Document 93N7K3k381Ja1NByeNoNdOeYL

DRAFT WORKER EXPOSURE TO VINYL CHLORIDE IN VINYL CHLORIDE AND POLYVINYL CHLORIDE PRODUCTION AND FABRICATION James H. Jones with contributions by W.L. Barnhart, C.R. Toney, and J.B. Devlin The Bendix Corporation # Launch Support Division Cocoa Beach, Florida NIOSH Contract CDC-99-74-50 U.S. Department of Health, Education and Welfare Public Health Service Center for Disease Control National Institute for Occupational Safety and Health Division of Surveillance, Hazard Evaluations and Field Studies Cincinnati, Ohio January, 1978 ucc 066418 ABSTRACT DRAFT The industrial hygiene surveys described in this report were a result of the finding in 1974 of angiosarcoma of the liver among workers exposed to vinyl chloride (VC). These surveys were con ducted during 1974 and 1975 by the National Institute for Occupational Safety and Health (NIOSH) and a contractror, Bendix Corporation, Launch Support Division. VC production plants, polyvinyl chloride (PVC) polymerization plants and PVC fabrication plants were surveyed. Worker in PVC polymerization plants were found to have the highest average VC exposure. VC production plant workers' average exposures was about four times lower and PVC fabrication plant worker's average exposures were about 60 times lower than polymerization plant workers. UCC 066419 DISCLAIMER DRAFT Mention of company names or products does not constitute endorsement by the National Institute for Occupational Safety and Health. UCC 066420 ACKNOWLEDGEMENT draft The surveys of VC production plants and PVC fabrication plants were conducted by The Bendix Corporation, Launch Support Division under contract No. CDC-99-74-50. Dennis Smoot of the Bendix Corporation assisted with these surveys. NIOSH personnel assisting with the PVC polymerization plant surveys were Robert Curtis, Geoffrey Langer, Howard Ludwig, Jack Proud, Cheryl Rea, Preston Rea, Ken Wallingford, Fred Wells, and Ralph Zumwalde. NIOSH analytical work was performed by J.C. Holt, C.B. Runkle, J.B. Nichols, and T. Lucero. ucc 066421 "s Introduction History Toxicological Studies Reported Worker Exposure Description of Production Processes Description of Study Results Conclusions Bibliography Appendixes A. Description of Plants B. Job Dictionary C. Analytical Methods D. Sample Data DRAFT 1 S 6 10 12 33 38 77 80 90 134 140 164 ucc 086422 INTRODUCTION DRAFT On January 30, 1973 as part of continuing effort to collect data to be used for establishing criteria for standards, the National Institute for Occupational Safety and Health (NIOSH), published a request in the Federal Register for information concerning potential hazards associated with occupational exposure to 23 chemical substances and physical agents, including vinyj. chloride (VC). 104 On March 16, 1973, the Manufacturing Chemists Association (MCA), announced that a group of U.S. chemical companies was sponsoring a research program to study the potential health effects from exposure to vinyl chloride beginning with a contract with Industrial Bio-Test Laboratories to study the toxicology of vinyl chloride through animal studies.^ Later, on June 27, 1973, MCA announced that they had sponsored a contract with Tabershaw-Cooper Associates, Inc., to conduct an epidemiological survey to document the health experience of past and present workers exposed to VC.On July 17, 1973, MCA met with NIOSH officials to present the pro tocols for the two studies to inform NIOSH of industry research efforts with regard to VC.^*^^ At that time MCA also informed NIOSH of prelim inary results of a European study showing tumors in animals after exposure to VC. There had been no reports at that time of tumors in humans caused by VC. On January 22, 1974, NIOSH was alerted by representatives of the B.F. Goodrich Chemical Company that the deaths of three of its Louisville, Kentucky plant employees, caused by angiosarcoma of the liver, may have been related to occupational exposure to VC. As a result of this report ucc 066423 a walk-through survey was conducted at the Louisville plant on January 24, 1974, by NIOSH industrial hygienists. Representatives from the Kentucky Department of Labor, the Occupational Safety and Health Administration (OSHA), and the Epidemic Intelligence Service (EIS) of the Center for Disease Control (CDC) participated in this survey at the request of NIOSH. As a result of the walk-through survey, NIOSH recommended on January 30, 1974, that certain monitoring and control procedures of a precautionary nature be Instituted at the Louisville facility.On the following day, NIOSH recommended to the MCA that similar measures be instituted at all facilities engaged in the polymerization of VC and requested that the MCA 4 disseminate this information to its members.1^4 On February 1, 1974, NIOSH and CDC briefed other Federal agencies with health research responsibilities including the National Cancer Institute (NCI), the Food and Drug Administration (FDA), the National Institute of Environmental Health Sciences (NIEHS), and the Environmental Protection Agency (EPA), about NIOSH findings concerning VC. On February 12, 1974, NIOSH met with management and labor representatives from the VC and polyvinyl chloride (FVC) industries. At this meeting held in Cleveland, Ohio, approximately 100 people were briefed by NIOSH and CDC staff about the information obtained up to that time. Following review of the problem, NIOSH presented plans for future activities including: (a) development of recommended standards; (b) medical surveillance and research programs; (c) additional toxicologic investigations; and (d) industry-wide epi demiologic studies. -2- ucc 066424 It was decided by the Division of Field Studies and Clinical Investigations (DFSCI) at the outset of the planning for the industry-wide study, that only PVC polymerization plants would be investigated baaed upon the belief that the highest exposures to VC would occur here and upon the limited availa bility of personnel with which to conduct the studies. A listing of all PVC polymerization plants in the U.S., including information on each plant's age, number of people employed, and type of manufacturing pro cesses used, was made to help decide which plants should be visited for Initial walk-through surveys. Criteria for plant selection were as follows: (a) The plant's age must be fifteen years or more. (b) The plant must have a workforce greater than 100 persons. (c) The plant should be located in a state of the union, where NIOSH had established follow-up sources for retrospective cohort studies. In the Spring of 1974, walk-through surveys were conducted at seven polymerization plants by a team consisting of an industrial hygienist, an epidemiologist, and a physician, that collected information concerning suitability of personnel records for follow-up of all persons ever employed, the extent and availability of environmental sampling results for VC, types of materials used and produced, and the physical layout. Based on this preliminary Information five plants were originally selected for epidemiological study. Two of these plants were selected for indus trial hygiene surveys because they were judged to be fairly typical of the industry and they used three of the four PVC manufacturing processes. -3. UCC 066-425 A third plant was chosen for industrial hygiene study because it used the fourth, newer, process for manufacturing PVC. During this time it was also decided by NIOSH to document VC exposures in the other two main segments of industry where VC occurs, VC monomer manufacturing and PVC fabrication. A contract was awarded to Bendix Launch Support Division to conduct industrial hygiene surveys at three typical VC monomer plants and at PVC fabrication plants using the following processes: compounding, extrusion, molding, calendering, thermoforming, bonding, and the production of foams, fibers and plastisols. The initial walk-through surveys of the selected polymerization plants by NIOSH industrial hygienists began in February, 1974. The industrial hygiene surveys conducted by the contractor began in June, 1974, and were completed for the monomer and polymerization plants by January, 1975, and for fabrication plants in April, 1975. While the study was under way several changes in the OSHA standard for VC took place. On April 5, 1974, a temporary emergency standard was promulgated which lowered the standard from a 500 parts per million (ppm) celling concentration to a 50 ppm ceiling concentration. On October 1, 1974, a permanent standard of 1 ppm for a time weighted average, with a 5 ppm celling was announced to be effective January 1, 1975, but subsequently was delayed by court action until April 1, 1975.^ All of th VC measurements in the NIOSH field study were taken before the permanent standard went into effect with the exception of one fabrication plant which was surveyed in April, 1975. HISTORY OF POLYVINYL CHLORIDE PRODUCTION PVC is first mentioned by Baumann in 1872 with a description of a white powder formed by the action of sunlight on VC contained in a sealed tube.13 Although the formation of VC had been reported earliar by Regnault in 1835,no further interest in VC was expressed by the scientific community until 1912. A surplus of calcium carbide in Germany in the early 1900's led to the development of a process for the synthesis of acetylene. In 1912, a patent was filed for the production of VC from acetylene, and in 1914 another patent was filed for the use of a family of catalysts in the polymerization of VC. Concurrently in Russia attempts were being made to use the polymer as an intermediate in the production of synthetic rubber. Realization of the significance of the German work failed to develop at this time and the patents were allowed to lapse in 1926. Interest was renewed by 1928 and patents involving polymerization of VC were filed by three companies in the U.S., but the main breakthrough came when B.F. Goodrich demonstrated that PVC could be plasticized. The system was improved, with significant quantities of PVC being produced by the late 1930's. During World War II, PVC was used for electrical insulation, waterproofing materials, and military rainwear. Only after the war, with the development of consumer products using PVC, did the industry mushroom. In 1945, the entire world pro- -5- UCC 066427 duction of PVC was 100 million pounds,^ while in 1974, the U.S. production alone was over 4 billion pounds.^ TOXICOLOGICAL STUDIES Acute Animal Studies Much of the initial animal experiments were conducted using concentrations of VC greater than 100,000 parts per million (ppm) to study acute effects. Patty, et al.,94 in 1930 found that 200,000 to 400,000 ppm was fatal to guinea pigs in a "very short time" and that 100,000 ppm for 30 to 60 minutes was "dangerous to life." They found lung edema and liver and kidney hyperemia in the higher exposure group. Peoples and Leaked in ^33 reported that 245,000 to 285,000 ppm for 10 minutes was fatal to mice and that 85,000 to 125,000 ppm for 10 minutes was the minimal anesthetic range. They also reported that 170,000 ppm produced narcosis in dogs and rabbits. SchaumannlO? in 1934 reported that 180,000 ppm exposure produced relative heart insufficiency in cats. Oster, et al., 52 m 1947, while conducting tests to determine the suitability of VC as an anesthetic, discovered serious cardiac arrhythmias in dogs exposed to 100.000 ppm. Narcosis and sensitization of the myocardium in dogs after exposure to VC was reported by Carr et al.^ in 1949. In 1960, Mastromatteo et al. tested mice, rats and guinea pigs at 100,000, 200,000, 300.000 and 400,000 ppm for 30 minutes and all animals showed deep narcosis with deaths occurring in all but the lowest exposure group. Animals that died showed lung edema, liver and kidney congestion and a clotting defect, but the survivors showed no changes other than pulmonary congestion. Lester et al. 69 tested rats, in 1963, at concentrations of 50,000, 70,000, 100,000 and 150,000 ppm. At the highest level the -6- ucc 066428 rats experienced deep narcosis with lung edema. Moderate intoxication, loss of balance and corneal reflex were the only effects noted at the lower concentrations. Prodan et al. have reported LD 50's for the following species: mice - 120,000 ppm; rats - 150,000 ppm; guinea pigs - 238,000 ppm; and rabbits - 236,000 ppm. Chronic Animal Studies The first chronic VC exposure studies were reported in 1961 by Torkelson et al.^0 They exposed rats, guinea pigs, rabbits and dogs to 50, 100, 200 and 500 ppm for 4*s to 6 months and found liver and kidney changes at all levels of 100 ppm and over. Lester et al. also reported on chronic exposure to rats in their 1963 paper. Exposure levels were 20,000, 50,000, 80,000 and 100,000 ppm for 8 hours a day, 15 days to 3 months. Liver changes were noted in all groups, with the highest exposure group also showing lung edema and spleen changes and death of over half of the animals in the group. Prodan et al. in 1975 reported that guinea pigs exposed to 100,000 ppm VC for 3 months showed liver, kidney, spleen and lung changes. Viol1a'll,in 1970, exposed rats to 30,000 ppm for 12 months and found liver, kidney, artery, skin, bone, brain and nerve abnormalities. The following year Viola1^ reported on another group of rats exposed to 30,000 ppm for 12 months and found severe hepatitis, kidney tubulonephrosis, Interstitial pneumonia, degenerative brain lesions and tumors of the skin, lung and bone. This was the first report of any carcinogenetic effects of vinyl chloride. Caputo et al22 reported in 1974 that rats exposed to VC concentrations down to 500 ppm had developed tumors of various sites. Maltonl and Lefemine, J exposed rats, -7- ucc 066429 mice and hamsters to 50, 250, 500, 2500, 6000, and 10,000 ppm for 12 months and found tumors at various sites at all exposure levels. Keplinger et al^ in 1975, also reported tumors in mice exposed to 50, 200, and 2500 ppm for 8 months. Basalaev et al^ have reported cardiovascular disorders, hyperadrenalinemia, changes in the bioelectric activity of the hypothalamus and bone resorption in rats and rabbits exposed to as low as 12 ppm VC. Vazin and Plokhova have conducted several tests with VC. They have reported changes in the electrical activity of th hypothalamus of rabbits exposed to 3770 ppm VC for 5.5 months.^6 Rabbits exposed to 3500 ppm VC for 5 months were found to suffer from cardiovascular disorders.^^ Rabbits exposed to 8-12 ppm VC for 5 months showed cardiovascular disorders resulting from hyperadrenallnemid caused by changes in the cells of the hypothalamus.*22 Rats exposed to 12-15 ppm VC for 5 months developed cardiovascular disorders^^ and alterations in the function of the central nervous system.^3 Human Studies Again, as was the case with animal studies, all early human studies con centrate on acute effects of VC exposure. Fatty et al^ reported that 25.000 ppm for 3 minutes and 6,000 ppm for 30 minutes produced giddiness and disorientation. Two cases of VC intoxication in workers were reported in 1933 by Dublin and Vana.^2 Lester et al reported on exposures from 4.000 ppm to 20,000 ppm for 5 minutes. They estimated that a prolonged exposure to a level of more than 6,000 ppm is necessary to produce minimum symptoms of intoxication. Danzinger,^ in 1960, reported on 3 VC poisoning -8- ucc 066430 cases, two of which resulted In death. Other studies reported in the literature have concerned chronic effects of VC exposure in workers. The first of these was by Tribukh121 in 1949 and found a "more or less marked hepatitis" in workers processing PVC. There is some question whether the health problem was a result of exposure to VC or to the plasticizers being used: chlorinated naphthalene and polychlorinated biphenyl (PCB). The author suggested that the predominant exposure was to PCB. Filatova, 39 in 1957, pointed out a prevalence of "toxic angioneuropathy" in VC polymerization workers normally exposed to 20-313 ppm. The first more detailed descriptive disease was done by Suciu^3 et al. They described gastrointestinal symptoms, central nervous system disturbances. Raynaud-like syndrome, pseudoscleroderma, alteration of thyroid function, hepatomegaly, and splenomegaly. Numerous authors have reported various combinations of these symptoms along with acroosteolysis, other liver damage, cardiovascular disorders and thrombocytopenia.3, 24,27,30,31,40,42,44,48,57,62-66,70,77-79,83,96,100,105,106,113,114,118,127,135 Pulmonary disorders have also been reported by several authors.88,7*^8 PVC dust has also been implicated in causing pulmonary disorders.18*82,116,128 Creech and Johnson,28 i& 1974, were the first to link angiosarcoma of the liver with exposure to VC. Since then approximately 30 cases have been reported.^ These reports have triggered a number of retrospective mortality studies.75,84,88,117,134 These studies have suggested that there are multiple tumor sites related -9- UCC 066431 to VC exposure. Besides angiosarcoma of the liver, excesses of lung cancer, brain cancer and lymphoma have been found. In addition, Rannug et al^^ have reported that VC shows mutagenic activity when metabolically activated in a microbial system. Chromosome aberrations in workers exposed to VC have been reported by Funas-Craviota et al^ and Purchase et al.^ Infante52 has reported an increased prevalence of congenital malformations In communities surrounding polyvinyl chloride polymerization plants. REPORTED WORKER EXPOSURE The first report in the literature of VC exposure levels for workers appears in the Russian literature. Filatova and Gronsberg2 in 1957 reported on VC levels in a Russian PVC polymerization plant using the emulsion process to produce PVC. They found that levels in the reactor areas varied from 15 to 16,000 ppm, but the most frequently found concentrations varied from 38 to 310 ppm. In the precipitator and centrifuge area levels were 8 to 3050 ppm and in the drying oven area 4 to 15 ppm. An evaluation of different types of driers used in the PVC industry was reported in 1959 by Gavruseyko and Filatova. 43 VC con centrations up to 27 ppm were found in areas near chamber-type driers. They also reported on PVC dust concentrations varying from 100 to 248 mg/m2 during drying operations and from 725 to 1200 mg/m2 during unloading. Levels of 257 to 417 mg/m2 were found while unloading vacuum-rabble driers. PVC dust levels encountered in screening operations varied from 72-170 mg/m2. In 1965, Filatova et al^ reported that levels of VC -10- ucc 066432 in a PVC latex polymerization plant as high as 115 ppm were found and 752 of their measurements were above the maximum allowable concentration (MAC) of 12 ppm. PVC dust concentrations varied from 1 to 6.5 mg/m^ except at the bagging station where levels as high as 78 mg/m were found. Filatova and Antonyuzhenko have reviewed the changes in worker VC exposure in the Russian PVC industry from 1953 to 1969. From 1953 to 1958 the percentage of samples exceeding the MAC reduced from 802 to 22. Also the maximum concentration of VC was reduced by a factor of 900. Increasing production rates brought an Increase in levels of VC until in 1969, 762 of samples exceeded the MAC.' However, maximum VC concentrations were 8-40 times lower than in 1954. There have also been a few-reports from other countries. Suciu et al1^ reported in 1967 that VC levels in a Romanian plant ranged as high as 2/20 ppm. Anghelescu et al in 1969 reported that levels of VC at work stations in a Hungarian plant ranged from 43 to 213 ppm. Gitsios4 reported that peak levels as high as 10,000 ppm were found in a Greek plant. Drums containing waste polymer were found to have VC levels as high as 600 ppm. Byren and Holmberg^ reported in 1974 that VC levels in Swedish plants averaged 18-20 ppm in reactor rooms and less than 5 ppm in drying and packing areas. Cook et al`J reported that levels of VC present during reactor cleaning were usually 50-100 ppm with peaks of 600 to 1000 ppm close to the -11- ucc 066433 workers hand during scraping. The remainder of the published data on workspace air concentrations of VC are from one plant. Baretta et al10 reported extensive exposure data in 1969 showing peak levels above 1000 ppm. Levels of exposure for different jobs exceeded 50 ppm from 5 to 65% of the time. Time weighted average (TWA) exposures ranged from about 5 to over 200 ppm. TWA exposures to VC for one job category showed a daily and shift variation of 105 to 240 ppm. Kramer and Mutchler63 reported on this same plant in 1972. TWA VC exposures from 1950 through 1965 had been determined. TWA's ranged from less than 10 ppm to 300 ppm. The average TWA exposure in 1950 was 155 ppm while the average in 1965 was 30 ppm. Ott et al93 provide yet another source of information on VC levels at this plant. TWA's during the period 1950-1959 range from 5 to 825 ppm, but only one job class was above 385 ppm. From 1960 to 1966 TWA's ranged from 5 to 240 ppm with only two job categories above 100 ppm. TWA's were reduced further until at the time of the report in 1975 they were approximately 10 ppm. Description of the processes involved, the jobs associated with each process and the VC exposures found for each are described in the re mainder of this report. DESCRIPTION OF PRODUCTION PROCESS Vinyl Chloride Process At the present time, VC is manufactured in the United States in 15 plants using three basic processes: (1) Acetylene-hydrogen chloride process. -12- ucc 066434 (2) Oxyhydrochlorination process. (3) Ethylene dichloride pyrolysis process. The oxyhydrochlorination process is now the most widely used. The acetylene-hydrogen chloride process had been the major commercial process until the 1960's when plants began switching over due to changing economics of feedstocks for their respective processes. These processes are described as follows: Acetylene-Hydrogen Chloride Process Dry acetylene and anhydrous hydrogen chloride are reacted in fixed-bed reactors containing mercuric chloride-impregnated carbon catalyst according to the following equation*. C2H2 + HC1------------------------------- CH2CHC1 The reaction products are compressed, cooled, and passed to a refrigera tion unit for separation of VC by condensation, the condensed vinyl chloride is then passed to a two-column purification train where lowboiling products are removed overhead in the first column and recycled to the fixed-bed reactor along with noncondensed vapors from the first column feed drum. A portion of the recycle is passed to a vent reactor where an additional reaction occurs with resulting vent reactor products returned to the distillation train and inerts vented to the atmosphere. The partially purified vinyl chloride is passed to the second column where the high-boiling compounds are removed and passed to an incinerator -13- UCC 066435 for disposal. The purified VC removed from the second column Is first transferred to holding tanks where purity is checked, and then to storage spheres.^- A flow schematic of this process is shown in Figure 1. Ethylene Dichloride Pyrolysis Process The ethylene dichloride pyrolysis process may be expressed as follows: C2H4 + Cl2---------------------------------- C1CH2CH2C1 cich2ch2ci-------------------------------- CH2CHC1 + HC1 Wet ethylene dichlorlde produced by the direct chlorination of ethylene is passed through a drying column for removal of water, combined with recycle ethylene dichloride, and sent through a purification train for removal of heavy ends. The purified ethylene dichlorlde is vaporized and fed into a cracking furnace. The reactants from the cracking furnace are cooled and partially condensed in a quench system. The condensate is fed to a recovery column where ethylene dichlorlde is removed from the bottom of the column, passed to a column for removal of light ends, and recycled to the purification train. Overhead vapors from the ethylene dichlorlde recovery column are combined with quench system vapors, com pressed, and fed to a hydrogen chloride recovery column where pur hydro gen chloride is removed overhead, transferred to other on-site plants, and used in other processes. The bottoms from the hydrogen chloride -14- ucc 066436 LEGEND: A - Reactor B - Compressor & Cooler C - Fractionation Train D - Vinyl Chloride Storage Tank E - Heavy Ends Storage Tank F - Vent Reactor1 2 3 1 - Hydrogen Chloride 2 - Acetylene 3 - Vinyl Chloride ucc 066437 FIGURE 1. Acetylene-Hydrogen Chloride Process # recovery column is passed to a fractionating column where purified VC is removed overhead and sent to storage spheres.1 A flow schematic for this process is shown in Figure 2. Oxyhydrochlorination Process The oxyhydrochlorination process may be described as follows: C2H4 + Cl2---------------------------------- cich2ch2ci cich2ch2ci-------------------------------- CH2CHC1 + HC1 C2H4 + 2HC1 + 1/2 02------------------ C1CH2CH2C1 + H20 Ethylene dichloride produced by reacting chlorine and ethylene is pyrolyzed to fora VC and hydrogen chloride. The hydrogen chloride is separated from the reaction products and reacted with ethylene and air (oxygen) to produce ethylene dichloride and water. The ethylene dichlorlde produced by this reaction is dried and pyrolyzed to form vinyl chloride and hydrogen chloride. Ethylene and chlorine are reacted in a water-cooled direct chlorination reactor to produce crude ethylene dichloride. The crude ethylene dichlorlde is sent through a purification train where light ends are removed overhead in the first column and heavy ends from the bottom of the second column. Purified ethylene dichloride removed overhead from the second column is sent through an ethylene dichloride cracking furnace. The reaction products from the cracking furnace are passed to a hydrogen chloride column where crude VC is removed as bottoms and sent to a purification column. Pure 16 ucc 066438 3 1 i 6-4 il I * W Legend: A - Drying Column B - Heavies Column C - Cracking Furnace D - Quench Unit E - Fractionation Column F - Hydrogen Chloride Recovery Column G - Compressor H - Light Ends Column I - Ethylene Dichloride Recovery Column Wet Ethylene Dichloride Water Lights Heavies Hydrogen Chloride Vinyl Chloride Sr ucc 066439 Figure 2 Ethylene Dichloride Pyrolysis Process VC is recovered from the top of the VC column and transferred to a storage area where it is stored in large spheres. The bottoms from the VC column are recycled to the ethylene dichloride purification train. Pure hydrogen chloride from the top of the hydrogen chloride column is sent to the oxyhydrochlorination reactor where it is reacted with ethylene and air to produce ethylene dichloride and water. The reaction products are sent through an oxyhydrochlorination primary recovery unit where the water is removed as bottoms and sent to waste. The overheads are passed to a second column where crude ethylene dichloride is removed as bottoms and cycled to the ethylene dlchloride purification train. The overheads are passed to a secondary oxyhydrochlorination recovery unit. Vent gas is removed overhead in the first column, and the bottoms are sent to a second column. The overheads from the second column are recycled to the second column of the oxyhydrochlorination primary recovery unit.^ A flow schematic for this process is shown in Figure 3. ----DESCRIPTION -OF POLYVINYL CHLORIDE POLYMERIZATION PROCESSES" VC is currently being polymerized using four processes (1) Suspension polymerization (78 percent of total production) (2) Emulsion polymerization (13 percent of total production) (3) Bulk polymerization (6 percent of total production) (4) Solution polymerization (3 percent of total production) 18 ucc 0664-40 uoc 0664-41 Legend: A - 0HCL Reactor B - OHCL Primary Recovery C - OHCL Secondary Recovery 0 - Direct Chlorination Reactor - EDC Purification F - EDC Cracking Furnace G - HCL Column H - VCL Column 1 - Air 2 - Ethylene 3 - Chlorine 4 - Waste Water 5 - Crude EDC 6 - Vent Gas 7 - Lights 8 - Heavies 9 - Recycle EDC .IQ.,-,, Vinyl -Chloride, Figure 3 Oxyhydrochlorination Process These are described as follows: Suspension Polymerization The suspension process Is a batch aqueous polymerization of VC to produce PVC granules In the approximate size of lOQym. Polymerization is carried out in glassllned or stainless steel reactors, most with 2000 to 6000 gallon capacity, but some considerably larger reactors are found In new plants with capacities up to 15,000 gallons. The reactor Is first charged with deionized water, VC, then a dispersing agent, a buffer, and an initiator after which the agitator is started and the contents of the reactor brought up to polymerization temperature (445-60C.) by steam in jected into the jacket of the vessel. After a short induction period, during which the exothermic reaction begins, cooling water is fed to the jacket to maintain a predetermined temperature. When the polymerization is essentially complete, the much reduced reaction rate makes it uneconomi cal to take the conversion above approximately ninety-five percent of completion. The contents of the reactor are dumped into a "blowdown tank" located directly beneath the reactor (usually each "blowdown tank" serves several reactors) and the excess VC is removed by a recovery system which usually consists of several compressors and a condenser to recover mono meric VC. The PVC slurry is sometimes heated to facilitate recovery of the monomer. The slurry is then blended with that from other reactors to reduce small variations in composition from batch to batch after which it is dewatered In a continuous centrifuge resulting in a polymer cake containing about ten to twenty percent moisture. The polymer par ticles are then dried in a rotary dryer, screened to remove coarse 20 ucc 066442 particles, and sent to storage silos, packed in multiwalled paper bags, or loaded into bulk railroad cars.^ a flow schematic of this process is shown in Figure 4. Emulsion Polymerization The emulsion process is also a batch aqueous polymerization of VC, but with emulsifiers, now generally used for the manufacture of paste forming polymers with particle size distribution of approximately 1 ym. This process is similar to the suspension process with the exception that the deionized water, emulsifiers, initiator, and VC are metered into a stirred pre-mix vessel. Here, the Ingredients are mixed and then fed through a homogenizer into the reactors. After the reaction is complete, the sluvry is dropped to a "blowdown tank" where excess VC is removed and then recovered. The contents of the "blowdown tank" are then dropped to a blend tank where it is blended with slurry from other reactors to reduce variations in composition. The slurry is then con centrated and fed to a spray dryer where it is dried, ground (to remove agglomeration), and bagged. Because of its small particle size, emulsion resin is not stored or shipped in bulk. A flow schematic of this process is shown in Figure 5. Bulk Polymerization The bulk process is a batch polymerization of VC, without the use of water or a solvent, to produce FVC. The bulk or mass process has only relatively recently been used commercially in the United States. The 21 UCC 066443 fcH'QQO FIGURE 4. Suspension PVC Polymerization Process To Warehouse 1-1 WHUGOHV)j oC SO4-yU*)i o v^l FIGURE 5. Emulsion PVC Polymerization process was developed by and Is licensed from a French company (Pechiney-St. Govain), and the major process equipment is manufactured in France. In this process, VC and initiator are fed to a prepolymeri zation reactor where the reaction is started and polymer seeds are produced in slurry form in liquid VC. The slurry is then transferred to other reactors where the polymerization is continued to form a free flowing PVC powder. Whan polymerization has reached the desired com pletion, unreacted VC is removed from the reactor and recovered. The granular polymer is then conveyed by air to a series of screens and grinders where the product is ground and classified before going to storage or bagging. A flow schematic of this process is shown in Figure 6. Solution Polymerization The solution process is the oldest commercial PVC polymerization process in the United States, but it is also the least used. This process is unique in that the polymerization is carried out continuously in an organic solvent in which both the reactants and products are soluble. VC is pumped as a liquid under pressure to a reactor along with the solvent and initiator. After the polymerization has reached the desired completion state, the solution is transferred to a stripping column where excess VC is removed and then recovered. Next, the PVC is pre cipitated, separated from solution in a centrifuge, washed, dried, screened, and packaged. A flow schematic of this process is shown in Figure 7. Polyvinyl Chloride Fabrication Compounding Compounding is the mixing of polyvinyl chloride resin with other materials, 24 ucc 066446 Nitorgen N> Ui FIGURE 6. liulk PVC PolyTccrJ zation ucc 06644? < FIGURE 7. Solution PVC Polymerization Ship ------ v 066448 i.e., plasticizers, stabilizers, pigments, toners, fillers, lubricants, blowing agents, anti-oxidants, fungicides, sanitizers, and modifiers to give the PVC specific properties so that it can then be used in the manu facture of desired products. Compounding is generally accomplished in blenders, Banburys, two-roll mills, and mixers. Combinations of the above equipment can be employed in a single compounding operation. Blenders are primarily used to make dry compounds. Mixers are normally used to make fluid-type compounds such as plastisols. Compounds containing solids are masticated using Banburys mixers, or two-roll mills. This mixture is then transferred to other operations for final processing. Extrusion Extrusion can be used to remove solids from plastic-type compounds, to de-aerate and compact compound, and to generate sufficient pressure to force the material through an extrusion die. The extrusion can be in the form of a rope that is fed to a calender, or a long length of material having a uniform cross section. Examples of extruded items are hoses, pipes, rods, threads, pellets, and shapes of intricate cross section. Extrusions can be rigid or flexible. A specific extrusion application is in the making of fibers. PVC fibers are thin threads produced from extrusion through a die con taining a number of small round or rectangular openings. The thread is passed through a cold water bath, dried, and wound onto spools. 27 ucc 066449 Fibers or webs of fibers can be pressed into or layered onto a sheet of hot polyvinyl chloride in a calender to produce a sheet stock containing fibers or a web of fibers Imbedded in the sheet. Polyvinyl chloride sheeting prepared in this manner has superior strength and resists tearing and stretching. Molding Molding can be divided into a number of types, l.e., Injection molding, blow molding, vacu-formlng, and embossing. The equipment used for each type of molding is entirely different in design and operation. Injection molding is accomplished by forcing a plastic or fluid-like compound into the cavity of a heated mold. The end product assumes the configuration of the mold cavity and can be solid, hollow, rigid, or flexible. Blow molding begins with the injection of a predetermined amount of plastic compound into the cavity of a mold. Air is then injected into the center of the Injection and expands the plastic compound until it reaches the wall of the cavity. Sufficient air pressure is used to make the injected compound assume the configuration of the mold. The mold is heated and sets the design of the molded item. Blow-molded products can be rigid, semi-rigid, or flexible. Examples are plastic containers, wheels for toys, and basketballs. 28 ucc 066450 Vacu-forming is accomplished by laying a sheet of preheated film on top of a mold. The air between the film and the mold is removed by a vacuum pump, and the atmospheric pressure above the sheet forces the hot film against the mold. The cold mold sets the mold design in the film. Vacuformed items can be semi-rigid or flexible. Embossing is the imprinting of a design into a sheet of plastic and is normally accomplished by feeding a plastic sheet through a set of rolls. One of the rolls contains the configuration that is to be imprinted into the plastic sheet. The other roll provides the pressure required to form the design in the plastic sheet. An example of embossing is the imprinting of a leather grain into plastic sheet stock. Calendering Calendering is generally accomplished using three or four-roll calenders. The calender most often used in the plastics industry is the four-roll "F" form calender which has a stack of three rolls in a vertical plane and two top rolls in a horizontal plane. In using this type of calender, a ribbon, cord, or belt of fluxed plastic is fed evenly across the "V" between the two top rolls of the calender to permit gravity feed of the stock to the calender. An adjustable gap between the calender rolls produces a continuous sheet of plastic having uniform thickness and longitudinal physical properties across the width of the sheet. The calender rolls also impart a smooth finish to both sides of the sheet as it passes through the rolls. A smaller-diameter roll strips the 29 UCC 066451 sheet of plastic from the last calender roll and passes the sheet through a series of tensioning and cooling rolls, the cooled sheet is edgetrimmed and then fed to the windup rolls where the sheet is wound under uniform tension into rolls of desired diameter. Thermoforming Thermoforming is the forming of various shapes in thermoplastic sheets through the application of heat and pressure, and employs molds or forming blocks to shape the plastic. Seven basic types of thermo forming are recognized by the plastics industry. Each type uses various modifications of the molds, forming blocks, clamping devices, frames, and pressures to form the desired end product. The seven types are: straight vacuum forming, drape vacuum forming, male form forced above sheet, vacuum snap-back forming, plug and ring forming, air pressure forming, and matched metal mold forming. Thermoformed products are finding usage in the packaging, automotive, furniture, toy, and garment industries. Bonding of Polyvinyl Chloride Bonding is the joining of two or more pieces of polyvinyl chloride through the use of adhesives, or the application of heat with or without pressure. Thermoplastic sheets and films can be jointed by heat sealing. Rigid thermoplastic materials such as laminate sheet, rod, and tubing can be jointed by adhesives or by hot gas welding. 30 IJCC 066452 Polyvinyl chloride adhesives contain solvents such as tetrahydrofuran to product tight, quick, and rapid assembly of components. Heat sealing can be accomplished through the use of one or two metal items containing electrical heating elements, oven heat, or high-frequency or electronic heating. Hot gas welding employs a gas or electrically heated gun and polyvinyl chloride welding rod to join the materials. This type of veld is similar in appearance to metal welds. Plastlaol Formulation Plastisol formulations are fluid or semifluid compositions used to make thin flexible films. Preheated molds are dipped into the mixture, causing a thick layer to coat and partially cure on the mold. The mold is then withdrawn and placed in an oven for final cure of the compound. After oven curing, the plaatiaol-coated mold is removed from the oven, * and the formed item is stripped from the mold using air pressure. The mold is then dipped in or sprayed with a release agent and returned to the preheat oven. The operation can be performed by hand or by automated units. Plastisol coatings can also be applied to a fabric in a uniform layer and then passed through an oven where the coated stock undergoes partial curing. The coated stock is final-cured in a hot platen press. The platens can be plain or configured, and any design on the platen will be reproduced in reverse on the surface of the finished stock. Foam PVC foams are sheets of PVC which contain cells or bubbles of gas within 31 UCC 066453 the material to give the sheet energy absorbing properties. Polyvinyl chloride foam formulations have a fluid or semifluid consistency and contain a blowing agent that produces a cellular structure in the finished item. In the case of sheet material, the formulation is spread onto paper or fabric and then passed through one or two ovens to expand and cure the sheeting. Normally, where paper is used as a backing material, the paper backing is stripped from the foamed sheet after leaving the first tunneltype oven. The foamed sheet can then be joined to a second sheet to make a sandwich-type sheet stock that is sealed and final-cured in a second tunnel oven. Multi-layer sheet stock can be manufactured by joining a foam-coated fabric to a second vinyl sheet after the foam-coated fabric leaves the first tunnel oven. Sealing of the two layers and final curing of the foam composite takes place in the second tunnel oven. Heated molds can be dipped into a plastisol formulation containing a blowing agent. A thick coating of the plastisol mixture adheres to and partially cures on the mold. The coated mold is withdrawn from the dip and is placed in an oven for the final cure and blowing operation. Now, plastisol-type polyvinyl chloride compounds can be added to rubbertype compounds and a blowing agent to produce a compound that is processed on a Banbury and a two-roll mill. The milled stock can be further processed in a tube-type extruder. The extruded stock can be cut into desired shapes and expanded and cured in a series of two ovens, or the tubular stock can be expanded and cured in a tunnel-type oven. 32 UCC 066454 DESCRIPTION OF STUDY Bendix Launch Support Division conducted the VC monomer plant and PVC fabrication plant part of the study and NIOSH personnel the VC poly merization plants. Walk-through surveys were first conducted in order to obtain information on processes used, number of workers at the plant, number of workers involved in the PVC operations, plant layout, raw materials used, other products produced at the plant, and any environmental sampling data available* Using this information plants were selected for full indus trial hygiene studies, including sampling for VC. Walk-through surveys were conducted at six monomer plants, six poly merization plants and thirteen fabrication plants. From the information obtained during these surveys, plants were selected for in-depth surveys. The criteria for selection of plants for in-depth study Included consideration of a representative cross section of the various process and production capacities in the PVC industry. The plants selected Included three monomer plants, three polymerization plants and seven fabrication plants. Monomer plants selected Included one plant using the acetylene-hydrogen chloride process, one plant using the ethylene dlchloride pyrolysis process, and one using the oxhydrochlorination process. The polymerization plants included one plant using the solution, emulsion, and a modified emulsion processes, one plant 33 UCC 066455 using the bulk and suspension process, and one using the suspension and emulsion processes. Processes used at the fabrication plants selected are shown in Table 1. The industrial hygiene surveys primarily consisted of the collection of personal VC samples from which exposures were determined. Also PVC dust measurements were made. Ventilation systems, in selected areas, changes in the process, of work practices to reduce VC exposures, and past and present industrial hygiene practices were described in Appendix A. Sampling and Analytical Procedures Sampling for VC was conducted by using a charcoal absorption method with subsequent desorption in carbon disulfide and analysis by gas chromatography. All samples were collected using Sipln Model SP-1 pumps at a flow rate of approximately SO milliliters per minute. Commercially available charcoal adsorption tubes were used: Mine Safety Appliance tubes at Plant D, SRC tubes at Plants E and F and tubes supplied by the Asatole J. Sipln Company for the remainder of the plants. The first study conducted (by NIOSH, at Plant D) utilized a sample volume of 1.2 liters. The number of samples collected was such, that a number of samples, for the same man on the same day, were combined to facilitate analysis time (due to heavy lab work loads) thereby reducing the number of analyses. The survey at Plant E utilized 34 UCC 066456 Table 1 FABRICATIONS PLANTS - POLYVINYL CHLORIDE SURVEY LIST Bonding Calendering Compounding Extruding Foam Formation Molding Thermoforming Company 1. Plant G 2. Plant H / 3. Plant I 4. Plant J 5. Plant K 6. Plant L 7. Plant M <0 *C0HO CO i0H, X XX X X XX X X XX XX XX XXXX X XX XX X XXXX X XX 35 ucc 066457 the same sample volume, but only a few samples were combined for analysis. At these two plants sampling was conducted according to NIOSH Physical and Chemical Analysis Branch Analytical Method (P&CAM) 12785 and its May 31, 1974, Supplement for Vinyl Chloride. This method is found in Appendix B. At Plant F a sample volume of 5 liters was used in accordance with P&CAM 178, 87 shown in Appendix B. All NXOSH samples were analyzed at the N10SH laboratory in Salt Lake City, Utah. At the plants sampled by the contractor a sample volume of 5 liters was used for Plants A, B, C, G, H, I and J. A 10 liter sample volume was used at Plants K, L and M because of the low VC levels experienced at fabrication Plants G, H, I and J. The contractor utilized P&CAM 12785 for analysis of the samples which they collected with the exception that Porapak type QS at 100C, and 0.4 percent Carbowax 1300 on Carbopak A at 50C were used as the chromatograph column materials.^ A small number of PVC personal dust samples were also taken in bagging areas of the polymerization plants and in a few fabrication plants. Primarily the samples were total dust - gravimetric samples taken for approximately 4 hours at a flow rate of 2 liters per minute. A few samples were collected to allow microscopic examination of airborne dusts. All gravimetric samples were collected on 37 mm diameter MSA PVC membrane filters with a 5 pm pore size. Samples collected for 36 UCC 086458 microscopic examination were collected on 37 mm Millipore AA membrane filters with a pore size of 0.8 ym. Three piece Millipore filter cassettes were used for all samples, with the cap removed for micro scopic examination samples. An MSA Model G portable air sampling pump was used to draw air through the filter. Gravimetric sample filters were tared and weighed on the twenty milligram "A" scale of a Cahn Gram Electrobalance. 37 UCC 066459 RESULTS Monomer Plants Plant A A total of 47 VC samples were taken at this plant. A summary of these samples by job may be found in Table 3. VC concentrations ranged from less than 0.01 to 5.89 ppm. None of the TWA concentrations for the various jobs was above 1 ppm with the operator having the highest TWA, 0.86 ppm. The overall plant TWA was 0.55 ppm. Plant B A total of 75 VC samples were taken at Plant B and a summary of the results may be found in Table 3. VC concentrations ranged from less than 0.01 to 84.77 ppm. All TWAs except for the loader were below 1 ppm. The TWA for the loader was 21.85 ppm. The overall plant TWA was 3.40 ppm. Plant C A total of 109 VC samples were taken at Plant C and a summary of the results may be found in Table 4. VC concentrations ranged from 0.02 to 21.8 ppm. TWA concentrations for all jobs except loader were below 1 ppm. The TWA for loaders was 5.22 ppm and the overall plant TWA was 1.54 ppm. Summary A total of 231 samples to determine VC concentration were collected in monomer plants. The VC concentrations found varied from less than 0.01 to 84.77 ppm. TWA concentrations for the different job categories 38 IjCC 066460 Table 2 Summary of Vinyl Chloride Sampling Data by Job in Monomer Plant A Job Operator Loader Maintenance Worker Lab Technician Foreman Total of Personal Samples Composite of All Area Samples _* X n (ppm) 7 0.86 8 0.71 4 0.17 8 0.71 7 0.10 34 0.55 13 1.51 Xg (ppm) 0.43 0.45 0.11 0.20 0.08 0,21 0.25 Range (ppm) 0.13-2.45 0.10-1.89 0.02-0.32 0.04-4.36 0.03-0.21 0.02-4.36 <0.01-5.89 * x * TWA 39 UCC 066461 Table 3 Summary of Vinyl Chloride Sampling Data by Job in Monomer Plant B Job Operator Loader Maintenance Worker Lab Technician Total of- Personal Samples Composite of All Area Samples _* X n (ppm) 32 0.34 9 21,85 4 0.17 12 0.18 57 3.40 18 0.18 X g (ppm) 0.12 13.97 0.09 0.08 0.23 0.12 Range (ppm) 0.01-3.46 3.00-84.77 0.01-0.33 <0.01-0.88 <0.01-84J7 <0.01-1.22 * x TWA 40 UCC 066462 Table 4 Summary of Vinyl Chloride Sampling Data by Job in Monomer Plant C -* X Job n (ppm) Operator 56 0.79 Loader 20 5.22 Maintenance Worker 8 0.35 Lab Technician 16 0.14 Total of Personal Samples 100 1.54 Composite of All Area Samples 9 1.97 Xg (ppm) 0.27 1.16 0.33 0.07 0.30 1.56 Range (ppm) 0.09-18.2 0.06-21.8 0.16-0.55 0.02.1.01 0.02-21.8 0.57-7.06 * x - TWA 41 UCC 066463 ranged from 0.10 to 8.04 ppm. Only the TWA for loaders was above 1 ppm. The average of all personal samples taken at VC monomer plants was 1.89 ppm A summary of these results Is found in Table 5. Plant D POLYMERIZATION PLANTS Solvent Process Area - Forty-five samples for VC were taken in this area. They reanged from none detected (ND) to 77.0 ppm. TWAs for the various jobs ranged from 0.6 to 2.9 ppm with only the reactor area oper ators and dryer area helpers above 1 ppm. The overall area TWA was 2.1 ppm A summary of these results may be found in Table &. Modified Emulsion Process Area - Thirty-five samples for VC ware taken in this area with a range of 0.1 to 82.8 ppm. A summary of these results may be found in Table 7. TWAs for the different jobs ranged from 3.5 to 38.7 ppm with an overall area TWA of 9.8 ppm. Emulsion Process Area - A total of forty-one VC samples were taken in this area with a range of 0.1 to 82.8 ppm. A summary of these results may be found in Table 8. TWAs for the different jobs ranged from 3.5 to 38.7 ppm with an overall area TWA of 9.8 ppm. Overall Plant - A total of 121 VC samples were taken in the plant with a range of ND to 82.8 ppm. TWAs for the various jobs ranged from 0.5 42 UCC 068464 Table 5 Summary of Vinyl Chloride Sampling Data by Job in All Monomer Plants Sampled Job Operator Loader Maintenance Worker Lab Technician Foreman Total of Personal Samples Composite of All Area Samples -* X n (ppm) 95 0.64 37 '8.04 16 0.26 36 0.28 7 0.10 191 1.89 40 1.09 X 8 (ppm) 0.21 1.67 . 0.18 0.09 0.08 0.26 0.30 Range (ppm) 0.01-18.2 0.06-84.77 0.01-0.55 <0.01-4.36 0.03-0.21 <0.01-84.77 <0.01-7.06 * x - TWA 43 uec 066-465 Table 6 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant D Solvent Process Area Job Operator - RA* Operator - DA** Helper - DA** Bagger Maintenance Worker Total of Personal Samples Control Room Area Samples Other Area Samples n 20 4 1 6 2 33 6 6 X (ppm) 5.6 2.2 2.3 0.7 0.6 3.9 0.6 3.4 X g (ppm) 2.3 1.5 2.3 1.0 1.1 1.8 0.5 2.4 Range (ppm) ND-77.0 ND-3.7 2,3 ND-1.1 ND-1.3 ND-77.0 0.2-2.6 0.9-7.1 TWA (ppm) 2.9 0.9 2.3 0.7 0.6 2.1 * Reactor Area ** Dryer Area 44 UCC 066466 Table 7 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant D Modified Emulsion Process Area Job Operator - RA* Bagger Foreman Maintenance Worker Total of Personal Samples Control Room Area Samples Other Area Samples n 24 1 2 1 28 6 1 X (ppm) 1.3 2,3 0.3 0.2 1,2 1.3 1.4 Xg (ppm) 1.3 2.3 0.2 0.2 1.0 1.4 1.4 Range (ppm) ND-4.2 2.3 0.1-0.4 0.2 ND-4.2 ND-2.4 1.4 TWA (ppm) 1.3 2.3 0.3 0.2 1.2 * Reactor Area 45 11 nr ' wv v 066467 Table 8 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant D Emulsion Process Area Job Operator - RA* Helper - RA* Operator - DA** Bagger Foreman Total of Personal Samples Control Room Area Samples n 14 12 2 6 3 37 4 X (ppm) 11.0 10.2 38.7 3.5 8.6 11.1 7.5 X S (ppm) 6.2 6.1 20.6 1.4 2.8 4.8 5.3 Range (ppm) 0.1-29.8 0.7-77.0 5.2-82.8 0.1-9.6 0.3-22.0 0.1-82.8 1.2-11.1 TWA (ppm) 8.2 8.9 38.7 3.5 8.6 9.8 * Reactor Area ** Dryer Area 46 i irr WVV 066468 to 13.5 ppm and the overall plant TWA was 4.8 ppm. A summary of these results Is found In Table 9. A total of 5 dust samples were taken with an overall average concentration of 3.83 mg/m . The baggers In the solvent process area had an average 3 exposure of 1.01 mg/m while the one sample taken for the emulsion process baggers showed 15.27 mg/m . The results are shown In Table 10. Plant E Mass Process Area - Eighty-five samples for VC were collected in this area with a range of ND to 71.4 ppm. TWAs for the three job classi fications ranged from ND to 4.6 ppm. The overall area TWA was 3.9 ppm. A summary of these results may be found in Table 11. Suspension Process Area - Ninety samples for VC were collected in this area with a range of ND to 245.0 ppm. TWA concentrations for the different job classifications ranged from 0.3 to 16.5 ppm. The overall area TWA was 12.2 ppm. A summary of these results are found in Table 12. Overall Plant - A total of 175 samples for VC were taken at the plant with a range of ND to 245.0 ppm. TWAs for the individual jobs ranged from 0.3 to 10.3 ppm with an overall plant TWA of 8.1 ppm. A summary of these results may be found in Table 13. Eight samples for PVC dust were taken, all personal samples for suspension resin baggers. The results of these samples can be found in Table 14. 47 ucc 066469 Table 9 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant D Overall Plant Job Operator - RA* Helper - RA* Operator - DA** Helper - DA** Bagger Foreman Maintenance Worker Total of Personal Samples Control Room Area Samples Other Area Samples n 58 12 6 1 13 5 3 98 16 7 * Reactor Area ** Dryer Area X (ppm) 5.2 10.2 17.6 2.3 2.0 3.5 0.5 6.0 2.6 3.1 X S (ppm) 2.3 6.1 3.6 2.3 1,3 1.0 0.6 2.3 1.3 2.2 Range (ppm) ND-77.0 0.7-77.0 ND-82.8 2.3 ND-9.6 0.1-22.0 ND-1.3 ND-82.8 ND-11.1 0.9-7.1 TWA (ppm) 3.5 8.9 13.5 2.3 2.2 5.3 0.5 4.8 48 UCC 068470 Table 10 Polyvinyl Chloride Dust Sampling Results Plant D Job Bagger - E.R. Bagger - St.R. Bagger - St.R. Fork Lift Operator Area Sample Dust Concentration mg/nr* 15.27 1.62 0.40 0.82 1.02 E.R - Emulsion Resin St.R. - Solvent Resin 49 UCC 066471 Table 11 Stannary of Vinyl Chloride Sampling Data by Job in Polymerization Plant E Mass Process Area i' Job Operator - RA*. Helper - RA* Bagger Total of Personal Samples Control Room Area Samples n 36 32 2 70 15 X (ppm) 4.0 6.7 ND 5.2 ------------ ?-----XS (ppm) 2.5 3.0 ND 1.4 Range (ppm) ND-22.6 ND-71.4 ND ND-71.4 1.4 1.5 ND-3.8 TWA (ppm) 3.1 4.6 ND 3.9 * Reactor Area 50 UCC 066472 Table 12 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant E Suspension Process Area Job Operator - RA* Helper - RA* Bagger Total of Personal Samples Control Room Area Samples n 54 8 10 72 18 X (ppm) 16.8 10.4 0.3 12.2 15.9 * Reactor Area X S (ppm) 7.4 6.2 1.0 4.6 4.4 Range (ppm) ND-245.0 ND-23.6 ND-0.9 ND-245.0 ND-96.5 TWA (ppm) 16.5 11.8 0.3 12.2 51 UCC 066473 Table 13 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant E Overall Plant Job Operator - RA*- Helper - RA Bagger Total of Personal Samples Control Room Area Samples n 90 40 12 142 33 X (ppm) 11.5 7.5 0.3 8.8 7.9 X g (ppm) 4.7 3.5 1.0 3.5 2.4 Range (ppm) ND-245.0 ND-71.4 ND-0.9 ND-245.0 ND-96.5 TWA (ppm) 10.3 7.7 0.3 8.1 * Reactor Area 52 UCC 066474 Table 14 Polyvinyl Chloride Dust Sampling Results Plant E Job Bagger - S.R. If If If If If If ft Shift 1 1 1 1 1 3 3 3 Dust Concentration mg/ni 0.69 0.72 2.50 1.02 0.70 0.38 1.06 0.57 S.R. * Suspension Resin 53 UCC 066475 Plant F Emulsion Process Area - A total of 111 VC samples were taken in this area with a range of 0.2 to 103.8 ppm. TWAs ranged from 1.4 to 16.3 ppm. The overall area TWA was 4.7 ppm. A summary of these results is found in Table 15. Old Suspension Process Area - Seventy-eight VC samples were taken in this area with a range of 1.0 to 160.6 ppm. TWA concentrations for the various jobs ranged from 7.2 to 19.8 ppm. The overall area TWA was 17.6 ppm. A summary of these results is found in Table 16. New Suspension Process Area - Forty-eight VC samples were taken in this area with a range of 0.1 to 78.6 ppm. TWAs for the two job classi fications were 6.4 and 8.0 ppm while the overall area TWA was 7.8 ppm. A summary of these results may be found in Table 17. Overall Plant - A total of 237 VC samples were taken at the plant with a range of 0.1 to 160.6 ppm. TWAs ranged from 1.7 to 16.8 ppm. The overall plant TWA was 9.4 ppm. A summary of these results may be found in Table 18. Ten PVC dust samples were taken. Emulsion resin 3 baggers showed an average exposure of 8.08 mg/m while the one sample for a suspension resin bagger showed 0.47 mg/mr*. The sample for a dryer 3 operator showed an exposure of 0.73 mg/m . The results of the dust sampling can be found in Table 19. Particle sizing on 2 samples showed 54 UCC 066476 Table 15 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant F Emulsion Process Area Job Operator - RA*** Helper - RA*** Operator - DA** Helper - DA** Bagger Maintenance Worker Total of Personal Samples Control Room Area Samples Other Area Samples -* I X n (ppm) 29 8.9 24 16.3 25 3.1 9 1.7 10 2.2 1 1.4 98 4.7 7 3.1 6 5.6 X S (ppm) 6.3 10.3 2.4 1.3 1.9 1.4 3.7 2.4 5.0 Range (ppm) 2.3-98.0 3.5-103.8 0.5-9.6 0.6-3.6 0.2-4.1 1.4 0.2-103.8 1.0-5.9 1.4-15.9 *** Reactor Area ** Dryer Area * x - TWA 55 UCC 066477 Table 16 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant F Old Suspension Process Area Job Operator - RA** Helper - RA** Maintenance Worker Total of Personal Samples Control Room Area Samples _* X n (ppm) 28 19,8 37 17.3 4 7,2 69 17.6 9 6,1 X g (ppm) 11.4 11.2 6.6 10.9 4.8 Range (ppm) 5.3-160.6 1.3-160.5 4.2-12.8 1.3-160.6 1.0-11.5 * x - TWA ** Reactor Area 56 UCC 066478 Table 17 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant F New Suspension Process Area Job Operator - RA*** Operator - DA** Total of Personal Samples Control Room Area Sample X n (ppm) 36 8.0 6 6.4 42 7.8 6 ' 0.5 Xg (ppm) 3.8 4.0 3.8 0.3 Range (ppm) 0.8-78.6 1.1-21.0 0.8-78.6 0.1-1.6 * x * TWA ** Dryer Area *** Reactor Area 57 ucc 066479 Table 18 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant F Overall Plant X Job n (ppm) Operator - BA*** 93 10.6 Helper - RA*** 61 16.8 Operator - DA** 31 3.7 Helper - DA** 9 1.7 Bagger 10 2.2 Maintenance Worker 5 5.3 Total of Personal 209 9.4 Samples Control Boom Area Samples 22 3.1 Other Area Samples 6 5.6 Xg (ppm) 5.6 10.7 2.6 1.3 1.9 4.0 4.7 . 1.5 5.0 Range (ppm) 0.8-160.6 1.3-160.5 0.5-21.0 0.6-3.6 0.2-4.1 1.4-12.8 0.1-160.6 0.1-11.5 1.4-15.9 * x - TWA ** Dryer Area *** Reactor Area 58 ucc 066480 Table 19 Polyvinyl Chloride Dust Sampling Data Plant F Job Dryer Operator Bagger - E.R. tl * fr ii it tt It tl Bagger - S.R. Dust Concentration mg/nr* 0.73 2.00 13.34 14.10 3.00 2.39 18.62 3.92 5.22 0.47 E.R. - Emulsion Resin S.R. Suspension Resin 59 UCC 066481 that all particles were below 6.7 um in diamet r and that 90% of the particles had diameters less than 2.4 ym. Emulsion Process A total of 152 samples were taken in emulsion process areas with a range of 0.1 to 103.8 ppm. TWAs for the various jobs ranged from 1.4 to 14.3 ppm with an overall TWA of 7.8 ppm. A summary of these results may be found in Table 20. Suspension Process A total of 216 samples were taken in suspension process areas with a range of ND to 245.0. TWAs ranged from 0.3 to 16.7 ppm with an overall TWA of 12.6 ppm. A summary of these results may be found in Table 21. Summary A total of 517 samples were taken in PVC polymerization plants with VC concentrations ranging from ND to 245.0 ppm. TWA concentrations for the various jobs ranged from 1.8 to 14.3 ppm. Reactor area helpers and operators had the highest TWAs - 14.3 and 9.1 ppm respectively. The average of all personal samples taken in polymerization plants was 8.4 ppm. A summary of these results may be found in Table 22. A total of 22 dust samples were taken. Emulsion resin baggers showed an average exposure of 8.88 mg/m^. The remainder of jobs averaged 1.01 mg/a^ dust or less. The overall average was 4.18 mg/nr*. These results can be found in Table 23. 60 UCC 066482 Table 20 Summary of Vinyl Chloride Sampling Data by Job in Emulsion Process Areas--All Plants Sampled _* X Job n (ppm) Operator - RA*** 43 9.4 Helper - RA*** Operator - DA** Helper - DA** 36 14.3 27 5.5 9 1.7 Bagger 16 2.5 Foreman 3 8.6 Maintenance Worker 1 1.4 Total of Personal 135 7.8 Samples Control Room Area Samples 11 5.0 Other Area Samples 6 5.6 X S (ppm) 6.3 8.7 2.8 1.3 1.8 2.8 1.4 3.9 3.4 - 5*0 Range (ppm) 0.1-98.0 0.7-103.8 0.5-82.8 0.6-3.6 0.1-9.6 0.3-22.0 1.4 0.1-103.8 1.0-11.1 1.4-15.9 * x TWA ** Dryer Area *** Reactor Area 61 UCC 066483 Table 21 Summary of Vinyl Chloride Sampling Data by Job in Suspension Process Areas--All Plants Sampled X Job n (ppm) Operator - RA*** 118 12.5 Helper - RA*** 45 16.7 Operator - DA** 6 6.4 Bagger 10 0.3 Maintenance Worker 4 7.2 Total of Personal Samples 183 12.6 Control Room Area Samples 33 6.3 X S (ppm) 5.6 10.6 4.0 1.0 6.6 6.1 1.6 Range (ppm) ND-245.0 ND-160.5 1.1-21.0 ND-0.9 4.2-12.8 ND-245.0 ND-96.5 * x - TWA ** Dryer Area *** Reactor Area 62 UCC 066484 Table 22 Summary of Vinyl Chloride Sampling Data by Job -- All Polymerization Plants Sampled _* X Job n (ppm) Operator - RA****** 241 9.1 Helper - RA*** 113 14.3 Operator - DA** 37 5.4 Helper - DA** 10 1.8 Bagger 35 1.9 Foreman 5 3.5 Maintenance Worker 8 4.2 Total of Personal 449 8.4 Samples Control Room Area Samples 55 3.8 Other Area Samples 13 4.4 X S (ppm) 4.2 8.2 2.7 1.4 1.5 1.0 2.6 3.8 1.5 3.3 Range (ppm) ND-245.0 ND-160.5 ND-82.8 0.6-3.6 ND-9.6 0.1-22.0 ND-12.8 ND-245.0 ND-96.5 0.9-15.9 * x - TWA ** Dryer Area *** Reactor Area 63 ucc 066-485 Table 23 Summary of Polyvinyl Chloride Dust Sampling Data Polymerization Plants Job Bagger - S.R. Bagger - St.R Bagger - E.R. Fork Lift Operator Dryer Operator Total of Personal Samples nX 9 0.94 2 1.01 9 8.88 1 0.82 1 0.73 22 4.18 S.R. Suspension Resin St.R. Solvent Resin E.R. - Emulsion Resin 64 ucc 066486 Plant G FABRICATION PLANTS A total of 68 samples for VC were taken in this plant with a range of ND to 0.02 ppm. TWAs for all job classifications were less than 0.01 ppm. A summary of these results Is found in Table 24. Plant H A total of 52 samples for VC were taken at Plant H with a range of less than 0.01 to 0,68 ppm. TWAs for all jobs were below 0.10 ppm and the overall plant TWA was 0.03 ppm. A summary of these results may be found in Table 25. Plant I Forty-eigfct samples for VC were taken in this plant with a range of ND to 0.06 ppm. TWAs for the two job categories were ND and 0.01 ppm. A summary of these results can be found in Table 26. Plant J Forty-eight samples for VC were taken in this plant with no VC being detected. A summary of these results is shown in Table 27. Plant K A total of 24 samples were taken at this plant with a range of ND to 0.13 ppm. TWAs for all jobs were 0.01 ppm or less. A summary of these results is found in Table 28. 65 ucc 066-487 Table 24 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plant G Job n Compounding Personnel 8 Extrusion.Personnel 24 Lab Personnel 4 ^Miscellaneous Personnel 16 Total of Personal Samples 52 Composite of All. ' Area Samples 16 X (ppm) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 X S (ppm) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Range (ppm) < 0.01-0.02 ND-0.02 < 0.01 ND-0.01 ND-0.02 ND-0.02 * x * TWA ** Engineers in Process Area Doing Experimental Work. 66 IJCC 066488 Table 25 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plant H Job Compounding Personnel Extrusion.Personnel Lab Personnel Maintenance Personnel Molding Personnel Total of Personal Samples Composite of All Area Samples n 8 16 8 8 8 48 4 _* X (ppm) 0.09 0.01 0.03 0.01 0.01 0.03 0.37 X S (ppm) 0.06 0.01 0.02 0.01 0.01 0.02 0.31 Range (ppm) 0.01-0.27 <0.01-0.02 0.01-0.06 <0.01-0.02 < 0.01-0.03 <0.01-0.27 0.13-0.68 * x - TWA 67 UCC 066489 Table 26 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plant I Job Lab Personnel Plastisol .Dipping Personnel Total of Personal Samples Composite of All Area Samples X n (ppm) 4 ND 40 0.01 44 <0.01 4 ND X (ppm) ND 0.01 <0.01 ND Range (ppm) ND ND-0.06 ND-0.06 ND * x - TWA 68 ucc 066490 Table 27 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plant J Job n Calender Personnel 12 Compounding Personnel 12 Extrusion Personnel 8 Molding Personnel 8 Miscellaneous Personnel 4 Total of Personal Samples 44 Composite of All Area Samples 4 _* X (ppm) ND ND ND ND ND ND ND x g (ppm) ND ND ND ND ND ND ND Range (ppm) ND ND ND ND ND ND ND * x - TWA 69 ucc 066491 Table 28 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plant K Job Calender Personnel Compounding Personnel Maintenance Personnel Total of Personal Samples Composite of All Area Samples n 6 12 2 20 4 X (ppm) <0.01 0.01 <0.01 <0.01 <0.01 x*5 (ppm) <0.01 <0.01 <0.01 <0.01 <0.01 Range (ppm) ND-<0.01 ND-0.13 ND-<0.01 ND-0.13 <0.01 * x * TWA 70 ucc 066492 Plant L Thirty six samples were collected at this plant with concentrations ranging from 0.02 to 2.44 ppm. TWAs for the various jobs ranged from 0.27 to 1.48 ppm with only one job having a TWA higher than 1 ppm. The overall plant TWA was 0.63 ppm. A summary of these results is shown in Table 29. Ten dust samples were also taken at this plant. All were area samples. The average dust concentration was 8.92 mg/m^* These results are shown in Table 30. Plant M A total of 24 samples for VC were collected at Plant M with a range of ND to 0.02 ppm. TWAs for the two job classifications were 0.01 and 0.02 ppm and the overall plant TWA was 0.01 ppm. A summary of these results may be found in Table 31. Seven area dust samples 3 were taken at this plant with an average dust concentration of 7.21 mg/m . These results are shown In Table 32. Summary A total of 300 samples for VC were taken in PVC fabrication plants with the concentrations ranging from ND to 2.44 ppm. TWA concentrations for the different jobs ranged from less than 0.01 to 0.57 ppm. The average for all personal samples taken in PVC fabrication plants was 0.14 ppm. A summary of these results may be seen in Table 33. A total of 17 area dust samples were taken in fabrication plants with an average of 8.22 mg/m^. 71 UCC 066493 Table 29 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plant L Job Calender Personnel Compounding Personnel Extrusion Personnel Lab Personnel Total of Personal Samples n 8 16 10 2 36 _* X (ppm) 1.48 0,42 0.27 0.33 0.63 X (ppm) 1.33 0.37 0.15 0.12 0.36 Range (ppm) 0.50-2.44 0.13-0.69 0.02-0.76 0.02-0.68 0.02-2.44 * x - TWA ucc 066494 Table 30 Polyvinyl Chloride Dust Sampling Data Plant L Location Near Blender i* it ii II Near Mixer II Near Calender II Dust Concentration mg/m3 12.5 7.22 6.67 8.75 11.67 10.0 6.06 11.67 8.33 73 UCC 066495 Table 31 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plant M Job Calender Personnel Compounding Personnel Total of Personal Samples n 2 22 24 --alt x (ppm) 0.02 0.01 0.01 -- x (ppm) 0.02 0.01 0.01 Range (ppm) 0.02 ND-0.02 ND-0.02 * x - TWA 74 ucc 066496 Table 32 Polyvinyl Chloride Dust Sampling Data Plant M Location ----------- -- Mixing Area Blender Area Mill Area Banbury Mixer Area Calender Area Plastisol Mixing Room Cast Film Line DUSt Concea^ation ________ mg/mJ 6.67 1.67 6.67 13.33 6.67 7.9 7.27 75 ucc 066497 Table 33 Summary of Vinyl Chloride Sampling Data by Job --All Fabrication Plants Sampled Job n Calender Personnel 28 Compounding Personnel 78 Extrusion Personnel 58 Lab Personnel 18 Maintenance Personnel 10 Molding Personnel 16 Plastisol Dipping Personnel 40 Miscellaneous Personnel 20 Total of Personal Samples 268 Composite of All Area Samples 32 X (ppm) 0.57 0.11 0.09 0.08 0.01 . <0.01 0.01 <0.01 0.14 0.04 X (ppm) 0.24 0.05 0.04 0.05 <0.01 <0.01 <0.01 <0.01 0.03 0.05 Range (ppm) ND-2.44 ND-0.69 ND-0.76 ND-0.68 ND-0.02 ND-0.03 ND-0.06 ND-0.01 ND-2.44 ND-0.68 * x - TWA 76 UCC 066498 Monomer Plants CONCLUSIONS Monomer plants had generally low concentrations of VC exposure for personnel. The only job category with a TWA higher than 1 ppm was that of loader. The work practices for this job were being modified to lower exposures. One plant had already lowered exposures below 1 ppm and plants were using self contained breathing apparatus or supplied air respirators to limit exposure to VC for this job. So the levels found are indicative of the potential exposure but not necessarily the actual exposure of these workers. These levels also suggest that this has been a high exposure job in the past, before respiratory protection was used. Polymerization Plants Jobs requiring the most time in the reactor areas had, as would be expected, the highest exposure to VC. Reactor area helpers had the highest TWA and it was these workers who did the job of cleaning reactor vessels when necessary. Again these workers were using supplled-alr respirators when inside vessels or performing other jobs, such as changing filters, that could have high exposures to VC, so the exposures may not be actual exposures. VC exposures in the past, though, were higher because vessels were not purged of VC nearly so well before workers entered. Reactor area operators also had high exposures. Baggers and dryer area helpers had the lowest twas, but were still not under 1 ppm. The workers involved with the solvent process had the lowest TWAs, then the mass process workers, the emulsion process workers 77 UCC 066499 and finally the suspension process workers had the highest TWA. One other variable which was impossible to measure was management attitude towards keeping VC exposures low. It was observed within plants that housekeeping and work practice procedures varied from area to area because of the attitude of foremen in the areas. Oust levels were relatively low for all jobs except the emulsion resin baggers. The high dust levels for this job are probably due to the small particle size of emulsion resin. Better dust control measures need to be initiated for this job. Fabrication Plants All job categories in the fabrication plants had TWA exposures that were quite low. Only calendar personnel had a TWA above the required action level of 0.5 under the new OSHA standard. Working locations in almost every instance of exposure to vc were amenable to the application of standard control measures, such as local exhaust ventilation. Dust levels were uniformly high for the two plants where measurements were taken. However, the dust is probably not all pvc, since fillers and other additives are being used in the operations. Better dust controls should still be implemented in areas where dusty materials are handled. Overall, polymerization plants had the highest TWA of 8.4 ppm and also the highest individual job TWA of 14.3 ppm. Also workers in poly merization plants had the widest range of VC exposures, with peaks as high as 245 ppm. Monomer plant workers had the next highest overall 78 UCC 066500 TWA of 1.89 ppm, a factor of 4 lower than polym rization plant workers. The TWA for one job category was 8.04 ppm, almost the same as the polymerization plant workers, while the remaining workers were con siderably lower. Fabrication plant workers had the lowest overall TWA of 0.14 ppm, a factor of 60 lower than polymerization plant workers and 13-1/2 lower than monomer plant workers. These results substantiate the initial emphasis of studies on polymerization plant workers as having the highest VC exposures. 79 ucc 066501 BIBLIOGRAPHY 1. Albright, L.F., "Manufacture of Vinyl Chloride," Cham. Eng.. 74:219-226, April 10, 1967. 2. Albright, L.F., "Polymerization of Vinyl Chloride," Chem. 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Manufacturing Chemists Association, "Vinyl chloride chronology" Press Release, pp. 1-12, 1974. 77. Markowitz, S.S., McDonald, C.J., Fethiere, W. and Kerzner, M.S., Occupational acroostsolysls". Arch. Dermatol., 106:219-223, 1972. 85 UCC 066507 78. Marsteller, H.J., Lelbach, W.K., Mueller, R., Juhe, S., Lange, C.E., Rohner, H.G. and Veltman, G., "Chronic-toxicity liver damage in workers in polyvinyl chloride production", Deut. Med. Wochenschr. 98(48):2311-2314, 1973. 79. Marsteller, H.H., Lelbach, W.K., Mueller, R. and Gedigk, P., "Unusual splenomegalic liver disease as evidenced by peritoneoscopy and guided liver biopsy among polyvinyl chloride production workers", Ann. N.Y. Acad. Sci., 246:95-134, 1975. 80. Mastromatteo, E., Fisher, A.M., Christie, H. and Danzinger, H., "Acute inhalation toxicity of vinyl chloride to laboratory animals", Amer. Ind. Hyg. Assoc. ., 21:394-398, 1960. 81. Miller, A., "Pulmonary function defects in nonsmoking vinyl chloride workers". Environ. Health Perspect.. 11:247-250, 1975. 82. Miller, A., Teirstein, A.S., Chuang, M., Selikoff, I.J. and Warshaw, R., "Changes in pulmonary function in workers exposed to vinyl chloride and polyvinyl chloride", Ann. N.Y. Acad. Sci.. 246:42-52, 1975. 83. Misgeld, V., Stolpmann, H.J. and Schulte, S., "Poisoning by means of polyvinyl chloride or its constituents", 2, Haut-Geschlechtskr., 48(11);425-436, 1973. 84. Monson, R.R., Peters, J.M. and Johnson, M.N., "Proportional mortality among vinyl chloride workers", Environ. Health Perspect., 11:75-77, 1975. 85. National Institute for Occupational Safety and Health, "Organic Solvents in Air" and "Vinyl Chloride Supplement", HEW, PHS, CDC, NIOSH, P&CAM 127, 1974. 86. National Institute for Occupational Safety and Health, "NIOSH recommended precautionary monitoring and control procedures for polymerization processes involving vinyl chloride", NIOSH, CDC, PHS, CHEW, February 1974. 87. National Institute for Occupational Safety and Health, "Vinyl chloride in air", HEW, PHS, CDC, NIOSH, P&CAM No. 178, 1974. 88. Nicholson, W.J., Hammond, E.C., Seidman, H. and Selikoff, I.J., "Mortality experience of a cohort of vinyl chloride-polyvinyl chloride workers", Ann. N.Y, Acad. Sci., 246:225-230, 1975. 89. Nitti, G., Petruzzellis, V. and Fasano, V., "Rheographic obser vations on workers in the plastics industry", Securitas, 55:683-694, 1970. 90. Okawa, M.T., "Health Hazard Evaluation Report No. 74-71-142; Delco Remy Division, General Motors, Anaheim, Ca.", HEW, PHS, CDC, NIOSH, 1974. 86 UCC 066508 91. Ottawa. M.T., "Health Hazard Evaluation Report No. 75-1-194; Storm Products Company, Palo Alto, Ca.", HEW, PHS, CDC, NIOSH, 1975. 92. Oster, R.H., Carr, C.J., Krantz, J.C, and Sauerwald, M.J., "Anesthesia XXVII. Narcosis with vinyl chloride". Anesthesiology. 8:359-361, 1947. 93. Ott, M.G., Langner, R.R. and Holder, B.B., "Vinyl chloride exposure in a controlled industrial environment". Arch. Env. Health. 30:333-339, 1975. 94. Patty, F.A., Yant, W.P., and Waite, C.P., "Acute response of guinea pigs to vapors of some new commercial organic compounds. V. Vinyl chloride", Public Health Rep.. 45(2):1963-1971, 1930. 95. Peoples, A.S. and Leake, C.D., "The anesthetic action of vinyl chloride", J_. Pharmacol. Exp. Ther., 48:284, 1933. 96. Popper, H. and Thomas, L.B., "Alterations of liver and spleen among workers exposed to vinyl chloride", Ann. N.Y. Acad. Sci., 246:172-194. 97. Prodan, L., Suciu, I., Pislaru, V., Ilea, E., and Pascu, L., "Experimental acute toxicity of vinyl chloride (monochloroethene)", Ann. N.Y. Acad. Sci., 246:154-158, 1975. 98. Prodan, L., Suciu, I., Pislaru, V., Ilea, E. and Pascu, L., "Experimental chronic poisoning with vinyl chloride (monochloroethene)", Ann. N.Y. Acad. Sci., 246:159-163, 1975. 99. Purchase, I.F.H., Richardson, C.R. and Anderson, D., "Chromosomal and dominant lethal effects of vinyl chloride". Lancet, pp. 410-411. Aug. 30, 1975. 100. Pushln, G.A., "Lesions in the liver and bile ducts in workers producing some kinds of plastics", Sov. Med.. 28(2):132-135, 1965. 101. Rannug, U., Johansson, A., Ramel, C. and Wachtmeister, C.A., "The mutagenicity of vinyl chloride after metabolic activation", Ambio. 3(5):194-197, 1974. 102. Ravier, E., Diter, J.M. and Plalat, J., "A case of liver angiosarcoma in a worker exposed to monomeric vinyl chloride". Archives des maladies profesaionnelles, de medecine du travail et de Securite Socials, 36(3):171-177, 1975. 103. Regnault, V., "The synthesis of chlorinated hydrocarbons", Justus Liebig*s Annalen der Chemie, 14:22-28, 1835. 104. Rose, V.E., "Statement for OSHA Fact Finding Hearing on Vinyl Chloride, February 15, 1975", HEW, PHS, CDC, NIOSH, 1974. 87 UCC 066509 105. Rumyantseva, E.P. and Goryacheva, L.A., "Glucocorticoid function of the adrenals in patients suffering from chronic poisoning with some unsaturated and chlorinated hydrocarbons". Gig. Tr. Prof. Zabol. 12(12):16-19, 1968. 106. Sakabe, H., "Bone lesions among polyvinyl chloride production workers in Japan", Ann. N.Y. Acad. Sci., 246:78-79, 1975. 107. Schaumann, 0., "Effect on the heart of some inhalation anesthetics", Medzin. Chemie, 2:132-140, 1934. 108. Stender, J., "Emergency temporary standard for exposure to vinyl chloride" Fed. Register. 39(67):12342-12344, 1974. 109. Stender, J., "Proposed standard for vinyl chloride", Fed. Register, 39(92)16896-16900, 1974. 110. Stender, J., "Standard for exposure to vinyl chloride", Fed. Register, 39(194):35890-15898, 1974. 111. Straub, W.E., "Health Hazard Evaluation Report No. 74-85-185; M.H. Ball Company, Lancaster, Pa.", HEW, PHS, CDC, NIOSH, 1975. 112. Straub, W.E., "Health Hazard Evaluation Report No. 74-89-189; New York Telephone & Telegraph Company, New York, N.Y.", HEW, PHS, CDC, NIOSH, 1975. 113. Stulova, E.A., "Characteristics of the state of thermoregulation in chronic vinyl chloride poisoning", Gig. Tr. Prof. Zabol.. 17(3):53-55, 1973. 114. Suciu, I., Prodan, L., Ilea, E., Paduraru, A. and Pascu, L., "Clinical manifestations in vinyl chloride poisoning", Ann. N.Y. Acad. Sci., 246:53-69, 1975. 115. Suciu, I., Drejman, I. and Valaskai, M., "Study of illnesses due to vinyl chloride", Med. Lavoro, 58(4):261-271, 1967. 116. Szende, B., Lapis, K., Nemes, A. and Pinter, A., "Pneumoconiosis caused by the inhalation of polyvinylchloride dust", Med. Lav., 61(8-9):433-436, 1970. 117. Tabershaw, I.R. and Gaffsy, W.R., "Mortality study of workers in the manufacture of vinyl chloride and its polymers", J,. Qccup. Med., 16(8):509-518, 1974. 118. Thiess, A.M. and Flentzel-Beyme, R., "Retrospective survey of the alleged diseases associated with vinyl-chloride in the Federal Republic of Germany", jJ. Qccup. Med., 17(7):430-432, 1975. 119. Thomas, L.B., Popper H., Berk, P.D., :Selikoff, I.J. and Falk, H., "Vinyl-chloride-induced liver disease1II 17-22, 1975. 88 UCC 066510 120. Torkelson, T.R., Oyen, F. and Rowe, V.K., "The toxicity of vinyl chloride as determined by repeated exposure of laboratory animals", Amer. Ind. Hyg. Assoc. J., 22(5):354-361, 1961. 121. Tribukh, S.L., Tikhomirova, N.P., Levina, S.V. and Kozlov, L.A., "Working conditions and measures for their improvement in production and use of vinyl chloride plastics", Gig. Sanlt. No. 10:38-44, 1949. 122. Vazin, A.N. and Plokhova, E.I., "Changes in adrenaline-like substances in rabbit blood following chronic exposure to vinyl chloride fumes", Gig. Tr. Prof. Zabol.. 13(6):46-47, 1969. 123. Vazin, A.N. and Plokhova, E.I., "Changes in the rate of inculcation of conditioned reflexes In rats on prolonged exposure to vinyl chloride vapor in concentrations approaching the maximum permissible concentration". Gig. Sanlt., 35(4/6):434-435, 1970. 124. Vazin, A.N. and Plokhova, E.I., "Changes of cardiac activity in rats chronically exposed to vinyl chloride vapors", Farmakol. Toksikol.. 32(2):220-222, 1969. 125. Vazin, A.N. and Plokhova, E.X., "Obtaining an experimental model of the toxic angloneurosis arising under the chronic effect of vinyl chloride vapor on the organism", Gig. Tr. Prof. Zabol., 12:47-49 126. Vazin, A.N. and Plokhova, E.I., "Pathogenic effect of chronic vinyl chloride exposure to rabbits", Farmakol. Toksikol.. 31(3):369--372, 1968. 127. Veltman, G., Lange, C.E., Juhe, S., Stein, G. and Bachner, U., "Clinical manifestations and course of vinyl chloride disease", Ann. N.Y. Acad. Sci.. 246:6-17, 1975. 128. Vertkin, Yu.I. and Mamontor, Yu.R., "On the state of the broncho pulmonary system in workers engaged in the manufacture of articles made of polyvinyl chloride". Gig. Tr. Prof. Zabol.. 14(10):29-32, 1970. 129. Viola, P.L., "Cancerogenic effect of vinyl chloride", Abstracts. Tenth Int. Cancer Conf., Houston, Texas, Session 56: 742 Abstract No. 29, 1970. 130. Viola, P.L., "Oncogenic action of vinyl chloride and vinylidene chloride", presented at XI Int. Cancer Cong., Florence, Italy, October 1974. 131. Viola, P.L., "Pathology of vinyl chloride", Med. Lavoro, 61(3):174-180, 1970. 89 UCC 066511 132, Viola, P.L., Bigotti, A. and Caputo, A., "Oncogenic response of rat akin, lungs, and bones to vinyl chloride". Cancer Res.. 31:516-522. 133. Warren, H. and Huff, J.E., "Health effects of vinyl chloride monomer: An annotated literature collection", Env. Health Per.. 11:251-252, 1975. 134. Waxweiler, R.J., Stringer, W., Wagoner, J.K., Jones, J., Falk, H. and Carter, C., "Neoplastic risk among workers exposed to vinyl chloride", Ann. N.Y. Acad. Sci., 271:40-48, 1976. 135. Wilson, R.H., McCormick, W.E., Tatus, C.F. and Creech, J.L., "Occupational acroosteolysis", JAMA, 201(8):577-581, 1967. 90 UCC 066512 Appendix A DESCRIPTION OF PLANTS I. Monomer Planes Plant A This facility manufactures VC using the Acetylene-Hydrogen Chloride Process portrayed in Figure 1. The plant normally operates at 10 percent of capacity and then only when acetylene, manufactured at the plant, is available for the manufacture of VC. Nearly all of the acetylene manu factured at this site is sold as product to nearby chemical plants. The VC plant was in operation during the survey. The VC plant had been in operation for 12 years and involves 25 people. A total of 375 people were employed at the facility, which manufactures acetylene, methanol, ammonia, and VC as major products, with vinyl acetylene, diacetylene, methyl acetylene, dimethyl ether, and 2-chloropropene as byproducts. Liquid air and liquid nitrogen were also manu factured at the facility. A VC surveillance program was established at this company In April, 1974. The manufacturing areas are monitored at various points using a Miran Infrared Scanner with chart readout, and a Century Organic Vapor Analyzer(OVA). Air samples are collected in mylar sampling bags on a regular basis. The air samples are analyzed for VC concentration using gas chromatography. The results of the company's sampling program showed a TWA concentration 91 UCC 066513 range of 0.01 to 67 parts per million (ppm) of vinyl chloride. Except for the control laboratory and control room, all operations are performed outdoors. The control laboratory and control room are air conditioned with one air change per minute. The following changes have been made to their industrial hygiene program. All employees are required to wear supplied air-respirators when the VC concentration is expected to be over 50 ppm. Signs are posted whenever area monitoring indicates high VC concentrations are in the air. Additional purging time is required on all vessels which handle VC prior to being opened. High priority has been placed on work designed to eliminate VC leaks. Gas masks and slicker suits are'worn in accordance with current OSHA regulations. Plant B This facility produces VC using the Ethylene Dlchloride Pyrolysis Process. The VC plant had been operating for 16 years and operates on a continuous basis. VC produced at the plant is sold as a product and was also used 92 ucc 06651-4 on site for the manufacture of polyvinyl chloride resin and 1,1,1-trichloroethane. A total of 2,500 people were employed at the facility; however, only 100 people were involved in the manufacture of VC. Other products produced at this facility were tetraethyl lead, tetramethyl lead, sodium, sodium hydroxide, methyl chloride, ethyl chloride, ethylene dichloride, tri chloroethylene, and perchloroethylene. The VC plant and storage areas were located outside with the exception of the control room, which was air conditioned, and the quality control laboratory. The laboratory was equipped with a supply air blower and exhaust air system via the hoods. The laboratory air was changed every 1.4 minutes. A flow diagram of the process that this company used to manufacture VC is portrayed in Figure 2. A surveillance program for VC was put into effect in April 1974. In this program, a Miran II Infrared Analyzer is used to monitor the plant air for VC on a continuous basis, and the OVA is used for searching out emission sources or wherever "spot" monitoring is desired. The charcoal tube method Is used to obtain 15-minute spot samples and 4-hour p rsonnel samples on a regular basis. Gas chromatography is used to determine the concentration of VC picked up in the charcoal tubes. The results 93 uee 066515 of this company's sampling program show VC concantration range of 0,01 to 62 ppm. The following work practice changes had been instituted to protect their employees. During loading, VC tank car spew guages were previously vented to atmos phere. The spew gauge vent system is now closed with a sensing device to detect liquid, indicating the car is loaded. After loading, VC tank car load and equalizing lines were previously disconnected with residual vent (mostly vapor) allowed to escape to atmosphere. These lines are now purged with nitrogen (to flare) prior to disconnecting. VC liquid samples were previously taken and disposed of in such a manner that the potential for release of material to the atmosphere was quite high. Closed systems have been provided to permit purging sample bombs and connections, obtaining samples, and disposing residual sample material without exposure of personnel. The former practice of draining a gage glass to verify the liquid level has been discontinued. Procedures for preparing equipment for opening have been revised, and extra precautions taken to minimize risk of VC release to atmosphere. 94 IUIUAOA 066516 Example: VC liquid product scrubbers were previously prepared for recharging by displacing liquid (with nitrogen) and venting to flare. Purging to remove residual vapors was minimal at best. The revised procedure calls for thorough purging of the scrubber, utilizing heated inert gas and heating panels on the scrubber shell to ensure negligible release of VC to atmosphere when the scrubber is opened. While respiratory equipment has always been available for use when needed, personal respirators are now issued to all individuals for use whenever the potential for exposure exists. It is imposible to ascertain the effect of each work practice change separately, but the cumulative effect is favorable as Indicated by the result of personnel and area monitoring. Changes to their industrial hygiene practices are described below. Prior to the establishment of the 50-ppm Interim standard, VC was con sidered as one of a family of chlorinated hydrocarbons produced in the Hydrocarbon Area. There ware no special hygiene practices in effect for VC. Respiratory equipment was available for use In the event of spills or in doing any job where exposure to excessive amounts of VC (other chlorocarbons, hydrogen chloride, chlorine) was likely to occur. The situation today, of course, is quite different. Area air monitoring for VC is essentially continuous, using a Miran II Infrared Analyzer. Portable OVAs are used for searching out emission sources or wherever 95 ucc 066517 "spot" monitoring is desired. Certain areas have been designated as requiring respiratory protection. All personnel have been issued respirators (and trained in their proper use) and have been instructed to wear them when doing any job (e.g., opening or closing valves) where the potential for exposure to VC exists. Supplied air respirator hook-ups are being extended to all areas of the VC plant. The Medical Department has instituted a program for routine personnel monitoring utilizing carbon tube adsorption units. A medical surveillance program for all personnel who may have been exposed to VC in the past has been instituted and will be continued. On-the-job eating, drinking and smoking policies have not been revised as these activities were already restricted to designated areas. Plant C The Oxyhydrochlorination Process was employed by this facility to manu facture VC from Ethylene and chlorine as illustrated in Figure 3. This company is a large producer of VC, normally operates on a continuous bases, and has been producing VC at this facility for 12 years. A total of 600 people were employed at this facility; however, only 242 employees were exposed to VC. Products produced at this facility were ethylene, chlorine, ethylene dichloride, hydrochloric acid, VC, trans-l,2,-dichloroethylene, benzene, chloral, carbon tetrachloride, chloroform trichloro ethylene, ethyl chloride, and chloropropane. No PVC resin was produced at this site. 96 ucc 066518 The manufacture of VC was a closed-system operation, and all of the pro duction equipment was located outdoors except for the instrument houses, control rooms, laboratory and offices. The offices, laboratory, control rooms and instrument houses were kept under positive pressure. In addition, the equipment in the instrument houses was purged with nitrogen. No VC was piped to the control rooms. All VC in the laboratory was kept and handled in high-volume ventilation hoods. All production employees had their own respiratory protection devices. Respiratory protection devices were kept in the control rooms for any maintenance personnel working in the area. All personnel had been trained in the use of the equipment and were required to wear respiratory protection equipment whan working areas or performing specific operations where the exposure to VC was higher than, or could have been higher than the permissible OSHA limit. Disposable or washable coveralls were pro vided for hazardous operations, and gloves were required for personnel performing tasks which could expose their hands to the chemicals. Shower facilities were provided, and safety showers were available in the VC manufacturing areas for emergency use. Smoking and eating were confined to the cafeterias and the control rooms. Good housekeeping was maintained throughout the plant. Loading personnel were required to wear air pressure demand respirators when performing any operation where exposure to VC was possible. Supplied-alr respirator hook-ups were provided thorughout the plant. 97 UCC 066519 Each instrument house contained an infrared analyzer and gas chromato graph to detect concentrations of VC and ethylene dichloride in the production areas. The instrument readout equipment was located in the control rooms and was checked out during each shift by the operator. In addition, portable Century OVA's were used to check areas where the exposure limits for organic vapors were higher than permissible. A surveillance program ofr VC was initiated in July, 1973, using the charcoal tube method to determine the concentration of VC that their personnel were exposed to, and the levels existing in the various work areas. In their-surveillance, program 50 percent of all personnel exposed to VC were monitored each week for approximately 10 minutes. The charcoal tube samples were analyzed using gas chromatography. In addition, all exposed personnel were given medical examinations meeting the requirements specified in OSHA regulation 29 CFR 1910.93q. The following average time-weighted average (TWA) exposures to VC had been determined using OSHA personnel monitoring techniques since August 1974. Operator Job Classification North and South Furnaces North Purification South Purification North and South Spare East Furnace and Purification East Spare East Synthesis Vinyl Chloride Tank Farm Laboratory Instrument Laboratory Maintenance TWA Average 0.3 ppm 0.7 ppm 0.6 ppm 0.7 ppm 5.2 ppm 1.7 ppm 0.2 ppm 8.5 ppm 0.6 ppm Insufficient Data Insufficient Data 98 UCC 066520 Samples were taken while performing activities which gave the greatest probability of exposure. Numerous changes have been made to the facility to reduce or eliminate the possible exposure of personnel to VC or other suspect agents. A number of these changes are described below. Major equipment changes that have been made to reduce possible exposure to VC monomer are: A VC vapor collection and recovery system had been installed in the tank farm. Essentially, this consisted of a compressor and condensing system. The recovered VC was transferred to off-specification storage. A VC emergency collection and flare system had been installed for the process areas. In case of a VC release from a relief valve or vent, the VC was piped to a flare. The caustic scrubbers had the greatest potential for exposing people to VC. A VC stripper system was installed to remove hydrogen chloride from VC and return the hydrogen chloride to the manufacturing unit without exposing people to organic vapors. A system had been installed to supply respirators with breathing air from conveniently located stations throughout the plant. A continuous monitoring system had been installed in the North ethylene 99 UCC 086521 dichloride unit. By means of a chromatograph, the atmosphere at ten different points in the unit was regularly analyzed for a number of chlorinated organics including VC and ethylene dichloride. Additional valves had been put on VC tank car loading hoses to almost eliminate exposure due to venting the VC from the hoses at the end of the loading cycle. The caustic scrubber blowdown had been piped to a blowdown knockout tank which eliminated exposure by venting the VC to flare. The hydrogen chloride columns had been re-trayed to extend periods between opening for cleaning. Changes in operating and maintenance practices and procedures which had reduced possible exposure to VC were: Shift monitoring of the plant areas by the operators for hydrocarbons and chlorinated hydrocarbons had been initiated. This is the single most Important change as it gave impetus to the leak detection program and brought the operators and maintenance personnel full awareness of the VC levels in the plant. Organic Vapor Level Above 50 ppm Between 25 and 50 ppm Below 25 ppm Respiratory Protection Required Supplied-air Respirator Cartridge Mask No Protection All vessels were being better prepared for entry and consequently they had shown levels no higher than the general atmosphere outside the vessel during personnel entry. It had not been necessary to use respiratory protection for personnel entry. Respiratory protection procedures had been improved. A self-imposed policy of requiring cartridge masks for potential exposures to vinyl chloride In the range of 25 to 50 ppm had been instituted. Above 50 ppm, a continuous-flow air-line respirator or self-contained breathing apparatus was used. The following general guidelines were being used to determine where, when, and what type of respiratory protection was required: Any job which released VC to the atmoshpere, and all work done on the domes of the tank cars would require air-line respirators. Any task to be performed downwind or Inside the sphere of contaminated air of a known VC leak would require an air-line respirator. Cartridge masks would be worn for only those equipment jobs where the VC was less than 2 percent by volume of the stream or equipment contents. 101 UCC 066523 and vhere the wind movement was such that an employee could stay upwind and outside of the sphere of contamination by the released gas. Casual observers or supervisors in the vicinity of any of the above operations would be required to wear the same respiratory protection as the person assigned to the job. Air-line respirator usage in the VC tank farm had been made more conven ient by providing a connection at each of the loading stations. Short hoses were easily moved from station to station. The operators in the areas handling VC used the OVA once each shift to monitor designated locations within their areas. Leaks were noted and corrected by the operator where possible. Otherwise the foreman was notified so maintenance personnel could immediately repair the leak. The Safety Department was using the OVA to thoroughly monitor the production areas at least once a week. Readings were tabulated for each area, and if leaks were noted, they were referred to the area foreman for correction. Most equipment containing VC was being depressured to the flare stack, to other equipment, or to remote vents to prevent employee exposure. The purge lines from the process analyzer instruments had been hooked to a common header which was exhausted in a remote area that prevented personnel exposure. VC in the Instrument houses had thus been elim- 102 UCC 066524 inated. The operator area OVA readings taken each shift quickly detect leaks that have developed. The process analyzer group then used the OVA to pinpoint the leak for correction. The laboratory "wet testing" hood had been updated to give higher volume ventilation and conform to the requirements for handling hazardous materials. Tests have shown no vapors were escaping from the hood. Collected VC samples were no longer permitted to be stored in the process area control rooms. Outside storage was required. Employees performing tasks where it was possible to contact liquid VC were being required to wear gloves impervious to VC. In shutting down hydrogen chloride and VC columns, quench towers, etc,, extra steps were taken to strip out the VC. When the topping column was down, ths overhead of the lights columns was collected by keeping the condensers very cold. In the past, this vapor had baen vented to the atmosphere. Exposure reduction projects that were in process were: VC process equipment drainage system VC tank car gauging system VC process enclosed sample system 103 UCC 066525 VC flare instrumentation Re-traying of East hydrogen chloride column Permanent air monitoring systems in all three cracking units Corrosion-resistant VC stripper condenser A method had been devised and tried which would eliminate employee potential exposure on much of the VC sampling. Hardware had been ordered to convert many sample points to closed sampling. A closed system for liquid blowdown from sodium hydroxide scrubbers was over 50 percent complete. A system was being worked out which will permit purging tank car loading lines to the flare before they were disconnected. A continuous analyzer for detecting water in VC would eliminate the need for many samples now taken by operators. An additional large caustic scrubber to eliminate the need for small scrubbers was planned. This would permit all caustic scrubber operations to be handled in one area, and not only reduce the number of employees potentially exposed, but additionally would make controlling emissions much more feasible. A program to eliminate pump seal leakage was under way. A full investigation of ethylene dichloride-VC pumps had been completed, and specific programs had been started which promise reduced pump seal failure. 104 UCC 066526 Quotations were being evaluated on providing a corrosion-resistant stripper condenser which would increase uptime and thus reduce exposure due to scrubber operation and stripper repair. A sampling method was being sought which would eliminate purging VC into the atmosphere during tank car sampling operations. One device had failed to be an improvement, but others would be tried. Reboiler venting system Topping column revisions Larger rebollers Better level indicators and purges This list is not all inclusive but is indicative of the planning and efforts going into further improvements. XI. Polymerization Plants Plant D This plant is a large chemical manufacturing complex with a long list of chemicals produced. Approximately 1800 persons were employed there with only 150 of them Involved in PVC operations. The plant has produced PVC since 1929 and at the time of the survey produced PVC using three processes; a solvent process, an emulsion process, and a modified emulsion process in which VC is copolymerized with acrylonitrile. All reaction equipment for the emulsion and modified emulsion processes were located outdoors. All equipment for the solvent process and the 105 UCC 066527 drying, bagging, and VC recovery operations of the other processes are indoors. The three processes are located in separate parts of the plant. The emulsion process control room, VC recovery compressors, and PVC drying and bagging operations are located in one building with the reactors adjacent to the building. The modified emulsion process control room is also loacted in the same building with the recovery compressors, while the reactors are outdoors adjacent to the building. The solution process has one building for the reactors and strippers, one for precipitation and drying of PVC, one for solvent recovery, and one for bagging of PVC. The plant operates three shifts per day, seven days per week. This facility has an inplant dispensary with a full time Medical Director and an assistant. Nurses are on duty 24 hours a day. A pre-employment physical examination is required with re-examination every one to two years depending on age and department. The safety department consists of a director and an assistant. There is also a person assigned to a respiratory protection program. Each pro duction department has its own safety committee, which reviews safety practices, in addition to a central safety committee and a union safety committee. Industrial hygiene matters are handled by the environmental protection 106 UCC 066528 group. They have 2 industrial hygienists and a technician plus men to take care of solid waste, water, and air pollution. Industrial hygiene surveys for various hazards are conducted on a routine basis. This plant also has a full time fire department which also handles rescue work. There is also a rescue squad made up of lab personnel trained in first aid. VC has been sampled at the plant since 1969, although somewhat sporad ically until 1974. The initial sampling was done with detector tubes and later with grab samples analyzed by gas chromatography (GC). In 1974 personal sampling using charcoal tubes and GC analysis was begun. Also continuous monitoring for VC in the process areas using GC analysis was started. A continuous monitoring Instrument was located in each process area. Each Instrument had 20 sampling points which were sampled sequentially. Each sample took two minutes to analyze so each point was sampled once every 40 minutes. Workers had begun wearing suppliad-air respirators while cleaning reactors or other tasks with possible exposure to high levels of VC. Several other changes had been made to reduce exposure to VC, among these were: Removing lab work from control rooms Sampling reactors less often Attempting to eliminate monomer filters Clean autoclaves less often 107 UCC 066529 Improved VC recovery system Installed vacuum system on reactors to vent reactors prior to and during entry. This replaced system that vented reactor to atmosphere. Eliminated several venting points Plant E This plant-is entirely a PVC production facility with PVC being produced by the mass process and the suspension process. The plant is a relatively new one, having opened in 1970 and the processes are computer controlled. The work force consisted of 260 persons, 50 of whom were inovlved in the PVC polymerization areas. Process equipment was located indoors. The suspension and mass processes occupy separate buildings with drying and bagging operations in buildings separate from the reactor buildings. The plant operated three shifts per day, seven days per week. This facility has an in-plant dispensary with a registered nurse on duty Monday through Friday during the day shift. All lead technicians have first aid training. In addition, two physicians each visit once a week. Emergency arrangements have been made with nearby hospitals. Pre-employment physicals are required. These include a general physical examination, audiometry and semi-annual SMA-12 blood tests. 108 UCC 066530 The Safety Department consists of a safety engineer and an assistant. Hard hat, safety glasses, respirator, and safety shoe programs are in operation. In addition, workers are supplied work clothes which they are required to change each day. Daily showers are mandatory for workers in the polymerization areas. Workers are required to wear supplied-air respirators when entering vessels for cleaning or whan performing other jobs, such as cleaning filters that have a high potential for VC exposure. VC was being sampled by the use of charcoal tubes at this plant. An automatic sequential sampling system had been Installed in each poly merization building in early 1974. This system consisted of a Bendlx total hydrocarbon analyzer with six sampling points. Analysis time for each sample was two minutes, so each point was sampled every 12 minutes. These sample results were fed to a computer which stored shift peak levels for each point and calculated shift averages. It also actuated a visual alarm in the production areas whenever levels went above a preset limit. This limit at the time of the visit was 25 ppm. In addition, one person per shift spent full time checking for VC leaks using an OVA. Also when a high VC level was shown by tha automatic sampling system, he determined the source of the leak, and saw that it was corrected. Plant F Plant P is predominately a PVC polymerization facility but also has other operations. PVC is milled and calendered and plasticizers, polyurethanes, and acrylate polymers are also produced. The plant began operations in 1951 with the production of PVC emulsion resins. At present the suspension 109 UCC 066531 and emulsion processes are in use here. The work force consists of approximately 700 persons, with 200 of them working in the PVC polymeriza tion areas. The plant operates three 8-hour shifts per day, seven days per week. The suspension resin is produced in two buildings, one old and one new, each with a separate dryer building nearby. The emulsion resin is pro duced in a third building and drying takes place in a separate building. A fourth building also has an emulsion process, but it is used to produce PVC latex. This process was not in operation at the time of the survey and was therefore not sampled. This facility has an in-plant dispensary with nurses on duty 24 hours per day, 5 days per week. All foremen and guards are trained in first aid. Two physicians each spend two hours per day at the dispensary five days per week. An emergency vehicle is available at all times. Hospitals are ten to fifteen minutes away. The corporate medical department sets guidelines for routine medical tests and physical examinations. Pra-employment physicals, including blood tests, pulmonary function tests, audiometry, and a medical history ara required. Ratesting of employees is done periodically depending on the work location. The safety department consists of two safety inspectors. Hard hat, safety glasses and rasplratory protection programs are in operation. Workers ara required to wear suppliad-alr respirators when entering vessels for cleaning or when performing other jobs, such as filter cleaning, that have a high potential for VC exposure. Safety is 110 UCC 066532 stressed to the workers through monthly safety meetings, short we kly safety meetings in the operating areas, special safety meetings to discuss new topics, and by posting information on bulletin boards. Equipment inspection is carried out by the plant guards under the super vision of the safety department. These inspections include such things as routine checks of relief valves, rupture discs, and fire extinguishers. All plant personnel receive fire extinguisher and hose training. The plant has a fire truck with foam generation and dry chemical equipment. A yearly safety audit is performed by corporate personnel. Semi-annual safety audits are conducted by plant safety personnel. Historically, industrial hygiene services were provided by corporate level people. Since 1973, plant safety and environmental control personnel have been performing this function under the guidance of the corporate industrial hygienists. A safety engineer and an environmental control engineer handle this activity. Routine industrial hygiene audits were in the planning stages at the time of our survey. At that time, the priority item was VC sampling to determine regulated areas for the new OSHA standard. Sampling was also being conducted in various parts of the plant for diisocyanate, carbon monoxide, vlnylidene chloride, and PVC dust. Also, two engineers were on full time temporary assignment to Implement changes to bring the plant in compliance with the new OSHA standard. One of these changes was the installation of an automatic sequential VC sampling system in each polymerization building. This sampling 111 UCC 066533 system consists of a Bendix total hydrocarbons analyzer in the suspension and emulsion resin buildings and a gas chromatograph in the latex building. Each of these instruments is tied into six sampling points with changes being mads to add six additional sampling points to each system. At the time of the visit* analysis time was two minutes for each point, so each point is sampled every twelve minutes. With the additional sampling points, analysis time would be reduced to one minute, so that each point would still be sampled every twelve minutes. These sample results are fed to a minicomputer, which stores peak values for each point and calculates eight hour shift averages for each point along with floor and building averages. These systems also actuate a visual alarm in the production areas whenever levels go over a pre-set limit. At the time of our survey this was twenty-five ppm. In addition to area sampling, workers on each shift use Century OVA to conduct a routine inspection of valves, pump seals, etc. for early detection of VC leaks. Also, when a high VC level is detected by the automatic sampler, they use the OVA to determine the cause of the reading and see that it is fixed. Several changes had been instituted to lower VC exposures in the plant. 1. Improved procedures to prevent PVC spillage. 2. Closed containers for waste and recovered PVC. 3. Separate eating facilities provided. 4. Daily change of clothing provided. 5. Recover all vapors before disconnecting tank cars. 6. Improved building ventilation. 112 UCC 066534 7. Improved compressor seals. 8. Improved reactor manhead gaskets. III. Fabrication Plants Plant G This facility processes PVC resins and compounds into numerous extruded, molded, and bonded items and yarn. The company has been fabricating PVC products for 25 years. The present facility was started up in August 1971. The company normally employs 150 people and operates 24 hours a day on a 5-day-week basis. All manufacturing operations are performed indoors in a modern, well-designed and laid out plant. Approximately 50 people are involved in the manufacture of PVC products. The manufacturing processes employed in the manufacture of PVC products at this plant are: bonding, in the lamination of extruded PVC with plated mylar, or printed PVC film to make automotive or decorating trim; compounding, in the mixing of polyvinyl chloride resin with plasticizers, fillers, lubricants, stabilizers, pigments, and other materials to produce a dry-blend compound; extrusion in the conversion of dry-blend or pelletized compounds into continuous plastic strips of a predetermined cross section; fibers, in the extrusion of pelletized compounds into spools of colored yarns used for the manufacture of woven products; and molding, by the injection of PVC compounds into a heated mold to produce items having a definite size, shape, and color. Compounding at this plant is 113 UCC 066535 accomplished in ribbon-type blenders, and conversion of the dry-blend or pelletized compounds into a plastic mass takes place in the extruders and injection molders. No basic changes have been made to their PVC fabrication operations. Ventilation in the plant is provided by 16 roof-mounted exhaust fans with a total rating of 50,000 cubic feet per minute at 1/2 inch static pressure which provide an air change once every 30 to 35 minutes. The adjoining offices are air conditioned. Overall housekeeping is very good and the equipment has been installed in a well-planned, uncrowded manner. An enclosed, air-conditioned cafeteria area has been provided for breaks and lunches. Smoking is restricted to special areas. Special clothing is not required. The company does not have a VC surveillance program; however, the plant has been surveyed for VC concentrations by an Insurance company. The company uses bulletin boards and meetings to keep their employees informed on health and safety programs. Figure A-l shows a flow schematic of the processes used by Plant G to manufacture PVC products. Plant H This facility processes PVC resins into a wide variety of extruded and injection-molded products. The company has 21 years of experience in the manufacture of PVC products. 114 UCC 066536 -r--e> 3_ D :zh-f . E... 1--F 1o T? G Legend: A - Bagged Materials B - Blender C - Storage Container D - Extruder E - Cooling Bath F - Cut-Off Machine G - Shipping Container H - Injection Molder Figure a-1 Flow Schematic, Plants c, H ucc 066537 The company normally employs 260 people and all of the employees are considered by the company to be exposed to VC. The plant operates on a 24-hour-per day, 5-day-per-week schedule, and all manufacturing operations are performed Indoors. The company uses the following processes In the manufacture of PVC products: bonding, by hot-seal welding of flexible extruded profiles such as refrigerator seals; compounding. In the blending of PVC resin with plasticizers, fillers, stabilizers, pigments, and other additives in a semi-automated blender with a 45,000-pound-per-day capacity; extrusion, In the production of a wide range of profiles from powder-type compounds; and molding of dry PVC compounds into items such as automotive seals and cable enclosures by injection molding. Ventilation throughout the plant is provided by air-circulating fans. Hoods vented to the atmosphere through a duct system have bean Installed on injection molding presses and the high-intensity compound mixer. Doors and windows are opened as required to assist the plant ventilation system. The only significant change in the plant is the addition, in July 1974, of the new high-intensity compound mixer. The mixer is vented to the atmosphere through a duct system and should serve to reduce the escape of VC to the plant air. The company does not have a VC sampling program and does not feel that it has concentrations of VC above the permissible limit in the plant. 116 UCC 066538 The company has an active safety and medical program. Figure A-l shows a flow schematic of the processes used by Plant H to manufacture PVC products. Plant I This facility processes PVC resins into numerous dip-molded and di-coated products using plastisol-type compounds. The company has been fabricating PVC products by the dip-molding process for 25 years and normally employs 110 people. Due to the design of the plant, all of the employees are considered to be exposed to VC. The plant normally operates on a ona- shift-per-day basis, 5 days a week. The company added blow molding units three years ago. Blow-molded products are made from polyethylene compounds. % This company used the following three processes to produce PVC products: (1) compounding, in the mixing of PVC resins with dlcapryl phthalate, dioctyl adipate, and tallates as plasticizers; barium, cadmium, and zinc organic solutions as stabilizers; pigments; and fillers; (2) molding, by dipping a heated mold Into a plastisol compound and curing the dipped mold In an oven; and (3) plastlsols, in the compounding of plastisol mixtures. The only change that has been made to their PVC manufacturing processes is the addition, 9 years ago, of an automated-conveyorlzed die-molding line. All of the other die-molding units are hand operated, batch-type 117 UCC 066539 units. Plant ventilation is provided by roof-mounted fans. All of the ovens and blow-molding units are equipped with hoods which are ducted over head to the atmosphere for removal of fumes. The adjacent offices are air conditioned. The company has an active safety program and performs area and personnel sampling using the carbon tube sampling method. The carbon tubes are analyzed by one of the PVC resin suppliers. The results of the sampling analysis are posted on employee bulletin boards along with other safety and health bulletins. Sampling results show a range of 0.01 to 18.0 ppm. An enclosed cafeteria is provided for smoking, drinking, and eating during breaks and the lunch period. Figure A-2 shows a flow schematic of the processes used by Plant I to manufacture PVC products. Plant J This facility manufactures closed-cell expanded products from blends of PVC and rubber compounds. The manufacturing operations are performed in several indoor locations. The company has been making closed-cell expanded PVC/rubber products for 19 years, and no significant changes have been made to the original process. 118 UCC 066540 =c CD o cn O Legend: A - Bagged Materials B - Blender C - Mixing Tub D - Mixer E - Plasticizers F - Pigments G - Mold Heating Oven H - Plastisol Dip Tank I - Heated Mold J - Curing Oven K - Shipping Container Tiie plant operates on a 24--hour--day, 5--day--per week schedule and performs a batch-type operation. The plant has 1,110 employees; however, only 160 of their employees are exposed to VC in their manufacturing operations. The manufacturing processes performed by this company involving PVC resins and compounds are compounding, extrusion, foams, and molding. The manufacture of the various closed-cell expanded product line produced by this company begins with the addition, to a Banbury mixer, of prede termined amounts of the materials required to make the desired compound. The Banbury-mixed compound is fed to a two-roll mill where further mixing takes place, and ends up as a sheet of compound on the mill roll. Sections of the sheet are cut off and placed on a portable rack. The milled slabs are fed into a tuber (tube-type extruder) where the extruded compound for the batch-type units is cut into sections. The sections are placed in* a multi-leaf platen press where the section is heated under pressure to a definite shape, and partial expansion takes place. The shaped pieces are removed from the presses, loaded onto racks, and moved to a second oven. The loaded racks are placed in the oven where the partially blown sections are further expanded to approximately four times in si2e. The racks are removed from the oven, and the expanded slabs are unloaded and stacked onto skids for packaging and shipment. In another building, the milled slabs are fed into a continuous tuber located at the head of a long tunnel-type oven. The tubed stock is 120 UCC 066542 cured and fully expanded into a continuous sheet in the ovens. The expanded sheet is cooled and passed to a cutter where it is cut into sections or wound onto rolls prior to packaging for shipment. In other operations, the milled sheet can be extruded through heated dies to form continuous profiles of closed-cell expanded extrusions. This type of product would be primarily used for gasket, insulation, or cushioning materials. The closed-cell expanded products can be coated with a plastisol compound and further cured to provide a clear or colored skin of desired thickness on the coated item. The company has established a program for personnel sampling using the method called for in the NIOSH publication P & CAM No. 178, Vinyl Chloride in Air and Personal Gas Sampling Pumps. Initial samples collected in May 1974 indicated`less than 1 ppm of VC for 10 area samples. The charcoal tube samples were analyzed by an independent laboratory. Figure A-3 shows a flow schematic of the processes used by Plant J to manufacture PVC products. Plant K This facility manufactures plasticized PVC calendered film and sheeting, expanded vinyl sheeting, and printed vinyl film. The company has been 121 uec 0665*3 ucc 066544 A ttoo Legend: A - Bagged.Materials B - Banbury Mixer C - Two-Roll Mill 0 - Slab Rack E - Tuber F - Tunnel Oven G - Product Rolls H - Tube Rack 1 - Hot Press J - Oven Rack K - Batch Oven L - Shipping Container Figure a-3 Flow Schematic, Plant making calendered products 35 years, and expanded (foam) type products eight years. The PVC plant normally employs 127 people and operates on a continuous basis seven days a week. All production operatons except the offloading of resins from truck-mounted sealed containers to storage bins located on the roof are performed indoors. No basic changes have been made to the manufacturing operations; however, a number of engineering improve ments have initiated to improve production and eliminate unsafe working conditions. The company uses the following processes to produce the PVC products manufactured in this plant: bonding, in the lamination of two sheets of PVC; calendering, in the conversion of a plastic mass of PVC compound into a film or sheet of controlled width and thickness; compounding, in the mixing of PVC resin with plasticizers, fillers, stabilizers, and other materials in ribbon-type blenders, and the conversion of the powdered blend into a plastic mass in Banbury mixers (color pigments and granulated trim are added to the charge in the Banbury mixers); extrusion, in the processing of the Banbury charge through a screen and extruder head to a "rope" that is fed to the calender; fibers, in the combining of a roll of fabric with a sheet of polyvinyl chloride plastisol; foams, in the expansion of a plastisol film in a blowing/curing oven; plastlsols, in the compounding of plastisol mixtures; and thermoforming, in the embossing of designs into PVC film and sheeting. 123 ucc 066545 Raw materials used in the production of PVC products are PVC resins, plasticizers, stabilizers (barium, cadmium, and zinc organic salts in solution form), fillers, pigments, and Celogen as a blowing agent. The plant uses overhead fans ducted to roof-mounted fans and stacks for ventilation. Hoods are located above equipment that gives off fumes, and the hoods are ducted to roof-mounted fans and stacks. The blenders and dryblend transport equipment are vented to the atmosphere through a dust collector. The company has an active safety and sampling program. Thirty-minute breifings are given to all personnel, explaining the vinyl chloride monomer problem. Annual medical checkups are offered to all employees on a voluntary basis, plus' a 6-month blood sampling and analysis program. Air sampling for personnel, and area sampling are employed to detect VC, using the carbon-tube collection method. In addition, Miran II infrared analyzers plus Century OVAs are used to check for VC. The charcoal tubes are sent to their test center or a commercial laboratory for analysis. The analysis on the charcoal tubes can also be performed at this site. The sampling program was initiated in April 1974, and the only change that has been made is an increase in the sampling frequency. The results of their sampling program indicate a VC range of 0.2 to 1.1 ppm for i their operating personnel. Housekeeping throughout the plant is good and their safety department is working to eliminate or reduce employee exposure to VC below the 124 UCC 066546 permissible working levels. Employees performing operations where exposures above the permissible limit are possible must wear protective clothing. Smoking, drinking, and eating are permitted only in enclosed air-conditioned cafeteria areas or offices. Figure A-4 shows a flow schematic of the processes used by Plant K to manufacture PVC products. Plant L This facility processes PVC resins into pelletized PVC compounds, thermoformed products, vinyl film, and vinyl sheeting. The company has been performing calendering operations since 1946, thermoforming since 1958, and compounding since 1959. The company employs 520 people; however, only 309 of the employees are considered to be exposed to VC. The facility operates on a 24-hour-perday schedule, 7 days per week depending on the work load. All of the production operations for the processing of PVC into finished products are performed indoors except for the offloading of resins to the rooflocated storage hoppers, and the loading of compounded resins into bulk shipping devices. The manufacturing operations performed in the conversion of PVC resins into salable products are compounding, calendering, and thermofarming. Compounding involves the mixing of PVC resins, plasticizers, stabilizers, fungicides, bacteriastats, lubricants, pigments, and fillers in continuous 125 ucc 066547 Legend: A - Roof Storage Silos B - Blender C - Dump Cart D - Storage Silo E - Weigh Hopper F - Banbury Mixer G - Extruder H - Conveyor I - Calender J - Cooling Drums K - Winder L - Product Rolls OK>' rr t 'h n O o a-a _j^lL a,: Tr-<, ucc 066548 Figure A-4 Flow Schematic, Plant ribbon-type blenders. After the ingredients are blended, they are further processed into a plastic mass, sheet, or rope in Banbury mixers, two-roll mills, extruders, or a combination of the three units. Calendering con verts a rope of plastic PVC compound into a continuous sheet or film of controlled width and thickness in a four-roll inverted "L" form calender, the plastic compound from the Banbury mixer in another product line is passed to an extruder-dicer unit to convert the dry-blend compound into a pelletized compound product. The pelletized compound is bagged and loaded onto skids for shipment as a salable product. Thermoformed pro ducts are produced by the vacu-forming process. In this operation, precut sheets of PVC sheet stock are fed to a vacu-forming unit, where the sheet stock takes the form of the hot die, using negative pressure during the forming operation, and positive pressure to strip the formed item from the die. The formed items are stacked and loaded into boxes for shipment. The vacu-formed products are used as custom-formed plastic packaging for the protection and display of items such as candy and fruit. Roof-type ventilators are used throughout the plant for ventilation. Dust-producing equipment and dust-laden atmospheres are ducted to baghouses and cyclone separators to remove airborne particulate prior to venting to the atmosphere. The company has an active health, safety, and sampling program to protect its employees and prevent VC excursion to the atmosphere. Safety and health information is transmitted to the employees by way of union- 127 ucc 066549 management meeting, and bulletin boards. Charcoal tubes and Sipin pumps are used to collect area and personnel samples. The air samples are analyzed by gas chromatography in their in-plant laboratory. The company is also very active in the development of more-advanced methods of ident ifying VC concentrations in the work, area through the use of instant readout instrumentation. The only suspected liver toxins that are used in this plant are VC, PVC resins, organic lead stabilizers, and tetrahydrofuran. The tetrahydrofuran is restricted to laboratory analysis usage. The results of their sampling program were not available. The company is constantly revising its production procedures and equip ment to take advantage of methods to increase production, lower operating costs, and increase the overall safety of its employees. The main changes that were made to the compounding operations are the changes in the mixing of compound ingredients in two-roll mills to Banbury mixers and then to ribbon-type blenders, A cafeteria and designated smoking, drinking, and eating areas have been provided for the employees. Respirators were not worn in the blender areas. Figure A-5 shows a flow schematic of the processes used by Plant L to manufacture PVC products. 128 UCC 066550 -- it- ft --I ft--i i----} # 4 4- - 1 t-.-J i-J I J I. -I 1 1 11 II l| 14 ll l I l Legend: A - Silo Storage Tanks B - Weigh Hoppers C - Blenders D - Two-Roll Hills E - Banbury Mixer F - Dicer G - Bagger Unit H - Bagged Resins I - Calender J - Cooling Drums K - Winder L - Product Rolls VtoO ucc 066551 Plant I H Figure A-5 Flow Schematic, Plant i. Plant M . This facility converts PVC resins and other compounding ingredients into calendered film and vinyl-coated supported and unsupported fabrics that are sold to a number of industries. The company has been in operation since 1947 for the manufacture of PVC products. The plant normally operates on a 24-hour-per-day schedule, 5 to 6 days a week. All manufacturing operations are performed indoors except the off-loading of resin from bulk resin trucks to ground level storage silos. Resin from the silos is transferred by an airveyor system to a gravity supply hopper located on the roof of the plant. The plant employs 325 people; however, only 50 workers are considered to be exposed to VC in their manufacturing operations. The following processes are used by this company to make their PVC product lines: bonding, in the lamination of two sheets of vinyl; calendering, in the high-speed conversion of a rope of PVC compound into continuous film or sheet stock of controlled width and thickness; compounding, in the mixing of PVC resins with plasticizers, stabilizers, fillers, lubricants, and other additives in ribbon-type blenders, and the conversion of the pow dered blend into a plastic mass in Banbury mixers (color pigments and granulated trim stock and scrap are added in the Banbury mixers); extrusion, in the processing of the Banbury charge through a screen and 130 UCC 066552 extruder head to form a rope of PVC compound that is fed to a calender; foams in the expansion of cast plastisol film in a blowing/curing oven; plastisols, in the compounding of plastisol mixtures used in the film casting line; and thermoforming, in the embossing of designs into PVC film and sheeting. The embossing operation is performed on the calendering lines and the cast film line. The plant uses roof-mounted ventilation fans, exhaust hoods, and ducts to supply fresh air and remove fumes and dust-laden atmospheres. The vented exhausts are passed through an electric precipitator to remove entrained solids prior to' venting to the atmosphere. The solids collected in the precipitator are burned as a fuel. Recent changes that have been made to the ventilation system to reduce VC concentrations within the plant are: a 30-horsepower, roo'f-mounted exhaust fan and duct system has been installed on each of the blenders to prevent the excursion of dry-blend compounds into the plant air; shrouded hoods have been installed on the mills to reduce emissions; and conveyors to the mills have been enclosed. A proposal is in the design stage to enclose the Banbury mixers with a duct system similar to the systems installed on the ribbon blenders. The company has an active safety program and has recently initiated an area and personnel sampling program using the carbon tube method and personnel sampling pumps. The analysis of the carbon tubes is performed by an Independent laboratory. The employees are kept up to date on 131 UCC 066553 safety and health problems by way of bulletin boards and safety meetings. All employees entering work areas where higher-than-permissible levels of VC have been found or are possible must sign a form that lists the specific work area entered, and the time the area was entered and exited. Chemical cartridge type respirators are worn by the employees when working in dusty areas or when higher-than-permissible levels of VC are suspected. A surveillance program for VC was initiated in November 1974. The results of the survey to date indicate a VC concentration range of Q.l to 30.81 ppm based on area sampling over a period of four months. t Eating, drinking, and smoking are restricted to specified areas or enclosed office areas. Figure A-6 shows a flow schematic of the cast film production line for Plant M. Figure A-7 shows a flow schematic of the calendered film lines for Plant M. 132 UCC 066554 ucc 066555 Figure A-6 Flow Schematic, Cast Film Production, Plant ucc 066556 Figure A-7 Flow Schematic, Calendered FiTm Production, Plant ORGANIC SOLVENTS IN AIR Physical and Chemical Analysis Branch Analytical Method Analyte: Organic Solvents (See Table 1) Matrix: Air Procedure: Adsorption on charcoal desorption with carbon disulfide, GC Date Issued: 9/15/72 Date Revised: 7/15/74 Method No: Range: P&CAM 127 For the specific compound, refer to Tables I&II Precision: 10.5% RSD Classification: See Table 1 1. Principle of the Method 1.1 A known volume of air is drawn through a charcoal tube to trap the organic vapors present. 1.2 The charcoal in the tube is transferred to a small, graduated test tube and desorbed with carbon disulfide. 1.3 An aliquot of the desorbed sample is Injected into a gas chromato graph. 1.4 The area of the resulting peak is determined and compared with areas obtained from the injection of standards. 2. Range and Sensitivity The lower limit in mg/sample for the specific compound at 16 x 1 attenuation on a gas chromatograph fitted with a 10:1 splitter is shown in Table 1. This value can be lowered by reducing the attenuation or by eliminating the 10:1 splitter. 3. Interferences 3.1 When the amount of water in the air is so great that condensation actually occurs In the tube, organic vapors will not be trapped. Preliminary experiments indicate that high humidity severely decreases the breakthrough volume. 3.2 When two or more solvents are known or suspected to be present in the air, such information including their suspected identities, should be transmitted with the sample; since with differences in polarity, one may displace another from the charcoal. 141 UCC 066557 3.3 It must be emphasized that any compound which has the same retention time as the specific compound under study at the operating conditions described in this method is an inter ference. Hence, retention time data on a single column, or even on a number of columns, cannot be considered as proof of chemical Identity. For this reason it is important that a sample of the bulk solvent(s) be submitted at the same time so that identity(ies) can be established by other means. 3.4 If the possibility of interference exists, separation conditions (column packing, temperatures, etc.) must be changed to circum vent the problem. 4. Precision and Accuracy 4.1 The mean relative standard deviation of the analytical method is 8%. (Ref. 11.4). 4.2 The mean relative standard deviation of the analytical method plus field sampling using an approved personal sampling pump Is 10% (Ref. 11.4). Part of the error associated with the method is related to uncertainties in the sample volume collected. If a more powerful vacuum pump with associated gas-volume integrating equipment is used, sampling precision can be improved. 4.3 The accuracy of the overall sampling and analytical method is 10% (NIOSH's unpublished data) when the personal sampling pump is calibrated with a charcoal tube in the line. 5. Advantages and Disadvantages of the Method 5.1 The sampling device is small, portable, and involves no liquids. Interferences are minimal, and most of those which do occur can be eliminated by altering chromatographic conditions. The tubes are analyzed by means of a quick. Instrumental method. The method can also be used for the simultaneous analysis of two or more solvents suspected to be present in the same sample by simply changing gas chromatographic conditions from isothermal to a temperatureprogrammed mode of operation. 5.2 One disadvantage of the method is that the amount of sample which can be taken is limited by the number of milligrams that the tube will hold before overloading. When the sample value obtained for the backup section of the charcoal trap exceeds 25% of that found on the front section, the possibility of sample loss exists. During sample storage the more volatile compounds will migrate throughout the tube until equilibrium is reached (33% of the sample on the backup section). 142 ucc 066558 5.3 Furthermore, the precision of the method is limited by the reproducibility of the pressure drop across the tubes. This drop will affect the flow rate and cause the volume to be imprecise, because the pump is usually calibrated for one tube only. 6. Apparatus 6.1 An approved and calibrated personal-sampling pump for personal samples. For an area sample any vacuum pump whose flow can be determined accurately at 1 liter per minute or less. 6.2 / Charcoal tubes: glass tube with both ends flame sealed, 7 cm long with a 6-mm O.D. and a 4-mm I.D., containing 2 sections of 20/40 mesh activated charcoal separated by a 2-mm portion of urethane foam. The activated charcoal is prepared from coconut shells and is fired at 6Q0C prior to packing. The absorbing section contains 100 mg of charcoal, the backup section 50 mg. A 3-"mm portion of urethane foam is placed between the outlet end of the tube and the backup section. A plug of silylated glass wool is palced infront of the absorbing section. The pressure drop across the tube must be less than one inch of mercury at a flow rate of 1 pm. 6.3 Cas chromatograph equipped with a flame ionization detector. 6.4 Column (20 ft x 1/8 in) with 10% FFAP stationary phase on 80/100 mesh, acid-washed DMCS Chromosorb W solid support. Other columns capable of performing the required separations may be used. 6.5 A mechanical or electronic integrator or a recorder and some method for determining peak area. 6.6 Glass stoppered micro tubes. The 2.5-ml graduated microcentrifuge tubes are recommended. 6.7 Hamilton syringes: 10 yl, and convenient sizes for making standards. 6.8 Pipets: 0.5 ml delivery pipets or 1.0 ml type graduated in 0.1 ml Increments. 6.9 Volumetric flasks: 10 ml or convenient sizes for making standard solutions. 7. Reagents 7.1 Spectroquality carbon disulfide (Matheson Coleman and Bell) 143 J ucc 066559 7.2 Sample of the specific compound under study, preferably chromatoquality grade. 7.3 Bureau of Mines Grade A helium. 7.4 Prepurified hydrogen. 7.5 Filtered compressed air. 8. Procedure 8.1 Cleaning of Equipment. All glassware used for the laboratory analysis should be detergent washed and thoroughly rinsed with tap water and distilled water. 8.2 Calibration of Personal Pumps. Each personal pump must be calibrated with a representative charcoal tube in the line. This will minimize errors associated with uncertainties in the sample volume'collected. 8.'3 Collection and Shipping of Samples 8.3.1 Immediately before sampling, the ends of the tube should be broken to provide an opening at least one-half the internal diameter of the tube (2mm). 8.3.2 The smaller section of charcoal is used as a back-up and should be positioned nearest the sampling pump. 8.3.3 The charcoal tube should be vertical duTing sampling. 8.3.4 Air being sampled should not be passed through any hose or tubing before entering the charcoal tube. 8.3.5 The flow, time, and/or volume must be measured as accurately as possible. The sample should be taken at a flow rate of 1 1pm or less to attain the total sample volume required. The minimum and maximum sample volumes that should be collected for each solvent are shown in Table 1. The minimum volume quoted must be collected if the desired sensitivity is to be achieved. 8.3.6 The temperature and pressure of the atmosphere being sampled * should be measured and recorded. 8.3.7 The charcoal tubes should be capped with the supplied plastic caps immediately after sampling. Under no circumstances should rubber caps be used. S 144 ucc 066560 8.3.8 One tube should be handled in the same manner as the sample tube (break, seal, and transport), except that no air is sampled through this tube. This tube should be labeled as a blank. 8.3.9 Capped tubes should be packed tightly before they are shipped to minimize tube breakage during shipping. 8.3.10 Samples of the suspected solvent(s) should be submitted to .the laboratory in containers furnished by NIOSH for such purpose. These liquid bulk samples should not be transported in the same container as the samples or blank tube. If possible, a bulk air sample (at least 501 air drawn through tube) should be shipped for qualitative Identification purposes. 8.4 Analysis of Samples 8.4.1 Preparation of Samples. In prepratlon for analysis, each charcoal tube is scored with a file in front of the first section of charcoal and broken open. The glass wool is removed and discarded. The charcoal in the first (larger) section is transferred to a small stoppered test tube. The separating section of foam is removed and discarded; the second section is transferred to another test tube. These two sections are analyzed separately. 8.4.2 Desorption of Samples. Prior to analysis, one-half ml of carbon disulfide is pipetted into each test tube. (All work with carbon disulfide should be performed in a hood because of its high toxicity.) Tests indicate that desorption is complete in 30 minutes if the. sample is stirred occasionally during this period. The use of graduated glass-stoppered, microcentrifuge tubes is recommended so that one can observe any apparent change in volume during the desorption process. Carbon disulfide is a very volatile solvent, so volume changes can occur during the desorption process depending on the surrounding temperature. The initial volume occupied by the charcoal plus the 0.5 ml CS2 should be noted and corres ponding volume adjustments should be made whenever necessary just before GC analysis. 8.4.3 GC Conditions. The typical operating conditions for the gas chromatograph are: 1. 85 cc/mln. (70 psig) helium carrier gas flow. 2. 65 cc/mln. (24 pslg) hydrogen gas flow to detector. 3. 500 cc/min. (50 pslg) air flow to detector. 4. 200*C Injector temperature. 145 ucc 066561 5. 200*C manifold temperature (detector) 6. Isothermal oven or column temperature - refer to Table 1 for specific compounds. 8.4.4 Injection. The first step in the analysis is the injection of the sample into the gas chromatograph. To eliminate difficulties arising from blowback or distillation within the syringe needle, one should employ the solvent flush injection technique. The 10 syringe is first flushed with solvent several times to wet the barrel and plunger. Three microliters of solvent are drawn into the syringe to increase the accuracy and reproducibility of the injected sample volume. The needle is removed from the solvent, and the plunger is pulled back about 0.2 to separate the solvent flush from the sample with a pocket of air to be used as a marker. The needle is then immersed in the sample, and a 5-ui aliquot is withdrawn, taking into consideration the volume of the needle, since the sample in the needle will be completely injected. After the needle - is removed from the sample and prior to injection, the plunger is pulled back a short distance to minimize evap oration of the sample from the tip of the needle. Duplicate injections of each sample and standard should be made. No more than a 32 difference in area is to be expected. 8.4.5 Measurement of area. The area of the sample peak is measured by an electronic integrator or some other suitable form of area measurement, and preliminary results are read from a standard curve prepared as discussed below. 8.5 Determination of Desorption Efficiency 8.5.1 Importance of determination. The desorption efficiency of a particular compound can vary from one laboratory to another and also from one batch of charcoal to another. Thus, it is necessary to determine at least once the percentage of the specific compound that is removed in the desorption process for a given compound, provided the same batch of charcoal is used. The Physical and Chemical Analysis Branch of NIOSH has found that the desorption efficiencies for the compounds in Table 1 are between 812 and 1002 and vary with each batch of charcoal. 8.5.2* Procedure for determining desorption efficiency. Activated charcoal equivalent to the amount in the first section of the sampling tube (100 mg) is measured into a 5cm, 4-mm I.D. glass tube, flame-sealed at one end (similar to commercially available culture tubes). This charcoal must be from the same batch as that used in obtaining the samples and can be obtained from unused charcoal tubes. The open end is capped 146 I ucc 066562 with Parafilm. A known amount of the compound is injected directly into the activated charcoal with a microliter syringe, and the tube is capped with more Parafilm. The amount injected is usually equivalent to that present in a 10-liter sample at a concentration equal to the federal standard. At least five tubes are prepared in this manner and allowed to stand for at least overnight to assure complete abosrption of the specific compound onto the charcoal. These five tubes are referred to as the samples. A parallel blank tube should be treated in the same manner except that no sample is added to it. The sample and blank tubes are desorbed and analyzed in exactly the same manner as the sampling tube described in Section 8.3. Two or three standards are prepared by injecting the same volume of compound into 0.5 mi of CS2 with the same syringe used in the preparation of the sample. These are analyzed with the samples. The desorption efficiency equals the difference between the average peak area of the samples and the peak area of the blank divided by the average peak area of the standards, or Area sample - Area blank desorption efficiency - ----------------------------------- ;-----" Area standard Calibration and Standards It is convenient to express concentration of standards in terms of mg/0.5 mi CSj because samples are desorbed' in this amount of CS2* To minimize error due to the volatility of carbon disulfide, one can inject 20 times the weight into 10 mi of CS2. For example, to prepare a 0.3 mg/ 0.5 mi standard, one would inject 6.0 mg into exactly 10 mi of CS2 in a glass-stoppered flask. The density of the specific compound is used to convert 6.0 mg into microliters for easy measurement with a microliter syringe. A series of standards, varying in concentration over the range of interest, is prepared and analyzed under the same CC conditions and during the same time period as the unknown samples. Curves are estab lished by plotting concentration in mg/0.5rai versus peak area. NOTE: Since no Internal standard Is used in the method, standard solutions must be analyzed at the same time Chat the sample analysis is done. This will minimize the effect of known day-to-day variations and variations during the same day of the FID response. 147 UCC 066563 10. Calculations 10.1 The weight, in mg, corresponding to each peak area is read from the standard curve for the particular compound. No volume corrections are needed, because the standard curve is based on mg/0.5 mil CS2 and the volume of sample injected is identical to the volume of the standards injected. 10.2 Corrections for the blank must be made for each sample. Correct mg mgg - mgb where: mgs " found in front section of sample tube mg found in front section of blank tube A similar procedure is followed for the backup sections. 10.3 The corrected amounts present in the front and backup sections of the same sample tube are added to determine the total measured amount in the sample. 10.A This total weight is divided by the determined desorption efficiency to obtain the total mg per sample. 10.5 The volume of air sampled is converted to standard conditions of of 25*C and 760 mm Hg. P 298 vs v * 760 T+273 where: V " volume of air in liters at 25C and 760 mm Hg s V - volume of air in liters as measured P * Barometric pressure in mm Hg T Temperature of air in degree centigrade 10.6 The concentration of the organic solvent in the air sampled can be expressed in mg per ra^, which is numerically equal to ug per liter of air mg/m^ * ug/i total mg (Section 10.A) x 1000 (ug/mg) 10.7 Another method of expressing concentration is ppm, defined as ui of compounds per liter of air ppm of compound/Va u of compound ppm 2A.A5 MH where: 2A.A5 molar volume at 25*C and 760 mm Hg MW molecular weight of the compound (Table 1) 1 /. O ucc 066564 IX. References 11.1 White, L.D., D.G. Taylor, P.A. Mauer, and R.E. Kupel, "A Convenient Optimized Method for the Analysis of Selected Solvent Vapors in the Industrial Atmosphere," Amer. Ind, Hyg, Assoc j., 31:225 (1970). 11.2 Young, D.M. and A.D. Crowell, Physical Adsorption of Gases. Butterworths, London, 1962, pp. 137-146. 11.3 Federal Register, 37_ (#202), 22139-22142 (October 18, 1972). 11.4 NIOSH Contract H5M-99-72-98, Scott Research Laboratories, Inc., "Collaborative Testing of Activated Charcoal Sampling Tubes for Seven Organic Solvents," pp. 4-22, 4-27 (1973). 149 UCC 066565 TABLE I PARAMETERS ASSOCIATED WITH P&CAB ANALYTICAL METHOD NO, 127 Organic Solvent Method Detection limit Classification (mg/sample) Sample Volume (1) Minimum Maximum^^ CC Column Temperature(C) Molecular Weight Acetone Benzene Carbon tetrachloride Chloroform Dlchloromethane p-Dioxane Ethylene dlchlorlde Methyl ethyl ketone Styrene Tetrachloroethylene 1,1,2-trlchloroethane 1,1,1-trichloroethane (Methyl Chloroform) Trichloroethylene Toluene Xylene D A A A D A D B D B B B A B A 0.01 0.20 0.10 0.05 0.05 0.05 0.01 0.10 0.06 0.05 0.05 0.05 0.01 0.02 0.5 0.5 10 0.5 0.5 1 1 0.5 1.5 1 10 0.5 1 0.5 0.5 7.7 55 60 13 3.8 18 12 13 34 25 97 13 17 22 31 60 90 60 80 85 100 90 80 150 130 150 150 90 120 100 58.1 78.1 154.0 119 84.9 88.1 99.0 72.1 104 166 133 133 131 92.1 106 (a) Minimum volume, In liters, required to measure 0.1 times the OSHA standard (b) These are breakthrough volumes calculated with data derived from a potential plot (reference 11.2) for activated coconut charcoal. Concentrations of vapor in air at 5 times the OSHA standard (reference 11.3) or 500 ppm, whichever is lower, 25"C> and 760 torr were assumed. These values will be as much as 50% lower for atmospheres of high humidity. The effects of multiple contaminants have not been investigated, but it is suspected that less volatile compounds may displace more volatile compounds (See 3.1 and 3.2) ucc 066566 TABLE II CHEMICALS WHICH HAVE GREATER THAN 80S DESORPTION EFFICIENCY BUT HAVE NOT BEEN THOROUGHLY TESTED BY NIOSH Class E (Proposed) Acrylonitrile Allyl glycidyl ether n-Amyl acetate 2-Butoxyethanol n-Butyl acetate n-Butyl alcohol n-Butylglycidyl ether Chlorobenzene Cyclohexane Cyclohexanone o-Dlchlorobenzene p-Dichlorobenzene Diethyl ether N,N-Dimethyl aniline Epichlorohydrin 2-Ethoxylethyl acetate Ethyl acetate Ethylbenzene Ethyl butyl ketone Fufural Heptane Hexane Isoamyl acetate Isobutyl acetate Isobutyl alcohol Isoctane Isophorone Isopropyl acetate Isopropyl glycidyl ether 2,6-Lutidine Methyl acetate Methyl acrylate Methyl n-butyl ketone Methyl ethyl ketone Methyl isobutyl ketone Methyl methacrylate a-Methyl styrene p-Methyl styrene n-Octane 3-Octanone Pentane 2-Pentanone a-pinene n-Propyl acetate 1,1,2,2-Tetrachloroethane Tetrahydrofuran Trichlorotrifluoroethane (Freon 113) Recommended Sample Size * 101 151 UCC 06656? VINYL CHLORIDE SUPPLEMENT TO P&CAM 0127 31 May 197A This document is designed to aid the analyst in adapting the procedures of P&CAM 0127, "Organic Solvents in Air" to the determination of vinyl chloride in workplace air. Since in-house research on vinyl chloride analysis is still in progress, the following information is as yet Incomplete. Sampling In-house experiments on the capacity of the 150-og two-section activated charcoal sampling tube suggest the following: (1) if a concen tration of vinyl chloride in air of around 2 ppm (v/v) Is anticipated, no more than 3.5 of the atmosphere should be sampled; (2) if a concentration of around 50 ppm (v/v) is anticipated, sample no more than 1.2 . Sampling flow rates of 200 ml/mln or less are recommended. Sample Storage Samples of vinyl chloride on charcoal appear to be stable for at least 3 weeks if stored at -20C or at least 2 days if stored at 25C. During storage at room temperature, the vinyl chloride slowly equilibrates throu* ghout the tube, giving the appearance of migrating to the backup section. At -20"C this equilibration is very slow. Analytical Procedure Vinyl chloride is desorbed from the charcoal with 0.5 ml or 1.0 ml of CSj* Vials having a volume of 2 ml are used (thus keeping the headspace 132 UCC 066568 -2- above the solution small) and are capped with septa after addition of the CS2 to the chare al. chloride by GC include: The columns used in the analysis of vinyl Column Temperature(C) Reference 20-ft 10% SE-30 on 80-100 mesh Chromosorb W AW DMCS 20-ft 10% FFAP on 80-100 mesh Chromosorb W AW DMCS 5-ft 5% SP-1000.on 80-100 mesh Chromosorb W AW DMCS 6-ft 20% Carbowax 600 on C-22 Firebrick 6-ft Porapak Q, 80-100 mesh 60 65 (initial) 65 (initial) ? 30-50 (initial) in-house in-house in-house 1 2 6-ft Carbowax 20M alkaline on 60-80 mesh Chromosorb W AW 100-ft Squalane coated capillary ? 30 3 4 100-ft 25% GE-96 silicone/75% oxybis(2-ethyl benzonte) coated capillary 25 4 200-ft hexadecane coated capillary 25 4 10-ft 7% 0V-101 on 60-80 mesh Chromosorb G AW 50 5 Using the 20-ft GC column of 10% RE-30 on Chromosorb W at 6Q*C, our standard curve extends as low as 0.2 ng/injection. Impurities in the CSj Interfered with the analyses for low levels of vinyl chloride using the FFAP or SP-1000 columns. 153 ucc 066569 3- SCandards are prepared in either of two ways. (A) Pure vinyl chloride is slowly bubbled into a tared amount of toluene (y 5 ml) t contained in a 10-ml volumetric flask. About 100-400 mg of vinyl chloride are collected in 3 min. The solution is reweighed and diluted to the mark with CSj. Standards are prepared from this stock solution using CS2 for the dilution. (3) A series of standard solutions are prepared by injecting known volumes of pure vinyl chloride (gas) into CS2 in 5- or 10-ml volumetric flasks and diluting to the marks. The relative accuracies of these and other methods has not been determined. The desorption efficiency is determined using a synthetic atmosphere of vinyl chloride in clean air contained in a Tedlar (in house) or a Seran (reference 5) bag. Known volumes of this atmosphere are sampled using the charcoal tubes and the vinyl chloride desorbed and determined by GC analysis. Concentrations thus obtained are compared with those from GC analyses of 1-ml aliquots of the synthetic atmosphere to give the desorption efficiency (DE): D2 m weight vinyl chloride on charcoal/volume atmosphere sampled concentration of vinyl chloride in atmosphere In house values of the desorption efficiency for about 300/tg of vinyl Chlor-fda on the charcoal fi.ihas have b*<?n around 0.?. ftlnca tha nn efficiency may -differ with loading on the charcoal, desorption procedure, and charcoal batch, each laboratory should determine its own values, preferably for the loading expected if an atmosphere containing vinyl chloride at the OSHA standard were sampled. 154 UCC 066570 i references / I 1* E.A. Boettner and F.A. Dallas, J Gas Chromatog, 3_, 190 (1965). 2. F.V. Williams and M.E. Umstead, Anal Chem, 40, 2232 (1968). 3. E.D. Baretta, R.D. Stewart, and J.E. Mutchler, Am Ind Hyg. Assoc J, 30, 537 (1969). 4. O.L. Hollis and W.V. Hayes, Anal Chem, 34, 1223 (1962) 5 A.A. Allemany, L.W. Severs, and L.K. Skory, Dow Chemical Company Analytical Method ML-AM-74-12, "Monitoring Personnel Exposure to Vinyl Chloride in an Industrial Work Environment," 17 April 1974. 155 UCC 066571 A^^CUUIA Li VINYL CHLORIDE IN AIR Physical and Chemical Analysis Branch Analytical Method Analyte: Matrix: Vinyl Chloride (Chloroethene, Chloroethylene) Air Method No.: Range: P&CAM #178 0.2-1500 ng per injection Procedure: Adsorption on charcoal, desorption with carbon disulfide, GC Date Issued: 9/3/74 Precision: Unknown Date Revised: Classification: D (Operational) 1. Principle of the Method 1.1 A known volume of air is drawn through a charcoal tube to trap the vinyl chloride present. 1.2 The charcoal in the tube is transferred to a small vial containing carbon disulfide where the vinyl chloride is desorbed. 1.? An aliquot of the desorbed sample is injected into a gas chroma tograph. 1.4 The area of the resulting peak is determined and compared with areas obtained from the injection of standards. 2. Range and Sensitivity 2.1 The mimmum detectable amount of vinyl chloride was found to be 0.2 nanograms per injection at a 1 x 1 attenuation on a gas chromatograph. 2.2 At the recommended sampling flow rate of 50 ml/min, the total volume to be sampled should not exceed 5.0 liters. This value is the volume which the front section of the charcoal tube will hold at 200 ppm before a significant amount of vinyl chloride is found on the backup section. (The charcoal tube consists of two sections of activated charcoal separated bv a section of urethan foam. [See Section 6.2.]) If a particular atmosphere 156 UCC 068572 is suspected of containing a high concentration of contaminants and/or a high humidity is suspected, the sampling volume should be reduced by 50%. 3. Interferences 3.1 When the amount of water in the air is so great that condensation actually occurs in the tube, organic vapors will not be trapped. Preliminary experiments indicate that high humidity severely decreases the capacity of the charcoal for organic vapors. 3.2 When two or more substances are known or suspected to be present in the air, such information, including their suspected identities, should be transmitted with the sample since these compounds may interfere with the analysis for vinyl chloride. 3.3 It must-be emphasized that any compound which has the same retention time as vinyl chloride at the operation conditions described in this method is an interference. Hence, retention time data on a single column, or even on a number of columns, cannot be considered as proof of chemical identity. For this reason it is important that a sample of the bulk material be submitted at the same time so that identity(ies) can be established by other means. 3.A If the'possibility of interference exists, separation conditions (column packing, temperature, etc.) must be changed to circumvent the problem. A. Precision and Accuracy The precision and accuracy of the total sampling and analytical method have not been determined. 5. Advantages and Disadvantages of the Method 5.1 The sampling device is small, portable, and Involves no liquids. Interferences are minimal, and most of those which do occur can be eliminated by altering chromatographic conditions. The tubes are analyzed by means of a quick. Instrumental method. The method can also be used for the simultaneous analysis of two or more components suspected to be present in the same sample by simply changing gas chromatographic conditions from isothermal to a temperature-programmed mode of operation. \ J 157 UCC 086573 5.2 One disadvantage of the method is that the amount of sample which can be taken is limited by the number of milligrams that the tube will hold before overloading. When the sample value obtained for the backup section of the charcoal trap exceeds 20% of that found on the front section, the possibility of sample loss exists. During sample storage, volatile compounds such as vinyl chloride will migrate throughout the tube until equilibrium is reached. At this time '33% of this compound will be found in the backup section. This may lead to some confusion as to whether breakthrough has occurred. This migration effect can be considerably decreased by shipping and storing the tubes at -20. 5.3 The precision of the overall method is limited by the reproduci bility of the pressure drop across the tubes. This drop will affect the flow rate and cause the volume to be imprecise, because the pump is usually calibrated for one tube only. Apparatus' 6.1 An approved and calibrated personal sampling pump for personal and area samples whose flow can be determined accurately at 50 milliliters per minute. 6.2 Charcoal tubes: glass tube with both ends flame sealed, 7 cm long with a 6-mm O.D. and a 4-mra I.D., containing 2 sections of 20/40 mesh activated charcoal separated by a 2-mm portion of urethan foam. The activated charcoal is prepared from coconut shells and is fired at 600C prior to packing to remove material possibly absorbed on charcoal. The primary absorbing section contains 100 mg of charcoal, the backup section 50 mg. A 3-mm portion of urethan foam is placed between the outlet end of the tube and the backup section. A plug of silylated glass wool is placed in front of the absorbing section. The pressure drop across the tube must be less than one inch of mercury at a flow rate of 1 2./min. 6.3 Gas chromatograph equipped with a flame ionization detector. 6.4 Column (20 ft x 1/8 in) with 10% SE-30 stationary phase on 80/100 mesh, Chromosorb W, acid washed, silanized with dimethyldichlorosilane solid support. Other columns capable of performing the required separations may be used. * 6.5 A mechanical or electronic integrator or a recorder and some method for determining peak area. 6.6 Two-ml vials which can be sealed with caps containing teflonlined silicone rubber septa. 6.7 Microliter syringes: 10 pi, and convenient sizes for making standards. 158 UCC 066574 6.8 Gas-tight syringes: 1 ml, with open/close valve. 6.9 Pipets: 0.5-m delivery pipets or 1.0-mi. type graduated in 0.1-mA increments. 6.10 Volumetric flasks: 10-mi or convenient sizes for making standard solutions. It is preferable to have plastic stoppers for the volumetric flasks. 7. Reagents 7.1 Spectroquality carbon disulfide. 7.2 Vinyl chloride, lecture bottle, 99.9% minimum purity. 7.3 Toluene, chromatographic quality. 7.4 Bureau of Mines Grade A helium. 7.5 Prepurified hydrogen. 7.6 Filtered compressed air. 8. Procedure 8.1 Cleaning of Equipment. All glassware used for the laboratory analysis should be detergent washed and thoroughly rinsed with distilled water. 8.2 Calibration of Personal Pumps. 'Each personal pump must be calibrated with a representative charcoal tube in the line. This will minimize errors associated with uncertainties in the sample volume collected. 8.3 Collection and Shipping of Samples 8.3.1 Immediately before sampling, the ends of the tube are broken to provide an opening at least one-half the internal diameter of the tube (2 mm). 8.3.2 The smaller section of charcoal is used as a backup and is positioned nearest the sampling pump. 8.3.3 The charcoal tube is placed in a vertical position during sampling, open end pointing upward, to prevent "channelling" of the charcoal. 8.3.4 Air being sampled is not to be passed through any hose or tubing before entering the charcoal tube. 159 UCC 066575 8.3.5 Bulk air samples are taken along with personal samples, i.e. sample 10-20 liters of the air in the environment using a separate charcoal tube. 8.3.6 The flow, time, and/or volume must be measured as accurately as possible. The sample is taken at a flow rate of 50 ml/min. The maximum volume to be sampled should not exceed 5.0 liters (See Section 2.2). 8.3.7 The temperature and pressure of the atmosphere being sampled is measured and recorded. 8.3.8 The charcoal tubes are capped with the supplied plastic caps immediately after sampling. Under no circumstances are rubber caps to be used. 8.3.9 One tube is handled in the same manner as the sample tube (break, seal, and transport), except that no air is sampled through this tube. This tube is labeled as a blank. 8^3.10 Capped tubes are packed tightly before they are shipped to minimize tube breakage during transport to the laboratory. If the samples will spend a day or more in transit, cooling (e.g., with dry ice) is necessary to minimize migration of vinyl chloride to the backup aactlon. 8.3.11 Samples received at the laboratory are logged in and Immediately stored in a freezer (~-208C) until time for analysis. Samples may be stored in this manner for long periods of time with no appreciable loss of vinyl chloride (2 months). It should be pointed out that during long periods of storage (more than 2 weeks), the vinyl chloride will equilibrate between the two sections of charcoal, i.e., will migrate to the backup section. This does not constitute breakthrough. 8.4 Analysis of Samples 8.4.1 Preparation and Desorption of Samples. In preparation for analysis, each charcoal tube is scored with a file in front of the first section of charcoal and broken open. The glass wool is removed and discarded. The charcoal in the first (larger) section is transferred to a small vial containing 1 ml of carbon disulfide. (Note the addition to the CS2 Is Important.) The vial is topped with a 160 UCC 066576 septum cap (See Section 6.6). The separating section of foam is removed and discarded; the second section is transferred to another small vial containing 1 ml of CS2. These two sections are analyzed separately. Tests indicate that desorption is complete in 30 minutes if the sample is stirred occasionally during this period. In any case samples should be analyzed within 60 minutes after addition of CS2. 8.4.2 GC Conditions. The typical operating conditions for the gas chromatograph are: 1. 40 cc/min. (80 psig) helium carrier gas flow 2. 65 cc/min. (20 psig) hydrogen gas flow to detector 3. 500 cc/min. (50 psig) air flow to detector 4. 230C injector temperature 5. 230C manifold temperature (detector) 6. 60C isothermal column temperature (oven). 8.4.3 Injection. The first step in the analysis is the injection of the sample into the gas chromatograph. To eliminate difficulties arising from blowback or distillation within the syringe needle, one should employ the solvent flush injection technique. The 10 u syringe is first flushed with solvent several times to wet the barrel and plunger. Two microliters of solvent are drawn into the syringe to 'increase the accuracy and reproducibility of the injected sample volume. The needle is removed from the solvent and the plunger is pulled back about 0.4 u to separate the solvent flush fromthe sample with a pocket of air to be used as a marker. The needle is then immersed in the sample, and a 5-yaliquot is withdrawn to the 7.4 y mark (2 u solvent + 0.4 piair + 5 p sample 7.4 uA). After the needle is removed from the sample and prior to injection the plunger is pulled back a short distance to minimize evaporation of the sample from the tip of the needle. Duplicate injections of each sample and standard are made. No more than a 3Z difference in area is to be expected. 8.4.4 . Measurement of area. The area of the sample peak is measured by an electronic integrator or some other suitable form of area measurement, and preliminary results a.re read from a standard curve prepared as discussed below. 8.5 Determination of Desorption Efficiency 8.5.1 Importance of determination. The desorption efficiency of a particular compound can vary from one laboratory to another and also from one batch of charcoal to another. Thus, it is necessary to determine at least once the percentage of vinyl chloride that is removed in the ) 161 ucc 066577 desorption process. Desorption efficiency should be determined on the same batch of charcoal tubes used in sampling. Results indicate that desorption efficiency varies with loading (total vinyl chloride on the tube) particularly at lower values, i.e., 2.5 ug. 8.5.2 Procedure for determining desorption efficiency. Charcoal tubes from the same batch as that used in obtaining samples are used in this determination. A known volume of vinyl chloride gas is injected into a bag containing a known volume of air. The bag is made of Tedlar (or a material which will retain the vinyl chloride and not absorb it) and should have a gas sampling valve and a septum injection port. The concentration of the bag may be calculated at room temperature and pressure. A known volume is then sampled through a charcoal tube with a calibrated sampling pump. At least five tubes are prepared in this manner. These tubes are desorbed and analyzed in the same manner as the samples (See Section 8.4). Samples taken with a gas tight syringe from the bag are also injected into the GC. The concentration in the bag is compared to the concentration obtained from the tubes. The desorption efficiency equals the difference betwe n the average weight of the samples and the weight of the blank divided by the average weight of the vinyl chloride standard gas mixture in the bag or Desorption efficiency " Weight on sample - Weight on blank Weight in standard gas mixture Calibration and Standards CAUTION: Laboratory Operations Involving Carcinogens Vinyl chloride has been identified as a human carcinogen and appropriate precautions must be taken in handling this gas. Specifically, the Occupational Safety and Health Administration has promulgated regulations for the use and handling of vinyl chloride. The regulations currently serve as an emergency standard and may be found in 29 CFR. 1910.93q (Section 1910.93q in Title 29 of the Code of Federal Regulations available in the Federal Register, . ,Vol. 39, No. 125, Thursday, June 27, 1974.) Note that the above Is an emergency standard (temporary) and will be replaced by a permanent standard in October of 1974. A series of standards, varying in concentration over the range of interest, are prepared and analyzed under the same GC conditions and during the same time period as the unknown samples. Curves are established by plotting concentration In ug/1.0 mi versus peak area. There are two methods of preparing standards and as long as highly purified vinyl chloride is used, both are comparable. 162 UCC 066578 NOTE: Since no internal standard is used in the method, standard solutions must be analysed at the same time that the sample analysis Is done. This will minimize the effect of day-to-day variations of the FID response. 9.1 Standard Preparation Gravimetric Method - Vinyl chloride is slowly bubbled into a tared 10-ml volumetric flask containing approximately 5 ml of toluene. After 3 minutes, the flask is again weighed. A weight change of 100-300 mg is usually observed. The solution is diluted to exactly 10 ml with carbon disulfide and is used to prepare other standards by removal of aliquots with different sized syringes. Subsequent dilution of these aliquots with carbon disulfide results in a series of points that are linear from the range of 0.2 nanograms per injection, the minimum detectable amount of vinyl chloride, to 1.5 micrograms per injection. Volumetric Method - A 1-ml gas sample of pure vinyl chloride is drawn into a gas-tight syringe and the tip of the needle is inserted into a 10-ml volumetric flask containing approximately 5 ml of CSj. The plunger is withdrawn slightly to allow the CS2 to enter the syringe. The action of the vinyl chloride dissolving in the CS2 creates a vacuum and the syringe becomes filled with the solvent. An air bubble (~2Z) is present and was found to be due to the void volume in the needle of the syringe. The solution is returned to the flask and the syringe is rinsed with clean CS2 end the washings added to the volumetric. The volumetric is then filled to the mark with CS2* Other standards are then prepared from this stock solution. . Standards are stored in a freezer at -20C and are found to be stable at this temperature for three days. Tight-fitting plastic tops on the volumetries seem to retain the vinyl chloride better than ground glass stoppers. 10. Calculations 10.1 The weight, in yg, corresponding to each peak area is read from the standard curve for vinyl chloride. No volume corrections are needed, because the standard curve is based on yg/1.0 ml CS5 and the volume of sample injected is identical to the volume of the standards injected. 10.2 Corrections for the blank must be made for each sample. Correct yg - ygs - yg*, where: Pgs pg found in front section of sample tube Pgb - Ug found in front section of blank tube A similar procedure is followed for the backup sections. 163 UCC 066579 10.3 The corrected amounts present in the front and backup sections of the same sample tube are added to determine the total measured amount in the sample. 10.A This total weight is divided by the determined desorption efficiency to obtain the total ug per sample. 10.5 The volume of air sampled is converted to standard conditions of 25C and 760 mm Hg. where: P 298 Vs - V x 760 x T+273 Vg volume of air in liters at 25#C and 760 mm Hg V volume of air in liters as measured P * Barometric pressure in mm Hg T "Temperature of air in degree centigrade 10.6 10.7 The concentration of the organic solvent in the air sampled can be expressed in mg/m3. which is numerically equal to ug/llter of air . .. total ur (Section 10.A) mg/m3 - Pg/t - ------------- v---------------------- 8 Another method of expressing concentration is ppm, defined as u of vinyl chloride/liter of air ppm y of vinyl chloride/Vs wherei ppm ug of vinyl chloride 2A.A5 Vs x 62.5 2A.A5 molar volume at 25*C and 760 mm Hg 62.5 molecular weight of vinyl chloride 11. References 11.1 Hill, R.H., C.S. McCanmon, A.T. Saalwaechter, A.W. Teass, and W.J. Woodfin, "Determination of Vinyl Chloride in Air," in preparation. 11.2 White, L.D., D.G. Taylor, P.A. Mauer, and R.E. Kupel, "A Convenient Optimized Method for the Analysis of Selected Solvent Vapors in the Industrial Atmosphere," Am. Ind. Hyg. Assn. J. 31, 225 (1970). 164 ucc 066580 ia t-- + Table Plant A Vinyl Chloride Sample Data Job Classification Operator Date 12/3/74 12/2/74 Loader 12/3/74 - 12/2/74 Maintenance Worker 12/3/74 Foreman Lab Tech 12/2/74 ' 12/3/74 12/3/74 ASEA SAMPLES General Area ' 12/2/74 1------------- "" Shift No. Tubes Combined Sample Volume (liters) 11 1 1 21 1 1 1 11 1 1 1 21 1 1 1 11 1 1 1 21 1 1 1 11 1 1 11 1 1 1 1 1 1 1 3.34 4.24 3.53 4.01 3.80 3.84 2.68 4.34 4.70 4.13 4.22 3.78 4.04 4.30 2.91 3.36 3.22 3.36 3.33 5.14 4.76 4.60 4.67 4.62 3.92 3.85 4.32 4.30 4.49 4.52 5.05 5.14 5.28 5.56 Sample Concentration ppm 0.21 2.45 0.13 0.74 0.22 1.57 0.17 0.10 0.74 1.62 1.89 0.17 0.32 0.35 0.41 0.25 0.09 0.02 0.32 0.04 0.08 0.20 0.13 0.03 0.04 0.21 0.37 0.07 0.04 0.15 4.36 0.27 0.05 0.32 21 1 1 1 1 3.77 3.63 3.49 3.44 9.18 0.56 2.19 4.03 1.10 1.03 165 ucc 066581 Job Classification General Area Loading Area Plant A - (continued) Vinyl Chloride Sample Data Date 12/3/74 12/2/74 No, Tubes Sample Volume Shift Combined (liters) 11 1 1 1 21 1 1 1 3.18 5.04 4.45 3.92 9.66 7.74 6.65 7.30 Sample Concentration ppm 1.28 5.89 2.03 1.33 <0.01 <0.01 0.01 0.01 166 UCC 066582 Table D-2 Plant B Job Classification Operator - Loader Maintenance Worker Date 12/10/74 12/12/74 I2/U/74 12/12/74 12/10/74 No. Tubes Sample Volume Shift Combined (liters) 21 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 31 1 1 1 1 i 1 1 1 1 1 1 1 1 1 1 11 1 1 1 1 31 1 1 1 11 1 1 1 4.02 3.83 3.96 4.30 3.56 3.65 3.25 3.54 4.08 3.28 2.59 3.19 4.27 4.54 4.57 4.40 4.32 4.52 4.42 4.46 4.08 4.02 3.93 3.81 3.83 3.70 3.85 4.01 4.41 3.37 3.69 3.52 2.61 2.92 2.66 4.57 4.22 4.54 4.62 4.88 4.48 3.85 3.48 4.25 3.54 Sample Concentration PPM 3.46 0.46 0.81 0.18 0.07 0.07 0.10 0.04 0.06 0.14 0.11 0.13 0.01 0.06 0.04 0.05 3.00 .0.29 0.73 0.13 0.10 0.08 0.11 0.13 0.20 0.06 0.02 0.09 0.10 0.06 0.06 0.07 10.80 28.52 13.12 19.32 14.63 84.77 3.00 7.13 11.59 0.33 0.26 0.01 0.08 167 UCC 066583 Plant B - (continued) Job Classification Lab Tech - . AREA SAMPLES Compressor Area Loading Area Stock Room Cracker Area Date 12/11/74 12/12/74 12/10/74 12/12/74 12/11/74 12/11/74 12/11/74 No. Tubes Shift Combined Sample Volume (liters) 11 1 1 1 1 1 1 1 31 1 1 1 3.67 4.26 4.16 4.93 4.71 4.20 3.98 3.98 4.26 3.87 3.75 3.54 Sample Concentration ppm 0.11 0.55 0.88 0.06 0.06 0.02 0.12 0.06 0.16 <0.01 0.09 0.03 11 3.17 1 3.12 1 3.30 1 3.22 31 3.50 1 3.23 1 3.34 1 ' 3.21 11 2.36 1 2.66 1 2.48 1 3.88 1 4.20 11 4.71 1 4.86 1 4.80 1 4.97 1 1 14.22 0,12 0.12 0.14 0.25 0.17 0.15 0.12 0.09 1.22 0.09 0.20 0.36 0.31 0.06 <0.01 0.05 0.38 0.09 168 UCC 066584 Job Classification Operator Table D-3 Plant C Date 12/16/74 12/17/74 Shift No. Tubes Combined Sample Volume (liters) 21 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 11 1 1 1 1 1 1 1 1 1 1 1 1 1 1 4.93 4.94 4.85 4.62 4.67 4.57 4.36 4.73 4.69 4.56 4.34 4.36 5.04 3.91 4.82 5.33 4.55 4.50 4.84 4.62 5.00 5.31 5.24 5.49 4.87 4.91 4.72 4.82 4.97 5.18 5.14 4.70 4.68 4.43 4.48 4.17 4.53 4.17 3.98 3.49 4.68 4.61 4.72 Sample Concentration ppm 6.24 0.22 0.21 1.95 3.35 0.20 0.25 0.10 0.46 0.19 0.66 0.09 0.11 0.21 0.21 0. 75 0.40 0,20 0.17 0.13 0.11 0.21 0.21 0.33 0.28 0.22 0.20 0.11 18.2 0.61 0.37 0.88 0.49 0.57 0.34 0.27 0.62 0.38 0.27 0.22 0.51 0.15 0.11 169 ucc 066585 Plant C - (continued) Job Classification Operator Loader . Maintenance Worker Lab Tech Date 12/17/74 12/18/74 12/19/74 12/17/74 12/18/74 No. Tubes Sample Volume Shift Combined (liters) Sample Concentration _________________________________________________________________ _- 11 4.70 0,24 14.760.13 1____________ 4.79 1 4.68 1 4.83 1 4.63 1 4.40 1 4.78 1 4.95 1 5.03 1 4.80 1 4.85 1 4.55 11 4,05 1 4.12 1 4.08 1 3.98 1 3.94 1 3.90 1 4.14 1 3.76 21 4.51 1 4.51 1 5.15 1 . 3.29 1 3.85 1 3.95 0.09 0.12 0.22 0.12 0.08 0.15 0.20 0.10 0.10 0.13 0-19 1.50 0.98 0.34 0.99 0.67 2.31 0.35 0.38 17.6 0.06 21.8 0.23 6.19 0.34 1 5.06 20.1 1 1.82 1 3.97 1 3.90 1 5.64 1.13 1.74 0.09 14.6 1 11 1 2.75 5,22 5.19 0.37 0.55 0.52 1 5.24 1 5.08 0.28 0.25 1 4.18 1 4.30 1 4.24 1 4.17 0.41 0.32 0.16 0.32 11 1 1 1 5.07 4.98 3.71 4.71 0.03 1.01 0.06 0.04 170 UCC 066586 Job Classification Lab Tech Lab Tech AREA SAMPLES Scrubbers ' General Plant VC Reflux Pumps Plant C - (continued) Date 12/18/74 12/19/74 12/18/74 12/18/74 12/19/74 Shift No. Tubes Combined Sample Volume (liters) 11 1 1 1 21 1 1 1 1 1 1 1 5.13 5.23 5.32 5.29 4.88 4.62 4.76 4.89 5.28 4.07 5.04 5.03 Sample Concentration . ppm 0.02 0.27 0.07 0.04 0.19 0.10 0.08 0.06 0.09 0.11 0.09 0.07 11 3.27 t 1 3.26 1 3.32 1 3.45 1 1 17.39 21 4.82 1 3.53 1 3.63 1 3.68 7.06 1.60 1.61 2.73 0.57 0.59 1.15 5.19 3.17 171 J ucc 066567 Table D-4 Plant D Solvent Process Area Job Classification Operator-Reactor Area Date 6/15/74 6/19/74- Operator-Drying Area Helper Bagger 6/15/74 6/19/74 6/15/74 6/19/74 Maintenance Worker AREA SAMPLES Control Room 6/15/74 6/15/74 6/19/74 Reactor Bldg. Solvent Recovery Bldg. Packaging Bldg. 6/19/74 6/19/74 6/19/74 No. Tubes Sample Volume Shift Combined (liters) 12 3.43 1 1.52 3 3.26 1 0.94 1 2.02 1 1.54 1 1.63 3 6.71 1 1.75 2 2.65 14 7.28 6 5.14 7 10.56 5 15.92 4 6.72 24 7.07 4 4.94 4 4.70 4 7.44 4 9.12 13 3.16 1 1.24 17 7.21 24 4.43 13 6.59 1 5 13.15 5 7.63 5 3.94 5 8.30 24 4.24 4 2.19 11 2.16 1 2.72 Sample Concentration ppm ND 77.0 1.6 5.4 ND 2.9" 5.4 5.4 ND ND 2.6 0.7 0.9 9.4 11.1 1.2 0.2 0.7" 7.8 8.8 2.4 ND 3.7 0.4 2.3 0.6 1.1 ND 0.9 1.0 ND 1.3 ND 13 2 15 6 24 4 13 23 13 2 172 4 3.95 4.77 11.13 12.43 7.97 4.22 6.55 8.64 7.93 5.35 ilL 4.56 2.6 1.5 0.3 0.4 0.3 0.2 1.9 1.3 7.1 6.5 2.3 0.9 ucc 066588 Job Classification Operator-Reactor Area - / Bagger Foreman Maintenance Worker AREA SAMPLES Control Room General Area Plant D - (continued) Modified Emulsion Resin Area Date 6/13/74 6/14/74 6/17/74 6/18/74 6/18/74 6/13/74 6/14/74 6/13/74 Shift No. Tubes Combined Sample Volume (liters) 11 2 2 2 1 5 1 1 1 1 1 1 1 1 1 14 2 3 2 5 4 ,1 3 3 4 14 12 13 12 1.65 1.97 3.51 2.75 1.52 6.71 0.91 1.51 2.40 1.79 1.52 1.58 0.87 1.03 1.50 3.71 1.02 5.24 3.12 6.55 8.44 3.32 6.25 3.96 3.38 5.58 8.67 1.80 Sample Concentration ppm 4.0 2.4 <0.1 0.1 2.6 1.2 4.2 ND 2.6 3.0 ND ND ND 2.7 2.1 1.6 3.5 ND 0.3 ND 1.2 3.9 0.4 2,3 2.3 0.1 0.4 0.2 6/13/74 6/14/74 6/17/74 6/18/74 6/18/74 1 1 3 5 5 6 6 5 3 3.14 4.75 3.60 7.67 9.33 9.23 2.00 ND 2.0 2.4 1.9 0.8 1.1 1.4 173 ucc 066589 Plant D - (continued) Emulsion Resin Area Job Classification Operator-Reactor Area Date 6/11/74 6/12/74 6/13/74 Helper-Reactor Area 6/18/74 6/11/74 Operator-Dryer Area Bagger Bagger AREA SAMPLES Control Room 6/12/74 6/13/74 6/18/74 ' 6/12/74 " 6/13/74 6/11/74 6/12/74 6/13/74 6/18/74 6/11/74 6/12/74 6/13/74 6/11/74 6/12/74 6/13/74 6/18/74 No. Tubes Sample Volume Shift Combined (liters) 11 1.99 2 3.61 2 3,34 2 1.91 14 1.89 4 2.61 3 3.09 4 6.98 15 3.33 1 1.97 1 0.90 2 4.83 12 2.45 3 3.92 13 8.79 3 $.19 3 6.41 2 6.43 12 2.54 2 4.10 4 4.60 1 3 11,14 1 2.39 4 5.47 11 1.39 1 3.96 14 5.06 14 6.65 17 7.71 14 6.80 4 4.34 14 4.98 4 5.15 12 2.41 12 3.57 11 2.87 12 2.46 Sample Concentration ppm 5.3 9.3 12.9 29.4 6.2 15.1 7.6 1.5 22.9 10.2 4.4 0.1 9.4 29.8 3.6 3.6 6.6 11.0 11.4 13.4 0.9 77.0 0.7 17.0 6.1 82.8 5.2 9.6 1.3 1.4 0.1 2.6 2.9 3.6 22.0 0.3 15 14 16 14 5.41 8.96 9.20 6.70 11.1 5.6 11.7 1.2 174 ucc 066590 Table D-5 Plant E Mass Resin Area Job Classification Operator-Reactor Area Date 8/5/74 8/6/74 - 8/7/74 8/8/74 8/9/74 Helper-Reactor Area 8/5/74 8/6/74 Shift No. Tubes Combined Sample Volume (liters) 21 1 2 2 21 1 1 1 1 1 1 1 1 1 11 1 1 1 1 1 1 11 1 1 1 1 1 1 1 1 31 1 1 1 1 1 21 2 1 1 2 21 1 1.13 1.05 2.47 0.87 1.41 0.85 1.57 1.05 1.05 1.23 1.-31 0.75 0.83 1.05 1.22 1.55 0.98 0.93 0.99 1.45 0.97 1.17 0.87 0.61 0.94 1.63 0.98 0.77 2.04 2.-02 1.56 1.36 1.15 1.40 0.88 1.10 0.92 1.48 1.08 2.71 0.43 1.15 1.14 Sample Concentration ppm 2.2 ND 6.3 9.3 7.3 4.0 19.9 ND ND ND 2.8 7.6 7.0 3.0 4.2 2.1 ND ND 2.9 2.8 3.4 2.5 22.6 4.9 ND 14.8 ND 13.7 ND 1.5 ND ND ND ND ND 1.6 2.9 2.7 20.7 2.0 13.4 1.8 1.5 UCC 175 066591 Job Classification Helper-Reactor Area - Helper-Reactor Area Basher AREA SAMPLES Control Room Plant E - (continued) Mass Resin Area Date Shift No. Tubes Combined Sample Volume (liters) 8/6/74 8/7/74 2 1 8/8/74 1 / 8/9/74 8/9/74 3 3 8/8/74 1 1 1 1 1 1 2 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 1.65 1.09 2.14 0.19 0.93 2.61 2.99 1.59 0.58 0.55 1.06 1.10 1.03 2.34 1.73 0.87 1.21 0.19 1.27 1.44 1.19 1.48 1.12 1.21 2.59 2.15 1.31 Sample Concentration .ppm 2.0 4.7 0.9 ND 2.3 2.2 5.1 1.8 4.4 5.3 11.1 14.3 ND 11.7 71.4 10.9 1.4 ND ND ND 5.9 ND ND ND 3.1 ND ND 8/5/74 8/6/74 2 2 8/7/74 8/8/74 8/9/74 1 1 3 2 2 1 1 1 1 1 2 2 1 1 1 1 1 1 3.00 3.28 1.42 2.27 1.42 1.45 1.22 3.16 3.61 1.53 1.60 1.44 0.95 1.27 1.85 3.8 3.6 ND 0.9 ND 2.0 1.7 1.8 1.8 ND ND ND ND ND ND 176 UC-C 086592 Plant E - (continued) Suspension Resin Area Job Classification Operator-Reactor Area Date 8/5/74 8/6/74 8/7/74 8/8/74 8/9/74 - No. Tubes Sample Volume Shift Combined (liters) 21 2 1 1 1 2 2 1 1 21 1 1 1 1 1 1 1 1 1 1 11 1 2 1 1 2 1 2 1 4 11 1 1 1 1 1 1 1 1 31 1 1 1 1 1 0.63 2.14 1.81 1.09 0.60 1.47 1.71 0.93 0.53 0.89 1.55 1.20 1.36 1.55 0.91 1.37 0.44 1.50 1.06 0.22 0.71 0.80 1.70 0.91 1.06 1.95 1.07 2.17 1.20 1.20 0.64 1.36 2.00 1.99 0.51 0.51 1.63 2.39 1.93 0.98 0.98 0.70 0.52 0.82 0.79 Sample Concentration ppm 8.0 4.7 2.3 8.7 3.1 23.8 11.5 6.0 10.7 25.8 11.5 30.6 18.6 36.8 37.9 51.4 80.0 8.1 14.5 22.9 245.0 8.0 6.6 ND 3.1 1.0 1.6 3.8 4.7 1.9 4.7 8.4 8.3 3.4 7.6 22.4 2.2 8.9 ND 1.7 ND 54.5 ND ND 6.2 177 ucc 066593 Plant E - (continued) Suspension Resin Area Job Classification Operator-Reactor Area Date 8/9/74 Helper-Reactor Area BaRRer 8/5/74 8/6/74 s/y/74 8/7/74 AREA SAMPLES Office 8/8/74 8/5/74 876774 877/74 8/8/74 8/9/74 No. Tubes Sample Volume Shift Combined (liters) Sample Concentration 31 1 1 1 1 1 1 1 1 22 2 21 1 1 11 1 1 12 1 2 1 2 1 12 2 2 2 0.52 0.42 0.99 0.37 0.51 1.03 2.46 0.79 1.22 1.60 3.02 0.64 2.34 1.52 1.59 1.16 0.77 2.77 1.22 3.12 1.33 0.83 0.11 2.56 2.61 4.35 2.78 191.0 ND 1.8 28.1 158.8 27.6 2.5 46.7 5.0 7.2 3.2 ND 23.6 16.0 6.9 16.9 ND ND ND ND ND ND ND 0.6 0.7 0.9 ND 22 1 21 1 1 1 1 12 2 1 11 1 1 1 31 1 1 1 3.13 0.61 1.50 0.59 0.65 2.25 0.56 2.27 2.99 0.80 1.04 2.50 1.05 1,07 0.41 1.04 0.56 0.71 8.3 8.2 43.09 23.8 8.7 96.5 50.6 ND 2.2 4.1 2.6 4.1 1.8 6.4 ND ND ND ND 178 ucc G66SQ4 Table D-6 Plant F Emulsion Resin Area Job Classification Operator-Reactor Area Date 12/4/74 12/5/74 * 12/6/74 Helper-Reaction Area Helper-Reactor Area 12/4/74 12/4/74 12/5/74 Shift Ho. Tubes Combined Sample Volume (liters) 11 1 1 1 1 1 11 1 1 1 1 1 1 1 1 1 1 11 1 1 1 1 1 1 1 1 1 1 1 11 1 11 1 1 1 11 1 1 1 1 1 1 1 1 4.31 5.10 5.54 4.74 0.02 1.91 4.30 5.39 5.76 5.14 3.28 2.24 5.7 84.62 7.22 5.67 6.30 4.87 9.11 5.80 5.64 7.30 5.28 4.94 9.24 6.20 4.24 7.63 5.45 4.32 4.23 9.09 8.63 4.99 5.19 4.82 5.97 4.75 4.76 2.85 6.10 4.74 2.77 5.94 Sample Concentration ppm 5.1 6.1 6.7 33.8 98.0 8.4 6.5 3.9 6.3 4.7 13.5 2.3 3.8 6.8 13.4 12.1 31.5 5.1 6.2 5.6 6.8 5.5 7.4 6.8 12.8 4.4 5.2 6.3 6.4 6.9 3.5 5.6 6.5 7.3 5.0 19.4 6.1 10.1 68.0 10.3 11.3 103.8 16.4 36.1 179 UCC 066595 Job Classification Helper-Reactor Area Maintenance Worker Operator-Dryer Area Operator-Dryer Area ielper-Dryer Area Plant F - (continued) Emulsion Resin Area Date 12/6/74 12/6/74 12/9/74 12/10/74 12/10/74 12/11/74 12/9/74 12/10/74 mum No, Tubes Sample Volume Shift Combined (liters) 11 5.27 1 7.06 1 6.01 1 3.05 1 5.11 1 0.64 i 4.10 l 8.97 i 5.99 1i 7.10 1 i 12.11 i 7.43 i 9.78 i 5.84 i 11.00 i 5.24 1i 6.97 i 12.19 1i 6.47 l 12.10 i 6.50 i 9.48 l 5.74 1i 4.21 i 4.92 i 5.27 l 2.85 l 4.46 l 4.71 i 3.95 l 5.83 l 5.49 l 3.99 l 6.12 l 4.62 1l 9.05 l 5.53 i 11.96 l 6.59 1l 8.38 l 4.07 1i 6.63 l 8.72 i 7.06 Sample Concentration ppm 16.2 8.7 7.4 12.5 10.2 9.2 21.1 8.8 5.0 1.4 3.6 5.5 4.2 3.9 4.3 5.4 1.6 1.2 1.3 1.2 1.4 1.9 1.5 9.6 1.4 0.5 9.5 3.8 2.6 4.9 2.3 2.9 4.5 1.9 4.8 2.4 3.3 2.3 3.6 0.6 0.8 1.0 0.7 0.7 180 ucc 066598 Plant F - (^continued) Emulsion Resin Area Job Classification Bagger Date 12/9/74 - AREA SAMPLES Control Room-Reactor Area 12/4/74 12/5/74 Operators Desk-Reactor Area 12/6/74 12/4/74 12/5/74 12/6/74 Shift No. Tubes Combined Sample Volume (liters) 1 1 10.71 1 6.82 1 10.94 1 6.75 1 10.84 1 5.60 1 17.20 1 10.31 1 11.13 1 7.09 Sample Concentration .. PPm 2.0 3.2 2.5 3.4 3.5 4.1 1.0 0.2 2.1 2.6 11 1 11 1 1 11 1 11 5.02 4.70 3.92 5.50 5.43 8.54 6.16 6.18 1 4.86 11 3.92 1 5.83 1 1 12.18 1 9.07 2.5 1.4 3.7 1.9 1.0 5.9 3.6 7.4 8.5 15.9 7.9 2.2 1.4 181 UCC 066597 Plant F - (continued) Suspension Resin Area - Old Job Classification Operator-Reactor Area Date 12/4/74 12/5/74 12/6/74 Helper-Reactor Area 12/4/74 12/5/74 No. Tubes Sample Volume Shift Combined Cliters) 11 1 1 1 1 1 1 1 1 1 1 1 11 1 1 1 1 1 1 1 1 11 1 1 1 1 1 1 11 1 1 1 1 1 11 1 1 1 1 1 1 1 1 1 3.13 2.47 1.76 2.94 1.79 2.26 4.01 3.23 2.25 3.04 3.28 2.15 4.69 2.76 5.68 5.14 3.13 2.88 3.61 4.81 4.42 0.68 0.43 3.01 0.53 2.49 2.16 4.36 2.86 3.02 2.19 2.87 2.70 1.69 2.90 2.33 4.20 0.76 3.55 3.05 5.73 4.44 3.33 4.77 Sample Concentration ppm 18.3 16.5 12.2 9.9 9.6 11.6 12.8 5.7 20.0 5.5 160.6 114.3 15.0 6.1 9.0 13.8 19.7 5.9 5.3 8.1 11.4 31.1 33.7 13.3 9.6 11.8 5.6 6.2 8.8 33.4 16.3 7.6 30.3 11.4 12.8 6.2 6.4 11.9 13.1 1.8 18.3 21.2 13.8 28.3 182 ucc 066598 Job Classification Helper-Reactor Area * Helper-Reactor Area Maintenance Worker AREA SAMPLES Control Room Plant F - (continued) Suspension Resin Area - Old Date 12/5/74 12/6/74 12/6/74 12/5/74 Shift No. Tubes Combined Sample Volume (liters) 11 1 1 1 1 1 1 1 1 1 1 1 11 1 1 1 1 1 11 1 1 1 11 1 1 1 4.43 3.30 5.37 5.18 4.11 2.82 4.46 3.25 2.67 3.85 3.45 5.85 1.37 2.66 3.77 1.55 4.85 3.42 1.11 5.37 4.30 1.94 3.43 2.98 3.88 4.31 Sample Concentration ppm 8.1 15.7 27.0 9.8 11.2 5.8 5.8 5.9 1.3 12.1 17.3 18.3 160.5 13.6 57.8 10.9 7.7 51.3 4.9 10.3 9.5 8.7 12.8 4.2 6.5 5.5 12/4/74 12/5/74 12/6/74 1 1 1 1 1 1 1 1 1 1 1 1 3.26 3.47 2.55 2.85 5.66 4.26 4.10 3.08 4.54 8.3 9.9 11.5 1.8 4.2 9.4 5.1 1.0 4.8 183 UCC 066599 Plant F - (continued) Suspension Resin Area - New Job Classification Operator-Reactor Area Date 12/9/74 12/10/74 Operator-Dryer Area 12/9/74 12/10/74 No. Tubes Sample Volume Shift Combined (liters) 11 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 11 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 11 1 1 11 1 1 5.56 6.41 5.14 6.02 7.02 5.80 4.66 5.69 4.67 3.99 6.83 3.74 4.27 5.99 4.29 5.46 7.17 4.82 3.80 8.15 5.37 6.35 7.32 4.77 4.45 5.55 4.58 5.14 6.63 5.14 3.9L 7.90 4.33 4.21 6.38 4.42 3.93 5.81 5.42 4.84 7.65 5.31 Sample Concentration 9.8 2.7 2.8 4.1 5.4 5.7 2.6 4.5 5.9 6.9 4.3 6.8 7.8 19.8 78.6 4.4 55.1 3.6 0.8 1.1 0.8 0.8 1.1 1.2 2.1 1.3 7.2 0.8 1.3 6.4 4.1 2.3 13.3 14.4 2.8 2.8 8.2 3.4 6.1 1.1 1.2 21.0 184 UCC 066600 Plant F - (continued) Suspension Resin Area - New Job Classification Date AREA SAMPLES Control Room-Reactor Area 12/9/74 12/10/74 Shift No. Tubes Combined Sample Volume (liters) Sample Concentration opm 11 3.19 1 5.17 1 4.09 11 6.82 1 11.22 1 7.27 1.1 1.4 1.6 0.1 0.1 0.1 185 UCC 066601 Job Classification Compounding Personnel Date 2/4/75 2/3/75 Extrusion Personnel 2/3/75 2/4/75 2/6/75 Extrusion Personnel Lab Personnel 2/5/75 2/5/75 2/6/75 Miscellaneous Personnel 2/4/75 2/5/75 Table D-7 Plant G Shift No. Tubes Combined Sample Volume (liters) 11 1 1 1 11 1 1 1 11 1 1 1 1 1 1 1 11 1 1 1 1 1 1 1 11 1 1 1 11 1 1 11 11 1 1 1 11 1 1 1 11 1 1 1 1 4.60 4.64 6.21 3.15 5.02 2.50 3.71 3.69 5.42 2.67 4.00 4.06 5.92 2.91 4.41 4.45 4.75 4.79 6.16 3.33 3.99 4.02 5.76 3.44 4.44 5.76 4.30 2.85 4.79 4.69 5.65 3.78 4.73 6.15 3.87 3.83 5.10 3.58 4.83 4.60 4.71 4.45 6.22 2.74 4.49 Sample Concentration ppm <0.01 0.01 <0.01 0.02 <0.01 <0.01 <0.01 <0.01 <0.01 ND ND <0.01 <0.01 <0.01 <0.01 <0.01 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 . 0.01 0.02 0.01 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.01 ND 0.01 0.01 0.01 0.01 186 UCC 066602 Plant G - (.continued) Job Classification Date Miscellaneous Personnel 2/5/75 2/6/75 AREA SAMPLES Extruder Area 2/5/75 ' 2/6/75 Blending Room 12/3/75 12/4/75 Shift Mo. Tubes Combined Sample Volume (liters) 11 11 1 11 1 1 1 4.51 5.71 3.29 4.26 5.52 4.60 3.15 Sample Concentration PPm 0.01 <0.01 0.01 <0.01 <0.01 <0.01 <0.01 11 1 1 1 11 1 1 1 11 1 1 1 11 1 1 1 4.88 4.71 6.08 3.83 4.60 6.25 4.67 3.16 5.01 2.56 3.76 3.91 3.94 4.22 5.69 3.17 0.02 0.01 0.01 0.01 0.01 0.01 0.01 <0.01 <0.01 0.01 ND ND <0.01 ND <0.01 <0.01 187 UCC 066603 Job Classification Compounding Personnel Date 2/10/75 2/II/75 Extrusion Personnel * 2/10/75 27ll/75 Molding; Personnel 2/10/75 2/11/75 Lab Personnel 2/10/75 2/11/75 Maintenance Personnel 2/10/75 2/11/75 Table D-8 Plant H Shift 1 1 1 1 1 1 1 1 1 1 No. Tubes Combined Sample Volume (liters) Sample Concentration 4.12 4.11 4.52 4.25 4.47 4.45 4.55 4.59 4.44 4.74 4.66 4.48 4.57 4.66 4.62 4.63 4.36 3.82 4.55 4.44 4.54 4.62 4.14 4.66 4.58 4.45 4.35 4.55 3.85 4.49 4.53 4.33 4.49 4.71 5.52 4.41 4.80 4.90 4.80 4.90 4.35 4.74 4.41 4.35 4.70 4.72 _________________ 0.03 0.06 0.02 0.01 0.15 0.11 0.27 0.11 0.02 0.01 0.01 0.02 0.02 0.01 0.01 0.01 0.01 0.01 <0.01 <0.01 0.01 <0.01 <0.01 <0.01 0.03 0.02 0.02 0.01 0.01 <0.01 <0.01 <0.01 0.05 0.06 0.01 0.02 0.04 0.01 0.02 0.01 0.02 0.01 0.01 0.01 0.02 <0.01 188 UCC 066604 Plant H. - (continued) Job Classification Maintenance Personnel AREA SAMPLES Mixing Area Date 2/11/75 2/10/75 No* Tubes Sample Volume Shift Combined (liters) 1 4.64 4.69 Sample Concentration PPtn <0.01 <0.01 1 4.39 0.24 4.39 0,43 4.40 0.13 4.37 0.68 189 ucc 066605 Job Classification Plastisol Dipping Personnel Lab Personnel Date 2/12/75 2/13/75 2/13/75 Table D-9 Plant I No. Tubes Shift Combined Sample Volume (liters) 5.17 5.44 5.13 5.99 4.82 4.30 5.10 4.89 4.73 4.74 5.11 5.24 4.84 4.47 5.33 5.22 5.58 5.16 6.02 6.06 5.17 4.86 5.49 5.23 4.74 4.29 4.64 5.29 5.36 4.77 5.19 6.38 5.29 4.96 5.19 5.90 4.92 4.43 4.59 5.52 4.83 4.77 5.18 5.08 Sample Concentration _____ EKB _ 0.06 <0.01 <0.01 ND 0.06 0.01 <0.01 ND 0.04 0.01 ND ND 0.03 0.01 <0.01 ND 0.02 0.02 <0.01 <0.01 0.02 0.01 <0.01 ND <0.01 ND <0.01 ND <0.01 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ucc 066606 Job Classification AREA SAMPLES Mixing Area Plant I - (continued) Date 2/13/75 Mo. Tubes Sample Volume Shift Combined (liters) 1 5.80 4.88 4.93 5,51 Sample Concentration PP ND ND ND ND 191 UCC 066607 Table D-10 Plant J Job Classification CompoundingPersonnel Date 2/17/75 2/18/75 Calender Personnel Extrusion Personnel 2/17/75 2/18/75 2/19/75 2/19/75 Molding Personnel 2/17/75 Miscellaneous Personnel 2/19/75 Shift 1 1 1 1 1 1 1 1 No, Tubes Sample Volume Combined (liters) Sample Concentration ___________________________________________________ 4.80 ND 4,99 ND 5.03 ND 5.49 4.62 4.64 5.39 4.21 4.78 ND ND ND ND ND ND 4.69 5.39 4.46 5.12 ND ND ND ND 4,67 ND 5.28 5.64 5.01 4.97 ND ND ND ND 5.51 4.45 5.30 ND ND ND 5.03 5.31 ND ND 6.35 4.93 4.45 4.84 ND ND ND ND 5.88 4.48 ND ND 3.94 ND 4.24 ND 5.25 ND 4.04 ND 4.06 4.47 ND ND 5.40 ND 5.29 4.91 7.03 5.37 ND ND ND ND 4.84 4.13 4.30 ND ND ND 5.23 ND 192 UCC 066608 Job Classification AREA SAMPLES Mixing Area Plant J (continued) Date 2/19/75 No, Tubes Sample Volume Shift Combined (liters) Sample Concentration ppm _ 1 4.20 ND 4.06 ND 2.58 ND 6.18 ND UCC 066609 Job Classification Compounding Personnel Date 3/11/75 3/12/75 - Calender Personnel 3/12/75 Maintenance Personnel AREA SAMPLES Blender Area 3/13/75 3/13/75 3/14/75 Table D-ll Plant K Shift No. Tubes Combined Sample Volume Cliters) 1 10.73 10.15 9.49 9,50 1 9.74 9.51 10.71 10.38 2 9.09 8.51 9.03 8.64 1 10.32 10.29 2 8.71 9.05 1 9.58 9.63 1 8.89 8.73 Sample Concentration ppm ND ND ND ND 0.13 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 ND <0.01 ND 1 10.63 < 0,01 11.46 < 0.01 8.77 < 0.01 10.09 < 0.01 194 UCC 066610 Table D-12 Plant L Job Classification Compounding Personnel Date 3/17/75 ' Calender Personnel 3/18/75 3/19/75 3/18/75 * Pelletizer Personnel 3/18/75 3/19/75 Pelletizer Personnel 3/19/75 Lab Personnel 3/19/75 Shift No. Tubes Combined Sample Volume Cliters) 1 8.39 5.32 10.53 7.11 10.91 7.37 10.52 05 9.59 5.10 4.88 8.41 1 9.88 12.90 1 10.62 10.86 1 8.80 11.16 10.49 10.42 9.17 11.48 7.98 9.63 1 11.27 11.39 1 8.27 9.64 4.58 15.77 10.23 1 10.18 9.31 3.61 8.27 9.64 10.62 11.78 Sample Concentration ........ppm 0.69 0.54 0.68 0.46 0.53 0.58 0.60 0.37 0.32 0.48 0.26 0.24 0.39 0.31 0.13 0.14 1.68 1.92 1.15 2.44 1.05 1.36 0.50 1.56 0.26 0.13 0.38 0.02 0.76 0.02 0.57 0.13 0.48 0.03 0.38 0.02 0.68 0.02 195 UCC 066611 Job Classification Compounding Personnel Date 4/9/75 4/10/75 Calender Personnel 4/9/75 Table D-13 Plant M No, Tubes Sample Volume Shift Combined (liters) 1 9.27 9.20 9.20 11.34 7.37 8.14 9.84 8.83 9.43 10.03 10.21 8.38 10.10 8.83 8.48 8.82 8.81 8.35 10.09 9.82 11.70 11.42 1 8.22 8.79 Samplo Concentre tion opm <0.01 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <6.01 <0.01 <0.01 <0.01 <6.01 .0.01 <0.01 <0.01 ND <0.01 <0.01 0.02 0.02 0.02 0.02 o.c: 0.02 196 UCC 066612