl chloride monomer and the exposure of workers to PVC. Vinyl chloride monomer is not soluble in pure polyvinyl chloride thus it can only be adsorbed on the surface or mechanically entrapped in the resin particle. The larger the resin particle and the less porous it is, the more slowly the contained vinyl chloride is emitted. Studies of monomer stripping at ambient temperatures have shown that the rate of emission is very slow and appears to reach a steady state concentration; i.e., a sample of suspension polymerized resin containing 50 ppm by weight RVCM emitted no VCM at 20F. Thus, it could be said that regardless of the RVCM concentration in a PVC resin at ambient temperature, the contained vinyl chloride is emitted to the air slowly, if at all. This rate is further slowed by the presence of a comonomer which tends to solubil ize the RVCM. 62/, 13/ In 1974 and 1975, Union Carbide Corporation con ducted extensive studies of vinyl chloride emission from .its resins.. In 1975, it was able to establish to OSHA's satisfaction that no hazard from vinyl chloride exposure UCC 069600 -15- existed from its solution and emulsion polymerized resins. 22/ 93/ - Emission studies of its suspension PVC resins showed the average RVCM content on shipment from the plant was 860 ppm. When these resins arrived at Perth Amboy and were sailed, the average RVCM content was 542 ppm showing a loss of 37% per month when handled in bulk. Storage of these resins in bags showed an 85% reduction in RVCM per week storage. The bulk process resins were not studied, however, assuming the same rate as suspension resin in bulk, they averaged 15 ppm RVCM on shipment and 9 ppm on bagging at Perth Amboy. The normal period from production to bagging was 32 days, including six days prior to ship loading, seven days on the ship and nineteen days in storage at Perth Amboy prior to bagging. Resin inventory at Perth Amboy averaged . 1.25 months or 47.5 days. 2/, 3/, 4/, 5/ Summarizing the salient points of the discussion, the following are to be noted: Resins handled by ATC during the period involved in litigation are: (a) Union Carbide Corporation solution polymerized PVC resins, which were all bagged, had negligible potential for vinyl chloride emission. (b) Union Carbide Corporation process bulk resins, which are generally sold in bags, had little potential for vinyl chloride emission. (c) Union Carbide Corporation suspension homo- and co polymer PVC resins, which are generally handled in bulk, contained appreciable residual vinyl chloride monomer. UCC 069601 16- The operations carried out by ATC or OTD were transferring resins from bulk shipboard containers to bulk hopper rail cars and to multi-wallpaper bags on pallets. Vinyl chloride emissions from PVC resins at ambient temperatures are very low. Resins were not heated in the ATC operations. VINYL CHLORIDE TOXICOLOGY Vinyl chloride despite its reported synthesis in 1835 did not become an article of commerce until 1928 when Union Carbide Corporation started research and pilot scale manufacture in 1928. This work was followed by commercial manufacture of vinyl chloride polymers in the United States by Union Carbide Corporation and in Germany during 1933. From this early start, the VC-PVC industry has grown to its present day level as one of the largest of the plastics industries. The earliest study of the toxicity of vinyl chloride was that reported by F. A. Patty. 51/ He found that human exposure to vinyl chloride at 2.5% for 3 minutes produced dizziness and disorientation and that guinea pigs exposed for eight hours at 0.5% showed no effect. Guinea pigs exposed to 2.5% for eight hours died. Patty also cited work by Schaumann 6 3/ that noted no hepatic or renal lesions occurred in mice or rats exposed at 0.5% for four hours daily over five to eight days. The apparent low toxicity of vinyl chloride as compared to chloroform, a widely used anes thetic at that timesed to its consideration as an anesthetic by Lehman and Flury 31/ after Peoples and Leak 53/ had confirmed its apparent low toxicity. Von Oettingen in 1933 cautioned against its use as an anesthetic. 88/ Later studies by Oster and Carr in 1947-1949 showed vinyl chloride used as an anesthetic caused 069602 -17- severe cardiac arrhythma. 4 8/ As late as 1955, vinyl chloride was still under consideration as an anesthetic. Von Oettingen cautioned as regards to its effect on the circulatory system. 87/ J ' Many researchers cite the report of Tribukh in 1949 74/ that 73 workers in a PVC compounding and calendering plant showed hepatitis, hypertension, anemia, gastritis and skin lesions as evidence of the highly toxic nature of vinyl chloride retained in the PVC. The compounding was done at temperatures of 160C. using diphenylene*and chlorinated naphthalene as well as various pigments and stabilizers. Chlorinated naphthalene is well known as a severe liver toxicant and such symptoms have been observed in others exposed to such materials. Between 1953 and 1959, other problems related to additives were noted but there was no reported liver disease. The availability of better plasticizers which were less toxic no doubt contributed to the lack of further problems. 30/ The American Congress of Governmental Industrial Hygienists set the threshold limit value of vinyl chloride at 500 ppm for an eight-hour exposure based on human experience and animal data. This was believed to be a safe level for worker exposure. 70/ Mastromatteo in 1960, following the accidental death of two vinyl chloride workers, exposed rats, mice and guinea pigs to 10%, 20% and 30% vinyl chloride for 30 minutes. 37/ At the higher concentrations, the animals showed narcosis and respiratory failure. All animals showed lung, hepatic and renal congestion. Prodan reported LD^q of mice, rats, guinea pigs and rabbits based on two-hour exposure. 57/, 58/ The vinyl chloride concen tration varied from 12% for mice and 24% for rabbits. Surviving animals rapidly regained their normal appearance on cessation of exposure. A 90-day guinea pig exposure at 10% vinyl chloride resulted in liver and kidney lesions and lung fibrosis. Torkleson, et al, in 1961, initiated the first studies of vinyl chloride chronic toxicity. They reported micropathological changes in rats after 4,5 months at the then acceptable 500 ppm exposure level. Their minimum level was 100 ppm where rat livers showed only a slight increase in weight. No effect was noted in * Diphenylene is not a known material and may be an erroneous refer nee to chlorinated diphenyl which was used as a plasticizer and was also a liver toxin. 30/ 696'03 -18 the other species (rabbits, dogs and guinea pigs) at this level. The researchers suggested a maximum worker exposure of 100 ppm with an eight-hour TWA of 50 ppm. 73/ - Lester, et al, in 1962 reported that repeated exposure of rats to 2% and 5% vinyl chloride concentrations cause no signifi cant problems. They noted liver changes but decided they were not significant. Lester recommended a 500 ppm Threshold Limit Value. 32/ The ACGIH chose to give more weight to Lester's work than to Torkleson's and cut the recommended vinyl chloride TLV from an eight-hour TWA to a 500 ppm ceiling value. 70/ This value was subsequently written into the Occupational Safety and Health Act of 1970 as a Standard. Suciu, et al, in 1963 have been widely cited as sounding the alarm for vinyl chloride chronic toxicity but they reported on a cohort of vinyl chloride workers exposed for one year at a reported average concentration of 900 ppm. 64/ Based on prior knowledge, the worker dizziness and other symptoms were not unexpected. A later report in 1967 indicated that the acute exposure symptoms reported earlier were disappearing in an estimated exposure environ ment of 38 ppm. The year 1966 marked the observed onset of acroosteolysis and Reynaud-s syndrome. Cordier, et al, reported skin lesions and acroosteolysis in reactor cleaners. 82/ B. F. Goodrich's Dr. R. H. Wilson reported his observations to the Manufacturing Chemists Association. 94/ He had noted evidence of acroosteolysis since 1962. The Manufacturing Chemists Association in a meeting at Cleveland, late in 1966, reviewed the apparently new occupational disease with VC-PVC industry representatives. These industry representatives agreed to cooperatively sponsor an investigation of the purported disease and the University of Michigan Institute of Industrial Health was employed to conduct an epidemiological study. 82/ After a wide-ranging investigation, the University of Michigan reported to MCA in 1969 that identification of the causative agent or agents was not conclusive; however, it would seem in order to reduce the severity of VC exposure by reactor cleaners and per sonnel in the reactor area. The value of 50 ppm recommended by 069604 19- Torkleson, et al, was endorsed. They also recommended that efforts to produce the disease in laboratory animals be supported by indus try. Dr. P. L. Viola, an industrial physician, 86/, 85/ was employed by Solvay, et cie, to study the acroosteolysis problem. In 1970 he reported that he had exposed 25 rats to 30,000 ppm vinyl chloride for twelve months. Thirteen died from cardio respiratory complications and two from abdominal hemorrhages. He noted lesions of the bone and connective tissue similar to acroosteolysis. 85/ He also noted degenerative processes of the parenthyma in the brain, liver and kidneys. Later that year at the Tenth International Cancer Congress in Houston, Texas, he reported that 26 rats exposed to 30,000 ppm vinyl chloride developed skin tumors (65%) and that 26% of those affected developed respiratory tract tumors. 83/, 84/ The epidermoid tumors were located in the vicinity of the ears. He stressed that the results applied only to rats and no implications to human pathology can be extrapolated. Later that year in an apparently unpublished paper, he noted that a maximum allowable concentration of 500 ppm for worker exposure gave an adequate margin of safety. 86/ The Manufacturing Chemists Association invited Dr. Viola to the United States to discuss his studies in greater detail. On May 5 and 6 of 1971, he reviewed his work in detail and referred to other research work underway in general terms. He claimed to have seen tumors in rats exposed to 5,000 ppm but reaffirmed his belief that 500 ppm TLV provided an adequate margin of employee safety from tumor induction. In November 1971 the Manufacturing Chemists Association convened a meeting of VC-PVC industry representatives to discuss the apparent vinyl chloride problem revealed by Dr. Viola. Dr. Le Fevre of Solvay, et cie, discussed European observations and stated generally that further European vinyl chloride toxicity studies were underway. Dr. Viola's work was discussed and the appearance of tumors in rats exposed to 5,000 ppm vinyl chloride confirmed. 91/ The group formed an Ad Hoc Committee under UCC 069605 -20- R. N. Wheeler, chairman, to plan a cooperative research program. The MCA Committee proposed a program involving a three level three species chronic inhalation toxicity study, a study of vinyl chloride metabolism and an industry-wide epidemiological study of mortality -w -- at a cost of $350,000. Kramer and Mutchler in 1972 reported on a cohort of Dow employees exposed to vinyl chloride. 27/ They reported that life time exposure to 300 ppm vinyl chloride may result in slight changes in physiological and clinical parameters. The possibility of impair ment of liver function must be considered. The ACGIH as a result of the Kramer and Mutchler's report lowered its recommended TLV for workers to 200 ppm 8-hour TWA. 70/ Sponsorship of the Manufacturing Chemists Association study did not meet the financial objective of $350,000 so the decision was made to do the long-term inhalation study and postpone the other studies pending collection of additional money. An MCA representative was sent to Europe to determine the nature of their program. He returned without any new information. During 1973 MCA,having collected sufficient sponsorship, con tracted for the long-term inhalation toxicity, the metabolism and the epidemiological studies. The inhalation study was late in getting started due to relocation of the contractor and his failure to provide proper facilities. An MCA group composed of corporation executives established liaison with the European consortium sponsoring vinyl chloride research under Dr. C. Maltoni. Informal reports on Dr. Maltoni's work revealed that the rats under test had shown tumors at the 250 ppm exposure level. These results and the substance of the planned research were discussed with Dr. M. Key and Associates at NIOSH in mid-summer. 92/ On January 23, 1974, B. F. Goodrich Company reported that five Louisville, Kentucky PVC plant employees had died of angio sarcoma, a rare form of cancer. The preliminary reports on the European research confirmed that this cancer maybe related to vinyl chloride exposure. 35/ UCC 069606 -21- A preliminary report from Dr. C. Maltoni stated that rats exposed to long-term inhalation of vinyl chloride showed zymbal gland carcinomas, nephroblastomas, angiosarcomas, angiomas, hepatomas, brain neuroblastomas and skin carcinomas. Mice developed angiosarcomas, angiomas,lung adenomas, mammary carcinomas and skin tumors. Hamsters developed angiosarcomas, skin tumors and lymphomas. Common to all species were angiosarcomas. Nephroblastomas were common to rats and mice but are not known to appear in humans. Angiomas were also common to rats and mice. 64/ The appearance of angiosarcomas in the mice used in the MCA test confirmed Maltoni's work. 64/ Juhe, Lange, et al, reporting in late 1973 on the vinyl chloride disease notes that at exposures of 60 to 1,000 ppm, they had seen fibrotic livers via laparotomy and seen possible lung fibrosis in employees of PVC plants. 26/ Skin absorption by vinyl chloride was studied by Hefner, et al, of Dow Chemical. A Rhesus monkey exposed to 7,000 ppm vinyl chloride via skin for two hours was estimated to be equal to the inhalation by a man of 0.185 ppm for eight hours. 95/ With the connection between animal biossay and human disease via angiosarcoma concern then shifted to the nature and extent of vinyl chloride caused neoplasms in the work force and in the people living in the area of VC-PVC facilities. Waxweiler, et al, in 1976 reported on a survey of four PVC plants whose workers were exposed to high levels of vinyl chloride. Based on 136 deaths, they reported excesses of brain, central nervous system, respiratory, liver and lymphatic neoplasms. 90/ Gamble, et al, in 1976 reported that vinyl chloride workers did not show chronic respiratory effects related to their exposure but smoking caused acute reductions. 19/ A study of Union Carbide Corporation workers at the South Charleston, West Virginia Plant showed excesses of angiosarcomas. All malignancies had a standardized mortality ratio of 87.7 compared to 111 for all other PVC-VC industry workers. Only leukemia and lymphomas were in excess but only eight cases wer reported. UCC 069607 -22- covered 1,314 workers and 211 deaths. Forty-nine percent of the study group had twenty years or more employment in vinyl chloride work. 16/ Fox and Collier in 1977 reported that an epidemiological study of vinyl chloride workers in Great Britain showed excess liver cancers but no evidence that vinyl chloride was a general carcinogen. The study covered 7,714 workers and 409 deaths. 18/ The Manufacturing Chemists Association industry-wide VC-PVC worker study on 10,173 workers and 669 deaths showed excessive standardized mortality ratios for brain tumors, miscellaneous cancers and leukemia but the numbers of cases were small. 72/, 96/ The conclusion of this study was that there maybe some support for the hypothesis that vinyl chloride is a general carcinogen. Con sidering that the previously noted Union Carbide Corporation study made up part of this study and the Union Carbide Corporation workers made up a major portion of those exposed for a long period, the conclusions from the comparison of the two studies are not. consistent. The PVC fabricating industry was the subject of two studi s. One by Organization Resources Counselors in the United States reported no angiosarcomas in 4,592 deaths. 14/, 45/, 46/ Proportional mortality ratios showed excess deaths in digestive, respiratory and all other neoplasms as well as deaths from circulatory disease. There was a significant depression in deaths from all other causes indicating a lack of complete data. Dr. G. M. Paddle in a letter to R. N. Wheeler observed that the apparent excesses in PMR's *-l were a common feature of industrial employee studies. 50/ Baxter and Fox in 1976 reported that there was no excess risk of lung, brain or liver cancer in PVC fabricators in Great Britain* the period 1963-1973, they found only one case of angio sarcoma relatable to VCM out of an average of four cases per year for the period. They noted that most of the four per year were mis diagnosed and there were actually only fourteen cases of AS *-2 in ten years. 9/, 10/ Brady, et al, in 1977 reported on twenty-six New York State angiosarcoma cases. Three had had contact with vinyl chloride in *-l Proportional Mortality Ratio *-2 Angiosarcoma ucc 069608 -23- their work and five lived within 4,500 feet of a VCM or PVC plant. They concluded that since the rate of AS cases in New York was 0.25 per million of population versus the national average rate of 0.14, there must be other causes of AS than Thorotrast, arsenicals and vinyl chloride. 97/ MacMahan 34/ and Downs, 15/ et al, in critcal reviews of the reports on mutagenesis, fetal anomalies or fetal death' reported while there was some evidence of VC caused chromosome aberrations there is no evidence of VC caused fetal wastage or birth defects. 89/, 24/ A tabulation of VC-PVC related angiosarcoma cases is as follows: Year Company and Location 1961 Goodyear, Niagara Falls, New York 1964 B. F. Goodrich, Louisville, Kentucky 1968 Union Carbide, South Charleston, West Virginia Goodyear, Niagara Falls, New York B. F. Goodrich, Louisville, Kentucky 1969 Firestone Plastics, Pottstown, Pennsylvania B. F. Goodrich, Louisville, Kentucky 1970 Goodyear, Niagara Falls, New York 1971 B. F. Goodrich, Louisville, Kentucky 1973 B. F. Goodrich, Louisville, Kentucky B. F. Goodrich, Louisville, Kentucky 1974 Union Carbide, South Charleston, West Virginia 1975 B. F. Goodrich, Louisville, Kentucky B. F. Goodrich, Louisville, Kentucky B. F. Goodrich, Louisville, Kentucky 1976 Union Carbide, South Charleston, West Virginia B. F. Goodrich, Louisville, Kentucky Great American Plastics, Massachusetts 1977 Union Carbide, South Charleston, West Virginia Union Carbide, South Charleston, West Virginia From this tabulation of angiosarcoma cases, it is evident that only B. F. Goodrich or Goodyear could have concluded that Iuou 069609 -24- they were experiencing an excess of angiosarcoma cases and not subject to random cases prior to 1974. Approximately 26 cases of angiosarcoma are diagnosed each year in the United States from all causes. From this survey of vinyl chloride toxicology, the follow ing conclusions may be drawn: 1. Based on the information available to it the VC-PVC industry and Union Carbide Corporation acted in a responsi ble manner. In retrospect, speedier action might have expedited the report of the carcinogenic properties of vinyl chloride by no more than one year. 2. Vinyl chloride exposure has been connected with angio sarcoma in humans. No other type of neoplasm has been identified as specifically caused by human vinyl chloride exposure. 3. Vinyl chloride exposure has been related to acroosteolysis in humans. POLYVINYL CHLORIDE TOXICOLOGY Toxicity of polyvinyl chloride was studied and reported more or less simultaneously by Smyth, H. F., Jr., and Weil, C. S. at Mellon Institute of Researchf67/ and by Harvard University for B. F. Goodrich Company. 21/ In both cases, PVC resin was fed to animals for two years and in both cases no effect attributable to the resin was noted. One resin (VYNU) was an emulsion polymerized vinyl acetate copolymer and the other was vinylidene chloride copolymer suspension polymerized. Both studies involved feeding 75 micron resin over a long period so certainly the particles UCC 069610 -25- were persorbed as noted by volkheimer. 64/ There was no analysis of the resins for residual vinyl chloride monomer content. In 1955, Oppenhiemer, et al, reported that PVC was carcino genic when imbedded in rat tissue as solid discs. 43/ - This study resulted in PVC being identified in later literature as a carcino gen. The effect noted resulted from implantation of a solid foreign body. Implantation of perforated discs did not result in cancers. 44/ Recently, United States dimes (Roosevelt) were identified as carcingogenic on implantation. In 1953, Boettner, et al, 98/ and in 1974, K. L. Paciorek, et al, 99/ reported that the products of combustion and thermal degradation of PVC were largely hydrogen chloride. Very small amounts of vinyl chloride were produced by thermal oxidation of PVC but the presence of hydrogen chloride would make human inhalation of the vinyl chloride produced problematical. Hydrogen chlorid even at concentrations of 10 or 20 ppm in air is extremely irritating thus any time equipment containing PVC is heated, such as is re quired in welding, large amounts of hydrogen chloride are generated. In 1969, Popow reported on the effect of PVC dust on the respiratory system of the rat. 56/ The PVC resin involved had 92% of its particles less than 5 microns in diameter thus it was largely respirable. Suggestions in Nature (1975) 41/ and in the New Scientist (1975) 42/ that PVC dust was harmful, again appear to be based on PVC resin containing large amounts of respir able particles. Studies by Adams and Purchase in 1975, 1/ as w 11 as Pigott, appear to refute any biological activity related to pure PVC dust. 55/ Any insoluble respirable dust however appears to lead to pneumoconiosis, a fact not entirely related to PVC dust. Epidemiological studies of PVC fabricating workers done in the United States by Organization Resources Counselors 14/, 45/, 46/, 50/ and in Great Britain by Baxter and Fox 10/ show that there are no significant PVC problems in the PVC fabricating industry. These studies must be interpreted, however, as being not as precise the work done in the PVC producing industry; i.e., both the United States and the British study deal with proportional excesses in a disease category and may not reflect a real increase UCC 069611 -26- or decrease in death rates over a comparative population. The Amboy Terminaling Company employees were engaged in a transportation and distribution function and were not a part of the'PVC producing industry or the PVC fabricating industry. In the first industry vinyl chloride monomer is the raw material and there is opportunity for excessive worker exposure. In the fabricating industry, the PVC resin is mixed with other materials and heated to fuse the mixture into a plastic mass thus driving off any contained vinyl chloride monomer and potentially exposing workers to excessive vinyl chloride concentrations. At ATC th workers were merely exposed to the resin powder at ambient temp erature thus exposure to vinyl chloride would not approach the levels found in the PVC producing industry and probably be much less than or equal to the PVC fabricating industry. A summary of salient points is as follows: 1. Polyvinyl chloride or its usual copolymers dis play a very low order of toxicity. 2. Polyvinyl chloride has caused no identified excessive mortalities in the PVC fabricating industry and by inference would show similar properties at ATC. 3. Polyvinyl chloride in the form of respirable dust has been related to pneumoconiosis in some workers and laboratory animals. UCC Q69612 -27UNION CARBIDE CORPORATION CHRONOLOGY OF PVC ACTIVITIES 1928 1933 1936 1937 1937 1940 1941 1942 1943 1943 1945 1946 1947 1947 Started pilot plant production of vinyl chloride monomer and development of resins made from vinyl chloride South Charleston, West Virginia. Commercial production of vinyl chloride by alkali dehy drochlorination of ethylene dichloride and the manufacture of vinyl chloride resins by the solution polymerization process - South Charleston, West Virginia. Expanded solution polymerization resin plant South Charleston, West Virginia. Commercial production of vinyl chloride resins by contin uous bulk polymerization - South Charleston, West Virginia. Chemical Hygiene Fellowship under Dr. H. F. Smyth established at Mellon Institute of Research at Pittsburgh, Pennsylvania. Studies of skin sensitization by PVC resins and compounds initiated at Mellon Institute of Research by Dr. H. F. Smyth. Initiated production of vinyl chloride by thermal dehydro chlorination of ethylene dichloride -- South Charleston. Initiated production of vinyl chloride by synthesis process using acetylene and hydrogen chloride. Built new continuous bulk polymerization plant for vinyl resins - South Charleston, West Virginia. Built new emulsion polymerization plant for vinyl resins. Built new facility for manufacture of synthetic fiber from vinyl chloride and acrylonitrile - South Charleston, West Virginia. Built new vinyl chloride monomer plant, a solution polymeri zation resin plant and a continuous bulk polymerization resin plant in Texas City, Texas. Discontinued manufacture of vinyl chloride by caustic dehy drochlorination of ethylene dichloride and manufacture of bulk polymerized resins at South Charleston, West Virginia. Smyth, H. F., Jr. and Weil, C. S. reported on work at Mellon Institute "Chronic Oral Toxicity to Rats of Vinyl Chloride - Vinyl Acetate Copolymer", Toxicology and Applied Pharmacology 9, 501-504, 1966. UCC 069613 -28 1954 1955 1957 1960 1961 1962 1965 1966 1967 1968 1968 1969 1969 1971 Expanded solution polymerization plant for resins in Texas City. Initiated manufacture of vinyl resins by the suspension resin process at South Charleston, West Virginia. Converted the emulsion polymerization plant to a dispersion resin plant at South Charleston, West Virginia. Expanded the solution polymerization plant at Texas City, Texas. Perth Amboy Bulk Terminal started operation under OTD management. Initiated manufacture of vinyl resins by the suspension resin process at Texas City, Texas under technology license from Wacker Chemie. Expanded the suspension vinyl resin plant at Texas City, Texas, reduced capacity for bulk resins by fifty percent at Texas City, Texas and discontinued manufacture of sus pension vinyl resins at South Charleston, West Virginia. Union Carbide Corporation representatives met with the Manufacturing Chemists Association to discuss reported acroosteolysis at the B. F. Goodrich Chemical Company plants. Support for an epidemiological study was pledged by Union Carbide Corporation. Discontinued manufacture of vinyl chloride at South Charleston, West Virginia. Expanded the suspension vinyl resin plant at Texas City, Texas. An employee of Union Carbide Corporation at South Charleston, West Virginia plant dispersion PVC unit died of liver cancer, subsequently diagnosed as angiosarcoma of the liver, a rare type of cancer. Discontinued manufacture of vinyl chloride at Texas City, Texas. The epidemiological investigation of the PVC industry co sponsored through MCA by Union Carbide Corporation show d no confirmed cases of acroosteolysis in any Union Carbide Corporation polymerization plants. Union Carbide Corporation co-sponsored a visit to the U.S.A. by Dr. P. L. Viola to discuss his reported oncogenic effectof vinyl chloride exposure to rats with the Manufacturing Chemists Association Occupational Health Committee. UCC 0696AA ) -29- 1971 - An Ad Hoc Planning Group for Vinyl Chloride Research was formed in MCA under the chairmanship of Mr. R. N. Wheeler, Jr., of Union Carbide Corporation. The Group recommended chronic toxicity studies, a metabolism study and an epidem- iological study of the effects of vinyl chloride at an estimated cost of $350,000. - 1972 Union Carbide Corporation agreed to co-sponsor the chronic toxicity and other studies.proposed by MCA. 1973 Union Carbide Corporation representative, Mr. R. N. Wheeler, along with representatives of MCA, Dow, Ethyl and Imperial Chemical Industries met with Dr. M. Key and Associates of the National Institute for Occupational Safety and Health to discuss the status of the possible vinyl chloride chronic toxicity problem. 1974 Union Carbide Corporation supplied the National Institute for Occupational Safety and Health and the Occupation Safety and Health Administration with written testimony and free access to its plants using vinyl chloride. It also reported promptly the second death of an employee from angiosarcoma of the liver. Union Carbide Corporation through Organization Resources Counselors co-sponsored an epidemiological study of the PVC fabricating industry as well as provided access to its records for the study. 1975 Union Carbide Corporation complied with the Occupational Safety and Health Administrations Standard for Vinyl Chloride. 1976 Discontinued the manufacture of vinyl chloride copolymer fiber and dispersion vinyl resins at South Charleston, West Virginia. Conclusions: 1. Union Carbide Corporation initiated or participated in actions to study and control the hazards related to vinyl chloride and polyvinyl chloride exposure as a responsible corporate citizen. 2. There is no evidence that Union Carbide corporation failed to act upon knowledge it had or obtained, concealed its knowledge from others or acted in a negligent manner with regard to the hazards relating to vinyl chloride or polyvinyl chloride exposure. UCC 069615 -30- ENGINEERING OPINION Maliko, Mazanowski, Wilkinson and Schaffer versus Union Carbide Corporation R. N. Wheeler, Jr. UCC 069616 Engineering opinion and data interpretation is necessary in three areas: 1. Odors reported by the plaintiffs. 2. Pneumoconiosis as a possible cause of emphysema reported by the plaintiffs. 3. Estimated levels of vinyl chloride exposure experienced by the plaintiffs. ucc 069611 -32- ODORS J ' The operations at Amboy Terminaling Company involved han dling vinyl chloride resins from three different processes, polystyrene, polyethylene and bisphenol A. Several of the plain tiffs have complained of nasal and bronchial irritation caused by the odors. In an effort to define the odors and the sources of irritation, the following are listed: Vinyl Chloride Resins Vinyl chloride polymers have no odor themselves but these do contain materials or may decompose into materials which have very distinctive odors: (a) Vinyl chloride monomer has a pleasant sweet odor 76/ detectable-by odor at 2,000 ppm by volume. Prolonged inhalation tends to anesthetize a person's olfactory senses causing the odor threshold to rise as high as 4,000 ppm by volume. (b) Vinyl acetate monomer has a sour sharp irri tating odor detectable by odor at 0.55 ppm by volume. 23/ (c) Acetaldehyde has a sweet green plant odor detectable at 0.2 ppm by volume. This odor is usually present in conjunction with vin^l acetate. 23/ (d) Acetic acid has a sour vinegary odor detectable by odor at 1.0 ppm. This odor is usually present in conjunction with vinyl acetate. 23/ (e) Acetone has a pungent fruity odor detectable at 140 ppm by volume. This odor would occur only in solu tion polymerized vinyl chloride resins. 23/ ucc 06961s 33- (f) Isopropanol has a sharp musty odor detectable at 28 ppm by volume. This odor would occur only in solution polymerized vinyl chloride resins. 23/ --* When vinyl chloride resins are overheated, as in a fire, a welding operation or simply a hot surface such as a motor, they emit hydrogen chloride which is quite pungent and irritating. Hydrogen chloride odor is detectable at 10 ppm. 23/ Polyethylene Resins Polyethylene resins have a characteristic paraffin wax odor. Some residual ethylene may be emitted but its pleasant olefinic odor detectable at 700 ppm by volume is largely masked by the resin's waxy odor. Polystyrene Resins Polystyrene resins have no characteristic odor except that of residual monomeric styrene. Styrene monomer has an aromatic naphthalene (mothballs) odor detectable at 0.05 ppm by volume. 23/ Bisphenol A Bisphenol A has a phenolic medicine-like odor presumably from the small amount of phenol present in the material. Phenol odor is detectable at.0.05 ppm by volume. 23/ Based on the foregoing data and the specific complaints regarding the vinyl chloride resins, the nasal and bronchial irritation noted by the plaintiffs was due to trace amounts of vinyl acetate and acetic acid given off by resins. Additionally, hydrogen chloride could be emitted during maintenance operations or equipment failures. ijcr 069619 -34PNEUMOCONIOSIS r - Pneumoconiosis caused by PVC resin was initially studied by Jerzy Popow 56/ with rats exposed to resin particles most of which were less than 5 microns in diameter in 1969. Szendi 71/ reported on a human case of pneumoconiosis but failed to obtain data on the resin particle size except via lung tissue inspection. He identified oval or polygonal particles 15 to 25 microns in diameter in 1971. Nature 41/ in August, 1975 reported on the biological reactivity of PVC dust. This report didn't direct itself to pneumoconiosis and dealt with a water extractible fraction in the resin sample. The New Scientist reported in June, 1975 that PVC dust felled mice based on work by Frongia which has not been formally reported. 42/ Adams and Purchase 1/ and Pigott 55/ don't believe that PVC dust is a hazard with regard to pneumoconiosis. The United States Atomic Energy Commission in 1961 defined "Respirable Dust" as that portion of the inhaled dust which pene trates to the nonciliated portions of the lung. 33/ Respirable dust was defined as follows Particle Size Percent Respirable 10.0 microns 5.0 microns 3.5 microns 2.5 microns 2.0 microns 0 25 50 75 100 Insoluble respirable dust particles are carried past the body's normal air filtering system and are ultimately deposited in the alveoli of the lungs from thence there is no bodily mechanism to eject them. Collection of insoluble dusts in the ucc 069620 -35- lung alveoli leads to reduced lung capacity such as is experienced in phenumoconiosis. Physiological damage via polyvinyl chloride dusts may occur i the dusts carry a high concentration of vinyl chloride monomer into the lungs where the vinyl chloride monomer passes into the bloodstream or if an appreciable volume of dust deposits in th lung alveoli reducing the lung's capacity to exchange oxygen for carbon dioxide in the bloodstream. Union Carbide Corporation and others have produced and marketed PVC dispersion resins for many years. These resins are produced by polymerizing vinyl chloride to a resin particle which is smaller than 1 micron in diameter. The water dispersion of these particles is stripped of unconverted monomer to a level of 2,000 to 6,000 ppm residual vinyl chloride monomer on a dry resin basis. This stripped latex is spray dried to remove the water. In the process of spray drying, the small resin particles are agglomerated into particles which vary from 1 micron to 20 microns. The dried resin is then ground to a median particle size of 2 mi crons. In the process of drying and grinding, the dispersion PVC resin essentially all of the contained vinyl chloride monomer is released to the air. Thus, when the resin is packaged in paper bags, the residual vinyl chloride monomer content is less than 1 ppm by weight. Dispersion PVC resin is almost always packaged in paper bags because .resin bulk handling equipment used for all other PVC resins cannot be used for this material. Based on knowledge of dispersion resins , I believe that PVC particles which are in the respirable size range contain less than 1 ppm by weight residual vinyl chloride monomer thus appreciable in gestion of vinyl chloride via dust inhalation is not possible. 93/ The Union Carbide Corporation PVC resins handled and packaged by Amboy Terminaling Company were produced by the UCC continuous bulk polymerization process, the UCC continuous solution polymerization process and by a conventional suspension polymerization process. Tests of representative resins from these processes performed at UCC's'laboratory showed the following UCC 069621 -36- content of dusts in the less than 10 microns range. these tests are as follows: Results of Process UCC Bulk Press VYNW Resin UCC Solution Process VYDH Suspension Process Homopolymer QSAN-7 Copolymer VSJE Percent Particles10 Microns or Less 0.4 mil mil 0.004 Attached are photomicrographs made of the various resins discussed: Figure I - shows the particles of UCC dispersion resin QYNV magnified 50 times. Figure II - shows the particles of UCC dispersion resin QYNV magnified 500 times. This second picture shows discrete particles in the <10 micron respirabie range. Figure III - shows particles of UCC bulk polymerized QYNL resin magnified 50 times. The tests indicate this type of resin contains 0.4% by weight particles less than 10 microns. Figure IV - shows the particles of UCC solution poly merized resin VYHD magnified 50 times. The tests showed no particles 10 microns or less present. Figure V - shows the particles of UCC suspension poly merized resin QSAN magnified 50 times. The tests showed no particles 10 microns or less present. To create airborne respirable dust, there must be a source of dust particles less than 10 microns in diameter and the resin containing the source of respirable dust exposed to a turbulent air stream which later becomes a part of the workspace air. Resin at rest in bags or even lying on the floor will contaminat the workspace air with some form of aeration. Process dust sources such as the bagging operation at ATC were provided with exhaust hoods. UCC 069622 -37- Summary Statements: 1. Research has not clearly shown that there is a relationship - between pneumoconiosis and PVC resin dust. - 2. The ingestion of vinyl chloride monomer via inhalation of respirable PVC dusts is negligible since such dust contains less than one ppm by weight of vinyl chloride monomer. 3. The UCC PVC resins handled and bagged by ATC contained very little, if any, respirable dust. 4. Local ventilation was provided at ATC for operations that were dusty. 5. Exposure to the PVC resin handled by ATC for Union Carbide Corporation is unlikely to cause chronic human disability via inhalation. UCC 069623 f5 i^. v t f^VV'A .!VWl'jS*J8i!'&7.v' SS^.T-, pm? v^ve 2? UCC DISPERSION PVC RESIN QYNV -- Particle Size 1-2 Microns Magnified 50 Times _ cs/? jr UCC 069624 ucc 089625 /77 ------- ucc 069626 V/ /^/CU/ZS ucc 069627 Times ucc 069628 -43- ESTIMATES OF EXPOSURE TO VINYL CHLORIDE MONOMER The Perth Amboy ATC facilities are located on 35 acres.of la_xd. adjacent to the bay. Tankers with deck loads or container ships are docked and unloaded by a large traveling crane which removes the containers (van boxes) from the ship and places them on the ground. At this point, the box is picked up by a straddle carrier and moved to the storage yard where as many as 1,500 con tainers may be stored in the open. On receipt of an order for a bulk shipment, hopper truck or hopper rail car, the appropriate box of resin is selected by the straddle carrier operator and placed on a tilting mechanism. The box is tilted and the product transferred from the box to the bulk carrier by gravity. (The product is literally poured from one container to another.) At the end of the transfer, the con tainers are closed. The empty van box is returned to the manu facturing plant by ship and the rail car or truck is moved to the ultimate customer. This operation is carried out in the open air. Resin packaging and package storage was carried out in a large masonry building encompassing approximately 250,000 square feet. This building was compartmentalized as follows: (1) Three large warehouse storage rooms of 60,000 square feet each. Warehouse room "A" was used for vinyl chloride resin bag storage. Warehouse rooms "B" and "C" were used for polyethylene, polystyrene and bisphenol A bag storage. These rooms were venti lated1 only by the open loading dock doors. (2) One palletizing room of approximately 40,000 square feet'contains six automatic bag palletizers. The filled multi-wall kraft paper bags of product enter the room via belt conveyor and are carried into the UCC 069629 -44- palletizer where 45 bags are stacked on a wooden pallet. These pallets are then transported by fork truck to the warehouse area. Room ventilation is provided only by open doors. (3) Three bagging rooms for vinyl resins have approximately 850 square feet each. These rooms, each of 16,500 cubic feet, are ventilated by a fan to provide one air change every 3.83 minutes. The vinyl resin enters the room through a closed chute into a closed hopper over the bagging machine. The closed hopper vents through a bag filter to an ex haust system. The multi-wallpaper bags are fabricated with an opening in one end consisting of a paper or plastic sleeve. The bagging machine fill nozzle fits into this opening and the product flows from the bagging machine into the bag. When the bag is at the proper weight, the flow of product shuts off and the bag is pulled off the fill nozzle by the operator. The material in the bag collapses the filling part on the bag, thus closing the bag. The filled bag is carried by conveyor through a metal detector, a roller flattener and thence to the palletizer in the next room. In order to make the produced resin flow from the packing machine into the bag, compressed air is injected into the resin contained in the packer compartment causing the powdered solids to become fluidized; i.e., flow like water. This fluidization plus a slight positive pressure within the packer forces the product through the fill nozzle into the bag. The bag walls are porous and the fluidizing air carried into the bag with the product passes through the bag walls to the outside leaving the product in the bag. For each bag filled, approxi mately 1.25 cubic feet of air are discharged into UCC 069630 45- the room. If too much fluidizing air flow is used, if the bag wall porosity is too low, or if the bag is poorly glued, it bursts during filling, fouling - the immediate area with product. The dust collection system is designed to handle minor spills and the 1 dribbles from the bags and packer on disengaging but when several bags burst, this must be cleaned manually using the vacuum collection system. In the resin bagging operation the appropriate bulk con tainer (van box) of resin is selected by the straddle carrier operator from those in the storage yard. The box is transported to a tilting frame outside the resin bagging room. The box is connected to the bagging machine through the building wall by a duct. To start the bagging operation, the box is tilted and the contained resin flows from the box through the duct into closed hopper on top of the bagging machine. When the box is empty, it is lowered to a level position and removed to the storage yard by the straddle carrier. The vinyl chloride resins handled, packaged and warehoused at ATC facilities in Perth Amboy, New Jersey, were manufactured by one of these three processes: 1. Solution polymerized vinyl chloride copolymer. 2. Continuous bulk polymerized vinyl chloride copolymer or homopolymer. 3. Suspension polymerized vinyl chloride homo polymer or copolymer. 'JCc 069S31 46- This description of ATC operations and facilities was provided by Mr. T. F. Archer, Union Carbide Corporation repre sentative to ATC. At the time these resins were shipped, the residual vinyl chloride was estimated to be: 2/, 3/, 93/ (a) Solution resin (b) Bulk resin (c) Suspension resin < 1 ppm RVCM 15 ppm RVCM 860 ppm RVCM The suspension resin was made up of three varieties; vinyl chloride homopolymer, vinyl acetate copolymer and ethylene copolymer. The estimate in "c" above is higher than homopolymer and ethylene copolymer but lower than vinyl acetate copolymer. Since vinyl acetate copolymer gives up its residual vinyl chloride less readily than the others, its contribution to the workspace air contamination in a unit time is lower. Vinyl chloride is not soluble in vinyl resins but is slightly soluble in vinyl acetate thus the vinyl acetate containing resins give up the uncoverted vinyl chloride less readily. Over a period of time, vinyl chloride resins emit the uncoverted vinyl chloride at varying rates depend ing upon the amount present, the size of the resin particle, the porosity of the resin particle, the molecular weight of the resin and the amount of residual vinyl acetate present. For purposes of this discussion, the rate of emission has been based on ethylene copolymer resin which contains up to 1,000 ppm RVCM and gives it up readily thus creating a worst case situation. 3/ Study has shown that ethylene copolymer yields 37% of its contained RVCM in container storage per month. It yields 20% of its residual'VCM with one hour of aeration at ambient temperature. It also loses 85% of its RVCM in one week of storage in bags in a warehouse. UCC 069632 -47- Storage and handling of vinyl resin in containers and bulk storage is estimated as follows: \ - Bin storage awaiting analysis Containers at ship dock Containers on the ship Containers stored at ATC (container inventory at ATC averaged 1.25 months sales) 2 days 4 days 7 days 19 days TOTAL Container Storage 32 days Resin RVCM at time of bagging at ATC was: 1. Solution resin (1.00-0.39) (< 1) 2. Bulk resin (1.00-0.39) (15) 3. Suspension resin(1.00-0.39) (860) < 0.6 ppm 9.0 ppm 525.0 ppm In a typical year, during the period 1960 to 1975, the material bagged was: Solvent resin Bulk resin Suspension resin 61.5% 12.8% 25.7% UCC 069633 -48- Resin handled and shipped in bulk is assumed to cause no exposure to dust or VCM since operations were outdoors and the resin was not aerated during handling. The resin bagging operation was carried out in a room 21" 4" x 39' 2" x 19' 9" for a total volume of approximately 16,500 cubic feet. With ventilation at a rate of one air change every 3.83 minutes, the amount of vinyl chloride emitted required to maintain a concentration in the bagging room of 1 ppm would be: (rO'3y) <*000001> * 0.00431 ft. 3/min. The resin feeds from a closed vented hopper to the bagging machine when it is aerated and bagged at a rate of 50 pounds per 15 seconds with 1.25 cubic feet of air. Assuming the conveyor is running at a minimum speed when the bagging rate is 400 pounds or 8 bags per minute, the 36-foot conveyor would contain six bags in the room allowing six feet of conveyor per bag. The conveyor storage plus two bags being filled would expose 400 pounds of aeriated resin per minute which is losing 20 percent of its con tained RVCM per hour thus: (400) (525) (0.20)(378) (1,000,000) (62.5j(60) 0.00423 cubic feet/minute Comparing this worst case, volume RVCM emitted versus 1 ppm volume shows the concentration of VCM in the bagging room would be 0.98 ppm when bagging suspension resin. UCC 069834 49- For solution resin, the concentration would be: (400) (<0.6)(0.20)(378) (17666766 0) (62.5) (60) = <0.000005 cubic feet/rainute or ,, 0.000005 < 0.004l"l_ = <0.001 ppm VCM For bulk resin, the concentration would be: (400)(9)(0.2)(378) (l,000,"ffff0) (62.5) (66) 0.000072 or 0.000072 0.00431"' 0.017 ppm VCM The average annual exposure for a bagger would be: (0.615) (0.001) + (0.128) (0.017) + (0.257) (0.98) = 0.25 ppm with a maximum of 0.98 ppm. In the palletizing room, the area was 40,000 square feet with a 20 foot ceiling yielding volume of 800,000 cubic feet. Since ventilation was random, one air change per hour is assumed. The worst case situation would involve operating three lines on vinyl resin bags thus suspension resin at (525)(1.0-0.2) = 420 ppm RVCM and bulk resin at 9 (1.0-0.2) =7.2 ppm RVCM.` Operating each line at 400 pounds per minute would involve exposure of 1,125 pounds of each resin type for six minutes. The bagged resin is losing its RVCM at a rate of 85% per week or 0.05% for six minutes. Thus: (420) (0.05) (378)(1,125) (1,000,000) (100) 162.5) , (7.2)(0.005)(378)(1,125) 117006,000) (100) (62.51 = or (0.48)(0.05)(378)(1,125) (1,000,000) (100) (6275)_ 0.00145 cubic feet/6-minutes 0.014549 cubic feet/hour UCC 069635 50 (0.0X4549)(1,000,000) 800,000 - 0.02 ppm for one air change per hour. For one air change per day? the maximum concentration at the end of the working day would be: (0.014549)(8)(1,000,000) =0.44 ppm 266,667 for an average exposure of 0.22 ppm The warehouse situation cannot be modeled mathematically due to the variety of unknowns. The personal monitoring data collected at ATC by Gollob Analytical Service Corporation reflects the minimal exposure. Report of April 25, 1974 Concentration Sample Time Suspension resin bagger Solution resin bagger 0.8 ppm 0.4 ppm (200) minutes ( 20) minutes Report of May 7, 1974 Bulk resin bagger Solution resin bagger 0.45 ppm 0.21 ppm ( 20) minutes ( 20) minutes Report of May 22, 1974 Suspension resin bagger Solution resin bagger 0.2 ppm 0.4 ppm ( 10) minutes ( 10) minutes Report of July 23, 1974 Solution resin bagger Suspension resin bagger 0.7 ppm 1.3 ppm (?) (?) Report of August 29, 1974 Bulk resin bagger 'Solution resin bagger 0.1 ppm ND* (?) (?) * ND - not detectable UCC 069836 -51- Report of October 30, 1974 Solution resin bagger Suspension resin bagger 0.3 ppm 3.7 ppm ( 13) minutes ( 20) minutes Report of November 14, 1974 Fork truck operator 1.9 ppm Report of December 9, 1974 Fans installed in warehouse Solution resin bagger Suspension resin bagger 0.47 ppm TWA 8 1.47 ppm TWA 8 Report of December 27, 1974 Fans in warehouse not operating Suspension resin bagger 2.28 ppm TWA 8 Solution resin bagger 0.24 ppm TWA 8 Fork truck operator 0.96 ppm TWA 8 Report of June 2, 1975 Suspension resin bagger 0.76 ppm TWA 8 Report of July 22, 1975 Bulk resin bagger 0.11 ppm TWA 8 Report of September 30, 1975 Warehouse ventilation change noted. Suspension resin bagger 0.45 ppm TWA 8 Report of December 17, 18 and 19, 1975 Change in packing room ventilation noted. Fork truck operator ND * TWA 8 Suspension resin bagger ND * TWA 8 Report of January 22, 1976 Fork truck operator 0.1 ppm TWA 8 Report of July 7, 1976 Bulk resin bagger Fork truck operator 0.05 ppm TWA 8 0.06 ppm TWA 8 * ND - not detectable ucc 069637 -52- Job- Summary of Gollob Measurements Average Concentration VCM Suspension resin bagger Solution resin bagger Bulk resin bagger Fork truck operator 1.22 ppm ND* 0.34 ppm ND* 0.18 ppm 0.05 0.6 ppm ND* * ND - not detectable - Range 3.7 ppm 0.7 ppm 0.45 ppm 1.9 ppm Based on the foregoing analysis of potential employee exposure and the work done by Gollob Analytical Service Corporation, the ATC employees at ferth Amboy were not exposed to toxic con centrations of vinyl chloride and were only rarely exposed in excess of the permissible exposure limits set by OSHA, October 21, 1974, UCC 069638 -53LITERATURE CITED * 1. * 2. * 3. * 4. * 5. * 6. * 7. 8. 9. 10. 11. 12. Adams, W.G.F. and Purchase, I.F.H.: "Is PVC Dust a Hazard?", . Unpublished Communication, Imperial Chemical Industries, Ltd., Welwyn Garden City, Herfordshire, England, July 23, llHS. Arnold, R. M.: "Current Data of the Residual Vinyl Chloride in Suspension/Non-Solvent Vinyl Resins", letter to Mr. M. E. Eisenhour, Union Carbide Corporation, Texas City Plant, dated March 14, 1974. Arnold, R. M.: "Analysis of Suspension Vinyl Resins for VCM Content Following Storage", Resins Laboratories, UCC, C&P Div,, Texas City Plant, dated April 29, 1975. Arnold, R. M.: "VCM Content in QSQF-7 Resin" - during bag storage at Perth Amboy Terminal. Letter to Messrs. E. Bell and G. Scott, Union Carbide Corporation, October 17, 1975. Arnold, R. M.: "Comparison of Original Blend and Shipping Container for Residual VCM in QYNL/VYNW Non-Solvent Vinyl Resins", Union Carbide Corporation, March 4, 1976. Arnold, R. M.: "Samples Forwarded for Evaluation of the Head Space Technique Proposed by EPA". Letter to Mr. A. E. Gabany, Union Carbide Corporation, March 12, 1976. Arnold, R. M.: "Particle Size Distribution UCC PVC Resins", Texas City Plant, Union Carbide Corporation, December 8, 1977. Baretta, E. D., et al,: "Monitoring Exposures to Vinyl Chloride Vapor - Breath Analysis and Continuous Air Sampling", American Industrial Hygiene Association Journal, p. 537, Vol. 30, 1969. Baxter, P. J., et al,: "Angiosarcoma of the Liver in Great Britian 1963-1973:, British Medical Journal, pp. 919-921, Vol. 2, 1977. Baxter, P. J. and Fox, A. J.: "Angiosarcoma of the Liver in P.V.C. Fabricators", The Lancet, January 31, 1976. Verband Kunststofferzeugende Industrie E.V. (VKE) "VC/PVC: Beispiel einer Problemlosung", Frankfurt/Main, 1975. Carr, J., et al,: "Chemical Constitution of Hydrocarbons and Cardiac Automaticity", Journal of Pharmacology Exptl, Ther. 97, 1, 1949. Copy Attached UCC 069639 -54- 13* Chan, R*., et al,t "Stripping of Vinyl Chloride Monomer from Resins in Aqueous Slurries and from Dry Resin Powders", Air - . Products'and Chemicals, Inc., October 1974. L . * 14. Chiazze, L., Jr., Nichols, W. E., and Wong, Otto: "Mortality Among Employees of PVC Fabricators", Journal of Occupational Medicine, Vol. 10, No. 9, September 1977. 15. Downs, T. D., et al,: "Vinyl Chloride, Birth Defects and Fetal Wastage, A Critical Review", The Society of the Plastics Industry, September 16, 1977. * 16. Equitable Environmental Health, Inc.,: "Epidemiologic Study of Vinyl Chloride Workers Employed by Union Carbide Corporation, South Charleston Plant", 2180 Milvia Street, Berkeley, California 94704, December 1976. 17. Falk, Henry, et al,: "A Cross-Sectional Epidemiologic Survey of Vinyl Chloride Workers", United States Department of Health, Education and Welfare, National Institute for Occupational Safety and Health, Cincinnati, Ohio, April 1977. 18. Fox, A. J., et al,: "Mortality Experience of Workers Exposed to Vinyl Chloride Monomer in the Manufacture of Polyvinyl Chloride in Great Britain", British Journal of Industrial Medicine, pp. 1-10, Vol. 34, 1977. 19. Gamble, J., Shuguey L., McMichael and Waxweiler: "Effect of Occupational and Non-Occupational Factors on the Respiratory System of Vinyl Chloride and Other Workers", Journal of Occupational Medicine, Vol. 18, No. 10, October 1976. * 20. * 21. Gehring, P. J., et al,: "Resolution of Dose-Response Toxicity Data for Chemicals Requiring Metabolic Activation: Example Vinyl Chloride", Dow Chemical U.S.A., Midland, Michigan 48640, July 12, 1977. Harvard University for the B. F. Goodrich Company: "Animal Feeding Studies on Geon 202" (Geon 202 is a copolymer of vinyl chloriae-vinylidene chloride.) B. F. Goodrich Company, Cleveland, Ohio, 1947. 22. Health and Safety Executive: "Vinyl Chloride, Code of Practice for Health Precautions", London, 1975. * 23. Heilman, T. M.: "The Characterization of .the Odor Properti s of 101 Union Carbide Corporation Petro-chemicals Using Sensory Methods:, Project No. 510A20, R&D Dept., C&P, Union Carbide Corporation, South Charleston, WV, July 10, 1973. 069640 Infante*, P. F., et al,: "Carcinogenic, Mutagenic and Teratogenic Risks Associated with Vinyl Chloride", Mutation`Research, pp. 131-142, Vol. 41, May 13, 1976. .. Johnson, L. F., and Arnold, R. M.: "A Study of Residual VCM in Suspension Resin", letter to Mr. M. E. Eisenhour, Texas City Plant, Union Carbide Corporation, June 18, 1974, Juhe, S., Lange, G., Stein, G., and Veltman, G.: "On the So-Called Vinyl Chloride Disease", University Skin Clinic of Bonn, Deutsche Medizinische Wochenschrife, 98 (43), pp. 2034-20377X973". Kramer, C. G., et al,: "The Correlation of Clinical and Environmental Measurements for Workers Exposed to Vinyl Chloride", American Industrial Hygiene Journal, January 1972. * Kuzmach, A. and McGaughy, R.,: "Quantitative Risk Assess ment for Community Exposure to Vinyl Chloride", United States Environmental Protection Agency, 1975. Lee, C. C., Bhandari, J. C., et al,: "Carcinogenicity of Vinyl Chloride and Vinylidene Chloride", Journal of Toxicology and Environmental Health; Pharmacology & Toxicology, Midwest Research Institute, Kansas City, Missouri 64110 and Environ mental Toxicology Branch, National Institute of Environmental Health Sciences, Research Triangle Park, N.C. 27709,ABSTRACT, 32, 1977, LeFaux, R.: "Practical Toxicology of Plastics", Ileffe Books Ltd, London, pp. 142-144, pp, 37-371, 1968. Lehman, K. B. and Flury, F., Toxicology and Hygiene of Industrial Solvents, Williams" and Wilkins Company, 1943. Lester, D., et al,: "Effects of Single and Repeated Exposures of Humans and Rats to Vinyl Chloride", American Industrial Hygiene Association Meeting, Washington, D.C., May 1962. Linch, A. L.,: "Evaluation of Ambient Air Quality by Personnel Monitoring", pp. 141-145, C.R.C. Press, Inc., 1975. MacMahon, Brian, M.D.: "Vinyl Chloride and Human Reproduction" The Society of the Plastics Industry, Vinyl Chloride - Poly vinyl Chloride Safety Group, August 15, 1977. ucc 069641 56- Manufacturing Chemists Association (MCA): "Vinyl Chloride Chronology", MCA-3846 - .1825 Connecticut Avenue, N.W., Washington, D.C. 20009, May 10, 1974. Maricq, Johnson, Whetstone & LeRoy: "Capillary Abnormalities in Polyvinyl Chloride Production Workers", JAMA, Vol. 236, No. 12, September 20, 1976. Mastromatteo, E., et al,: "Acute Inhalation Toxicity of Vinyl Chloride to Laboratory Animals", American Industrial Hygiene Association Journal, p. 394, Vol. 5V I960. Bulletin Hygiene, 36:244. Mutchler, J. E., et al,: "Report on the Relation of Exposure to State of Health of Dow Chemical Workers", Gordon Conference, Tilton, New Hampshire, August 1968. National Institute for Occupational Safety and Health: "Recommended Standard for Occupational Exposure to Vinyl Chloride", United States Department of Health, Education and Welfare, 1974. Nass, L.: "Encyclopedia of PVC", Vol. I, p. 480, Muriel Decker, New York, 1976. Nature, "Biological Reactivity of PVC Dust", Vol. 56, August 21, 1975. New Scientist, " PVC Dust Fells Factory Mice Suggesting New Work Hazard", June 1975. Oppenheimer, B. S., et, al,: "Further Studies of Polymers as Carcinogenic Agents in Animals", Cancer Research, Vol. 15, pp. 335-340, 1950. Oppenheimer, E. T., et al,: "Observations on the Effect of Powdered Polymer in the carcinogenic Process", Cancer Research, p. 132, Vol. 21, 1961. 5. -Organization Resources Counselors, Inc.: "Report on a Mortality Study Covering Employees of PVC Fabricators", 1625 I Street, N.W., Washington, D.C. 20006, February 1976. i6. Organization Resources Counselors, Inc.: "Report on a Case Control Study' Covering White Female Employees of PVC Fabri cators", May 1977. ucc 069842 57- * 47. Occupational Safety and Health Administration Emergency - Temporary Standard for Exposure of Vinyl Chloride, United States Department of Labor, April 5, 1974. 48. Oster, R. H., et al,: "Narcosis with Vinyl Chloride", Anesthesiolocrv, Vol. 8, p. 359, 1947. 49. Ott, M. G., Langner, R. R., and Holder, B. B.: "Vinyl Chloride Exposure in a Controlled Industrial Environment", Arch Environ Health, Vol. 30, July 1975. * 50. Paddle, G. M.: "Report on a Mortality Study Covering Employees of PVC Fabricators". (Personal Letter to Mr. R. 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Prodan, L., et al,: Intoxicatia conica cu clorura de vinil, Ses. St. 1 MF Cley Romania, 1969. 58. Prodan, L. and Suciu I, et al,: "Experimental Acute Toxicity of Vinyl Chloride". Toxicity of Vinyl Chloride - Polyvinyl Chloride, New York Academy of Sciences, Vol. 246, pp. 154-158, 1975: UCC 069643 * -58- 59. Richardson, H. L.: "Angiosarcoma of the Human Liver",: U.S. Environmental Protection Agency, April 17, 1974. * 60.^ . Roeh, W. V.: "Residual VCM Suspension Vinyl", letter to Mr. Ed Bell - material stored one month in Palroer-Warehous , Union Carbide Corporation, March 26, 1975. 61. Sarvetnick, H. A.: "Polyvinyl Chloride", Reinhold Plastics Applications Series, 1969. 62. Scamehorn, J. F. and Yang, Kang: "Diffusion of Vinyl Chloride in Polyvinyl Chloride Below the Glass Transition Temperatur ", American Institute of Chemical Engineers, New York Meeting, November 1977. 63. Schaumann, 0., MED U. CHEMIE, Vol. 2., p. 139 (cited by Dr. P. L. Viola), 1931. 64. Selikoff, I. 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