Document aJ5qyKK2jMKjpGQB7rQvDYM3Y

' Bibliography Page Three 28- Suciu, J., Drejman, I., and Valaskii, M., (1963), Contributions to the study of disease by vinyl chloride. Med. Interna. 15. 967. Tabershaw, I.R., and Gaffey, W.R., (1974), J. Occup. Med., 16, 509. Tanburro, C.H., and Greenberg, R., (1981), Environ. Health Perspect., 41, 117. Thomas, L.B., and Popper H., (1975), Ann. N.Y. Acad.Sci., 246. Viola, P.L. (1969), Pathology of vinyl chloride. International Congress on Occupational Health, Tokyo. Proceedings of the 16ch Viola, F.L., (1970) Pathology of vinyl chloride. Med. Lavoro, 61, 174. Viola, P.L., Bigotti, A., and Caputo, A., (1971), Oncogenic response of rat skin, lungs and bonps to vinyl chloride. Cancer Res. 31.516. Whelan, J.C., Creech, J.L., and Tanburro, C.H., (1976), Radiology, 118(3), 549. Wilson, R., (1979), Analyzing The Risks of Life, Technology Review, M.I.T., 81 (4). AP00018966 .'icCS'VL-D rci 0 7 1983 **r<K Worker Exposure to virwi Chloride in Vinyl Chloride and Po' *vinyl Chloride Production and Fabrication <U.s) National Inst, for Occupational Safety and Health, Cincinnati, OH PB83-116053 i i i U.S. Department of C--uici National Technical Information Service } 1 APOOO18967  -*** v iurns PB03-H6053 7 tf- $>*3*> ***+-& tejjCfc-a. K0R1S& EXPOSURE TO VIKYL CHLORIDE IN VINYL CHLORIDE AND POLYVINYL CHLORIDE PRODUCTION AND FABRICATION * n ;-4 !r>*,4 Janes H. Jones u..4 U.S. Dupartoent 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 45226 August, 1977 IWOKli It NATIONAL TECHNICAL INFOBJR. BpMCtwrAilatMTxSiI*Ol.ONf*.CaDSmHETiReiVICE M * APOOOI8968 KIOSK 00121751 ---------- -------------------------------- a ____________*A Worker Exposure to Vinyl Chloride in Vinyl Chloride and Polyvinyl Chloride Production and Fabrication Jones, J. H. Hazard Evaluation and Technical Assistance Branch, Division of Surveillance, Hazard Evaluations, and Field Studies, KIOSH, Cincinnati, Ohio Same as Above Pft** tiAn*;? t> 0,44 i. 15A U eaiiii4i# fiiriwiM* *. a. . NA iO. MnVTnWVlm Uiui Mau KA 21. r^Knnin 4* OmUO Ha. <o da Hi T,p W flltart 4 >iw Crmu 14. KA ___ 1C. ftlaitw Zo assessment of worker exposure to vinyl-chloride (7S014) (VC) end polyvinyl-chloride (9002862) (PVC) was reported. Toxicological data were presantedi Including acute and chronic anloal and human studies, as wall as reported worker exposures. Common methods of VC production including Che acetylene-hydrogen-chloride, oxyhydrochlorination, and echylene-dichloride pyrolysis processes ware described. A description of PVC polymerisation processes, including suspension, emulsion, bulk and solution polymerisation, were presented. A study to determine worker exposure to VC in monomer, polymerisation and fabrication plants was described. Monomer and fabrication plant personnel had generally low levels of VC exposure, as compared to workers in polymerization plauts. Workers In polymerization plants had the highest VC exposures. The author concludes that VC concentrations in polymerization plants are hazardous to the workers. Z. flan-nm tin^ii *. fliwuiw Chlorinated-ethylenea, Medical-research, Industrial-processes, Industrial-hygiene, Occupational-medicine, Toxicology ^ ^XHlHan/QgMi C+49* \ \| *^ ;j i' 'i AP60bl8969 CONTESTS 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 90 134 140 164 i i 1} I APOOOf8970 INTRODUCTION On January 30, 1973 as pare 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 vith occupational exposure to 23 chemical substances and physical agents, including vinyl chloride (VC). 106 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 vith Tabershaw-Cooper^AsTocifrCe*, Inc., to conduct an epidemiological survey to documentydhe health experience of past and present workers exposed to VC.* On/July 17, 1973, MCA pet with NIOSH officials to present the pro tocols fpr the two studies tjo inform NIOSH of industry research efforts with regard to kt that time MCA also informed NIOSH of prelim inary result 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 i walk-through survey va* conducted at the Louisville plane on January 2d, 1974, by KIOSK industrial hygienists. Representatives froo the Kentucky Department of Labor, the Occupational Safety and Health Adalniieration (OSHA), and the Epidemic Intelligence Service (EIS) of the Center for Disease Control (CDC) participated in this survey et the request of KIOSK. As a resule of the walk-through survey, NtOSH recommended on January 10, 1974, chat 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 aeasures be inatituted at all facilities engaged In the polymerisation of VC and requested that the MCA disseminate this information to its mettbers.10* On February 1, 1974, NIOSH and CDC briefed other Federal agencies with health ceteerch responsibilities including the national Canesr Institute J (NCI), the Food and Drug Adcinistraeion (FDA), the Kaelonal Institute of Environmental Health Sciences (NXEHS), and the Environmental Protection Agency (EPA), about KIOSH findings concerning VC. On Februtry 12, 197&, NIOSH met with management and labor represantatlvea from the VC and polyvinyl chloride (PVC) Industries. At this meeting held in Cleveland, Ohio, approximately 100 people were briefed by HXOSB and CDC staff *bout the information obtained up to that time. Following review of the problem, KIOSK presented plena 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- \' t I APOOb18972  SUW*. ri \; ti . [- 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 FVC polymerization "lenta 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 FVC polymerization plants in the U.5., including information on each plant's age, number of people employed, end type of manufacturing pro rI cesses used, was made to help decide which plants should bs visited for ;< initial walk-through surveys. Criteria for plant selection were as follows] (a) The plene'a ege must be fifteen yeers or more. ;J (b) The plant must have a workforce greater than 100 persons. (c) The plant should be located is a state of the union, where NIOSH had established follov-up sources for retrospective cohort studies. 4 I In the Spring of 1974, walk-through surveys were conducted st seven # polymerization plants by a teas consisting of sn industrial hygienist* an epidemiologist, and a physician, chat collected information concerning I suitability of personnel records for follov-up of all persons ever employed, the extent and availability of environmental sampling results for VC, types of materials used end produced, end the physical layout, p-sed 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 vera Judged to be fairly typical of l the industry and they used three ox the four PVC manufacturing processes. * t,' -3- APOOO18973 \_ A third plant was chosen for industrial hygiene study lacaust it used the fourth, newer, process for aanufacturing PVC. During this time it was also decided by KIOSK to document VC exposures in the other two nain segments of industry where VC oceurs, VC monomer aanufacturing and PVC fabrication. A contract vaa awarded to Bendix Launch Support Division to conduct industrial hygiene surveys at three typical VC aonoaer plants and at PVC fabrication plants using the following processes: eoapounding, extrusion, molding, calendering, theraoforming, bonding, end the production of foens, fibers end plestlsole. The initial walk-through surveys of the selected polymerisation plants by KIOSH industrial hygienists began in February, 1974. The industrial hygiene surveys conducted by the contractor began in June, 1974, and ware completed for the aonoaer and polymerization plants by January, 1975, and for fabrication planes in April, 1975. While the study was under way several changes in the OSKA standard for VC took place. On April 5, 1974, a temporary emergency standard was promulgated which lowered the standard from a'500 parts par million (ppo) ceiling 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 ceiling was announced to be effective January 1, 1975, but subsequently was delayed by eeurt action until April 1, 1975.^ ^ -4- } ! I \ i | < ' t I i1 i ( 1 4 J APOOO18974 All of ehe VC measurements In the NIOSH field study vara taken before tha permanent standard went Into effect with the exception of one fabrication plant which was surveyed in Aprils 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 cube.^3 Although the formation of VC had been reported eerlier by Regnault in 1835,^3 no further interest in VC was expressed by the scientific community until 1912. A surplus of calcium carbide in Germany in the eerly 1900's led to the development of e process for ths synthesis of scetylene. In 1912, s potent ves filed for the production of VC from acetylene, and in 1914 another patent wee filed for the use of a family of catalysts in ehe polymerization of VC. Concurrently in Russis attempts vara being made to use the polymer as an intermediate in the production of synthetic rubber. Realisation of ehe significance of Che German work failed to develop at this time end ehe patents ware allowed to lapse in 1926. Interest was renewed by 1928 and patents involving polymerisation 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 plasticised. The system was Improved, with significant quantities of PVC being produced by the laee 1930*e. During World War It, PVC was used for electrical Insulation, waterproofing materials, and military rainwear. Only after the war, with the development of consumer produces using PVC, did the industry mushroom. In 1945, the eneire world pro* 5- APOOO18975 Auction of ?VC vat 100 million pound*,17 while in 1974, tha 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 par Billion (ppm) to study acuta effects. Batty, at el.,9^ in 1930 found Chat 200,000 to 400,000 ppm was fatal to guinaa pigs la a "very short time" and that 100,000 ppm for 30 to 60 minutes vac "dangerous to Ufa." They found lung edema and liver and kidney hyperemia in the higher exposure group. Feoplea and Leake?5 1933 reported that 245,000 to 285,000 ppm for 10 minutes vet fatal to mica and that 65,000 to 125,000 ppm for 10 minutes was the minimal anesthetic range. They also reported that 170,000 ppm produced narcosis in dogs end rabbits. Schsuaann^7 in 1934 reported that 180,000 ppm exposure produced relative heart insufficiency in cats. Otter, at el., in 1947, while conducting teses to determine the suitability of VC es an anesthetic, discovered serious cardiac arrhythmias in dogs exposed to 100.000 ppm. Narcosis end sensitization *>f the myoeardiwa in dogs efeer exposure to VC was reported by Carr at el.** in 1949. In 1960, Maacrom&tteo at el. tested mice, rats and guinea pigs at 100,000, 200,000, 300.000 and 400,000 ppm for 30 minutes and ell animals showed deep . Tcosis with deaths occurring in all but the lowest exposure group. Animals chat died shoved lung edema, liver end kidney congestion and a dotting defect, but the survivors shoved no changes other than pulmonary congestion. Leaser at el. tested rats. In 1963, at concentrations of 50,000, 70,000, 100,000 and 150,000 ppm. At the highest level the I'---1 .-k^*--**!* rat* experienced deep narcosis vlth lung edema. Hoderate intoxication, loss of balance and corneal reflex vara eha only effaces noead at tha lower concentrations. Prodan at al.^ have reported ID 50*a for eha following species: mice - 120,000 ppm; rats - 150,000 ppa; guinea pigs - 238,000 ppm; and rabbits * 236,000 ppa. Chronic Anical Studies The first chronic VC exposure studies were reported in 1961 by Torkelson at al.110 They exposed rets, guinea pigs, rabbles and dogs to 50, 100, 200 and 500 ppm for AJj to 6 months and found liver and kidney changes at all levels of 100 ppm and over. Lester et al.^9 also reported on chronic exposure to rats in their 1963 paper. Exposure levels were 20,000, 50,000, 80,000 end 100,000 ppa for 8 hours a day, 15 days to 3 months. Liver changes were noted in ell groups, vlth the highest exposure 'group also showing lung edema and spleen changes and death of over half of the anisals in the group. Prodan at al.96 in 1975 reported that guinea pigs exposed to 100,000 ppa VC for 3 months showed liver, kidney, spleen end lung changes. Viola,131 in 1970, exposed rats to 30,000 ppa for 12 months and found liver, kidney, artery, akin, bona, brain and I narve abnormalities. The following year Viola131 reported on another group of rats exposed to 30,000 ppa for 12 sonths and found severe hepatitis, kidney tubulonephro*la, interstitial pneumonia, degenerative brain lesions and tunon of the akin, lung end bone. This was the first report of any carelnogenetic effeeca of vinyl chloride. Caput at al reported in 1974 that rets exposed to VC concentrations down to 500 ppa had de veloped tumors of various sites. Maltosl end Lefeolne,^3 exposed rate, ti x APOOO18977 V4 ' --r*-.'. `IT.' tr k 1 1 nice and hamsters to 50, 250, 500, 2500, 6000, and 10,000 ppm Jor 12 months I and found cursors at various sites at all exposure levels. Keplir.ger ee al in 1975, also reported tumors in mice exposed Co 50, 200, and 2500 ppm for 6 months. Basalaev ee al22 have reported cardiovascular > disorders, hyperadrenalineoia, changes in ths bioelectric activity of ths hypothalamus and bone resorption in rats and rabbits exposed to es lov ss 12 ppm VC. Vasin end Plokhova have conducted several tests with VC. They have reported changes is the electrical activity of the hypothalamus of rabbits exposed to 3770 ppm VC for 5,5 months.126 Rabbits expesad to 3500 ppa VC for 5 months vers found to suffar from / cardiovascular diee-ders.223 Rabbits exposed to 8-12 ppm VC for 5 months showed cardiovascular disorders resulting from hypersdrenelinemid caused by changes la ehe cells of the hypothalamus.222 t Rats exposad to 12-15 ppm VC for 5 months developtd cardiovascular disorders224 and alterations in tha function of the central nervous system.222 id i 1 aj t i \ i}t i i5 j t Human Studies Again, es wee the case with animal studies, all early human studies con centrate on acute effecte of VC exposure. Petty at al94 reported that 25.000 ppm for 3 minutes and 6,000 ppm for 30 minutes produced glddlneea and disorientation. Two cases of VC intoxicstlon in workers were reported in 1933 by Dublin and Vane.32 Lester ct al69 reported on exposures from 4.000 ppm to 20,000 ppm for 5 minutes. They estimated that e prolonged exposure to a level of more than 6,000 ppm Is necessary to product minimus symptoms of intoxication. Dansinger,29 in I960, reported on 3 VC poisoning i i i 1 i ) AP00018978 cases, two of vhieh resulted in death. Other studies reported ia the literature have concerned chronic effects of VC exposure In workers. The first of these was by Tribukh121 in 194$ and found a "more or less narked hepatitis" in workers processing PVC. There Is sose question whether the health problem was s result of exposure to VC or to the plasticizers being used: chlorinated naphthalene and polychlorinated biphenyl (PCS). The author suggested that the predominant exposure was to PCB. Filatova, in 1957, pointed out a prevalence of "toxic angicneuropathy" in VC polymerisation workers normally exposed to 20-313 ppm. The first more detailed descriptive disease was dona by Suciu2,2^ at 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 aeroosceolysts, other liver damage, cardiovascular disorders and thrombocytopenia,58* 24,27,30* 31,40,42,44,48,57,62-66,70,77-79,83,96,100,105,106,113, 11&,116,127,135 Pulmonary disorders have also been reported by several authors.^8*2,18 PVC dust has also been Implicated In causing pulmonary disorders.^*62,116,128 Creech end Johnson,2* in 1974, were the first to link angiosarcoma of the liver with exposure to VC. Since then approximately 30 cases have been reported.7 These reports have triggered a number of retrospective mortality studies.75,84,88,117,134 These studies have suggested that there ere multiple tumor sites related -9. J- APOOOI8979 to VC exposure. Besides angiosercona of the liver, excesses of lung cancer, brain cancer and lymphoma have been found. In addition, Rannug et al** have reported that VC shows sutegenlc activity whan metabolicaliy activated In a microbial system, Chrososome aberrations In workers exposed to VC have been reported by Funas-Craviota *t al*3 and Pu:chase at al.*9 Infante33 has reported en Increased prevalence of congenital malformations in communities surrounding polyvinyl chlorida polysarlsatien plants. j 3 f2. i 1 i t REPORTED WORKER EXPOSURE i The first report in the literature of VC exposura levals for workers i appears in tha Russian literature. Filatova and Greasberg3 in 1917 f \ reported on VC levels in e Russian PVC polymerisation plant- using tha \ nulsion process to produce PVC. They found that levels In the reaceor areas varied from 15 to 16,000 ppm, hut the most frequently found concentrations varied from 38 to 310 ppm. Zn the precipitator and centrifuge area levels were 8 to 3050 ppm end In the drying oven area >I i \t 4i A to 15 ppm. An avaluation of different types of driers used in the PVC Industry was reported in 1959 by Gavruseyko and Filatova. A3 VC con centrations up to 27 ppm ware found in areas near chamber-type driers. They also reported on PVC dust concentretlons varying from 100 to 248 ag/m3 during drying operations end from 725 to 1200 ag/m3 during unloeding. Levels of 257 to 417 mg/m3 were found while unloading vacuum-rabble driers. PVC dust levels encountered in screening operations varied from 72-170 mg/m3. In 1965, Filatova et al60 reported that levels of VC -10- APOOO18980 in a PVC latex polymerization plant te high at 115 ppm west found and 751 of their measurements vere above the maximum allowable concentration (MAC) of 12 ppm. PVC dust e; centrationa varied from 1 to 6.5 ag/m^ except at the bagging station where levels as high as 78 ag/o* were found. Filatova and Antonyuzhenko^ have reviewed the chenges in worker V.; exposure m the Russian PVC iadusery from 1952 to 1969. Proa 1955 to 1956 the percentage of samples exceeding the MAC reduced froa SOS to 2X. Alto the aaxisua concentration of VC wee reduced by a factor of 900. Increasing production rates brought an inereeee in levels of VC until in 1969, 763 of samples exceeded the MAC. However, aaxisua VC concentrations vere 8-40 timet lower than ir 1954. There have also been e few reports froa ocher countries. Suciu at al13^ reported in 1967 that VC-levels In a Romanian plant ranged ee high as 2/20 ppa. Anghelascu at el5 in 1969 reported that levels of VC at work atations In a Hungarian plant ranged froa 43 te 213 ppa. GitSloi^ reported that peak levels as high a* 10,000 ppa were found in a Greek plane. Drums containing waste polyaer were found to have VC lavals aa high as 600 ppm. Byres end Holaberg2^ reported in 1974 that VC levale in Swedish plants averaged 16-20 ppa in reeetor rooms and laas than 5 pgp>-in"deging and packing treat. Cook et el2^ reported that lavels of VC present during reeetor cleaning were usually 50-100 ppa with psaks of 600 to 1000 ppa close to the -11- '*' r v> <MN workers hand during scraping. The remainder of eh# publisher-data on j workspace air concentrations of VC are from one plant. Syrette at al^y reported extensive exposure data in 1969 showing peak levWtSbove-- 1000 ppm. Levels of exposure for different jobs exceeded 50 ppm from 5 eo 652 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 dally and shift variation of 105 to 240 ppn. Kramer and Mutchler reported on this same plant in`1972. TWA VC exposures from 1950 through 1965 had bean datarained. IWA's ranged from less than 10 ppm to 300 ppm. The average TWA exposure in 1950 vas 155 ppm while Che average in 1965 was 30 ppm* Ott at al93 provide yet another source of information on VC levels et this plant* TWA's during the period 1950*1959 range from 5 eo 825 ppm, but only one job elasa was above 385 ppm. From 1960 to 1966 TWA* a ranged from 5 to 240 ppa with only two job eaeegorles 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 essocleted with each ' process and the VC exposures found for each are described In the re* aainder of this report. DESCRIPTION OF PRODUCTION PROCESS Vinyl Chloride Process At the present else, VC is manufactured in the United States in 15 plants using three basic processes: (1) Acetylene-hydrogen chloride proecas. rtfwiii -12- ^ i j i } {' 5 \ i i! I Jj APOOO18982 ^wwu'.muiiw.iw I .w '"****1*- (2) Oxyhydrochlorinaticn process. (3) Ethylene dichleride pyrolysis proeess.^^ Thi oxyhydrochlorination process is now the most widely used. The acetylene-hydrogen chloride process hed been the major coanerelal process until the I960'* when plants began switching ever due to changing econonics of feedstocks for their respective processes. These proeessee ere described as follows: Acetylene-Hydrogen Chlotida Process Dry eestylene end anhydrous hydrogen chloride ere reacted in fixed-bed reactors containing mercuric chloride-impregnated carbon catalyst according to the following equation: C2H2 + HC1------------ ---------- ------------ CUjCHCl The reaction products ere compressed, cooled, end passed to e refrigera tion unit for separation of VC by condensation, the condensed vinyl chloride is then passed to e two-column purification train where lowboiling products ere removed overhead in the first column and recycled to the fixed-bed reactor along with noneondensed vapors from the first column feed drum. A portion o5 the recycle is passed to e 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 sre removed end passed to an incinerator ii i > ;i ]i !i it -13- 4: * 4 --------- SiJ b APOOO18983 5, I for disposal. The purified VC removed from the second column Is first transferred tc 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 he expressed ss follows: C2K4 + ci2*; cich2ch2ci* C1CH2CH2C1 CHjCHCI + HC1 Vet ethylene dichlcride 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 dichloride ia vaporised and fad 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 dichloride is removed from the bottom of the column, passed to a column for removal of light ends, end recycled to the purification train. Overhead vapors from the ethylene dichloride recovery column are combined with quench system vapors, com** pressed, end fed to s hydrogen chloride recovery column where pur hydro gen chloride is removed overhead, trsnsfsrred to other on-site plants, and used in other processes. The bottoms from the hydrogen chloride Uttttk 14- APOOOI8984 APOOO18985 LEGEND: A - Reactor B - Compressor A Cooler C - Fractionation Train D - Vinyl Chloride Storage Tank E - Heavy Ends Storage Tank F - Vent Reactor ' 1 -- Hydrogen Chloride 2 - Acetylene 3 - Vinyl Chloride FIGURE 1. Acetylene-Hydrogen Chloride Process 1 I I i b V recovery coition Is p&ssed to a fractionating eelumn where purified VC is removed overhead and sene to storage spheres.1 A flow schematic for this proeess It shown in Figure 2. Oxyhvdrnchlorlnatlon Process The xyhydrochlorination process may be described at follows: c2K4 + ci2--------------------------------------- cich2ch2ci cich2ch2ci------------------ --------CH2CHC1 + HC1 C2H6 + 2HC1 + 1/2 02------ ---C1CH2CH2C1 + H20 Ethylene dichloride produced by reacting chlorlna and athylene la pyrolyrtd Co 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 dicHloriie produced by this reaction is dritd end pyrolysed to font vinyl chloride end hydrogen chloride* Ethylene end chlorine are reacted in e water-cooled direct chlorination reactor to produce crude ethylene diehlorlde. The crude ethylene dlehlorlde lc 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 dichlorida removed overhead from the second column is sene through an ethylene dichloride cracking furnace. The reaction products from tha cracking furnaca are passed to a hydrogen chloride column where crude VC is removed as bottoms and sant to a purification column. Furs 16 a* wssmsMm \i A\ V* AP00018986 3 Legend: A - Drying Column 0 - Heavies Column C - Cracking Furnace 0 - Quench Unit E - Fractionation Column F - Hydrogen Chloride Recovery Column G - Compressor H * Light Ends Column 1 - Ethylene Dichloride Recovery .olumn i A3 1 - Wet Ethylene Oichloride 2 - Water '' 3 - Lights 4 - Heavies 5 - Hydrogen Chloride - 6 - Vinyl Chloride . 3 Figure 2 Ethylene Dichloride Pyrolysis Process VC la recovered from the top of the VC column ind transferred to a etorage area where It is stored in large spheres. The boetoas 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 oxyhydrochlcrinetion reactor where it la raactad with ethylene end air to produce ethylene dlehlorlde and water. The reectlon products ere sent through an ewyhydroehlorlnation primary recovery unit where the veter is removed as bottoms end sent to waste. The overheads ere passed to a aecoad column where crude ethylene dlehlorlde is removed as bottoms and eyeled to the ethylene dlehlorlde purification train. The overheads are psssed to a secondary osyhydrochlorlnaelon recovary unit. Vant gas Is removed overhead in the first column, and the bottoms are'seat to a sacond column. The overheads from the second column are recycled to the second column of the oxyhydrochlorination primary recovery unit.3, A flew schematic for this process is shown in Figure 3. ---- DESCRIPTION OF POLYVINYL CHLORIDE POLYMERIZATION PROCESSES' VC is currently being polymerised using four processesi35 (1) Suspension polymerisation (78 percent of total production) (2) Emulsion polymerisation (13 percent of total production) (3) Bulk polymerisation (6 percent of eotal production) (4) Solution polymerisation (3 percent of eotal production) *ii uka M?, ,,* Legend: * A - GHCL Reactor B - OHCL Primary Recovery C - OHCL Secondary Recovery D - Direct Chlorination Reactor E - EDC Purification F - EOC Cracking Furnace G - lid Colunn H - VCL Column 1 - Air 2 - Ethylene 3 - Chlorine. 4 - Haste Mater 5 - Crude EDC 6 - Vent Gas 7 - Lights 8 - Heavies 9 - Recycle EDC IQ r Vinvl Chloride Figure 3 Oxyhydrochlorination Process APOOO18989 x... $ i i| \ ( | |1 i; i I I; g ^ l I I , These ere described as follows: Suspension Polymerization The suspension process i a batch aqueous polymerization of VC to produce PVC granules in the approximate site of lOOum. Polymerization is carried out in glaseliaed or stainless stsel reactors, Dost with 2000 to 6000 gallon capacity, but some considerably larger reactors are found in new plants with capacities up to 13,000 gallons. The rceetor le first charged with deionized water, VC, then a dispersing agent, e buffer, end en initiator after which the agitator is started end the contents of the reactor brought up to polymerization temperature (445-60C.) by eteaa in jected into the jaeket of the vessel. After a abort induction period, during which the exothermic reaction beglne, cooling water la fed to the jacket to maintain a predetermined temperature. When the polymerisation is ecsentially complete, the much reduced reaction rate makes it uneconomic cel to take the conversion above approximately ninety-five percent of completion. The contents of the reactor art dumped into a "blowdown tank" located direeely beneath the reactor (usually each "blowdown tank" serves several reactors) end the excess VC is removed by e recovery eystem which usually consists of several cospreseere and a eondenser 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 t* reduct smell variations in composition from batch to batch after which it is dewatered is a continuous centrifuge resulting la a polymer cake containing about ten to twenty percent moisture. The polymer par ticles ere then dried in e rotary dryer, screened to remove coarse 20 APOOOI8990 f :I particles, and sent to storage silos, pecked In multlvalled paper bags, cr leaded Into bulk railroad cars.* A flow schematic of this process Is shown in Figure 4. Emulsion Polymerization The smulsion process Is also e batch aqueous polymerisation of VC, but I with emulsifiers, now generally used for the manufacture of paste* forming polymers with perticls else distribution of approximately 1 un. 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 end then fed through a homogenlcer Into the reactors* After the reection is complete, the slurry Is dropped to a "blowdown tank" where excess VC it removed end then recovered. The coneents of the "blowdown tank" are , i 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 la dried, ground (to remove agglomeration), end bagged. Because of its small perticls size, emulsion resin is not stored or shipped in bulk. A flow schematic of this process is I shown in Figure 5. Bulk Polymerisation The bulk process is s batch polymerization of VC, without the usa of water or a solvent, to produce PVC. The bulk or mass process has only relatively recently been used commercially in the United States. The \ \ k tie Mi 21 APOOO18991 AP00018992 I i v *i '/ / ao u -f * FIGURE 5. Emulsion PVC PolyaerIzation > o O: O. 00; S "O t w I process was developed by and ia 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 prepolymerisation reactor where the reaction la started end polymer seeds era produced in slurry form in liquid VC. The slurry is then transferred to other reeccers where the polymerization is continued to fora a free flowing PVC powder. When polymerisation has reached the deeized com pletion, unreacted VC la removed from the reactor end recovered. The granular polymer ie then conveyed by elr to e eerie* of ecreene and grinders where the product ie ground end deeaified before going to etorage or bagging.^ A flow schematic of this process is shown in Figure 6. Solution Polymerization The solution process is the oldest commercial PVC polymarlzatlon process in the United States, but it is also the lease used. This process Is unique in Chet the polymerization is carried out continuously in an organic solvate in which both the reactants and products are soluble. VC is pumped a* a liquid under pressure to e reactor along with the solvent and initiator. After the polymerization has reached the desired completion state, the solution ia transferred to a stripping column where excess VC is removed end then recovered. Next, the PVC ie pre cipitated, separated from solution in centrifuge, washed, dried, screened, and packaged. A flow schematic of this process is shown in Figure 7. Polyvinyl Chloride Fabrication Compounding Compounding ia the mixing of polyvinyl chloride resin with other materials, N. 24 AP000I8994 I ii \' \\ APOOO18995 I IiTAi> ii -- `FIGURE 6. Bulk PVC Folyacclxation u 26 BBSS AP000I8996 FIGURE 7. S o lu tio n PVC F o ly v c rlz a tlo n  r * plasticizers, stabilizers, pigments, toners, fillers, lubricants, bloving agents, anti-oxidants, fungieidta, sanitizer*, end modifier* to give the PVC specific properties o 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 ceapounde such as plastisols* Compounds containing solids art masticated using Banbury* 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 foree 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 cress section. Examples of extruded items are hosas, pipes, rods, threads, pellets, and shapes of intricate cross section. Extrusions can ba rigid or flexible. A specific extrusion epplication is in the making of fibers. PVC fibers ere thin threads produeed from extrusion through a die eon* taining a number of small round or rectangular openings. The thread is passed through a cold water bath, dried, and wound onto spools. I; ?i \! l! AP000I8997 Fibers or webs of fibers can be pressed into or layered onto a sheet of i hot polyvinyl chloride In a calender *:o produce a sheet stock containing iI fibers or a web of fibers imbedded in the sheet. Polyvinyl chloride sheeting prepared In this manner has superior strength and resists I tearing and stretching. Molding Molding can be divided into a nuaber of types, i.e,, injection molding, blow molding, vscu-fonslng, 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 tha cavity of a heated mold* The and product assuats the configuration of tha mold cavity and can be solid, hollow, rigid, or fltxlble. J Blow molding begins with tha injection of a predetermined aaoune of plastic compound into the cavity of a mold. Air is than injected into ( Che center of tha injection and expands the plastic compound until it reaches the vail of the cavity* Sufficient air pressure is ussd to make the injected compound assume the configuration of the mold. ( The mold la heated and sacs the design of the molded item. Blow-molded products can ba rigid, semi-rigid, or flexible. Examples art plastic containers, wheels for toys, and basketballs. httiaibpmsmsssamamatma^KSBmBi AP00018998 I Vacu-formiag is accomplished by laying a sheet of preheated fila on top of a doId* The air between the fila and tha mold la removed by a vacuus pump, and the atmospheric pressure above the sheet forces the hoe fila against the mold. The eold mold sees the mold design in the film. Vacu~ formed items can be semi-rigid or flexible. Embossing Is the imprinting of a design Into e sheet of plastic and is normally accomplished by feeding e plastic sheee through a set of rolls. One of the rolls contains tha configuration chat Is to be imprinted into the plastic sheet. The other roll provides the pressure required to fora the design la the plastic sheet. As example of embossing is the Imprinting of a leather grain ineo pleatle sheee stock. Calendering Calendering is generally accomplished using three or four-roll calenders. The calender most often used la the plasties industry is the four-roll "7" form calendtr which has a stack of three rolls in e vertical plane end two top rolls in e 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 f aed of the stock to the calender. As adjustable gap between the calender relit produces e continuous sheet of plastic having uniform thickness and longitudinal physical properties across the width of tha sheet. The calender rolls also impart a smooth finish to both sides of the sheet is It passes through the rolls. A smaller-diameter roll strips the 29 I sheet of plastic from the last calender roll end pass** tha sheet throueh a aeries of tensioning and cooling rolls. The cooled sheet Is edgetrimmed and then fed to the windup rolls where che sheet Is wound under unifora tension into rolls of desired diameter. Thernoforalng Thermoformihg is the forming of various shapes in thermoplastic sheets through the application of heat and pressure, and employs olds or forming blocks to shapa tha plastic. Seven basic types of therooforaing are recognized by tha plastics industry. Each type uses various modifications of the molds, forming blocks, clamping devices, fracas, end pressures to foza the desired end produet. The seven types art: straight vacuum forming, draps vacuum forming, mala fora foresd above sheet, vacuum snap-back forming, plug and ring forming, air prassure forming, and matched metal mold forming. Theraeforaed products are finding usage in the packaging, automotive, furniture, toy, and garment industries. Bonding off Polyvinyl Chloride Bonding is the Joining of two or mora places of polyvinyl ehlorlde through the use of adhesives, or the application of heat with or viehout pressure.' Thermoplastic sheets and films can ba Jolnesd by heat sealing. Rigid ehatsoplasele materials aucb as laminate sheet, rod, and tubing can be jointed by adhaalves or by hot gee welding. ; 30 AP00019000 Polyvinyl chloride adhealves contain solvents such as cetrahydrcfuran to product tight, quick, and rapid assembly components, Heat seeling can he accomplished through the use of one or two metal lieas containing eleetrieal heating .neats, oven heat, or high-frequency or electronic heating. Hot gas welding employs a gas or elsccrieslly heated gun and polyvinyl chloride welding rod to join the materials. This type of weld is similar in appearancs to metal velds. Plastisol 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 It then withdrawn and placed in an oven for final cure of the compound. After oven euring, the plastisol-eeated mold is removed from the oven, l and the formed item is stripped from the mold using sir pressure. The mold is then dipped ia or sprayed with e release agent end returned to the preheat oven. The operation can be performed by hend or by automated units. Plastisol coatings can also be applied to a fabrie in a uniform layer and then passed through an ovea where the coated stock undergoes parelal curing. The eoated stock Is final-cured In a hoc 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 FVC which contain cells or bubbles of gas within 31 Si l ' APOOO19001 *ni'wtiw 1 / I < > chs material to give the sheet energy absorbing properties Polyvinyl chloride foes formulation# have a fluid or semifluid consistency end contain e blowing agent chat produces a cellular structure in the finished item* In the case of sheet materiel* the formulation ia spread onto paper or fabric end then pasaed through one or two ovens to expend and cure the sheeting. Normally, where paper la used as a becking material, the paper backing is stripped from the foamed sheet after leaving the first tunnel" type even. The foamed sheet ean then be joined to e second sheet to asks e sandwich-type sheet stock that ia sealed and final-cured in a second tunnel oven. Multi-layer sheet stock can be manufactured by joining e foam-coated fabric to a second vinyl sheet after the foao-coaced fabric leevea the first tunnel oven. Seeling of the two layers end final curing of the foam composite takes place in the second-tunnel .oven. Heated molds can ba dipped into a plastisol formulation containing a blowing egene. A thick coating of the plastisol mixture adheres to a'nd partially eures on the meld. The coated mold is withdrawn from the dip * end is pieced in an oven for the final cure end blowing operation. Mow, plascisol-type polyvinyl chloride;compounds can be added eo lubbertype compounds and a blowing agent to produce e coopound that Is processed on e Banbury and a two-roll mill. The milled acock can be further processed la a tube-type extruder. The extruded stock can be cut Into desired shapes end expended and cured iu e series of two ovens, os the tubular stock can be expanded end cured in e tunnel-type oven. 32 V i* APbbbi9b02 DESCRIPTION OF STUDY Bandix 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 plane, number of workers involved In the PVC operations, plant layout, rev aatariala used, other products produced at the plant, and any environmental sampling data available. Using this inforaaslon 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 planes and thirteen fabrication planes. From the information obtained during these surveys, plants ware selected for in-depth surveys. The criteria for selection of plents for in-depth study included consideration of a representative cross seetion of the various process and production capacities in the PVC industry. The plants selected included three monomer plants, three polymerisation plants and seven fabrication plants. Monomer plants selected included one plant using the acetylene-hydrogen chloride process, one pleat using the ethylene dlcklorlde pyrolysis process, and one using the oxhydrochlorlnatlon process. The polymerization plants included one plant using the solution, emulsion, and a modified emulsion processes, one plane ____ Wua 33 * i APOOO19003 using the bulk end suspension process, and one using ths suspension end collision processes. Processes used at the fabrication plants selected are shown in Tabk 1. The Industrie! hygiene surveys primarily consisted of the collection of personal VC samples from which exoosuces were determined. Also PVC dust measurements were made. Ventilation systems, In aeleetsd areas, changes in the process, of work practices to reduce VC exposures, end past and present industrial hygiane practices were described In Appendix A. Sampling and Analytical Procedures Sampling for VC was conducted by using a charcoal adsorption method with subsequent desorption la carbon disulfide end enelysls by ges chromatography. All samples vers collected using Slpin Model S?-l pumps at a flow rate of approximately 50 milliliters per minute. Commercially available charcoel adsorption tubes were used: Mine Safety Appliance' cubes at Plant 0, SKC tubes at Plants S and P and tubes supplied by the Anatol* J. Slpin Company for the remainder of the plants. The first study conducted (by H10SH, at Plant 0) utilised a sample volume of 1.2 liters. Ths number of samples collected was such, that a number of samples, for the seme men on the seme day, were combined to facilitate analysis time (due to he&vy lab work loads) thareby reducing the number of analyses. The survey at Plant E utilized 34 AP00019004  it. i Table 1 FABRICATIONS PLANTS - POLYVINYL CHLORIDE SURVEY LIST t. *> >i \ i I Company * Bonding C a le n d e rin g Compounding E x tru d in g Foam Form ation H o ld in g wee*a cocHas E < Ui>n9 At H \ |I 1. Plane G X XX X 2. Plant B X XX X 3. Pla.it I X XX i I 4. Plant J j XX XX 5. Plant K * XXXX X XX i 6. Plant L XX X 7. Plant M X XXX X XX AP66019605 th **n# sample volume, but only a few samples were combined for analysis. AC these tv plants sampling was conducted according to NXOSH Physical and Chemical Analysis Branch Analytical Method (F&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&CAH 178, 87 shown, in Appendix B. All KXOSH samples were analysed at the KIOSK laboratory in Salt Lake City, Utah. At the plants sampled by the contractor a sample volume of 5 liters was used for Plants A, 3, C, G, H, 1 and J. A 10 liter sample volume was used at Plants K L and M because of the low VC levels experienced at fabrication Planes G, H, I and J. The contractor utilized F&CAM 127^ for analysis of the samples which they collected with the exception that Porapak type QS at 100C and 0*4 percent Carbowax 1500 on Caxbopak A at 50C ware used as the chromatograph column materials. A small number of PVC personal duse samples were also .taken in bagging areas of the polymerization plants and In a few fabrication plants. Primarily the samples wore total dust - gravimetric samples taken for approximately 4 hours at a flow rate of 2 liters per minute. A few samples wste collected to allow microscopic examination of airborne duata. All gravimetric samples were collected on 37 mm diameter MSA PVC membrane filtera with a 5 wm pore size. Samples collected for 36 bil i fieSnSi i ieamtaw iiiiiiM --sun ... . riaaaTer. - .......................................................... AP00019006 i *>: \ microscopic examination were collected on 37 m Millipore AA nembrane filters with a pore else of 0.8 us. Three piece Hillipore filter cassettes were used for ell samples with the cap removed for micro scopic examination samples. Aa MSA Model G portable air sampling pump was used to draw ar through the filter. Gravimetric sample filters were cared end weighed on the twenty milligram UAH scale of e Cahn Gram Elaetrobalance. 4 . i ! i iC i j i > .V . \ `v B 37 APOOO19007 RESULTS Monomer PLenta Plant A A eonal 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. Hone of the TVA concentrations for the various jobs was above 1 ppm vlch Che operator having the highest TWA, 0.65 ppm. The overall plant TWA was 0.55 ppm* Plane B A total of 75 VC samples were taken at Plant B and a sumsy of the results may be found in Table 3* VC concentrations ranged from ' lese then 0.01 to 84.77 ppm. All TWAs except for the loader were below 1 ppm. The TWA for the loftier was 21.85 ppm. The overall plant TVA wee 3.40 ppm. Plant C a total of 109 VC samples were taken at Plant C and e summary of the results may be found in Table 4, VC concentrations ranged from 0.02 to 21.8 ppm. TVA conceneratlona for ell Jobe except loader were below 1 ppm. The TVA for loaders was 5.22 ppm and the overall plane TWA was 1*54 ppa. Summary A total of 231 samples to determine VC concentration ware collected in monomer plants. The VC concentrations found varied from less then 0.01 to 84.77 ppm. TWA concentrations for the different Job categories AP00019008 > I Table 2 Susaary of Vinyl Chloride Sampling Data by Job in Monomer Plane A .* X xg Range Job n (pps) (ppm) (ppm) 1 Operator 7 0.86 0.43 0.13-2.45 Loader 8 0.71 0.45 0.10-1,39 Maintenance Worker 4 0.17 0.11 0.02*0.32 1 Lab Technician 8 0.71 0.20 0.04-4.36 Foreman 7 0.10 0.08 0.03-0.21 Total of Personal 34 0.55 0.21 0.02-4.36 Staples Composite of All 13 1.51 0.23 <0.01-5.89 Area Sasples I * X TWA I ! AP00019009 V. Table 3 Suonary 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 Samplaa _* X n (ppm) 32 0.34 9 21.85 4 0.17 12 0.1S 57 3.40 13 0.18 X 8 (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 <O.Ol-84J7 <0.01-1,22 * X TWA i AP000I9010 Table 4 Susaary of Vinyl Chlorlda Sampling Data by Job in Monomer Plane 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 X 8 (ppm) 0.27 l.lfi 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 i < j i Iri1 41 APdobmif ranged from 0.10 to 8.04 ppn. Only the Ttfi for loaders wee above 1 ppn. The average of all personal samples taken at VC monomer plants was 1*89 ppm. A summary of these results is found la Table 5. POLYMERIZATION PLANTS Plant 0 Solvent Process Aree - Forty-five sasples for VC were taken in this are*. They reanged from none detected (ND) to 77.0 ppn. TWAa for the various jobs ranged froa 0.8 to 2.9 ppa with only the reactor area operators and dryer area helpers ebove 1 ppa. The overall area TWA va*. 2.1 ppa* A eunmary of ehesa reaulta may be found in Table & Modified Emulsion Process Area - Thirty-five samples for VC wars taken in this area vieh a range of 0.1 to 82.8 ppa. A summary of these results may be found in Table 7. TWAa for the different jobs ranged froa 3.5 to 38.7 ppn with an overall area TWA of 9.8 ppa. i I i ! i jI Emulsion Process Area - A total of forty-one VC samples were taken in this area with a range of 0.1 to 82.8 ppa. A eunaary of these results may ba found in Table 8. TWAa for the different jobs ranged from 3.5 to 38.7 ppa with an overall area TKA of 9.8 ppa. Overall Plane - A total of 121 VC saaples were taker, in the plant with a range of NS to 82.6 ppa. TWAa for the various jobs ranged froa 0.5 k mmm 42 mam* AP000I9012 I1 Table 5 Summary of Vinyl Chloride Sampling Data by Job in All Monomer Plants Sampled *i X Range Iji Job n (ppm) (ppm) (ppa) .11 1 Operator 95 0.64 0.21 0.01-18.2 Loader 37 6.04 1.67 0.06-84.77 Maintenance Worker 16 0.26 0.18 0.01-0.55 r Lab Technician 36 0.28 0.09 <0.01-4.36 )ii Foreman 7 0.10 0.08 0.03-0.21 Total of Personal 191 1.89 0.26 <0,01-84.77 i Samples Composite of All Area Samples 40 1.09 0.30 <0.01-7.06 * X - TWA / i i i i; il i \ K \ ..vw 43 APOOOI9013 Table 6 Summary of Vinyl Chloride Sampling Data by Job In Polymerisation Plane D Solvent Prooaee Area Job n Operator - RA* 20 Operator - DA** 4 Helper - DA** .1 Bagger 6 Maintenance Worker 2 Total of Personal Samples 33 Control Room Area Samples 6 Other Area Samples 6 X (ppm) 5.6 2.2 2.3 0,7 0.6 3.9 0.6 3.4 *S (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 HD-1.1 HD-1.3 HD-77.0 0.2-2.6 0.9-7.1 * Reactor Area ** Dryer Area : i ii t TWA (ppm) 2.9 0.9 2.3 0.7 0.6 2.1 i ! > i i i* i; 1\ ;: ii ii t! AP000190I4 I Table 7 Summary of Vinyl Chloride Sampling Data by Job in Polymerisation Plant D Modified Emulsion Process Area I X *8 Range TWA Job' a (ppm) (ppm) (ppm) (ppm) i I Operator - M* 24 1.3 1.3 HD-42 1.3 i Begger 1 2.3 2.3 2.3 2.3 Foreman I 2 0.3 0.2 0.1-0.4 0.3 Maintenance Worker Total of Personal Samples 1 28 0.2 1.2 0.2 0.2 0.2 1.0 HD-4.2 1.2 ji : I Control Room Ares 6 1.3 1.4 HD-2.4 Samples Other Area Samples 1 1.4 1.4 1.4 i: t i \ * Reactor Area 1 i li \ i 1 ki !; >; <; f! i 45 4 AP00019015 Table 3 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plane D Emulsion Process Area X X Range TWA 8 Job n (?p) (ppm) (ppm) (ppm) Operator - RA* 14 Helper - RA* 12 / Operator - DA** 2 Bagger 6 Foreman 3 Total of Personal Samples 37 Control Room Area Samples 4 11.0 10.2 38,7 3.3 8.6 11.1 7.5 6.2 6.1 20.6 1.4 2.8 4.8 5.3 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 8.2 8.9 38.7 3.58.6 9.8 * Reactor Area ** Dryer Area r 46 N. .......'' n APOO0I9O16 p* f\ Si b v. t t {. [I 5 it 1; l to 13.5 ppm and eh* overall plane TVA was 4.8 ppo. A suasary of chest results Is found in Table 9. A total of 5 dust staples were taken vlth an overall average concentration of 3.83 mg/a^. The baggers in the solvent process area had an average exposure of 1.01 og/^ while throne staple taken for the emulsion process bsggsrs showed 15.27 ng/a^. The results are shown in Table 10. Plant Mass Frocess Area - Eighty-five staples for VC were collected in this area with a range of ND- to 71.4 ppa. TWAs for the three job classi fications ranged froa ND to 4.6 ppa. The overall are* TVA vee 3.9 ppts. k eunnary of these results nay be found in Table 11. Suapaneion Process Araa - Ninety samples for VC vara collected In this araa with a range of ND to 245.0 ppa. OTA concentrations Scr the different Job classifications ranged from 0.3 to 16.5 ppa. The overall araa OTA was 12.2 ppa. A summary of these results are found In Table 12. Overall Flant - A total of 175 samples for VC were taken at the plant vlth e range of ND to 245.0 ppa. TWAs for the individual jobs ranged froa 0.3 to 10.3 ppa with an overall plant OTA of 8.1 ppa. A turnery of these results may be found in Table 13. Sight staples for pvc dust were Ctken all personal samples for suspension resin baggers, The results of ehese staples can be found in Table 14. APb66f90f7 Table 9 Sunnna-v of Vinyl Chloride Sampling Data by Job in Polymerization Plane 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 i 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 *8 (ppm) 2.3 6.1 3.6 2.3 1,3 1.0 0.6 2.3 1.3 2.2 Range (ppm) HD-77.0 0.7-77.0 HD-82.8 2.3 HD-9.6 0.1-22.0 HD-1.3 ND-82.8 HD-11.1 0.9-7.1 TWA (pptO 3.5 8.9 13.5 2.3 2.2 5.3 0.5 A.8 ! \ j j j i 68 AP00019018 -J iI t; Table 10 Polyvinyl Chloride Duse Sampling Results Plant D I Dust Concentration Job ________ ttg/*3 Bagger - E.R. 15.27 Bagger Sc.R. \ Bagger - Sc.R. 1.62 0.40 Fork Life Operator 0.82 Area Sample 1.02 E.R * Emulsion Resin St.R. Solvent Resin I 1 I 49 iifI i AP00019019  Table 11 Summary of Vinyl Chloride Sampling Dace by Job in Polymerisation Plant E Haas Process Area > : 1 job X n (ppm) X S (ppm) Range (ppm) TWA (ppm) f 1 Operator - RA* 36 4.0 2.5 ND-22.6 3.1 1 Helper - RA* 32 6.7 3.0 NO-71.4 4.6 j 1 Bagger 2 ns NS NO ND t Total of Personal 70 5.2 1.4 ND-71.4 3.9 Samples i Control Room Area 15 1.4 1.5 110-3.8 1 .Samples - | * Reactor Area I i f f f* Unsfea 50 .J AP00619626 J -t / c Table U .t \j Job Sunmary of Vinyl Chloride Sampling Data by Job in Polymerization Plant E Suspension Process Area X * Range u (ppm) (ppm) (ppa) TWA (ppm) it \ i X'< Operator - RA* 54 14.8 7.4 ND-245.0 16.5 Helper - RA* 8 10.4 6.2 ND-23.6 11,8 ! Bagger 10 0.3 L'.O ND-0.9 0.3 :j - Total of Personal 72 12.2 4.6 HD-245.0 12.2 ! V Samples il j* Control Room Area 18 15.9 4.4 HD-96.5 Samples iji l * Reactor Area -i \/ V" . \; -7 X . fctogaiBiiaftaifiiiiMiiSM 51 i< APOOO19021 // i . __ i j / Table 13 Sutsnary 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.S 7.5 0.3 8.8 7.9 X8 (ppm? 4.7 3.5 1*0 3.5 2.4 Range (ppm) ND-245.0 HD-71.4 ND-0.9 HD-245.0 HD-96.5 TVA (ppm) 10.3 7.7 0.3 a.i * Reactor Area !ii _r 1 J i AP000I9022 Table 14 Polyvinyl Chloride Duse Sampling Results Plant Z Job Bagger - S.R. m it m tt It 11 ti Shift 1 1 1 1 1 3 3 3 Dust Concentration tae/sr 0.69 0.72 2.50 1.02 0.70 0.38 1.06 . 0,57 S.R. Suspension Resin . }<11 i t? i t 1 j i AP66619623 \ Flint F Evulsion Process Arcs - A total of 111 VC samples were taken In this area with a range of 0.2 to 103.3 ppa. 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 Tabla 15. Old Suspension Process Arte - Seventy-eight VC samples were taken is this area with a range of 1.0 to 160.3 ppm. TWA eoaeentrations for the various jobs ranged from 7.2 eo 19.8 ppm. The overall area TVA was 17.6 ppm. A summary of thesa results is found in Table 16. Hew Suspension Process Area - Forty-eight VC samples were taken in this area with range of 0.1 to 78.6 ppm. TWAs for the two job classi fications wera 6.4 and 8.0 ppm while the overall area TttA was 7.8 ppa. A summary of thesa results may be found in Tabla 17. Overall Plant - A total of 237 VC samples were taken.at the plant with a range of 0.1 eo 160.6 ppa. TWAs ranged froa 1.7 to 16.8 ppn. ' The overall plane TWA was 9.4 ppa. A summary of thesa results may be found in Table 18. Ten PVC dust sasplas were taken. Emulsion resin baggers showed an average exposure of 8.08 mg/a* while the one sample for a suspension resin bagger showed 0.47 mg/m3. The sample for e dryer operator shoved an exposure of 0.73 mg/m^, The results of ths dust sampling can be found in Tabla 19. Pareiele sizing on 2 samples showed 54 j i , j ; j j; i1 *j APOOO19024 Table _1S Summary of Vinyl Chloride Sampling Data by Job in Polymerisation 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 _* X n (ppm) 29 8.9 24 16.3 25 3.1 9 1.7 10 2.2 1 1.4 96 4.7 7 3.1 6 5.6 ** (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 1 J I \ j AP00019025 1 Table 16 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant 7 jld Suspension Process Area Job Operator - RA* Helper - RA** Maintenance Worker Total of Personal Samples Control Room Area Samolea _* X n (ppm) 28 19,8 37 17.3 4 7,2 69 17.6 9 6,1 *8 (ppm) 11.4 11.2 6.6 10.9 4.8 Range (ppm) 5.3-160.6 1.3-160,5 4.2-12.S 1.3-160.6 1.0-11.5 * X - TWA ** Reactor Area j j > fr ; 5I | i 56 APOOO19026 Table 17 Summary of Vinyl Chloride Sampling Data by Job in Polymerization Plant F Hew Suspension Process Area Job Operator - RA*** Operator - DA** Total of Personal Samples Control Room Area Sample -* X n Cppm) 36 3.0 6 6.4 42 7.8 6 0.5 *g (pptn) 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 AP000I9027  '* 1 Table 13 Summary of Vinyl Chloride Stapling Data by Job in Polymerization Plane F Overall Plant .* X Job n (ppm) Operator - RA*** 93 10.6 Helper - RA*** 61 16.3 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 Room Area Samples 22 3.1 Other Area Samples 6 5.6 *8 (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 1.4-12.3 0.1-160.S 0.1-11.5 1.4-15.9 * X m TWA ** Dryer Area *** Reactor Area ? ' i ii ! i \ \ % j < :I ^fcfciirfi 58 iL APOOO19028 Table 19 Polyvinyl Chloride Duse Sampling Data Plane F Job Dryer Operator Bagger - E.R. " v 1C M It It II Bagger - S.R. Dust Concentration rna/ta^ 0.73 2.00 13.34 14.10 3.00 2.39 18.62 3*9.2 5.22 0.47 E.R. Emulsion Resin S.R. Suspension Resin k I 1 i i ! L ! 1 ( 1 j !j j: ,| !I uwi.imu i.jj-- 59 ansa u APOOOt9029 chat all particles vert below 6.7 um la diameter and that 90S of the particles had diameters less than 2.4 pa. Emulsion Process A total of 152 staples vcre taken In emulsion process areas with a range of 0.1 Co 103.8 ppm. TVAs 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 say be found in Table 20* Suspension Process A total of 216 sasplcs vsrs taksn la suspsnslon process arses with a range of HD to 245.0. TWAs reaged froo 0.3 to 16.7 ppm with aa overall TWA of 12.6 ppm. A suaasry of tbase results may be found in Table 21. Summary A total of 317 samples were taken la PVC polymerisation planes with VC concentrations ranging froo NO to 245.0 ppn. TWA concentrations for the various jobs rengsd from 1.8 to 14.3 ppm. Reactor area helpers and opsraeors had ths highest TWAs - 14.3 and 9.1 ppm respectively. The average of ell 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 ware taken. Emulsion resin baggers showed aa average exposure of 8.88 mg/m3. The remainder of jobs averaged 1.01 mg/m3 dust APOOO19030 Table 20 Suuanacy of Vinyl Chloride Sampling Data by Job in Emulsion Process Areas--All Plant.) Sampled _* X Job n (ppo) Operator - KA*** A3 9.4 Helper - RA*** 36 14.3 Operator - DA** 27 5.5 Helper - DA** 9 1.7 Sagger 16 2.5 Foreman. 3 S.6 Maintenance Worker 1 1.4 Total of Personal 135 7,8 Samples Control Room Area Samples 11 3.0 Other Area Samples 6 5.6 *8 (ppm) 6.3 8.7 2.8 1.3 1.8 2.8 1.4 3.9 3.4 . 5.0 Range (ppo) 0.1-98.0 0.7-103.S 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 mmitmumtim i \ AP00019051 rtf Table 21 Summary of Vinyl Chloride Sampling Data by Job in Sue nsirn Process Areas--All Planes Sampled _* X Job n (ppa) Operaeor - RA*** 118 12.5 Helper - RA*** 45 16.7 Operaeor - DA** 6 6.4 Bagger 10 0.3 Maintenance Worker 4 7.2 Toeal of Personal Samples 183 12.6 Control Roots Area Samples 33 6.3 X 9 (PP) 5.6 10.6 4.0 1.0 6.6 6.1 1.6 Range (ppa) ND-245.0 ND-160.5 1.1-21.0 ND-0.9 4.2-12.8 HD-245.0 KD-96.5 * x - TWA ** Dryer Area *** Reactor Area ; ,j 62 < ; AP066i9032 t Table 22 'Summary of Vinyl Chloride Sampling Data by Job -- All Polymerisation Plante Sampled I X *g Range Job n (ppm) (ppm) (ppm) 1 Operator - RA*** 241 9.1 4.2 ND-245.0 Helper - RA*** 113 14.3 8.2 ND-160.5 Operaeor - DA** 37 5.4 2.7. ND-82.8 1 Helper - DA** 10 1.8 1.4 0.6-3.6 Bagger 33 1.9 1.5 ND-9.6 Foreman 3 3.5 1.0 0.1-22.0 Maintenance Worker 3 4.2 2.6 ND-12.8 Total of Personal 449 B.4 Samples 3.8 HD-245.0 1 Control Room Area 55 3.8 1.5 HD-96.5 Samples Other Area Samples 13 4.4 3.3 0.9-15.9 * x - TWA ** Dryer Area *** Reactor Area I I APOOO19033 SI V. I t w> P fj i r r rj, [1 1 1 *; * / I r i a Table 23 Summary of Polyvinyl Chloride Dust Sampling Data Polymerization Plants Job Bagger - S.R. Bagger - Stt.R Bagger - E.R. Fork Lift Operator Dryer Operator Total of Personal Samples n 9 2 9 1 1 .22 x 0.94 1.01 a.83 0.82 0.73 4.18 S.R. Suspension Resin St.R. Solvent Resin E.R. - Emulsion Resin APOOO19034 FAiRICAIIQH PLANTS Plane G A total of 68 sasplec for VC vara taken In this plane with a rang* of NO to 0.02 ppa. TWAs for all job elasalfleaeions war* laaa than 0.01 ppa. A summary of that* results ia found in Tabla 24. Plane K A total of 32 samples for VC war* taken at Plant H with a ranga of last chan 0.01 eo 0.68 ppm. TWAs for all jobs warn balov 0.10 ppa and the overall plant TWA vaa 0.03 ppa. A summary of thasa results uay b found In Table 23. Plant Z Forty-night samples for VC vara taken In this plant with a range of NO to 0.06 ppm. TWAs for Che two job categoriea vara SO and 0.01 ppa A summary of chase raaules can bn found In Tabln 26* Plane J Forty-night samples for VC vara taknn in this plant with no VC baing detected. A summary of thnsn results is shown in Tabln 27. Plane K A total of 24 samples vara takan ae this plant wish a ranga of HO to 0.13 ppa. TWAs for all jobs vara 0.01 ppm or lass. A summary of these results is found in Tabla 28. 63 * 'l i' APOOb19035 V I i A \ Table 24 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plane G Job n Compounding Personnel 8 Extrusion Personnel 24 Lab Personnel 4 Miscellaneous Personnel 16 Total of Personal Samples 52 Composite of All 16 -* X (ppm) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 *8 (ppor) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Range (ppm) < 0.01-0.02 HD-0.02 < 0.01 HD-0.01 HD-0.02 HD-0.02 * x TWA ** Engineers in Process Area Doing Experimental Work. TV- - 1 l t i! i> ; ! I 1 I i i I i !' i' f 66 mmm . \. s APOOO19036 Table 25 Summary of Vinyl Chloride Sampling Data by Job in Fabrication Plane 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 o.oi 0.03 0.01 0.01 0.03 0.37 Xg (ppm) 0.06 0.01 0.02 o.oi 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 APOOO19037 Table 26 Summary of Vinyl Chloride Sampling Oaca 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 NS X (ppm) ND 0.01 <0.01 ND Range (ppm) ND ND-0.06 ND-0.06 ND * X TWA ii \ i! 'i ' ii jt Ii i \ N. \ f.'Sc-A AP00019038 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 Holding Personnel 8 Miscellaneous Personnel 4 Total of Personal Samples 44 Composite of All Area Samples 4 _* X (ppm) m> HD ND HD HD HD HD X* (ppm) HD HD ND HD HD HD HD Range (ppm) HD ND HD HD ND HD HD * x TWA \ \ M APOOO19039 table 23 Summary of Vinyl Chloride Sampling Data by Job is Fabrication Plane K Job Calender Personnel Compounding Personnel Maintenance Personnel Toeal 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 (ppm) <0.01 <0,01 <0.01 <0.01 <0.01 Range (ppm) KD-<0.01 NO-0.13 ND-<0.01 NO-0.13 <0.01 * * - TWA T 'i *n? iatffiHHH 70 V AP00019040 Plane L Thirty six saaplee were collacsed at this plant with concentrations ranging from 0.02 to 2.64 ppa. TWAs for eht various job* ranged froa 0.27 to 1.63 ppo with only oca Job having a TWA highar than 1 ppn. Tha ovarall plant TWA was 0.62 ppa. A avaaary of these results is shown in Table 29. Ten dust saaples wsre also taken at this plant. All were area saaples. The average dust concentration was 3.92 ag/a3* These results are shown In Table 30. Plant M A total of 24 sacplss for VC wars collected at Plant M with a range of ND to 0.02 ppa. TWAs for the two job classifications were 0.01 and 0.02 ppa and the overall plane TWA was 0.01 ppa. A summary of chase results may be found in Table 31. Seven area dust samples wsre eaken at this plane with an average dust concentration of 7.21 ag/a3. Theas results are above in Table 32. Summary A total of 300 samples for VC wera eaken in PVC fabrication plants with the concentrations ranging froa KB to 2.44 ppa. TWA concentrations for the different jobs ranged froa less than 0.01 to 0.57 ppm. The average for all ptrsonal saaples taken in PVC fabrication plants was 0.14 ppa* A summary of these-results may be seen la Table 33. A total of 17 area dust saaples were taken in fabrication plants with an average of 6.22 ag/a3. 71 I t 1 Table 29 Summary of Vinyl Chloride Sampling Daca by Job in Fabrication Plant L Job Calender Personnel Compounding Personnel Extrusion Personnel Lab Personnel Total of Personal Sample* 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 72 i L APOOO19042 \ Tabla 30 Polyvinyl Chlorida Dust Saapling Data Plant L AP00019043 ) 1i . I > Tabic 31 Summary of Vinyl Chloride Sampling Daca by Job in Fabrication Plant M ) Job _* X a (ppm) X (ppm) Range (ppm) I Calender Personnel 2 0.02 0.02 0.02 Compounding Personnel 22 0.01 0.01 ND-0.02 Total of Pertonal Samples 24 0.01 0.01 ND-0.02 * x TWA > \ i l APOOO19044 I VTT' "`'"ri-pCr * Table 32 Polyvinyl Chloride Duse Sampling Data Plane M j Location Dust Concentration og/nr Mixing Area i Blender Area 6.67 1.67 i Mill Area Banbury Mixer Area Calendar Area Plaatieol Mixing Room Cast Film Line 6.67 13.33 6.67 7.9 7.27 ji j ) i 5 i i 1 1 ii >i i <i & 73 MilfiaMMlMiMMMMii I J f Mi AP00019045 > V Table 33 Summary of Vinyl Chloride Sampling Daca by Job --A. Fabrication Plants Sampled Job n Calender Personnel 28 Compounding Personnel 78 Extrusion Personnel 58 Lab Personnel 18 Maintenance Personnel 10 Molding Personnel 16 Pleseisol Dipping Personnel 40 Miscellaneous Personnel 20 Total of Personal Semples 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) 0.21 0.05 0.04 0.05 <0.01 <0,01 . <0.01 <0,01 0.03 0.05 Range (ppm) ND-2.44 XD-0.69 HD-0.76 HD-0.68 HD-0.02 HD-0.03 HD-0.06 HD-0.01 HD-2.44 KD-0.68 * x * TWA APOOO19046 i i | I CONCLUSIONS *i Monomer Planes Monomer plants had generally low concentrations of VC exposure for I personnel. The only job category with e TWA higher than 1 ppm was that of loader. The work practical for chle job were being modified co lower exposure!. One plane had already lowered exposuree below 1 ppm and plants | were using self contained breaching apparatus or supplied air respirators to limit exposers to VC for this job. So the levels found are indicative of the potential exposure but not nacesearily the actual exposure of I these workers. These levels also suggest that this has been t high exposure job in the past* before respiratory protection was used. . Polymerisation Plants Jobs requiring the mote tine la the reactor areas had, as would bs expseted, the highest exposure to VC. Reactor area helpers hsd the I highest TVA end it was these workers who did the job of deeming reactor ' vassals when necessary. Again these workers were using supplted-air respirators when inside vessels or performing other jobs, such as I changing filters# that could have high exposures to VC# so the exposures may not be actual exposures, vc exposures in the past, i 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 vers still not under 1 ppm. , ! J The workers involved with the solvent process had the lowest \k ' APOOO19047 and finally the suspension process workers had the highest TWA. One other variable which was inpossible to measure was management attitude towards keeping VC exposures low. It was observed within plants that housekeeping and work practice procedures varied frost area to area beeause of the attitude of foreaen in the areas. Dust 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. Setter dust eontrel 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 calender personnel had a TfrA above the required action level of 0.5 under the new OSKA 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 teken. However, the dust is probably net all PVC, sinee fillers and other additive are being used in the operations. Better dust controls should still be implemented in areas where dusty materials are handled. Overall, polymerisation plants had the highest TWA of 8.4 ppm and the highest individual job TWA of 14.3 ppm. Also workers in polymeri2Ation plants had the widest range of VC exposures, with peaks as high as 245 ppm. Monomer plant workers had the next highest overall 78 .itU APOOOt 9048 I WA of 1.89 ppo, a faetor of 4 lover than polymerization plant workers. The TWA for one Job category was 8.04 ppo, 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 ppn. a factor of 60 lower than polymerisation plant workers and 13-1/2 lower than monomer plant workers. These results substantiate the initial emphasis of studies on polymerisation plant workers as having the highest VC exposures. > j APOOO19049 % \ / X:. I .A T BIBLIOGRAPHY 1. Albright, L.F., "Manufacture of Vinyl Chlorida," Chao. Eng.. 74:219-226, April 10, 1967. 2. Albright, L.F., "Polymerization of Vinyl Chlorida." Chan. Eng.. 74:151-158, May 8, 1967. -------- 3. Albright, L.F., "Vinyl Chlorida Polymerization by Emulsion, Bulk and Solution Proteases", Cham. Eng.. 74;85-92 July 3, 1967, 4. Albright, L.F., "Vinyl Chlorida Polymerization by Suspension Processes Yields Polyvinyl Chloride Resins", Chen. Eng.. 74:145-157., June 5, 1967. 5. 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D'yachuk, l.A., "A contribution to the hygienic evaluation of Pvc floor tiles for apartments", Gl<?. Sanit., 35 (1-3) :424-427, 1970. 34. Environmental Protection Agency Task Force, "Preliminary assessment of the environmental problems associated with vinyl chloride and polyvinyl ehloride: a report on the activities and findings of the vinyl chloride task force", Environmental Protection Agency, Washington, D.C. 1-29, Sept. 1974* 35. Environmental Protection Agency, "Scientific and technical assessment report on vinyl ehloride and polyvinyl chloride", EPA Report Ho. ESA60Q-6-7S-004, 1975. 36. Falk, H., Creech, J.L., Heath, c.w. Jr., Johnson, M.H. and Key, M.M., "Hepatic disease among workers at a vinyl chloride polymerization plant", JAMA, 230 (l):S9-63, 1974. 37. Filatova, V.S., "The Hygienic evaluation of new technological processes < 1 ; -X. % JJTW AP00019052 39* ttlatove, V.S. and Antonyurhenko, V.A., "Changes in hygienic conditions of work and occupational disiaaa-ineidenee among worxer* engaged in tha production of polyvinyl chlorida ever a pariod of years', Gig, Tr. Prof, zabol., 15(4):32-34, 1971. 39. Filatova, v.s. and Gronsberg, E.S., "Sanitary-hygienic cenditiona of work in tha production of polyvinyl reains and measures of improvement". Gig. Sanit. 22(l)38-42, 1957. 40. Filatova, V.S., Gronabasg, .S., Smirnova, N.A., Sttulova, E.A., and Qreshkavieh, L.V,, "Industrial hygiene and tha atata of haalth ir. workers engaged in tha production of polyvinyl chlorida latex". Gig. Tr. Prof. Zabol., 9 (8):9-14, 1965., 41. runea-Cravioto, T., Lambert, B., Lindstan, J, Ehrenfcerg, L., Natarajan, A.r. and oseeman Golkar, S., "Chromosome abarraticr.s in workara exposed to vinyl chloride". Lancet, p. 459, Fab. 22, 1975. " 42. Gabor, S., Rada, M., Prtda, N., Abrudcan, S. Ivanof, L., Anea, Z., and valaczkay, C., "Biochanical changaa in workara occupied in vinyl chloride aynthasit and polymerisation", Iclena, 13(5}:409418, 1964. 43* Gavruaeyko, O.M. and Filatova, V.S., "Hygienic evaluation of certain types of drying units used in tha chemical industry". Gig. Tr. Prof. Zabol.., 2)32-39, 1959. 44. Gedigk, P., Mueller, R. and Bechtelshaimsar, H., "Morphology of liver damage among polyvinyl chloride production workers. A report or 51 casaa", Ann. H.Y, Acad. Sci., 246)278-285, 1975. 45. Gillas, D., "Health haxard evaluation Report No. 74-134-193: PHC industries, Inc., camdan, N.J.", DHEN, phs, esc, niosk, 1975. 46. Gitsios, C.T., "Acro-oataelysis in PVC workers". Mad. Bull. (Standard oil Co., NJ), 31(1-3} 149-56, 1971. "* \ 47. Hardie, D.W.F., "Vinyl chloride", Klrk-Othmer Encyclopedia of Chemical Technology, 2nd ed., 5:171-177, 1964. i\ 48. Harris, D.K. and Adana, W.G.F., "Acro-oateolyaia occurring in man engaged in tha polymerisation of vinyl chloride", Brit. Med. J,, (3)r712-714, 1967. 49. Heath, C.W., Jr., Falk, H. and Creech, J.L., "characteristics of cases of angiosarcoma of tha liver among vinyl chlorida workers in tha United States", Ann. w.Y. Acad. Sci.. 246)231-236, 1975. x. AP000I9053 1 \ 50. Heimann, H., Lilia, R. and Hawkins, D.T., "A bibliography on the toxicology of vinyl chlorida and polyvinyl chloride", Ann. N.Y, Acad, Scl., 146:322-337, 1975. 51. Hoti, M., Kobayasni, Y. and Ota, Y., "Vinyl chlorida nononar odor concentration", Plage. Ind. Hews, 18(11):164-168, 1972. 52. Infanta, P.F., "Oncogenic and mutagenic risks in cosau&itlas with polyvinyl chloride production facilities", Ann. M.Y, Acad. Scl., 271:49-57, 1976. 53. Japanese PVC Association, "Vinyl chloride monomer problea in Japan", Jap. PVC Assoc. Report, July, 1974. ' 54. Jones, J..H., "Industrial Hygiene Survey of ehe B.F. Goodrich Chemical Coapany polyvinyl chlorida operations, Avon Lake, Ohio", DREW, PHS, CDC, NIOSH, 1975. 55. Jones, J.H., "Industrial hygiene survey of B.F. Goodrich Cheeleal Company polyvinyl chloride operations, Ftdricktavn, Haw Jersey", DHEW, PHS, CDC, NIOSH, 1975. < I i i : 26. Jones, J.H., "Industrie! hygiene survey of the Union Carbide Corporation polyvinyl chloride operations South Charleston, West Virginia", USDHEW, PHS. CDC, NIOSH, 1975. ! l 57. Juhe, S. and Lange, C.E., "Scleroderae-like skin alteration*, Raynaud's ayndroae, and acrooataolysis in workers in the polyvinyl chlorida industry", Deut. Mad. Wochenschr. 97:1922-1923, 1972. 58. Kal'manovich, F.L., "Sanitary-chemical characteristics of polyvinyl chloride floor costings". Gig. Sanic.. 33(1-3):274-280, 1966. 59. Kapli&ger, M.L., Coode, J.W., Cordon, D.E., and Calandra, J.C., "Interin results of exposure of raes, hamsters, and mice to vinyl chloride", Ann. H.Y, Aced. Sci., 246:219-224, 1975. 60. Key, M.M., "KIOSK recommended stauderd for occupational exposure eo vinyl chloride", HEW, PHS, CDC, NIOSH, 1974. 61. Key, M.M., "Statement ae OSKA vinyl chloride fact-finding hearing, June 24, 1974", HEV, PHS, CDC, NIOSH, 1974. 62. Kovac, A., Kurajlca, L., Juric-Ruzic, D. and Parac, B., "Acropathia xtremitacus in polymerisations vinylehloridl -- caw occupational disease", LUecnlckl Vlesnik (Med. J.), 91U):5-17, 1969. 63. Kramer, C.G. and Mutchler, J.E., "The correlation of elinical and environmental measurements for workers exposed eo vinyl chloride", Aaer. Ind. Kve. Assoc. J,., 33(l):19-30, 1972. AP00019054 1 64. Kudryavtseva, O.F., "Characteristics of electrocardicgtaphie changes in patients with vinyl chloride poisoning", Gig. Tr. Prof. Zabol., 14 (8) 154-56, 1970. --------------------------- 65. Lange. C.E., Juhe, S., Stein, 0. and Veltaan, G., "Further results in polyvinyl chloride productior. workers", Ann. K,Y. Acad. Sei., 246:18-21, 1975. ----------------------------------- 66. Lange, C.E., Juhe, S., Stein, G. and Veltnan, G., "The so-called vinyl chloride sickness - ea occupation-related systemic sclerosis?", lot. Arch. Arbeitsned., 32:1-32, 1974. 67. Lange, C.E., Juhe, S., end Veltnan, G., "Liver angiosarcoma in two workers in e PVC-produciag factory", Deuc. Med. Wochenschr. * 99:1598-1:99, 1974. 68. Lee, 7.1. and Harry, D.S., "Angiosarcoma of ths liver in e vinylchloride worker". Lance"t. 1(7870): 1316-1318. 1974. 69. Lester, D., Greenberg, L.A. and Adans, W.R., "Effects of single end repeated exposures of humans and rats to vinyl chloride", Araer. Ind. Hvg. Assoc. J., 24:26S-275, 1963. 70. Lilis, R., Anderson, H., Nicholson, W.J., Deua, S., Fisehbein, A.S. end Selikoff, X.J., "Prevalence of disease among vinyl chloTide and polyvinyl chloride workers", Ann. M.Y. Acad. Sci.. 246:22-41, 1975. 71. Malconl, C., "Occupational carcinogenesis", Intcrnetlonel Congress Series No. 322 (ISSN* 90-219-0228-1) Cancer detection end prevention, Proceedings of ehe 2nd International Symposium on Cancer Deeeccion and Prevention, Bologna, Italy, April 9-12 (1973) 19-26, 1973. 72. Malconl, C., Clllbartl, A., Gianni, L. and Chleco, P., "Occurrence of angiosarcoma in rata following oral administration of vinyl chlorida: Preliminary Report", Osoedal. di Bologna, pp. 65-66, 1975. 73. Malconl, C. and Lefemlae, G., "Carcinogenicity bioessays of vinyl chloride: Current results", Ann. M.Y. Acad. Sc. 246:195-218, 1975. 74. Haltoni, C., Lefemlne, G., Carcinogenicity bioassays of vinyl chloride. I. Research plan and early results". Environ. Reg. 7(3):387-405, 1974. 75. Manufacturing Chemists Association, "Supplementary epidemiological study of vinyl chloride workers I - Report", MCA, Wash. It.C., Key 30, 1975. 76. Manufacturing Chemists Association, "Vinyl chloride chronology" Press Release, pp. 1-12, 1974. 77. Markowitz, S.S., McDonald, C.J., Fethlsro, W. and Kerzner, M.S., Occupational aeroosteol/sls". Arch. Pereacol.. 106:219-223, 1972. ; i i 1 \ ! it ' j i i ' , , i / AP00019055 "* 1 73. Marsteller, H.J., Laibach, W.K., MualLtr, R., Juhe, S. , Lange, C.S., Rohner, H.c. and Veltaan, G. , "Chronic-toxieity liver damage in uekets 1 polyvinyl chloride production". Dauc. Mad. Wochenachr. 93(48)52311-2314, 1973. ------- ---------------------------- 79. Marsteller, K.H., Laibach. W.K., Mueller, R. and Cedigk, P., "Unusual splenoaagalie liver disease as evidenced by peritoneoscopy end guided liver biopsy among polyvinyl chloride production workers", Ana. N.Y. Acad. Scl.. 246:95-134, 1975. -------- 80. Mastrooattao, , Fisher, A.M., Christie, H. and Dantinger, H.t "Acute inhalation toxicity of vinyl chloride to laboratory animals", Acer. Ir.d. Hvt. Aaaoc. J., 21:394-398, 1960. 81. Miller, A,, "Pulmonary function defects in nonsmoking vinyl chlorids workers". Environ. Health Parspect.. 11:247-250, 1975. 82. Miller, A., Telrateln, A.S., Chuang, M., Selikoff, I.J. end Varshaw, R.. "Changes in pulmonary function la workers exposed to vinyl chloride and polyvinyl ehloride", Ann. N.Y. Acad.Sci.. 246:42-52, 1975. 93. Misgeld, V., Stolpaann, H.J. and Schulte, S., "Poisoning by means of polyvinyl chloride or its constituents". 2. Hauc-Geschlechtskr.. 48(11):425-436, 1973. 84. Monsoa, R.R., Peters, J.M. and Johnson, M.N., "Proportional mortality among vinyl chloride workers". Environ. Health Parspect.. 11:75-77, 1975, 85* National Institute for Occupational Safety and Health, "Organic Solvents in Air" and "Vinyl Chloride Supplement", HEW, PHS, CSC, NIOSH, P&CAM 127, 1974. 86. National Institute for Occupational Safety end Health. "NIOSH recommended precautionary monitoring and control procedures for polymerization processes involving vinyl chloride", NIOSH, CSC, PHS, DHEW, February 1974. 87. National Institute for Occupational Safety and Haalth, "Vinyl chloride In air", HEW, PHS, CSC, NIOSH, P&CASt No. 178, 1974. 88. Nicholson, W.J., Hammond, E.C., Seidsan, 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* 69. Nlttl, G., Petruttellla,' V, and Fasano, V., "Rhaographic obser vations on workers in the plastics industry", Securitas. 55:683-694, 1970. 90. Okaws, M.T., "Health Hazard Evaluation Report No. 74-71-142; Delco Remy Division, General Motors, Anaheim, Ca.", HSU, PHS, CDC, NX0SK, 1974. AP00019056 ! 91. Okava, M.T., "Health Hazard Evaluation Report Ho. 75-1-194; Stem Products Company, Palo Alto, Ca.", HEW, ?HS, CDC, XIOSH, 1975. 92. Oscar, R.H., Carr, C.J., Krancz, J.C. and Sauetueld, M.J., "Anesthesia XXVII. Wareosia with vinyl chloride". Aneschesioloev. 8:359-361, 1947. ---------------------- **" 93* Ott, M.G., Lsagner, 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., Yane, W.P., and Waita, C.P., "Aeuta response of guinea pigs to vapors of some new commercial organic compounds. V. Vinyl chloride", Public Haalth Reo.. 45(2):1963-1971, 1930. 1 4 ' ; 95. Peoplea, A.S. and Leake, C.D., "the anesthetic action of vinyl chloride", J.. Pharmacol. Exp. Ther.. 48:284, 1933. ' j J i i 1 96. Popper, H. and Thomas, L.B., "Alteration* of liver and spleen among workers exposed to vinyl chloride", Ann. N.Y. Acad. Sci. 246:172-194. t1 97. Prodan, 1., Suciu, I., Pislaru, V., Ilea, E., and Paseu, L*, j "Experimental acute coxieiey of vinyl chloride (senoehloroethene)", Ann. N.Y. Acad. Jei., 246:154-158, 1975. 98. Prodan, L., Suciu, I., Pislaru, V., Ilea, . and Paseu, L., "Experimental chronic poisoning with vinyl ehloride (mocochloroathsna)", Ann. N.Y. Acad. Sci.. 246:159-163, 1975. 99. Purchasa, I.F.H., Richardson, C.R. and Andersen, D., "Chromosomal and dominant lethal effects of vinyl chloride". Lancet, pp. 410-411. Aug. 30, 1975. 100. Pushin, G.A., "Lesions in ths liver and bils ducts in workers producing some kinds, of plastics", Sov. Med.. 28(2):132-135, 1965, 101. Rannug, U., Johansson, A., Kamel, C. and Vachtneister, C.A., "The autsgenieity of vinyl chloride after metabolic activation", Amblo. 3(5):194-197, 1974. 102. Ravier, E., Dicer, J.M. and Plalat, J., "A case of liver angiosarcoma in a worker exposed to monomeric vinyl chloride". Archives das maladies professionnelles. de nedaclne du travail de Securtte SocialeT 36(3):171-177, 1975. 103. Regnaulc, V., "The synthesis of chlorlnaeed hydrocarbons", Justus Liebig*s Annalen der Chemie, 14:22-28, 1835. 104. Rose, V.E., "Statement for OSKA Feet Finding Hearing on Vinyl Chloride, February 15, 1975", HEW, PKS, CDC, NI0SH, 1974. 87 JE AP00019057 A 105. Rumyantseva, E.P. and Goryacheva, L.A., "Glucocorticoid function ef tha adrenals In patients suffering from chronic poisoning with son* unsaturaead 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. K.Y, Acad. Sci., 246;78-79, 1975. 107. Schaumann, 0.. "Effect on tha heart of eome inhalation anesthetics", Medzln. Chemie. 2:132-140, 1934. 108. Stender, J., "Emergency temporary eeandard for exposure to vinyl chloride", Fed. Register. 39(67):12342-12344, 1974. 109. .110 .111 .112 Stender, >T., "Proposed eeandard for vinyl chloride", Fed. Register. 39(92):16896-16900, 1974. Stender, J., "Standard for expoeure to vinyl chloride". Fed. Register, 39(194):35890-15898. 1974. Straub, W.E., "Health Hazard Evaluation Report Ho. 74-85-183; M.H. Ball Company, Lancaster, Pa.", HEW, PHS, CSC, NIOSH, 1975. Straub, W.E., "Health Hazard Evaluation Report Ho. 74-89-189; New York Telephone i Telegraph Company, New York,' H.Y.", HEW, PHS, CSC, NIOSH, 1973. 113. Stulova, E.A., "Characteristics of the etaet of thermoregulation in chronic vinyl chloride poisoning", Gig. Tr. Prof. Zabol.. 17(3):53-55, 1973. 114. Suciu, I., Prodan, L., Ilea, Z., Paduraru, A. and Paacu, L., "Clinical manifestations in vinyl chloride poisoning". Ana. K.Y. Acaa. Sci.. 246:53-69, 1975. 115. Suciu, I., Drejman, Z. and Valaskal, M., "Study of lllr.4 to vinyl chloride", Ked. Lavoro. 58(4):261-271, 1967. due 116. Ssande, B., Lapis, K., Hemes, 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 Gaffey, W.R., "Mortality study of workers in the manufacture of vinyl chloride and its polymers", J,. Occup. Med.. 16(8):509-518, 1974. 118. Thlass, A.M. and Flentzel-Beyae, R., "Retrotpective survey of tha sileged diseases associated with vinyl-chloride in the Federal Republic of Germany11, 2* Qeeuo. Med.. 17(7):430-432, 1975. 119. Thomas, L.B., Popper H., Berk, P.D., Selikoff, I.J. end Talk, H., "Vinyl-chloride-induced liver dlseeae", if. Engl. Med. 292(1): 17-22, 1975. 88 AP000I9058 i i 120. Torkelsen, T.R., Oyen, F and Revs, V.K., "The toxicity of vinyl ; chloride as determined by repeated exposure of laboratory animals", Amer. Tnd. Hvj. Assoc. J., 22(5):334-361, 1961. 121. Tribukh, S.L., Tikhomirova, N.P., Levina, S.V. and Kotlov, L.A., 'Working conditions and measures for their improvement In production and use of vinyl chloride plasties", Gig. Sanlc. Ho. 10:38-44, 1949. ; 122. Vstia, A.N. and Plokhova, E.I., "Changes in adrenaline-like substance* in rabbit blood following chronic exposure Co vinyl chloride fumes", Cig. Ir. Prof. Zabol.. 13<6):46-47, 1969. i j ' 123. Vatin* A.N. and Plokhova* E.I., "Changes in Che rate of ineulcecion of conditioned reflexes In rats on prolonged exposure to vinyl chloride vapor In concentrations approaching the rrsv*^iw permissible concentration", Gig. Sanit.. 35(4/6):434-435, 1970. 124. 125. Vatin, A.N, and Plokhova, .1*, "Changes of cardiac activity in rats chronically exposed to vinyl chloride vapors", Farmskol. Tokeikol.. 32(2)1220-222. 1969. " * Vatin. A.N. and Plokhova, S.Z., "Obtaining an experimental model of the toxic angioneurosls arising under ehe chronic effect of vinyl chloride vapor on the organism", Cig. Tr. Prof. Zabol.. 12:47*49 1968. j I I jj 1! j 126. Vatin, A.N. and Plokhova, E.I., "Pathogenic affect of chronic vinyl chloride exposure to rabbits", Farmakol. Toksikol., 31(3):369-372, 1968. 127. Veltman, C., Lange, C.E., Juhe, S., Stein, C. and Bachner, U., "Clinical manifestations and course of vinyl ehlorlde disease", Ann. N.Y. Aced. Sei., 246:6-17, 1975. 128. Vertkln, Yu.I. end Haaoneor, Yu.R., "Os ehe eeaee of the broncho* pulmonary system is worker* engaged in the manufacture of ereiclas made of polyvinyl chloride", Cig. Tr. Prof. 2abol.. 14(10):29-32 1970. ; j 1 I 129. Viola, P.L., "Cancarogenle effect of vinyl chloride"* Abstracts. Tenth Inc. Cancsr Conf., Houston, Texer* Session 56: 742 Abstract No. 29, 1970. 130. Viola* P.L., "Oncogenic aetion 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. tavoro. 61(3):174-lfi0, 1970. 89 ir,iribnHViSi APOOOl9059 132. Viola, P.I., Bigotti, A. and Capuco, A., "Oncogenic response of rat kin, lungs, and bones eo vinyl chloride". Cancer Res.. 31:516-522, 1971. 133. Warren, H. and . f, J.E., "Health effects of vinyl chloride nonoser: As annotated literature collection", Eny. Health Per.. 11:251-252, 1975. 136. Waxueiler, R.J., Stringer, W., Wagoner, J.K., Jones, J., Falk, H. and Carter, C., "Neoplastic risk aaong workers exposed to vinyl chloride". Arm. N.Y, Acad. Sci.. 271:40r48, 1976. 135. Wilson, R.H., MeCoraick, W.E., Tatus, C.F. and Creech, J.L., "Occupational acroosteolyeia", JAMA, 201(8):577-581, 1967. 1 1 5 < > I i 3 I j f j j I j; j 1; I i attittfRi 90 ; 4 1 \i | \. I '* \. 5 A APOOO19060 u ( iV ;i S' ( I UA. Wr .. f*1 Appendix A DESCRIPTION 07 PLANTS I. Monomer Plants Plant A This facility manufactures VC using cha Acetylene-Hydrogen Chloride Process portrayed in figure 1, The plane normally operates at 10 percent of capacity and then only when acetylene, manufactured at the plant, is available for Che manufacture of VC. Nearly all of the aeeeylene manu factured at this site is sold sc product to nearby cheaaeal 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 tha facility, whleh manufactures acetylene, methanol, ammonia, and VC as major products, with vinyl aeetylene. diacetylene, methyl acetylene, dimethyl ether, and 2-ehloroprcpece aa byproducts* Liquid air and liquid nitrogen were also manu factured at the facility. A VC surveillance program was established ae this company in April, 197A, The manufacturing areas ara monitored at various points using a Mi ran Infrared Scanner with ehert reedout, and a Century Organic Vapor Analyzer(OVA). Air semplee ere collected in myler sampling begs on e regular basis. The air samples ere analysed for VC concentration using gas chromatography, The results of the company's sampling program shoved e TWA eonceneraclon 91 .i v A .. tt }/-> . \" .4 11 itmm' AP00019061  1 1 r*nge of 0.01 to 67 perts per Billion (ppai) of vinyl chloride* Except for the control laboratory and control room, all oparatiena are performed outdoors. The control laboratory and control room ara air conditioned with one air change per ninuee. Tha following changes have bean mad* to their industrial hygiene program. i All employees are required to wear auppllad air-respirators whan tha VC concentration is expected to bu over 50 ppm. -1 \ A. f 4 Signs ere posted whenever area laonitexing indicates high VC concentrations ara In eha air. Additional purging time is required on all vessels which handle VC prior to being opened. Vx ..l '/ / i` High priority has bean placed on work designed to eliminate VC leaks. Gas masks and slicker suits are*worn in accordance with currant OSHA regulations. Plant B This facility produces VC using the Ethylene Bichloride 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 produet and was also used beta 'V . 1 / / v\- 92 i I SLJ r-- APOOdl9062 on sice 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, tetraoethyl 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 wae 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. j j i* ! j [ i 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 chsrcoal tube method is used to obtain 15-minute soot samples end 4-hour personnel samples on e regular basis. Cas chromatography is used ee determine the concentration of VC picked up in the charcoal tubes. The results 93 J AP00019063 - ^.^f^V^WVTrvrtJVl'a i of thi* company's sampling program show VC concentration rang* of 0.01 to 62 ppm. The following work practice changes had bean Instituted to protect their employees. - During loading, VC tank ear spew guages ware previously vanead to atmos phere. The spew gauge vent system is now closed with a tensing device to detect liquid, indicating the eer is lotded. After loading, VC tank car load and equalising lines were previously disconnected with residual vent (mostly vapor) allovad to ascapa to etmoaphara. Thasa lines are now purged with nitrogen (to flare) prior to disconnecting. VC liquid staples were previously taken and disposed of In aueh a r,inner that the potential for release of material to the atmosphere was quite high. Closed systems have been provided to permit purging sample bombs end connections, obtaining samplesi and disposing resldusl sample material without exposure of personnel. The former practice of draining a gaga glass to verify the liquid level has been discontinued. Procedures for prtparlng equipment for opening have been revised, and extra precautions takan to minimize risk of VC relaasa to atmosphere. 94 ? t j T > i1 i 1 t J i APOOO19064 1 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 beat. The revised procedure cells for thorough purging of the scrubber* utilizing heated inert ges and heating panels on tha scrubber shell to ensure negligible release of VC to atmosphere when the scrubber Is opened. While respiratory equipment hes always been eveileble for use when needed, personal respirators are now Issued to all individuals for use whenever the potential for exposure exists. It is iaposiblt to ascertain tha 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 ere described below. Prior to the establishment of the 50-ppm Interim standard, VC was con- sidered as one of a family of chlorinated hydrocarbon* produced in the Hydrocarbon Area. Thera were 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 chlorocarbone, hydrogen chloride, chlorine) was likely to occur. The situation today, of course, it 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 < i t j i j i r ' 1 I | AP00019065 *>'1 '* W* "spot" monitoring is desired. Certain areas have been designated as requiring respl; .ory protection. All personnel have bean issued respirators (and trained in their proper use) and have been instructed to vear them when doing any job (e.g., opening or dosing valves) where the potential for exposure to VC exists. Supplisd air respirator hook-ups art being extended to all areas of tbs VC plant. The Medical Department has instituted a program for routine personnel monitoring utilizing carbon tube adsorption units. A medical survalllanca program for all personnel who may have been exposed to VC in the pest has been instituted and will be continued. j I i | i * . On-the-job eating, drinking and smoking policies have not been revised i as thase activities ware already restricted to designated areas. < i Plant C i I The Oxyhydroehlorlnatlon Process was employed by this facility tv manu facture VC from Ethy'use and chlorine as illustrated in Figure 3. This i company is a large producer of VC. normally operates on a continuous bases, and has bean producing VC at this facility for 12 yaara. A total of 600 people were employed at thla facility; however, only 242 employees were exposed to VC. Products produced at this facility were ethylene, chlorine, ethylene diehlorlde, hydrochloric acid, VC, trans-l,2,-dichloroethylene, benzene, chloral, carbon tetrachloride, chloroform trichloro ethylene, ethyl chloride, and chloropropane. Ho PVC resin was produced at ehls site. 96 AP000I9066 The manufacture of VC was a closed-ays ten operation, and all of the pro duction equipment was located outdoors except for the instrument houses, control rooms, laboratory end offices. The offlcesi laboratory, control rooms and instrument houses vers kept under positive pressure. In addition, the equipment in the Instrument houses wes purged with nitrogen. Ko VC ves piped to the control rooms. All VC in the*leberatory was kept end handled in high-volume ventilation hoods. All production employees had their own respiratory protection devices. . Respiratory protection devices vere kept in the control rooms for any maintenance personnel working in the area. All personnel had been trained in the use of eha equipment and were required to wear respiratory protection equipment when working areas or performing specific operations where the exposure to VC was higher than, or could hava been higher than tha permissible OSHA limit. Disposable or washable coveralls were provided for heserdous operations, end gloves were required for personnel performing tasks which could expose their hands to ths chemicals. Shower ! facilities were provided, and safety ahowcrs were available in the VC manufacturing areas for emergency use. Smoking end eating were confined to the cafeterias end the control rooms. Good housekeeping was maintained throughout the plant. . Loading personnal vera required to wear air prassure demand respirators when performing any operation where exposure to VC was possible. Supplied-eir respirator hook-ups vere provided ekorughout the plane. ........- \ . 97 - ......................... I j i i I ' j i: ii AP00019067 I i / } t Each instrument house contained an infrared analyzer and gas chrcmacegraph ce 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 additlont portable Century OVA'e were used to cheek areas where the exposure limits for organic vapors were higher then permissible. A surveillance program ofr VC wee initiated in July* 1973, using the charcoal tube method eo determine the concentration of VC that their personnel were exposed to, end 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 vert analyzed using gas chromatography, In addition, all exposed personnel were given medical examinations meeting the requirements specified in OSKA regulation 29 CFR 1910.93q. The following average time-weighted average (TWA) exposures to VC had been determined using OSKA personnel monitoring techniques since August 1974. Operstor 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 9.6 ppm Insufficient Data Insufficient Data 98 t t } Ii I | i i I ir i i i AP00019068 Samples vert taken while perforating activities which gave the greatest probability of exposure. Humorous changes have been made to the facility to reduce or eliminate the possible exposure of personnel to VC or ocher suspeet agents. A number of these changes are described fellow. Major equipment changes that have been made to reduce possible exposure to VC monomer ere: A VC vapor collection and recovery system had bean installed in the tank farm. Essentially, this consisted of a compressor and eondansing system. The recovered VC was transferred to of^specification storage. A VC emergency collection and flare system had been Installed for the proeess arees. In ease of a VC release from relief valve or vent, the VC was piped eo 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 Horth ethylene i f j t i ( i i APOOO19069 r M. \ dichloride unit. By means of a ehroaaeegrsph, the atmosphere at ten different points in the unit ves regularly analysed for a number of chlorinated organics Including VC and ethylene dichloride. J Additional valves had bees pun on VC teak cer loading hoses to almost eliminate exposure due eo venting the VC from the hoses st the end of the loading cycle. The caustic scrubber blowdown had been piped to e blowdown knockout tank which eliainateo exposure by venting the VC to flare. The hydrogen ehloride columns had bean re-trayed to extand periods between opening for cleaning. Changes in operating and maintenance practices and procedures which hed reduced possible exposure to VC were: Shift monitoring of the plane 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 snd maintenance personnel full awareness of the VC levels in the plant. i t t i ] AJ < J > J 1i i4 i 1 ] 3 I ? i 100 I... AP00019070 "v Organic Vapor Level Above 50 ppm Between 25 end 50 ppa Below 25 ppm Respiratory Protection Required Supplled-alr Respirator Cartridge Mask No Protection All veteele were being better prepared for entry end 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 ppa, a continuous-flow air-line respirator or self-contained breathing apparatus wasused. The following general guidelines were being used to determine where, when, and vhaetype of respiratory protaecion was required: Any job which released VC to the atsoshpere, 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 jebe where the VC was less than 2 percent by volume of the etresm or equipment contents, i f i \ i j I l < j 1 i AP0bbi9071 *cd where 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 veer the same respiratory protection aa the person assigned to the job* Air-line respirator usage In '^he VC tank farr. nad b^an rtade core 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 aress handling VC used the OVA onee each shift to monitor designated locations within their areas. Leaks wars noted end corrected by the operator where possible. Otherwise the foreman was notified -so maintenance personnel could immediately repair the leak. The Sefety Department was using the OVA to thoroughly monitor the production areas at least onca 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 flsre 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 I i { | I t ; I i i i i i iI 1 AP00019072 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 "vet testing1' hood had bean updatad to give higher voluse ventilation and conform to cht requirements for handling hazardous materials. Tests have shown no vapors vert escaping from the hood. Collected VC staples vere no longer permitted to be stored in the process area control rooms. Outside storage wee required. Employees performing tasks where it vaa possible to contact liquid VC vera being required to wear gloves impervious to VC.- In shutting down hydrogen chloride and vc colusns, quench towers, etc., extra steps vere taken to strip out the VC. When the topping column was down, the overhead of the lights columns was collected by keeping the condensers very cold. In the past, this vapor had bean vented to the atmosphere. Exposure reduction projects that ware in process were: VC process equipment drainage system VC tank car gauging system VC process enclosed sample system < | I AP00019073 V*-1 VC flare instrumentation Ra-traying of Ease hydrogen chloride coluan Permanent atr monitoring systems in all three cracking units Corrosion-resistant_VC-.strip&er condenser A method had been devised and triad which would eliminate employee potential axposura on much o the VC sampling. Hardware had baen ordered to convert many sasple points to closed sampling. A closed system for liquid blowdown from eodium hydroxide scrubbers was over 50 percent complete. A system wss being worked out vhieh will permit purging tank ear loading lines to the flare before they were dlaconneeted, A continuous analyzer for detectiAg vatar in VC would eliminate the need for many samples now taken by operators. An additional large caustic scrubber eo eliminate the need for email scrubbers was plannad, This would permit all caustic scrubber operations to be hendled in one area, and not only reduce the number of employees potentially exposed, but additionally would make controlling emissions much more feasible. A program eo eliminate pump seel leekage was under way* A full investigation of ethylene diehloride-VC pumps had baen completed, and specific pto^rams had been started which promise reduced pump seal failure. i J \ i i J \J ) j 'l j I i j J j [ AP00019074 Quotations were being evaluated on providing a corrosion-resistant snippet 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 ethers would be tried. Reboiler venting system Topping column revisions Larger rebeilers Better level Indicators and purges This Use la not all inclusive but is indicative of the planning end efforts going inee further improvements* II. Polymerization PIants Plant P This plane is large chenieal manufacturing complex with a long list of chemicals produced. Approximately 1800 persons wart employed there vl only 150 of them involved in PVC operations. The plant has produced PVC since 1929 end at the time of the survey produced PVC using three processes; a solvent proses* an emulsion process, and a modified emulsion process in which VC is copolymericed with aerylonitrlle. All reaction equipment for the emulsion end modified emulsion processes were located outdoors. All equipment for the solvent process and the I I Ii i Ii! 1 1 l i AP00019075 T 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 art located in one building vith the reactors adjacent to ehe building. The modified emulsion process control room is also loactad in the same building with the recovery compressors, while ehe realtors ere outdoors adjacent to the building. The solution process has one building for tha reactors and strippers, one for precipitation end drying of PVC, one for solvene recovery, and one for bagging of PVC. The plant operates three shifts per day, seven days per week. This facility has an inplant dispensary vith a full time Medical Director and an assistant. Nurses ere on duty 24 hours a day. A pre-enpJoyrient physical examination la required vith re-examination every one to tvo 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 e central safety committee end e union safety committee. Industrial hygiene matters are handled by the environmental protection i i j l \ 1 j i i - t ` I \ APOOO19076 Broup. They have 2 industrial hyjienist* and a technician plus nan to take care of solid waste, water, and air pollution. Industrial hygiene surveys for various hazards are conducted on routine basis* This plant also he - a full tine fire departaent which also handles rescue' work* There Is also a rescue squad made up of lab personnel trained in first aid. VC has been schpled at the plant since 1969, although somewhat sporad ically until 1974. The initial sampling was dona with detector tubes and later with grab staples analysed by gat chromatography (GC)* In 1974 personal stapling 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 wars sampled sequentially. Each sample took two minutes to analyze to saeh point vas sampled onea every 40 minutes. Workers had begun wearing supplied-alr respirators while cleaning reactors or other teaks 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 allninate monomer filters Clean autoclaves less often J 4 | [ ! i v'\ \ ----------- . i i APOOO19077 Improved VC recovery system Installed vacuum system on reactors to vent reactors prior to and during entry. This replaced system that vented reaetcr to ataosphere. Eliminated several venting points j Plant E This plant is entirely a PVC production faeiliey vith PVC being produced by ebe masa procasa and tha suspension process. The plant it a relatively new one, having opened in 1970 and the processes are computer controlled. The work ^orce consisted of 260 persons, 60 of vhea vara inovlvad in the PVC polymerisation ataaa. Procasa equipment was located indoors. The suspension and mass proeaases occupy aaparata buildings vith drying and bagging eparaeions in buildings aaparata from the reactor buildings. The plant operated three shifts per day, seven days per week. This facility has an in-plant dispensary vith a registered nurse on duty Monday through Friday during tha day shift. All lead technicians have first aid training. In addition, two physicians each visit ones a week. Emergency arrangements have been made with nearby hospitals. j > I j f l t I j j Pre-employment physicals era required. These Include e general physical examination, audiometry and semi-annual SMA-12 blood testa. 108 1a i J\ APOOO19078 ' ^ ! ,, '* \ \ The Sefeey Department consists of a safety engineer and an assistant. Hard hat, safety glasses, respirator, and safety shea progress are in operation. In addition, wot..nr* ara supplied work, clothes which they ara required to change each day. Daily showers are nandaeory for workers in the polymerization areas. Workers ara required to wear supplied-eir respirators whan entering vassals for cleaning or when performing other Job*, such as cleaning filters that have a high potential for VC exposure. VC was being sampled by the use of charcoal tube* *t this plant. An automatic sequential sampling system had been installed in each poly- merlzaeion building in early 1974. This system consisted of a Sendix total hydrocarbon analyser with six sampling points. Analysis tiea for each sample was two minutes, so each point was sampled every 12 minutes. These sample results were fed to a computer which stortd shift peak levels for eech point and calculated shift averages. It also actuated a visual alarm In tha production areas whenever levels wane above e preset limit. This limit at the time of tha visit was 2S ppm. In addition, one person per shift spent full time checking for VC leaks using an OVA. Also whan a high VC level was shown by the automatic sampling system, he determined the source of the leak, and saw that it was corrected. 1 .i ' { i j ' j Plant F Plant T is predominately e PVC polymerization facility but also has other operations. PVC Is milled end calendered and plasticizers, polyurethanes, and acrylate polymers are else produced. The plant began operations in 1951 with ths production of PVC emulsion resins. At present the suspension 1 * ..................... .................... 109 ................... APOOOt 9079 1 *nd emulsion processes are in use here. The work-force consists of approximately 700 persons, with 200 of them working la the FVC polymerisa tion areas. The plant operates three 8-hour shifts per dey, seven deys per week. - ^h* suspension resin is produced in two buildings, one old end one nev, each with a separate dryer building nearby. The emulsion resin is pro duced in a third building and drying takes piece in a separata building. A fourth building also has an emulsion process, but it is used to product ?VC latex. This process was not in operation at che time of the survey and was therefore not templed. This facility has an in-plant dispensary with nuraaa on duty 2A hours per day, 5 days per week. All foreman and guards are trained in first aid, Two physicians each spend evo hours per dey at the dispensary five days per week. An emergency vehicle is available at ell times. Hospitals are ten to fifteen minutes away. The corporate medical department sets guidelines for routine medical testa and physical examinations. Pre-em ployment physicals, including blood tests, pulmonary function cases, audiometry, and a medical history are required. Retesting of employees is done periodically depending on the work location. The safety department consists of two safety inspectors. Hard hat, safety glasses and respiratory protection programs are In operation. Workers are required to wear suppliad-air respirators when entering vessels for cleaning or when petforalng other jobs, such as filter cleaning, that have a high potential for VC exposure. Safety is 110 V, -------------------- ..... ----------- APOOO19080 stressed to the workers through monthly safety Bastings, ahott weekly safety nestings in the operating arses, special safety eastings to discuss new topics, and by petting information on bulletin boards. Equipment inspection it carried out by the plane guards under the super vision of the safety department. That* inspection* include such things as routine checks of relief valves, rupture discs, end fire extinguishers. All plant personnel receive fire extinguisher and hose training. The plane hae a fire truck with foam generation and dry chemical equipment. A yearly safety eudic is performed by corporate personnel. Seal-annuel eefety audits are conducted by plant safety personnel. Historically, Industrial hygiene services were provided by corporate i t 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. Ac that time, the priority item was VC sampling to determine regulated erase for the new OSHA standard. Sampling was also being conducted in various parts of the plant for diisocyanate, carbon monoxide, vinylidene chloride, end PVC dust. Also, two engineers were on full time temporary assignment to Implement changes to bring the plant in compliance with the new OSKA standard. One of these changes vss the installation of an automatic sequential VC sampling system in each polymerisation building. This templing I j j j ,1 APOOO19081 ym consists of a Bendlx total hydrocarbons analyser in the suspension and aaulaion resin buildings and a gas ehromatograph in Che latex building. Each of these inseruBcnes Is tied into six sampling points with changes being made to add six additional sampling points to each system* At the time of the visit* analysis tine was two minutes for each point, so each point is stapled wary twelve minutes. With the additional sampling points, analysis time would be reduced to one minute, eo that each point would still be aaapled every twelve minutes* Thsse sample results art fed to a minicomputer, which stores ptak values for sach point and ealeulaees eight hour shift averagss for each point along with floor and building averages. Thesa systems also actuate a visual alarm in the * production areas whenever levels go over a pre-eat limit* At the time of our survey this was twenty-five ppm. 1 Zn 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, whan a high VC level is detected by the automatic sampler, they use the OVA to determine the cause of Che reeding end sea that le 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 vesta and recovered JVC. . 3* Separate eating facilities provided. 4. Daily change of clothing provided. 5. Recover ell vapors Before disconnecting tank cars* 6. Improved building ventilation. U2 APOOO19082 7. Improved compressor seals. B. Improved reactor aanhead gaskets. III. Fabrication Planes 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 vas started up in August 1971. The company,normally employs 150 people end operates 24 hours a day on 'a S-day-veek basis. All manufacturing operations are performed indoors la s modem, veil-designed and laid out plant. Approximately 50 people are involved la 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 trio} compounding, la the mixing of polyvinyl chloride resin with plasticisers, fillers, lubricants, stabilisers, pigments, and ocher materials to produce a dry-bland compound} extrusion in the conversion of dry-bland or pelletized compounds into continuous plastic strips of predetermined cross section} fibers, in the extrusion of pelletised compounds into spools of colored yams used for the manufacture of woven products: and molding, by the injection of PVC compounds into a heated mold to produce items having definite size, shape, and color. Compounding at this plant Is 113 accomplished in ribbon-type blunder*, and conversion of the dry-blend or pelletized compounds into pltetic cess cakes pleee la the extruders and injection solders. Ho basic changes have been made to chair PVC fabrication operations. Ventilation in the plane is provided by 16 roof-aounted exhaust fens with a total rating of 50,000 cubic feet per minute at 1/2 inch etatlc pressure which provide an air change once every 50 to 55 minutes. The adjoining offices ere sir conditioned. Overall housekeeping Is very good end the equipment has been installed in a wall-planned, uncrowded manner. As enclosed, air-conditioned cafeteria area has been provided for breaks and lunches. Smoking Is rsstrietad to special areas. Special clothing is not required. i * e The company does not have a VC surveillance program; however, the plane has been surveyed for VC concentrations by en insurance company. . The company uses bulletin boards and meetings to ksep their saployees informed on health and safety programs. / Figure A-l shows a flow schematic of the processes used by Plant C to manufacture PVC produets. Plant H This facility processes PVC resins into s wide variety of extruded and injection-molded products. The company has 21 years of experienea In the manufacture of PVC products. 114 V Ku Legend: A - Bagged Materials' B - Blender C - Storage Container 0 - Extruder E - Cooling Bath F - Cut-Off Machine G - Shipping Container II - Injection Molder Figure A-l Flow Schematic, Plants C, II APOOO19085 Nv V kernes Tha company normally employs 260 people end all of the employees are considered by Che company to be exposed to VC. The plant operates on a 24-hour-per day, 5-day-per-veek schedule, and *11 manufacturing operations are performed Indoors. The company usee the following processes in the manufacture of PVC product#: bonding, by hot-seal welding of flexible extruded profiles such as refrigerator seals; compounding, in the blending of FVC resin with plasticizers, fillers, stabilisers, pigments, and other additives in semi-automated blender with e 45,000-pouad-per-day capacity; extrusion, in the production of a vide range of profiles from powder-type compounds; end molding of dry PVC compounds into items such as automotive seels end cable enclosure# by `injection melding. Ventilation throughout the plant is provided by air-circulating fans. Hoods vented to the atmosphere through e duce system have been installed on injection molding presses end the high-intensity compound mixer. Doors and windows are opened as required to assist the plant ventilation system. The only significant change in the plane 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 i* the plant. 116 eefaessaMiAtteM jS2&u*i AP000f9086 The company has an activa safety and medical program. Figure A-l ahowa a flow schematic of cha processes uaad by Plane H to manufacture PVC produces* Plant I This facility processes PVC resins ineo numerous dip-molded and dl-coated produets using plastlsol-type compounds. The company has been fabricating PVC produces by the dip-molding process for 25 years and normally employs 110 people. Due to the design of Che plant, all of the employees are considered to be exposed to VC. The plent normally operates on e one- ehift-per-day basis, 5 days a week. The company added blow molding units : three years sgo. Blow-molded products are msde from polyethylene compounds. This company used the following three processes to produce PVC products: (1) compounding, is the mixing of PVC resins with dieepryl phthalate, dioctyl adipate, end tallates as plasticisers} barium, eadmiua, and sine organic solutions as stabiliser*! pigments} and fillars} (2) molding, by dipping a heated mold into a plastisol compound and curing cha dipped t mold in an oven; and (3) plastisol*, in the compounding of plastisol mixtures. The only change that has been mede to their ?VC manufacturing processes is the addition, 9 years ago, of an aucoaaced-conveyorised die-molding line. All of the other dle-moldlng units era hand operated, batch-type \ V V im units. Plant ventilation it 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. i it i < } i! i The company has an activa safety program and performs area and personnel sampling using ths carbon tubs sampling method. The carbon tubes are analyzed by one of the PVC resin suppliers. The results of the sampling analysis ara posted on employes bulletin boards along with ocher safety * a and health bulletins. Sampling results show a range of 0.01 to 18.0 ppm. An enclosed cafeteria is provided for smoking, drinking, end eating during breaks and the lunch period. Figure A-2 shows a flow schematic of the processes used by ?lanc Z to manufacture PVC products. i i i i i 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-call expanded P'/C/rubber products for 19 years, and no significant changes have been made to the original precast. 118 AP000I9088 i i I i Legend: A - Bagged Materials B - Blender C - Mixing Tub D - Mixer - Plasticizers F - Pigments G - Hold Heating Oven H - Plastisol Dip Tank I - Heated Hold J - Curing Oven K - Shipping Container i 4 APOOO19089  I I I \ t i l Tlie plant oparaeas on a 24-hour-day, 5-day-per week schedule and performs a batch-type operation. Tha plant has 1,110 employees; however, only 160 of their employees are exposed to VC in their manufacturing operations. The manufacturing processes perfoioed by this company Involving PVC resins and compounds are compounding, extrusion, foams, and molding. Tha manufacture of the various closed-cell expended produet line produced . by ehls company begins with the addition, to m Banbury mixer, of predetermined amounts of the materials required to make the desired compound. The Banbury-mixed compound is fed to a two-roll mill where further mixing i cakes piece, end ends up as a sheet of compound on the mill roll. Sections of the sheet ere cut off and placed on e portable reek. The milled slabs 1 ara fed into e tuber (rube-type extruder) where the 'extruded compound for the batch-type units is cut into sections. The sections ere placed in a multi-leaf platen press where Che section is heaeed under pressure to a definite shape, and partial expansion takes place. The shaped places ere removed from the presses, loaded onto racks, and moved to aeoond oven. Tha loadad raeks ara placed in tha oven where the'partially blown sections are further expanded to approximately four times In size. Tha raeks are removed from tha oven, and the expanded slabs are unloaded and stacked onto skids for packaging and shipment. ' ; ^ * (# t \ i i ' * i In another building, the milled slabs are fed into e continuous tuber located at tha head of a long tunnel-type oven. The tubed stock is APOOO19090 cured end fully expended Into e continuous sheet in the ovens. The expanded sheet is cooled end passed to s cutter where it is cut into sections or worn. onto rolls prior to packaging for shipment. > \ ' In other operations, the milled sheet een be extruded through heated dies to form concinuous profiles of closed-cell expended extrusions. Shis type of product would be primarily used for gasket, insulation, or cushioning materials. t I She closed-cell expended products can be coated with a plastlsol 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 HIOSB publication P & CAM Ho. 178, Vinyl Chloride in Air and Personal Css Sampling Pumps. Initial saaplss collected In Hey 1974 indicated'less than 1 ppm of VC for 10 area samples,. The ehareoal tube samples were analysed by an independent laboratory. Figure A-3 shows a flow schematic of the processes used by Plent J to manufacture PVC products. | ii * Plant K This facility manufsecures plestleiaed PVC calendered film end sheeting, expanded vinyl sheeting, and printed vinyl film. The company has been . 121 AP00019091 w MM X ! ! Legend: A - Bagged Materials B - Banbury Mixer C - Two-Roll Hill 0 - Slab Rack - Tuber -F - Tunnel Oven G - Product Rolls H - Tube Rack ' I - Hot Press J - Oven Rack 1C - Batch Oven LShipping Container Figure A-3 Flow Schematic*^Plant AP00019092 nuking calendered products 35 years, and expanded (foes) type products sighe years. The PVC plane normally employs 127 people and operates on a continuous basis seven days a week. All production operaeens 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 Bade to the manufacturing operations; however, a number of engineering improveneats have inlcieted to laprove production end eliminate unsafe working conditions. The eoapsny uses the following processes to produee the PVC produces Bsnufactured 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 plasticisers, fillers, stabilisers, and ocher 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 eha charge in the Banbury sixers); extrusion, in ehe procsssing of ths Banbury charge through a screen and extruder head to a "rope" that is fed to the calender; fibers, in ehe combining of e roll of fabrie with a sheet of polyvinyl chloride plastisol; foams, in the expansion of a plaatlsol film in a blowing/curing oven; plastlsols, in the compounding of plaatlsol mixtures; and thermoforming, In the embossing of designs into PVC film and shestlng. Riv materials used in the production of JVC products ere PVC resins, plasticizers, stabilizers (barium, cadmium, and zinc organic salts in solution form), fillers, pigments, and Celogen as a bloving 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 art vented to the atmosphere through a dust collector, < i1 j j } l J * The company has an aeeive safety and sampling program. Thirty-minute brelfinga 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, Miraa 11 infrared analyzers plus Century OVAs are used to cheek for VC. The charcoal tubes are sant to their test esnter or a commercial laboratory for analysis* The analysis on the charcoal tubes can also be performed at this site. The sampling progrsa vas initiated in April 1974, and the only change that has been made ia an increase in the sampling frequency. The results of their sespling program Indicate a VC range of 0.2 to 1>1 ppm for their operating personnel. 1 1 ; I Housekeeping throughout the plant is good and their safety department is working to eliminate or reduce employee exposure to VC belov the 124 i ttMtfiiaaai / ... I' AP00019094 7 permissible working levels. Employees performing'operations where exposures above the permissible limit are possible must wear protective clothing. Smoking, drinking, and eating ere permitted only in enclosed air-conditioned cafeteria areas or offices. Figure A-4 shows e flow schematic of the processes useo by Plant K to manufacture PVC products. Plant L This facility processes PVC resins into pelletized PVC compounds, thermo- i formed products, vinyl film, and vinyl aheeelng. The company has been * performing calendering operations since 1946, thenaoforming since 1958, r and compounding since 1959. The company employs 520 people; however, only 309 of the employees ere considered so be exposed to VC. The facility operates on a 24-hour-perday schedule, 7 days per week depending on the work loed. All of the produeeion operations for the processing of PVC into finished products are performed Indoors except for the offloading of resins to the rooflocated storage hoppers, end the loading of compounded resin* into bulk shipping devices. The manufacturing operations performed in the conversion of PVC resins into salable product* are compounding, calendering, end thermoforming. Compounding involves the mixing of PVC resins, plasticizers, stabilisers, fungicides, bacteriastats, lubricants, pigtnente, and fillers in continuous 125 AP000I9095