Document R2LMzX4e9ZwaVK66JBK31LrdE

Safety nnd Environmental Concerns In Resin Manufacture John T. Barr Air Products and Chemicals, Inc. Box 538 Allentown, PA 18105 Volume I, Chapter 5 Encyclopedia of PVC Second Edition Final Draft March 1984 o jjc -f 1 SPI-00050 ~T Table of Cottents I. Introduction II. Toxicity Considerations A. Vinyl Chloride 1. Acute Toxicity 2. Metabolism 3. Chronic Toxicity 4. Carcinogenicity 5. Reproductive Effects B. Vinyl Acetate 1. Acute Toxicity 2. Chronic Toxicity C. Trichloroethylene 1. Toxicity 2. Carcinogenicity D. 1,2-Dichloroethane 1. Acute Toxicity 2. Chronic Toxicity 3. Carcinogenicity E. Polyvinyl Chloride Regulatory Status A. The Food and Drug Administra tion B. The Occupational Safety ana Health Administration C. The Environmental Protection Agency 1 . Air Emissions 2. Water T Pas 1 1 1 1 5 6 9 18 21 21 22 23 23 24 26 26 27 27 28 30 30 32 34 34 38 SP1-00051 Tabln of Contents (continued) 3. Solid Wastes 4. New Product Manufacture IV. General Safety Procedures A. Raw Material Handling and Storage 1. Vinyl Chloride 2. Vinyl Acetate 3. DCE and TCE 4. Initiators B. Monomer Production C. Polymerization 1. Reactor Control 2. Worker Exposure 3. Other Considerations D. Stripping E. Downstream Operations v. Waste Streams A. Water B. Liquids and Gases C. Solids VI. Analytical Methods VII. Vinyl Acetate Copolymers VIII. Acknowledgement IX. Glossary of Acronyms X . References Page 40 40 40 42 42 45 46 46 48 48 49 52 56 58 60 61 61 63 63 64 66 68 69 SPI-00052 Tables 1. Selected Physical Properties of Vinyl Chloride 2. Selected Properties of Substances Discussed in this Chapter 3. Summary of ASL Cases by Country 4. U.S. Cases of ASL by Company 5. U.S. Cases of ASL by Date of Death 6. Regulatory Status of Various Substances 7. SADT and Recommended Storage Temperatures for Typical PVC Initiators 8. Summary of Major Vinyl Chlor de Accidents Page 2 4 12 13 14 31 47 53 Figures 1. Fault Tree for Pressure Failure of Recovered Monomer Tank 2. Fault Tree for External Fire in the Process Area after 41 after 41 SPI-00053 Safety and Environmental Concerns in Resin Manufacture Introduction Significant changes have occ jrred In PVC manufacture in recent years because of developments in s ifety and environmental concerns in general and the concerns for vinyl ci loride (VC) specifically. For many years the primary safety hazards o' VC were thought to be its flammability and anesthetic properties, plus the need to prevent overpressuring of equipment by uncontrolled po ymerization. Data became available in the 1960`s which gave reason for concern at exposures below the anesthetic/explosive range, Vinyl chloride was shown to be toxic to the liver In animals, to cause ac roosteolysis (AOL), a degenerative disease of the bone tufts, in humans and by 1973 it was found to cause angiosarcoma of the. liver (A$ L), a rare and usually fatal liver cancer, in both animals and humans, There are lesser health concerns for the other components of the resi manufacturing process, although each has been found to have some unde$ irable effects. A summary of the toxicity data for VC and some of the ijiore important constituents in PVC is presented in Part II. These findings have resulted in regulatory action by several governmental agencies, inducing the Food and Drug Administration (FDA), the Consumers Product Safety Commission (CPSC), the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA), which are discussed ir Part III. Extensive changes have been made in manufacturing practic es and procedures in order to meet the challenge to reduce worker ard environmental exposure, as well as because of technological adva nces. Some of these are presented in Part IV. Part V describes me thods for safe disposal of the waste streams encountered in polymer manufacture, and Part VI discusses some analytical procedures spedfi cally applicable to safety and health matters. Some problems relat ing to copolymer manufacture are discussed briefly in Part VII. A gloss ary of common acronyms can be found in Part IX. Toxicity Considerations This section is intended to rovide a general perspective on vinyl chloride and the materials mos t closely associated with it in PVC manufacture from which the s pe cific safety hazards and work practices can be reviewed in the later sections. A. Vinyl Chloride See Table 1 for a listing of some physical properties of VC; Table 2 contains data on selected properties of other substances often associated with VC polyme ization processes. 1. Acute Toxicity The anesthetic prope rty of VC was recognized in the early 1930`s (1) and has b en investigated by several workers (2-5) Death occurs rapidly in animals at concentrations much aoove SPI-00054 Table 1 Selected Physical Properties of Vinyl Chloride Formula Weight Heat of Formation, 25*C, gas Kcal/mol Free Energy of Formation Btu/lb Density, liquid, g/ml 32*F, 0*C 50*F, 10*C 68*F, 20*C 86*F, 30*C 104'F, 40#C Refractive Index, d1* Freezing Point, *C/*F Bolling Point, 760 mm *C/*F Liquid Viscosity, absolute, CP 32F 50F 68*F 86*F Heat of Fusion, cal/g Heat of Vaporization 57#F, Btu/lb Specific Heat Liquid, 25*C K cal/kg Vapor, 25#C, constant pressure, Kcal/Kg-mol Vapor, constant volume Heat of Polymerization, Btu/lb Explosive Limits in Air Lower, wt. 7. vol . 7. Upper, wt. 7. vol. X Minimum Oxygen Content for Ignition, 7. Flash Point, open cup Autoignition Temperature Critical Temperature,K Critical Pressure, atm Critical Oensity, g/cc /apor Cloud Explosion Yield, lbs to yield the equivalent of ton of TNT 62.50 7.5 -3310 0.9471 0.9293 0.9109 0.8918 0.8721 1 .398 -153.7/-244.7 -13.37/7.9 0.225 0.207 0.193 0.181 18.14 158.4 0.38 12.83 10.84 660 8.3 3.5 37.8 22 12 -78*C 472C 431 .4 52.7 0.370 24,305 2 SP1-00055 Table 1 (continued) vapor Pressure, psla -10*C 0*C 10C 30*C 50C 70C Heat of Combustion, Kcal/mol Latent Heat, Btu/lb 0*C 50*C Solubility In Water, 30C, I by wt. Partial Pressure, 0.5 atm 1.0 atm autogenous Solubility of Water In VC, X 18 26 35 48 115 180 2826 147 126 0.5 1 2 0.11 3 SPI-00056 T x - T Table 2 Selected Properties of Substances Discussed In this Chapter Odor Threshold (ppm in air) Explosive limits in Air (VI) Flash Point (F>, COC LDso, rat (mg/kg) LC so* rat (ppm) Aquatic Toxicity (ppm) Vapor Pressure, 20C (mm Hg.) Solubility in Water, 20#C <g/100g) Vinyl Vinyl Chloride D1 cl^loroethane Trichloroethylene Acetate 1,000 50 20-80 0.4 3.6-33 i.2-15.9 12.5-90 2.6-13.4 108 56 None 18 500 770 4,920 2,920 >50,000 >1,000 -- 00-1000 8,000 (4 hr.) 100-1000 4,000 (4 hr.) 10-100 1 ,600 1 (1 atm.) 62 0.8 47 88 0.1 2.4 r ( 4 SPl-00057 T "T T the anesthetic levels of 8-12X (1,6,7) but "no histological damage" was reported at 5% exposure for 100 days (8). A review of the toxp city of VC in 1943 concluded (9) that "vinyl chloride Is one of the least dangerous of the chlorinated hydroca bons." Our present knowledge of the toxicity of this cl ass of compounds does not let us derive as much comfort from t lat statement now as may have been felt then. However, careful examination of liver effects in animals at 100-500 ppm for 4-6 months led investigators at Dow (10) to recommend a human e posure limit of 50 ppm time-weighted average (TWA). The American Conference of Governmental and Industrial Hyglenis s (ACGIH) accepted the 500 ppm recommendation of Hirvard investigators (11) instead, and published this first as a TWA, and then as a celling value (12). This was the value set by 0SHA in 1971 during its mass adoption of voluntary consensus standards as regulations, and remained in effect intil 1974. The Dow workers late stated (13): "Had our recommendations based upon relative ly simple toxicology been followed then, the difficulties of todaly may never have occurred." Human response to a cute exposures is very close to that of animals. The human narcotic range is given variously as 7-10%, wi th 12% being dange|rous (4,11). Deaths have been reported of workers exposed to high but unknown concentrations (14) and there are several a necdotal reports of workers losing consciousness tempora rily (15-17, 59). The odor threshold has been reported as v/ ary ing over a very wide range (17A) but the most reasonable fiigur e seems to be either 1200-2000 ppm (18) or 500-1000 ppm (19). Some sensations from exposure are reported as confusion, intoxi cation, burning of the soles of the feet, and subsequent heada|c hes (20). There are no immediate effects noticed at 50-500 ppn (21). Vinyl chloride had been considered as a potential dental anesthetic, but the Finding of serious cardiac arrhythmias in dogs and the deve opjnent of sensitization (2,5,22) discouraged this application. Vinyl chloride is au rocryogenic and can cause frostbite if the liquid contacts the skin. Adequate protective clothing should be worn to avoid thi contact. Metabolism Vinyl chloride is me abolized by the mixed-function oxidative action in the Cytoch tome P-450 component of cells ( 23,23A) . This pathway is satu liable (24,25) and if an excess of vinyl chloride is inhaled, the liver capacity is overwhelmed and metabolism to the ca cinogenic intermediate then occurs in SPI-00058 other organs of the body, allowing tumor formation to occur there also. This res t has been seen In animals (26), and Bartsch (26A) has shovn that rat and mouse lungs can metabolize VC at 10-201 of the r ^te of their livers. Epidemiological data (27-32) do not show 1 to occur In humans at either the ambient or occupational conce ritrations now experienced. Humans and animals hav e similar metabolic routes (33) but that In humans Is much sloter. This has been used to adjust risk, estimates based on an mal data to give figures which are much closer to actual human experience (34-35). The rhesus monkey appears to resemble ht|imans much better than do rodents (36-37). An equilibrium is est^bl ished quickly between the ambient and blood concentrations of vinyl chloride (3,33,36) and the blood level decreases just as rapidly upon cessation of exposure, Thus, analysis of brea th samples can be used as a rough indication of recent Exposure levels. It has been estimated that consumption of 2(J) ppm VC in all fluid intake is equivalent to 2 ppm exposure by nhalation for 24 hours (36A). Administration of Cyt6chrome P-450 inhibitor blocks the respiratory uptake (3$ ,39). Skin absorption by monkeys of the vapor Is only 0.1X as rapid as absorption through the lungs (24). However, there are anecdotal reports of deep anesthesia in humans exposed to xtensive skin exposure. 3. Chronic Toxicity There are few animal ttudies extending past 6 months except for carcinogenic bioassays. Viola (40) attempted to reproduce AOL in rats by exposing ttam to 37. VC for 4 hrs/day, 5 days/week for 12 months. He reported that the animals were slightly soporific, and began :o show a decrease in weight and reaction to external stimuli. Half of the animals died of cardiorespiratory com Ij 1ications and two of hematoperitoneum. Most showed pathologi al involvement of the brain, liver. kidney, and thyroid, Six showed pathological alterations of the skeleton, bone me rap 1 asia, and changes in the cartilage. This latter effect may have been the rat equivalent of AOL. There were, in addition, tumors at various sites. Feron and Krees (41) exposed rats to 5,000 ppm, 7 hr/day, 5 days/week for up to one year and found tubular nephrosis, focal degeneration of the myocardium, anp spleen damage, in addition to various primary tumors. Several articles appe^ red before 1974 describing what has come to be called "VC poi so ning" or "VC disease", although the latter term now has b come more closely associated with AOL than gastro/neural pr oblems. Many of these reports are not particularly useful b cause there are no exposure data and there often is known xposure to other recognized toxic materials. It does a spear, however, in light of subsequent SPI-00059 TT Information, that tie exposures must have been quite high for these symptoms to hive appeared so quickly. Some of these reports are listed briefly below. One article which ha s been cited frequently as supplying an ear y warning of thfc toxicity of VC is that by Tribukh in 1949 which discusses hea th conditions in a PVC processing plant In Russia (42). The a jjthor actually does not ascribe the health problems to any spef ific material, but mentions diphenyl chloride, hydrogen fhloride, and other toxic materials as being present. No measure ments were made for VC, but it is unlikely that any signficant quantities could have been present in the workplace because of the type of PVC being used at that plant. Other early papers Reported various gastro/neural symptoms: spastic angioneuros s (43), a decrease in catalase and an Increase in peroxl da se activities and glutathione levels (44), a decrease in album n and an Increase in beta- and gammaglobulins (45,46), cardiac disturbances (47), and lowered thyroid activity and production of 17-ketosteroids (48,49). Kramer and Mutchler (50) made a statistical analysis of the difference between group who had been exposed to VC for up to 25 years1 work histdry at up to 300 ppm versus other chemical workers, and found n|iinor changes in certain blood chemistry and 1iver functions. More recent articles have examined workers from cohorts which include AOL or ASL isease. They find portal fibrosis and portal hypertension, thrombocytopenia, espohageal varices, and abnormal sinusoidal lining cell development (49, 51-58). It has been postulated that these are early stages of ASL, but there have not been enough observations to confirm this hypothesis general1> It may well be correct for certain fibrotic conditions (58A). The other major area of concern, AOL, was described earlier as a degenerative disea se of the bone tufts. It usually is accompanied by Reyn aluds syndrome, and frequently also by scleradoma. Suciu (48) first reported this disease, then Cordier (59). These were followed by Harris and Adams (60), Hi 1 son, et al., (61) and Basalaev (62). One industry-sponsored urvey (63) identified 25 definitive cases and 16 suspect cases in the U.S. No certain etiological agent was found, but the c ases were clearly associated with hand cleaning of reactors (64), where there is a combination of physical joint insul t and VC exposure. The disease is most often seen in the ha nds and fingers, but occasionally in the feet or back (60). Dodson (65) could find no obvious medical reason for predelict ion to the disease in the four cases which he studied. It appe ars to be reversible after cessation of exposure (66). A to tal of 126 confirmed cases had been identified worldwide by 1979 (17A). 7 SPI-00060 IT Mar icq (67) found a s trong association of capillary abnormalities in the hands with workers suffering from AOL. Lillis (58) reported that an abnormal Allen test for circulatory efficiency was found in many affected workers, as well as many other or ganic symptoms related to the liver and circulatory systems. 8ertozz1, et al., (68) studied the status as of 1975 of a group of 4,777 workers, some of whom had been employed since 1952 in VC/PVC production faci lities. No control or comparison data are given, and many di fferent laboratories performed the analyses so only relat ive trends within the cohort can be Identified. They stated that the highest exposures were "above 800 ppm". Confirmed tjnd suspected cases of AOL Increased with the degree of exposure and the age of the worker, but not with the length of exposure "Abnormal" liver results increased with length of exposur e but not the degree. Heavy drinking appeared to act synerg istically with duration of exposure in affecting hepatomegaly and elevated GGT. Grainger, Walker, and Ward (66) reviewed the literature on symptoms associated wi th VC exposure, and discussed the symptoms of 88 workers from a factory, 9 of whom were stated to have definite VC disea se. They report a gradiation of findings from those with the s ytmptoms to those without, but do not make comparisons with unex p|osed controls. They postulate that vascular and/or immunc|l ogical changes are responsible for the observed effects, and state that they expect no new cases to develop at current ex plosures below 5 ppm. Knowledge of the exact exposures of these cases would be of great assistance in evaluating the concern for exposures experienced at present but there have been no definitive estimates made. Suciu (69) reported clinical symptoms associated with exposujres that appear to be far too low, in 1ight of industry expesriences since 1974. OSHA (70) estimated that reactor cleaners had been exposed to 1,600 ppm in their work. A CEFIC publication (71) has estimated the average exxppoossu.r.e. f.o..r a..l.l _E_u_ropean PVC workers in the 1945-1960 era as "up to and beyond 100C ppm", and there is no reason to believe that the U.S. conditicjns were much different, but even this is an average for all worjkers, and the symptoms of AOL, chronic 1iver damage, and ASL are more closely associated with reactor entry and cleaning than with other joos. The National Toxicology Program (72) quotes IARC data which also cites very khiig"hk p--o^ten-tiali exposures, and- Fishbein (73) quotes several other sources that report high values. The EPA requires (74) all PVC processors to displace the vapor from reactors with wa te r before opening for entry, or to employ a procedure of equival ent efficiency. This is based on a study (75 , page 4-71) which showed that this reduced the residual content of the reactor vapor to 8,000 ppm. This is a new procedure which had nc t been in general use before 1975. It 3 SPI-00061 ' 7T had been the practice of some companies to force air through an opened reactor before entry, but this was generally an unmonitored procedure. Cook, et al., (64) reported that unventilated reactors were often over 3,000 ppm, and Filatova and Gronsberg (76) stated that excursions were seen up to 34,000 ppm. These comments, coupled with the anecdotal reports of anesthesia of wcrkers (15-17, 59), support the conclusion that reactor cleaners certainly were exposed to recurring concentrations in the several thousand ppm range. This fact must be considered In any attempt to evaluate the hazard to workers at the present time, or to the population at large. Carcinogenicity The first report of carcinogenicity in animals came as the result of the attempt by Viola to reproduce AOL-like symptoms in rats (40). This work was sponsored by a group of European VC/PVC producers, aid used a 3X (30,000 ppm) concentration for 12 months. The attempt to....cause AOL was not total ly successful, but instead tumors developed at many sites, especially in conjunction with the Zymbal gland, and in the lungs, skin, and bones. This gland is an organ near the ear whiCh secretes the oi1 usedby the rat to groom itself.and is not found In humans Most Of the Other tumors were thought to be metastasized from the Zymbals, and net primary tumors. Perhaps because the exposures were so high, and the tumors were not associated with human organs, this report attracted little response from regul itory agencies. The sponsors then u r|dertook a much larger study at lower concentrations under the direction of Maltoni. Partial reports from this study beg an appearing by 1973 (76A), but final results were not ava ilable until 1979 (26). In summary, it was found that tumors appeared in rats at several sites depend ing on the concentration used. The lowest doses at which stati stically significant elevations of various tumors were seen wer e reported as: Forestomach Papi 11oma s 30.000 ppm Neuroblastomas 10.000 ppm Zymbal Gland Carcinomas 10,000 ppm i.Nephrol astomas 250 ppm A5L, Male 250 ppm, 50 mg/kg Female 50 ppm, '16.7 mg/kg Mammary Adenocardinoma 5 ppm SPI-00062 The reported finding of an increase in mammary adenoma at very low exposures led to concern for female workers, particularly when a study of fabricator employees found an excess of breast cancer among females (30). However, a case-control follow-up (31) found no relatiorship to VC exposure in the cases seen in those workers. In any event, the very high and variable incidence of such turners in the controls, about which Maltoni has often commented ir his oral presentations, makes it very difficult to support e conclusion that the test animals actually did respond at such doses. Schaeffer and coworker s (76A) found that the Maltoni data fit an exponential express ion which predicts a no-effect level for liver cancer in rats at about 3 ppm, and predicted an average latency period greater than normal lifetime at about 29 ppm. Many attempts have bee n made to estimate human risk from the animal data, but none of these have been successful unless proper biotransformat'on factors were applied (265). A number of other bioassays were conducted by various industrial and governnental groups (41,77-83). In general, these confirmed the f'ndings by Maltoni. It was determined that mice are the mosi: sensitive species, followed by rats. HI star rats appear more resistant than the Sprague-Dawley strain. Rabbits and hamsters are much more resistant. Either ingestion or Inhalation produces tumors, with the latter route tending to give tumor:; at more diverse sites. This result is consistent with the saturable metabolic process discussed earlier. Both very young and older rats appear more sensitive than juveniles. This may be explainable by the differing repair and detoxification capacities at various ages. There is a regular decrease in the latency period as the dose increases, with liver tumors appearing only at the end of the lifetime at 50 ppm or less (26) fit rats. Mice show a dose response to below 10 ppm for pulmonary tumors after exposure for 4 weeks (83A). Drew and coworkers published data (88A) which they believe contradict the statements by Maltoni (26) and Groth (88B) that older animals appear i|nore susceptible. They found that withholding exposures until later in life produced fewer tumors in the animals. They did not take into consideration that the low doses used (50 ppjn for mice, 100 ppm for rats) yield long atency times, and thus the animals died of other causes before the VC-Induced tumors could kill them. It is true that fewer deaths occur if expos jre is delayed, but that is not necessarily because o increased resistance. In fact, the time-to-tumor increas d in Drew's experiments, as the age at exposure decreased, Thus, any rigorous examination of such data must include a p open consideration of the time factor. The first connection Detween VC and cancer in humans was made in 1973 when physician s at the Louisville, Kentucky plant of B. F. Goodrich, Inc. recognized the association between three 10 gpl-00063 deaths of workers fr om ASL (84). A review of company records (85) revealed severa other cases at that plant. This tumor is rare A review (86) of all cases reported in the United States for th e period from 1964 to 1974 revealed 167 cases, of which 19 were ascribed at that time to occupational VC exposure, 26 to Thorotrast given medically, and 9 to arsenic in Fowler's soluti 01 also used medically. The remainder were of unknown etiology with no connection to VC. There are references in the 1 iterature to one case (87) thought to be associated with hai spray use. The high level of interest in this specific tumor is such that any subsequent cases associated with env ronmental exposure to VC would most certainly have been reported, and none have. For a time, NIOSH published a summary of VC-related cases, but this task was taken over by Dr. Jolhn Stafford of ICI, England (88). His most recent compi1ation ihows a total of 32 cases in the U.S., and 107 worldwide. A stimmary of the number of cases by countries and of the U.S. cas is by company and by date of death as given in Stafford's repor 1:s are shown in Tables 3-5, respectively. The average latency period in the U.S. has been 25 years, but with a mode of about 22 years. The latency period in Europe, and particularly Germany, has been somewhat shorter. There is an unusual clustering of cases in relatively few plants (Table 4). All of he U.S. occupational cases, and almost all of the cases in the rest of the world, are closely associated with the job of reacjtor cleaning, which was once done manually at the end of the polymerization cycle. It may be speculated that differing work programs and job progressions have had some effect on the rates at various plants. Ten cases of ASL have been reported in one plant in Canada, the last in 1976, with n ' new cases since that time (89,90). These cases are completely typical, both as to the clustering and the medical symptoms. It also is worthy of note that there is, at most, one case of both AOL and ASL in the same person (88), although both of these diseases are a|s sociated with VC exposure as a reactor c1eaner. An industry-sponsor ed epidemiological surve y of workers in the VC/PVC industry cove ed 8,384 men with at 1 east one year of exposure before 1973 The expected excess of ASL was found. There were also sugg stions of an excess of cancers in the brain, respiratory, ind at unknown sites, a nd of lymphoma. This study was expan |ed to 10,173 workers ( 27,92), where the excess of brain and espiratory cancers con tinued to be seen without, however, an association between th e brain cancer and exposure. In additi on most of the lung ca ncer cases come from the same facility, w th many plants having no cases. A fo1 low-up study of ti is cohort to determine the status of the workers as of the en of 1980 is underway. SPI-00064 Angiosarcoma Cases In the VC/PVC Industry _________________ bl Country________________ United States West Germany France Canada United Kingdom Sweden Yugoslavia Italy Czechoslovakia Japan Norway Belgium Total 32 21 17 10 8 5 4 4 2 2 1 1 107 Includes 3 U.S.A. cases still alive. Adapted from Stafford (88). 12 SPI-00065 Table 4 Angiosarcdma Cases In the U.S. by Company__________ Goodrich, Loul sv Ille Union Carbide, S. Charleston Goodyear, Nlagaf a 5 Others Total 14 9 4 _5 32 sp\-00066 Table 5 Chronology of U-S. Deaths From Angiosarcoma 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 1976 1977 1978 1979 1980 1981 1982 1983 Total Deaths 1 0 0 1 0 0 0 3 2 1 1 0 3 1 4 3 1 2 0 4 0 1 J_ 29 Year of First Exposure 1946 1944 1944, 1951, 1952 1949, 1950 1946 1955 1945, 1948, 1958 1942 1945, 1947, 1954, 1962 1943, 1947, 1955 1946 1941, 1944 1 942, 1951 , 1955, 1964 1946 1 944 Three cases living (first exposures 1 954, 1955, and 1956) Data from Stafford (33). 14 SPI-00067 T TT Marsh (92A) followed 2,490 workers who had been exposed for at least one year betvreen 1949 and 1966 in a piastics-producing plant which included PVC production. Vital status was determined for 99.17. of these as of the end of 1 976. Oeath records for 98* of the 603 deceased workers showed a slight, but not statistica ly significant, excess of genitourinary system cancer (SMR 154). A follow-up case-control study did not relate these f ndings to either type or length of occupational exposi,re. One case of ASl occurred in this cohort in 1979 (88) Several studies hav e been conducted on smaller groups of workers which are Iso subsets of the larger study discussed above. Monson, Pet ers, and Johnson (93) found an excess of brain and lung canc ers in the plant which developed the most ASL cases in the Un ited States. Waxweiler, et a 1., (94) studied 1,151 worke rs who had at least five years' exposure in four older PVC pla nts and reported an excess of brain, respiratory, and lymiphatic cancer, as well as the known cases of ASL. A later s tudy (95,96) expressed the opinion that it was not VC exposure that was responsible for the excess of respiratory cancer and speculated that it may be due to PVC dust. However, pre liminary results on a study of subsequent lung cancer cases that same plant (97) do not show an association with PV dust. Theriault and Allard (90) and Falk and Waxweiler (98) also state that it is unlikely that PVC exposure is respons ible. The method used in the follow-up study was an elabor^i te method for determination of exposure indices for workers potentially exposed to several chemicals (99) which is useful in identifying which exposure may be most closely associated vith the cases. Beaumont and Breslo1 (100) evaluated the statistical power of nine epidemiologica studies dealing with possible lung cancer from VC exposure and concluded that the lack of a general trend in these results inp icated that VC is not a human lung carcinogen. This wfis supported by the negative results in the two studies with thd highest statistical power (27, 29). They concluded that the eported studies were compatible with a relationship betwee VC and brain cancer. This was based, however, on the ass umption that the result of the EEH study (27) was positive, conclusion that is not altogether clear. Tamburro and his as :;ociates at the University of Louisville have fol owed close y the histories of the ASL cases at the Goodrich plant. Th s work has been summarized by Dannaher, et al., (101 ). Diagnoi tic methods, treatment and survival are described The prog ression of the disease from the initial focal nod ular hype n> lasia through fibrosis to necrosis is described in more d<` tail by Tamburro (102) An extensive medical r egimen for VC-exposed workers was proposed by Tamburro, et al . , ( 103). A 1 iver scan appears to be me most effective diagnos ti tool (103.103A). Of the various tests required bv the OSH/ medical program, the GGTP test provided SPl-00068 the highest positive predictive value, but the least specificity, and the PG clearance test was recommended as the preferred screen (104) , although none is very effective. It has been suggested that human data shows the transport of some metabolic interme^J iate from the hepatocyte to the adjacent sinusoidal 1inlng to 1 nitiate the first stage of tumor development (87,105-6) Ottenwalder and Bolt (107) came to the same conclusion from an Imal studies, and this mechanism is supported by other work at Louisvilie (108). An extensive multiyear research program at the University of Louisvi1le was sponsor ed by the Chemical Manufacturing Association. Much unp Lib 11 shed material on the subjects of metabolism, immune resp'onse, and ASL detection and surveillance methods is contained 1 the final report on this project (108A). In addition, nore than 40 papers and talks have resulted from this efffcart. Many of these articles have been cited in the preceding paragraphs. Duck, Carter, and Coombes (109) found no excess of mortality, including cancer, in British workers for 1948-1973, while following 2,120 workerk Wagoner, Infante, and Saracci (110) criticized the mathematical treatment of the data and stated that there was an excels mortality in the longer-exposed group. Duck and Carter (111) then made corrections to the numerical results, but did not change the conclusion. Berry and Rossiter (112) cri ticized both the original calculations and the changes proposed by Wagoner and Infante, as did Fox (113) but neither founj any evidence of excess mortality in the group. Fox and Col 1ier (29) studied 7,000 men .who had worked with VC in Great Brita in between 1940 and 1974 and found no evidence that cancers other than that of the liver are associated with VC exposure. Frentzel-Beyme, Schmitz, and Thiess (32) reported on 1,618 VC-PVC workers in Germany, and could not confirm the U.S. reports that tumors at other sites than the liver were in excess, and suggested that this may be because of the consistently low expos jres at the plant which they studied. paper by Reinl, et al. (114) reported excess deaths in German workers, but the authors have since found calculation e-rors in the processing of the jata. A later summary of this study (115) found an e1evati pn of lymphatic tumors in addition to the expected ASL cases, but no elevation of lung or brain tumors in PVC production workers PVC processing employees did have a smal1 elevation of bra n tumors. Molina, et al., (116) found that the Swedish work group had an elevated heart disease rate, but no tumors other th an ASL. A follow-up study of Texas chemical workers found no relationship between vinyl ^chloride exposure and brain tumors (1I6A). A case-control studv of 7,736 Japanese beautic ians who may have used hair spray containing a VC propel ant showed a slight elevation for stomach cancer, but no t for liver, lung, or brain (1166). 16 SPI-00069 Workers who fabric ited PVC were of Interest as a group whose exposure to VC was significantly less than the workers in the VC/PVC Industry (1 7), but much higher than any expected exposure to the gep eral population. Chiazze, Nichols, and Wong (30) studied 4,341 deaths of employees of 17 PVC fabricators, and found no ASL. There was an excess of deaths from Intestinal cancer n both sexes, and breast and urinary cancer In females, using proportionate mortality ratios based on an external standard, A case-study follow-up on the breast cancer deaths showed (31) no relationship to VC exposure. Baxter and Fox (118) found ver y similar results in a study of 707 deaths of male fabrication workers in Great Britain. There was no excess of lung or brain cancer in either cohort. There Is no cons is tent trend In these occupational studies for an excess of tumor; other than ASL, and it appears that the occasional report of elevated incidence at some other site Is only a quirk of sti tisties because of the many site/incidence ratios being evalu 4ted. On an overal1 basis about 0.1% of the estimated working population in VC-PyC plants has been affected by ASL. All of these have been in the most exposed group of reactor cleaners or associated duti es and in this group the incidence is about 1%. It has been suggested that some genetic difference, such as metabolic or rep),air rates, distinguish this susceptible fraction from the 99% who have not developed the disease from similar exposures. However, it is difficult to see how that explanation is compat ible with the geographic clustering which is observed. Those who did develop ASL probably inhaled more than 25 Kg of VC dur ing their work exposure (17A). Several studies hav4 been made of the general population using ASL as the marker d isease in an effort to detect an association with possible envi rpnmental exposure to VC. There was no association with 1 i ving near a VC handling plant in the general U.S. survey conduct ed by the Center for Disease Control (86). Brady, et al., (11 surveyed 26 ASL deaths in New York State between 1970 and 1 5, and found five who lived nearer VC handl ing plants thafi did their matched controls, but could not establish a direct connection with the disease to exposure. Ten cases of ASL in Wisconsin were examined for possible connection with VC exposure, and none was found (120). Baxter, et al., (121) found no relationship between distance of residence from VC ein itters and the 47 cases of ASL in the general population <t)f Great Britain reported in 1 963-1973. A later update (122) ound one case which had lived the last six years of his life n ar a PVC plant and three cases where the man had worked in th e plastics fabricating industry, but for whom there were no tecords to indicate exposure to VC. The lack of relationshi between residence near vinyl chloride operations and case of unknown etiology was confirmed. Saric, et a 1 . , (123) studi 4d the deaths during the years 1968-1971 in an area surrounding a PVC plant that had been in operation SPI-00070 since 1949 and in whi ch three workers had died of ASL. No relationship was found for liver or lung/bronchial cancer and place of residence for the general population. A similar study for communities near Swedish plant which had operated since 1945 and had found foi r ASL cases showed (124) no unexpected elevation of fetal morjtallty, deaths from all cancers, or cancer of the 1iver or lungs during the years 1961-1974. Pancreatic cancer in ales was elevated in the age group over 60. A1l ASL cases in Holland since 1950 (27 cases) were studied, and none had any traceable contact with VC (125). Iturra (126) observed an excess of cancer deaths in a city in Canada with a PVC plan t as compared to a similar nearby city, This difference was pr incipally found in males aged 20-64, which is not indicativ e of a general pollution effect. The author drew no cone?us ion as to why the condition existed. Representatives of the Environmental Protection Agency have stated (127-8) that it has been unable to establish a link between living near VC handling plants and ASL. It awarded a contract in 1978 (Contract 68-02-2986 to Science Application Incorporated) to examine the present health of a cohort which was presumed to have teen exposed to VC as children, but this project was not completed. The disease ASL 1s di ff icult to diagnose (129-30), is almost invariably fatal wlthi n a short time, and presents a variety of symptoms Including porftal fibrosis and hypertension with splenomegaly and vari qes, proliferation of the sinusoidal lining, megalocytosia and thrombocytopenia (54,131). Metastasis is frequen ijly involved. These symptoms are very similar to those seen in the mouse (132) and rat (41) and the pathology also is simi lar (133). No really adequate early warning tests have bee n devised (103-4), although the gammaglutamyl transpef sidase test is promising, along with ICG clearance and SGOT. Fad iographic liver scans and tomography and sonography (134) re said to be useful confirmatory tests. In summary, VC is a classical procarcinogen, and is clearly a human carcinogen, causing ASL in a small percentage of highly exposed workers. There is suggestive evidence that it may be a weak general carcinogen at high concentrations, perhaps through an immunosuppressive mechanism, but more data are required to confirm this suspicion. Several studies of large populations have not shown a connection between general ambient exposure and increased incidence of cancer. 5. Reproductive Effects Testing of vinyl chlor ide for mutagenicity has given mixed results, possibly bee iuse of the need for metabolic activation to an active species and because of its volatility. However, it is clear that it i: a mutagen to several strains of bacteria and yeasts and in fru t flies under proper conditions (135). 18 p\-00071 Chromosome damajj e has been reported in workers with "VC illness" (136) )ut the changes do not appear to be permanent, and are repaired after exposure is stopped (137-8). Picclano (139) toncluded that any cytogenic observations were probably related to length and degree of exposure, and that any genetic risks wore avoidable by adequate control of exposure. Basler and Rohrliorn (140) found that this was true for the bone Chinese hamsters exposed to high levels of VC j_n vivo. Concurrent exposure to alcohol enhances the changes in rat mitochondria on exposure to VC (140A). A test was made of the significance of the chromosomal damage to possible gen 4tic risks by performing a dominant lethal study in male mice, wli 1ch were mated with two untreated females for 8 successive week;, after exposure to 3-30,000 ppm of VC for 6 hrs/day for 5 ys. There was no increase in the number of early deaths per Implantation, and it was concluded that any expression of hi, rm to the chromosomes of somatic cells was not carried over to stem cells (141). Short, et al., (142) performed a sim lar experiment with longer exposures to lower concentrations, and also found no effect on reproduction or survival. Himei o and coworkers also confirmed the lack of effect on male i ice at 5,000 and 10,000 ppm, and reported that there was no cha nge in sperm shape or mobility (141A). Hehir, et al <|83> included a three-generation study in their program in which parent rats were exposed to 50 or 500 ppm VC 1 hr/day, 5 days/ v^eek for 10 weeks before mating and the subsequent three generations were examined for litter size, percent stillbor n, growth, viability, and reproductive anomalies. No Effect on the parents or the offspring from VC exposure was see n. Studies by Schwe tz, et al., (143) and by John, et al., (144) found no excess fetal wastage in mice, rats, or rabbits at VC exposures suffic ient to cause maternal toxicity. The authors also found that VC, either alone or in combination with ethanol, was not teratogenic when dams were exposed on days 6-15 at 50-2,500 ppm VC. The combination of alcohol and VC did cause delayed de velopment and a higher incidence of some skeletal variati ons. Rice (145) concl uded that there is no evidence that exposure to VC has produced increased tumors in the offspring of these animal tests. Infante (146) has reported finding an excess of congenital birth malformat ibns in three communities in Ohio that are near VC processing pi ants. However, the Center for Disease Control (CDC) performed follow-up study and stated (147) that "it could not establ ish any association between cases and vinyl chloride exposu re." Edmonds (148) has discussed the methodology of the follow-up study which was of'the SPI-00072 case-control type, and stated that no relationship was found between the cases and their parents' employment or place of residence relative to the VC plants. The CDC performed [two other birth defect studies in areas possibly associated with vinyl chloride. In one (149) the hospital records for a city in Pennsylvania where a PVC plant is located were re/iewed, and no increase In birth defects was seen. In another [148) hospital records for Kanawha County, West Virginia were reviewed for 1970-74 and all cases of birth defects were compared for residence and employment by case-control methodology. The study concluded that "no relationship betwe ;n infants with malformations and parents exposure to VC cou d be established." Theriault and Goul ;t (150) reported a comparison of two cities in Canada, and fouid an increase in birth defects in the city which contained a /C processing plant. The increase was spread over a wide variety of types of defects, and only raw statistics were usd. There was no attempt to compare exposures of the parents, nor were there controls for any other environmental factors. Thus, the significance of this finding cannot be evaluate!, and the authors were careful not to ascribe excess significance to their data. A more detailed study of birth defects in Shawinigan, Canada led to the conclusion that stillbirths were not in excess. There was no relationship betwejn the cases of defects and the parental occupation or residence, nor were the cases confined to any particular body system (151). Ambient concentrations up to 45 ppb were reported in this study. Infante, et al., 152) have reported an increase in fetal wastage among the vives of workers in a PVC plant. This study has been criticii ze j by Paddle (153), MacMahon (154), Downs, Stallones, and Fran kowski (155), and by Monson (156) on the grounds of improper data gathering techniques, incorrect statistical treating nt, and incomplete reporting. Many of the reported incidents occurred prior to the date of employment at that plant (157). In addition, the statistical significance of the reported excesls of fetal wastage of exposed workers' wives disappears if those women subject to chronic spontaneous abortion are omii tte d. Hass and Schottenfeld (158) and Clemmesen (159) con eluded that the inferences by Infante could not be sustained by the data. Hatch (160) explor ed the statistical power of the various studies on reprodu|c tive effects. She found that the Ohio birth defect study (146) was deficient in power, but that the negative CDC rechefc k (147-8) of this report had adequate power to detect a signif leant effect, as did the CDC (149) study in West Virginia, whi ch also was negative. Similarly, the worker study (152) on abok tions and miscarriages had design deficiencies that prevented its results from being accurate. 20 SPI-00073 Her conclusion was that "there are no data which point unambiguously to a relation between VC and reproductive outcome." In summary, VC doe not appear to be teratogenic, nor to cause excess fetal wastab e in animals or humans. It can cause reversible chromospime damage in somatic cells, but apparently not in stem cells and thus does not present a risk of reproductive effect s. B. Vinyl Acetate Vinyl acetate (VAc) hyd'olyzes readily in body fluids to acetic acid and acetaldehyde, both of which are normal metabolic products (161-2). The acetaldeh^de is converted rapidly to acetic acid, also. Thus, there are Only minor effects on mammals from moderate exposure to VAc. Both :he acute and chronic toxicity of VAc have been reviewed extensive y recently <162), and only the highlights will be summarized here The EPA is in the process of developing a chemical Information hat ard profile (CHIP) for VAc and has requested that unpublished health studies be submitted for inclusion. 1. Acute Toxicity The LDS0 doses in rfodents by ingestion are reported as 2920 mg/kg for rats, 500 for guinea pigs, and 1613 for mice. The equivalent inhalat on dose in 4 hours for rats is 4,000 ppm (163). Humans experience dye irritation at 22 ppm. Rabbits suffer eye irritation from a 500 mg dose and skin irritation after 24 hours from 10 mg. Toxic effects in aquatic life are seen at 10-50 ppm in the s iiandard 48-96 hour tests (163). The current TLV is 10 ppm based on human eye irritation. NI0SH has recommended a rr a ximum exposure of 250 mg/m3, about 83 ppm, and states "The irritations reported have all been reversible, and the re are no known residual systemic effects" (162). Exposure aqove the TLV causes throat and bronchial irritation. The ol factory threshold is well below 1 ppm in air (162A) and about 0. 25 ppm in water solution. It is probable that the ready hyd ro ysis to acetaldehyde is responsible for this low threshold, and is responsible for the sharp odor around most acetate copolymer plants. This, along with the irritant effect, se rves as a sensitive warning to potentially harmful exposures However, olfactory fatigue can occur on prolonged exposures A subchronic test ( 61) found that there was an 8"/. reduction in body weight in rats , but not mice, dosed with 5,000 ppm in the drinking water for three months. This result was not seen at 1,000 ppm or lower and there were no other hematological or histopathologic eff sets. Inhalation exposure at 1,000 ppm for three months caused decreased weight gain in both species, and 2! SPI-00074 T In mice at 200 ppm. I rltatlon In the lungs also occurred, and mice developed hyperpl isia and metaplasia in the bronchi at the higher dose. Similar effects were seen from 1,500 ppm for 4 weeks. There was no evidence in the same study for teratological effects In rats from u 3 to 5,000 ppm In the water during days 6-15 of gestation. Imalation of 1,000 ppm was slightly fetotoxlc; lower levels were not. Metabolic conversion was found to be rapid with most being expired as carbon diox ide within two hours of exposure. There was no evidence of si giificant binding to tissues. Vinyl acetate shares ti e property of most organic liquids of being an irritant to tp e skin by its defatting properties as a solvent for skin oi1s Proper precautions should be taken to avoid direct skin contk ct during handling (164). The sulfhydryl group appears to be involved in the detoxification of meta oolized VAc, much as it is in VC. Sharply lower free non -protein thiol levels are found in rodents after vinyl ac etate treatment (164A). Chronic Toxicity In the first chronic tDixicity study reported, Maltoni exposed rats to 2,500 ppm VAc in air for one year. Survival was only 501, and the results h ve not been reported in detail, but no neoplasms were found ( 165). It is understood, but not confirmed, that simi la negative results and low survival was seen at 1,000 ppm in a later study. A recent small lifetime feeding test of vinyl acetate in water (166A) resulted in an increase in neoplasms of the thyroid and uterus in female rats at the high dose rate (2,500 mg/1, or about 100 g/Kg lifetime dose) but no increase in neoplasms in the male high dose rat or in rats of either sex at 1,000 mg/1. The vinyl acetaite solution was prepared twice a week, so the actual applied dose was smaller than indicated, and considerable acetaldehyde and acetic acid were ingested. The authors described the results as "not negative", and recommended a study with larger groups and fresh solutions. is report has prompt.ed a group of producers and users to onsor through the So ciety of the Plastics Industry a rge-scale bioassay ram, and to conduct an epidemiological rvey of industry wor kens. The latter study should be mplete i n 1984, and bioassay results in 1985. The ACGIH quotes data showing no pathologic effects at exposures as hign as 6 30 ppm, or to repeated doses at 100 ppm in rats (166). SPI-00075 Study of a worker c ohort with a mean service of 15 years at average exposures of 5-10 ppm, with excursions In the 50-300 ppm range, revealed no evidence to suggest chronic effects or serious residual i n[jury from the excursions If treated promptly (164). One recent report s tates that there is a slight elevation of abnormal chromosome^ in exposed workers after 3 years as compared to control (167). Only negative mutagp nicity tests have been reported for VAc (168-9) with or wi 11lout activation.- References to teratology studies other than the report cited above (167) were not found. Trichloroethylene Trichloroethylene (TCE) pr other highly chlorinated aliphatic compounds are used as chit In transfer agents in the manufacture of low molecular weight polyimers, particularly the copolymers with vinyl acetate. This cl a;: s of substances shares many toxicological features, so this discus ion will center on TCE as the prototype for the class. 1. Toxicity Exposure to TCE in the manufacture of PVC will be largely by inhalation, although skin absorption can occur also. The end effects, except for the skin irritation from contact with the 1iquid, are general y the same by either route, and occur primarily in the cer tral nervous, cardiovascular, and biliary systems. The symptq?ims are related, and thus usually are seen together. Some critical toxici ty data for TCE are summarized in Table 2. More extensive infor mation is available in references 178 and 179. Death has been reported in humans from inhalation of 2,900 ppm. The LDS0 in rats is 4,920 mg/kg. Oral doses of 6-7 g/kg causes deat h in humans and rodents, but death from injection occurs at doses as low as 0.1 g/kg. TCE was used as an nesthetic for many years because of its strong narcotic effec t on the central nervous system. Several patients developed tr igeminal palsies following such treatment, possibly due to reac tion products formed with the soda lime in the closed circuit a nesthesia apparatus (170). Rapid, shallow breathing is a typic al symptom. Industrial overexposures have been reported to cau se headache, dizziness, nausea, and occasionally permanep t nerve deficiencies (171-4). Death often involves ventricular fibrilation. Deliberate misuse, as in glue sniffing, resu1 ts in respiratory and cardiac failure in extreme cases and 1i /er and kidney damage in less extensive use (175-6). 23 SPI-00076 Chronic low exposures (up to two or three hundred ppm) cause tremors, loss of motor function, insomnia, and cardiac disturbances (177-8) In general, these same symptoms have been reproduced in ro'dents. Liver damage occurs irjfrequently in humans, but usually is massive and fatal, suggesting that some other complication has contributed to the ev<nt (179). The purity of the TCE may be important also (180), because of the various toxic corrosion inhibitors that may b< present. Mice are more sensiti e than are rats to liver damage from exposure to TCE at low doses (181). Increased liver size, cell damage, and ce11 death are seen. This probably results from the higher ratio of mdtabo'ps- in mice as compared to rats. Alcohol has long been recognized as intensifying the toxicity of TCE (182) through competition for the metabolism/ detoxification steps, The combination of TCE exposure and alcohol intake can rev uit in development of red splotches on the skin that have bew n called "degreaser's blush". TCE is metabolized by the same general process as is vinyl chloride, however, th< re is a major difference in the rates and in the detoxification stage. Little or no TCE is bound to the DNA, but is excreted is small metabolized molecules (183). The putative metaboliteiss do not cause skin cancer in mice (183A) nor bind to glutathliioohne or to DNA directly (183B). Theoretical considerations suggest that the chlorine-containing epoxide metabolites should decrease in reactivity as the chlorine content increases, ang this has been confirmed experimentally (1830 The principal metabol c product in humans is trichloroacetic acid, w*!can be det ected in the urine, and used as an exposu-. -mi tor. So eo ana coworkers recently suggested that exposu'-. in the 15- 20 ?:m range produce urine concentrations of this metabolic product wnich they consider safe (183D) An equi librium is estii b1ished between the blood and expired breath contents of TCf and breath analysis can be used, along with urine analysis, o estimate exposures (183E) . 2. Carcinogenicity The carcinogenicity o,r TCE is a very controversial subject, The regulatory agenci us follow a general rule that any positive mutagenicity or bioas say tests requires classification of a substance as a potent al human carcinogen, and thus TCE often is referred to in the public literature as a carcinogen, However, the data are less dogmatic. T 't SPI-00077 ( ( Mutagenicity test results have been mixed, with both positive and negative repor s. Often, the positive results are from technical grade material containing a few percent of an inhibitor, and the pure material is very weakly positive, so it is not clear as to what substance is the cause of the results (179A). The putati ve metabolic intermediates are not mutagenic (184) and, as discissed above, there is considerable evidence that they do not bi nd to DNA, or possess any of the expected properties of a car cinogen. Similar problems ex 1st with the carcinogenic bioassays, Positive results ha|v e been obtained with mice at doses that clearly were toxic, using technical material (185). Rats and hamsters have been negative consistently, as have other tests with mice, using pur ified material (185-8). It is of especial Interest that inhal ation, as compared to gavage, produced a negative bioassay ( 188A). Recent press report^ (189) have stated that preliminary evaluation of a rep sat bioassay by the NCI using pure TCE has shown elevated tumo' incidence. This study, as were several previous ones, was ronducted at doses causing extensive systemic toxicity, This latest series of studies used four different strains o- male rats at the NTP, and preliminary results indicate that only one of these four has given a positive response, However, that bioassay program is under review because of p rocedural difficulties discussed during a quality audit (189A Several authors (23A,183C,189B) have developed data whiclji indicate that the intermediate oxide product from metabo ism is not a carcinogen, as is the case for vinyl chloride. Thu s the relationship of these results to the hazards to humans al current ambient level is not clear, Epidemiological stuc ies have been uniformly negative, and place an upper limit on ar y risk which TCE may present to humans (190-194) The EPA has performe d an in-depth review of the health effects of TCE (179) and has concluded "that long-term exposure of humans to environme nltal (ambient) levels of (TCE) is not likely to represent a heal th concern -- signs of liver dysfunction have been observed c nly in experimental animals during exposure to excessively high levels (>1,000 ppm)." In regard to human carcinogenicity it as stated that "the more conservative scientific sentiment would regard (TCE) as a probable human carcinogen, but ther is considerable scientific sentiment for regarding (TCE) as a agent that cannot be classified as to its carcinogenicity for tumans." No evidence of domin int lethal mutations was seen at 450 ppm, nor was there any lo >s of ferti1ity or feta 1 development (194A). SPl-00078 t Teratology studies, although unrelated directly to carcinogenic?ty, have also been negative In mice, rats, and rabbits, further reducing the concern for harm from exposure to TCE (195) See (179) for a review of several other earlier reports. TCE appears to belong to that class of materials which do not cause direct harm to tne genetic DNA, but may, if given in sufficient dose, produ|c e tumor formation in animals by severe organ damage. This cl ass of substances has been termed nongenetlc or epigeneti c carcinogens and it seems probable that they are not actually carcinogenic at doses which do not produce permanent orga^i damage (196). A Committee of the National Academy of Sci ence concluded that the low carcinogenic potency of TCE requii res that no special precautions are needed beyond normal good iindu strial hygiene practices (197). Another NAS review group stated (198) that "additional long-term studies -- should be conducted with purified TCE in order to determine if TCE is a toxicant, mutagen, or carcinogen, and the minimum times and doses that are required to produce adverse effects." Thus, TCE sh ould be handled with respect, but it appears that it can be used with safety under proper conditions. Meanwhile its human carcinogenicity remains controversial (197A) IARC places it in category 3, "cannot be classified as to its ca rcinogenicity to humans" (197B). 1,2-Dichloroethane Many of the toxic propertie s of 1,2-dichloroethane (EDC or DCE) are very similar to those of TdlE, and the same general precautions should be taken for both substances 1. Acute Toxicity The LDS0 in rats for a single oral dose has been reported as 680 mg/kg (199) and 0. 77 ml/kg (200). Deaths in humans have resulted from doses es timated to be in the range of 20-50 ml, and the ability of dogs and humans to regurgitate, which rodents do not have, a ppears to permit them to survive higher ingested doses than rodents (201-2). Skin absorption occurs readily, and gives the same symptoms as inhalation or injection, in addition to the irritation effect on the skin by defatting (178). Severe pain and irritation results from eye contact, and foxes and dogs, but not other species, develop an irreversible clouding of the cornea, apparently from the production of a secondary metabolic product (203). Inhalation produces th e typical halogenated solvent symptoms of drowsiness, nausea, di zziness, and other signs of central nervous system depress ion. Liver and kidney damage may also occur (201-2). Rats urvive 2-300 ppm for 7 hours, but only 1 hour at 3,000 ppm anld 2 minutes at 20,000 ppm (204). No LC5o data as such have been reported for inhalation 26 SPI-00079 exposures, but can 3e inferred from other data as about 2,000 ppm. The siightly sweet, typical chlorinated solvent odor at 100-200 ppm becomes unpleasant for most persons at 1-2,000 ppm and can cause drows ness at 2,000 ppm in as little as 5 minutes. Heparin hi s been used successfully in treatment of acute poisoning (206 ). 2. Chronic Toxicity Animal studies (204 207-9) show little effect on health at prolonged exposures of 100-200 ppm, but levels of 4-500 ppm or higher resulted in iver damage, and there was pulmonary congestion, kidney (jlamage, and deaths at 1,000 ppm. Review of human cas' s (210-211) shows kidney and liver damage Many of the fatal c<. ses were from accidental ingestion, Exposure data are u rcertain for occupational inhalation. Studies collected by NI0SH (201) suggest toxic effects at exposures as low as 10-15 ppm, but this is not confirmed. 3. Carcinogenicity The same controversy exists as to the carcinogenicity of DCE as for TCE. One NCI bi oassay (212) gave increased tumor formation. The ini tjial dose was stongly toxic and had to be reduced during the experiment to maintain the animals alive. Other studies (186, 209,213) found no such effects. A National Academy of Science rleview group concluded that further tests are needed to settle the issue (198). Meanwhile, the regulatory agencies sometimes list DCE as a potential human carcinogen, but it is not included on the NTP list of carcinogens. The mutagenicity data to support this conclusion are mixed, Several tests are av aiTable which report both positive and negative results, Tiere is concern that the putative metabolites chloroe tianol and chloroacetaldehyde may be the active species, but these also show mixed results. See references (198,205) for a review of these data. A multigeneration reproductive study at doses up to 50 mg/kg/day showed no significant dominant lethal or teratogenetic effect^ on mice in either of the two generations of offspring, nor on survival or weight gain (206). EDC al so has been fo|i nd not to be teratogenic in rats, chickens, or rabbits nor does it affect reproductive capacity at doses high enough to show severe maternal toxicity (208-9, 214-15). Thus, DCE appears to have well-established no-effect levels for its toxicological eft ects, and if it is a carcinogen, must act through a nongenetic process such as that discussed earlier for n SPI-00080 TCE. See references (178,198,201-2,215) for more detailed discussion of these points. Polyvinyl Chloride PVC Is an inert, indigesti bl e material with no known direct toxic effects. There has been co ncern for problems which may be associated with residual mopnomers or polymerization adjuncts, but there are none which are as sociated with the polymer itself (216). The principal health concerh for PVC is from Inhalation. PVC is regulated as an inert or "nu isance dust" by OSHA (29 CFR 1910.1000 table Z-3) which sets exposu re limits at 5 mg/m3 for the respirable portion and 15 m g/m3 for total dust. The ACGIH recommendation is 5 and 10 ng/m3, respectively. Various reports have been 1 ssued concerning the effects of PVC dusts on animals and humans, most of them originating in Europe. Miller and coworkers (217) found d iminished pulmonary function in long-term workers exposed to VC and PlVC. Arnoud, et al., reported (218) that a bagger with 23 years' experience had PVC entrapped by the microphages of his lungs, Waxwieler, et al., speculated that his finding of no association between VC exposure and lung cancer in a plant cohort could throw suspicion on the PVC as a causative factor (95). However, this was shepwn later not to be the case (90,97,98). Mastrangelo, et al., studied 20 workers with high PVC dust exposure and found observable X-ray abnormalities and some respiratory impairment (219). Cordoscol, et al., (220) found similar symptoms in three patients. These reports give very little detail on the degree of exposure or the type of resin or other materials which may have been present. Two more detailed studies of workers at ICI plants in England have been reported. Chi vers, et al., (221) examined the respiratory function of 509 workers, i4eluding 112 controls, and concluded that "PVC dust has not produced deleterious effects on ventilatory functions." A more extensive study of 8(18 workers, many of whom had worked in older plants manufacturing pi a s tisol resins, included X-rays and several lung function tests (222). Their conclusion was that there was evidence of a slight, Nonspecific respiratory effect that was difficult to distinguish fr om the effects of aging and smoking. A follow-up study performed albout a year later included the original 818 workers plus'others in that plant for a total of 1,047 persons, and a group of 127 workers from a second plant which produced only suspension resins. The res ults of the first study were confirmed, with the exception that the men in the second plant appeared to have siightly less response than those in the first (222A). OSHA issued a call for infc rmation on the occupational effects of PVC, and a symposium was he d in March 1980 (223). The effects discussed above were review ed, but no additional data were 28 SPI-00081 presented. The proceedl rigs of this symposium were published as Vol. 41 of Environmental Health Perspective, Dec. 1981. Similar effects have been observed in animals after exposure to PVC dust as have been report >d for humans (224-227). An unpublished NIOSH study exposed rats (12 months), monkeys (22 months), and guinea pigs (12 months) to more than 10 mg/m3 of respirable PVC dust <pi as11 sol grade) for 6 hrs/day, 5 days/week. Extensive biochemical, pathologica , and respiratory tests (monkeys only) were performed on the animals It was concluded that no liver damage was seen, some accumulation f)f dust in the microphages occurred, and for the monkeys, there was no impairment of respiratory function (228). In general, these authorfe remark on the mild effect of PVC dust, and compare it to other nonto xic substances. Some PVC dusts show greaj: er 1_n vitro cytotoxicity and fibrogenicity than do others (229) and these two properties run in parallel, Richards and coworkers f^iund (230-31) that the biological activity was due to the surface a ct ive agents present on plastisol resins, and that sodium dodecylb^ nzene sulfonate was the most active of those tested. Washing w th ethanol or water reduced the activity greatly. Wheeler has emphasized the need to distinguish between plastisol and suspension resins when considering health effects (223). Chronic feeding studies of PVC, copolymers, or extracts of these to rats and dogs has not shc^1wn any serious effect (232-4). These resins are prior sanctio rjed by the FDA for food and cosmetic applications (21 CFR 121 106). PVC is like other sol ids that it will induce local sarcomas when the proper size pieces are i ^planted in rodents. These results have been reviewed in several places (162,235-6) and are not considered relevant to risks for hunk,ans (195). The difficulty of ignitic n of PVC dust is a function of its particle size. Very little yield is obtained from material 100 pm or larger, while 10 pm mater ial is about as explosive as baking flour (237). The presence of mall amounts of flammable gas increases the hazard. Solid PVC is non supportive of combustion, and most fabricated products earn the Underwriters rating of SE-0 unless sufficient modifier or pi asticizer is added to offset the lack of flammability (238). It is well known that PVC will produce hydrogen chloride upon heating, and this is the basis of the need for stabilizers during processing. This hydroge n chloride is the principal toxic hazard during fires that are lar ge enough to force continued burning of PVC articles (239-40), along with the carbon monoxide that may be present in any combustion gases. This aspect of polymer' toxicity will be di scussed in more detail in Chapter 26 of Volume III of this Encyclopedia. 29 SPI-00082 Some evolution of HC1 occur at any elevated temperature, but studies have shown (241-3) that this is not a significant risk to those who handle the hot malt erials, such as meat wrappers, when adequate ventilation is proy ided. This is no depolymerization of PVC to the monomer, and the amount of vinyl chloride found in decomposition gases at processing temperatures is only that e<pected to be present as residual monomer (244). Regulatory Status The current regulatory status of the materials discussed in Section II is summarized in Table 6 where in X indicates that there is a document or rule by that agency for the substance listed in the column heading, These rules are discussed in more detail in the following pages. A. The Food and Drug Administration The first specific regullator y initiative toward vinyl chloride was in 1973, after it was found that up to 20 ppm of vinyl chloride could migrate into the contle nts of miniature liquor bottles. The Bureau of Alcohol, Tax, and Firearms of the Department of the Treasury (8ATF) proposed < 38FR12931, Sept. 1973) to withdraw the prior sanction status of PV C for use in these bottles. The proposal was based on adulteration of the bottle contents, and not on any specific health issue at tha t time. Bottlers stopped this use of PVC voluntarily, and no fur ther action has been taken on this proposal. The BATF has indicated to the FDA that it is willing to reconsider the use of PVC for liquor bottles if the FDA would clarify the status of PVC for that use. The FDA replied in a letter of January 13, 1981 from the Deputy Director of Foods to the Assistant Director of BATF that the FDA was still considering its policy in regard to indirect food additives Two proposals concerning that policy were published for public comment at 47FR4972, February 2 and 47FR14464, April 2, 1982. Thus, this issue still is not resolved, The BATF has removed forma barr i ers to the manufacture of liquor bottles from plastics in ge neral (47FR43944, October 5, 1982) but has not approved PVC specifically Earlier, the FDA published in September 7, 1975, at 40FR40529, notice of intent to withdra w its sanction for the use of rigid and semi-rigid PVC as food pack aging material, while allowing the use of flexible materials to conti nue. This was based on the finding that residual vinyl chloride in flexible film was undetectable, but could be found to be present in r igid sheet, and therefore was presumed to migrate into foods. No act ion has been taken on this proposal, either. One of the reasons has been the strong activity by members of the Society of the Plast ics Industry (SPI), who presented data to the FDA that the current ve ry low residual vinyl chloride in PVC does not result in detectab le quantities of vinyl chloride in the packaged food (245). In additi on, the District of Columbia Circuit Court of Appeals ruled in f*jons anto v. Kennedy [631F 2nd 947 (D.C. 30 SPI-00083 Table 6 Regulatory Status of Various Substances OSHA TLV ppm Standard ACGIH NIOSH Crlt. Doc. EPA Standard Priority Pollutant Hazardous Substance RCRA CERCLA (Superfund) FIFRA FDA BATF DOT CPSC VC 1/5 X 5 X X X X X X X X VAC 10/20 X X X X TCE 100/300 (50/150) 100/150 X X X X X X EDC 50/200 10/15 X X X X X X 31 SPI-00084 Circuit 1979)] that risks c annot be inferred or assumed, but must be found by a reliable sclent! fic process. The Second Annual Report on carcinogens (246) states that the FDA is reconsidering this proposal, and may withdraw it. Meanwhile, the polymers and copolymers of vinyl chloride continue to be prior sanctioned for foo|<d and cosmetic packaging. Concern over possible action by the FDA has significantly affected this application, however. A relcent Industry survey by the SPI found that about 7.81 of the nati ons' food supply is now packaged in PVC, and estimated that this cou Id rise to about 111 if the proposal were withdrawn (246A). No signi ficant exposure to Ingested VC can be expected at this level of use and the current low residual monomer 1evels. Vinyl chloride was used as a propellant in a variety of pesticides and cosmetics up to 1973, xhen this use was withdrawn voluntarily. When the first reports of ASl issued, the three agencies having jurisdiction over these uses promulgated bans, the FDA at 39FR30830, the EPA at 39FR14753 and tte Consumers Product Safety Commission (CPSC) at 39FR30112. The CPSC action was upset on procedural grounds and was later reinstated (43FR12308) without a by then useless recall provision, The FDA noted (39FR14215) in its proposal that a generally effective voluntary recall of unused packages had occurred in early 1974. The Occupational Safety anc Health Administration OSHA adopted the recommendations of the American Conference of Governmental Industrial Hygienists (ACGIH) for occupational exposure to various substances as a part of its rulemaking by reference. These appear at 29CFR1910. 00, tables Z-l and Z-2. There is no listing for vinyl acetate, OSHA has not kept up with the subsequent revisions of this list by ACGIH, so that current ACGIH recommendations (shown in parenthesis in Table 6) differ from the official OSHA exposure lim ts. The ACGIH recommendation at the time of adoption by OSHA was 500 ppm. See the discussion of this point in Part II.A.1 above. The allowable occupational exposure for vinyl chloride of 1 ppm is set by the OSHA workplace standard at 29CFR1910.1017. This was adopted in 1974, after extensive public hearings and became effective in April 1975. OSHA first set an emergency temporary standard of 50 ppm, and proposed a permanent limit of nondetectable exposure by a test sensitive to 1 ppm. Economic impact studies sponsored by both OSHA and industry showed that such a limit was not feasible (245A), and OSHA then promulgated a final standard of an 8-hour time-weighted averaje (TWA) of 1 ppm, and a 15-minute ceiling of 5 ppm, without regard ta respirators. In brief, the regulation s 51 s: 1. An action level of 0. ppm below which no response is required. This gener illy exempts most fabrication plants and laboratories and many monomer Diants. 32 SPI-00085 A regulated area w hbre exposures are above 0.5 ppm which restricts entry to authorized persons. 3. Medical examination schedules and exposure record retention for authorized employee^ 4. A list of acceptabl a respirators for use at exposures over l ppm. 5. Monitoring and alarin systems for the workplace, and routine measurement of workb r exposure. 6. Labeling and signs For regulated areas and containers of vinyl chloride and PVC. 7. Work procedures for hazardous operations, and 8. Training programs for employees. OSHA described this as a "feasible" standard, and states that it was not derived from health considerations, therefore should not be considered a safe exposu e limit. It is difficult to detenn ine the cost to the industry for compliance with this standard becau? e of the work going on at the same time to respond to the expected :PA emission standard. In addition, some steps had been undertake^ earlier by industry in response to the concern for AOL (63) Th e immediate effect was a sharp drop in productivity as new work practices were instituted and equipment was installed. Some of this productivity loss was recovered later, but there is a general indus :ry consensus that there has been at least a permanent 5--1 OX loss (24t -8). A few of the smaller older plants shut down, amounting to ^bout a 5% loss of capacity and jobs (248A). Trade associati estimates prepared a few years later indicate an overall capi i:al expenditure of about $200 million that can be ascribed directly to OSHA, and added annual expenses of about $25 million. Several authors have att^ mpted to estimate the cost-effectiveness of this standard on a cost- (ier-1 ife-saved basis. This is an especially difficult approach, bee an se of the uncertainty of what exposures may have been in the absence of a standard, the inaccuracy of the risk assessments which were m,4de from animal data, and the reluctance of most persons to accept a monetary value for a life. Nevertheless, Graham and Vaupel <249> stimated that the OSHA rule cost $7.5 million per 1ife saved a nd $490 thousand per life-year saved over the option of leaving th4 limit at 50 ppm. Luken and Miller (250) arrive at an imputed val e of $4 million per life, while Morrell (251) derived the higher cost of $200 million per life, assuming that the residual incideri ce rate would have been 0.1 cases per year without the standard. Nq rthrup (252) calculated that the cost was $9 million per life, or 450,000 per year of life saved, based on no voluntary action by indu try. 33 SPI-00086 There are no specific OSHA standards for the other materials In this group except for the 8-hour exposure limits of 40CFR1910.1000 that are shown In Table 6. C. The Environmental Protection Agency 1. Air Emlssions There are no recognized biological sources for the materials discussed In this chapter. Vinyl chloride is suspected to be formed by the photochemical decomposition of other halogenated materials, but this has not been confirmed. It is formed by the biological degradation of other chloroolefins (see below). Hoffm--an r--e--p-o--r/t-eicd-is(2-5th3a) t vinyl chloride was found in tobacco smoke, aWnWd specu'la<**te*<d! that i' t* mi5g"ht *b* e pr resen*t in WcWo1m..WbK u< s* tiVon gases from all chloride-contaminated organic materials, and therefore may be ublqu itous. Grlnard calculated (2 54 ) that the steady state, worldwide ambient concentration in 1973 was about 1.4 ppt based on emissions at that time Vinyl chloride is active photochemically with a half-life in sunlight of about 5 or 6 hours (255-8). The r eaction rates are slightly less than those of ethylene in the rea ction with NO, and considerably less in the reactions with ozo|ine. The residence time in the atmosphere was estimated as 1.8 days by Singh, et al. (259), with a 43% loss per 12 hours of unlight, based on the rate of reaction with hydroxyl radical only. Smog chamber data were used to predict a consumption rate of 12% per hour, and the study showed a rate of about 18% (259A). The EPA has conducted three ambient monitoring programs around VC handling plants (117,255). The first, in 1974, found measurable quantities at distances up to 0.5 km from a PVC plant. The third program failed to find significant quantities at the fence line of five large fabricating plants. The results of the second program have not been released formally, but an analysis of the data has shown that the average concentration in early 1975 at the plant tested was about 40 ppb at 500 meters f rom the plant center, 10 ppb at 1 km, and 2 ppb at 2 km. The EP A had calculated (75) an average exposure of 17 ppb to persons esiding within five miles of a typical PVC plant, using emiss ion data and modeling techniques which were strongly disputed by industry. The estimated 95% reduction of emissions by the current standard presumably reduces the current exposure to those within five miles of 0.4 ppb, by the EPA as sumptions. The generally accepted field monitoring method for VC has a lower sensitivity of 10 ppb so that these estimates dannot be verified broadly, but recent tests in one plant sudgest that the actual values are only 10-25% of this estimate (248) ( f 34 T *T SPI-00087 Vinyl chloride, TCE and DCE currently are found in the ppb range in the air a rjound industrial locations, but generally not in detectable quantliities at rural sites (179,259-262). There are diurnal and seals onal variations which link the emissions to human activity. A summary of an extensive EPA-sponsored survey is available in papie r copy or on computer tape (262A). The EPA formed a s tudy group early In 1974 while OSHA was conducting Its rul elmaklng. Several publications discussed the environmental aspec ts of VC (75,255,263-4) and the EPA ultimately conclude^ that there were nearly 5 million residents within 5 miles of Vi 2/PVC production facilities that had been exposed to an averajje annual concentration of 17 ppb for 30-40 years, and that thi led to the possibility of 10-20 deaths per year (127). This r sk estimate has several serious flaws (265) and a more realisti estimate is several orders of magnitude lower. In any event there have not been any cases of ASL which have been attr ibuted to general ambient exposure. See the discussion in I .A.4 above. The final EPA standard was calculated by the ElfA to reduce environmental exposure by 951. and thus the projec ed death rate to less than 1 per year (266). The final EPA standard (74) established the following conditions: Fugitive emissions controls by leak patrols and design standards for ptjmp and compressor seals, agitators, and loading devices. b. Work practices fjor vessel openings and sampling. c. Stripping requirements for residual monomer in resins and wastewater. d. Abatement of al1 point source emissions to 10 ppm. e. Prohibition of relief valve discharges, except for emergencies. f. Extensive monitoring, reporting, and recordkeeping requirements, anj g. Specific analyti cal procedures. The Agency prepared i model plant by choosing among the best control devices existent in the industry (75) and it now judges the compliance of a particular plant by the projected emissions from that mode 1. As was stated earlie , it is difficult to separate the compliance costs for this standard from those of the OSHA standard. An Agency report (267) estimated that the cost of comp 1iance was 5296 m '''ion through July 1981, and that an 35 SPI-00088 additional $470 million would be spent in the next five years, all calculated in 1977 dollars. A more recent update of this report prepared for the Agency put the costs for 1981-1990 at $981 million. If the Agency estimate of 20 deaths per.year is accepted, this would be a cost of about $5 million per life saved. However, there Is no evidence that any lives have been saved by this standard and we do know that at least two workmen were killed during the compliance efforts of the industry. The Industry position has been that the OSHA standard had provided adequate protection to the environment, and that the EPA-generated costs we re unnecessary. Environmental groups chal lenged the standard as being too lax, and as part of a settl ement agreement EPA proposed additional restrictions on emissi ons (42FR28154, June 2, 1977). No further official actia|in has been made on this proposal. The Agency has stated more recently that it is again reviewing the emission standard for vinyl chloride, and plans to propose revisions in 1984 (48FR47914, October 17, 1983). Meanwhile, the U.S. Di strict Court for the Middle District of Louisiana dismissed ca ses brought by the EPA against Ethyl Corporation and Occide ntal Chemical Corporation for violations of the emergency disch arge rule (40 CFR 61.65(a)) on the grounds that the stanqard is a work practice standard and not an emission standard, and as such was not authorized by the Clean Air Act as it ex isted in 1976 (267A). Work practices were authorized by 1977 and 1978 amendments to Sec. (112) of the Clean Air Act, but this was after promulgation of the standard, and thus the court noted that the present standard was subject to the Sup reme Court ruling in Adamo Wrecking Co., United States 334 US 2(75 ( 1978), which held that work practices were not authorized at the time of promulgation. At the same time, the District Court for Massachusetts has denied the petition by Borden, Inc., for dismissal of a similar suit. It ruled that the Adamo decision did not apply, and that Borden was barred from challenging the standard at this time. The Agency has filed rjotice of appeal in the Louisiana rulings and has continued to ile additional cases against other faci1ities on an iden tical basis. It appears that this matter may be in litigation for some time. Industry argued the same point that was made by the Louisiana court during the rulemaking procedures, but was net successful at that time, After promulgation, attempts to obtain a clarifying guide ine from the Standards Setting Group in the Air Office were unproductive, and the Enforcement Office issued a series of memoranda which took a itera1 view of an "emergency' being 1 i 11: e other than an "Act of God". The effort to attain relief here was complicated by the outstanding proposed amendments to the standard of June, 1 977, pub 1ished as 36 SPI-00089 the result of the ne gotiated agreement with the National Resources Defense Co unci 1 after their petition for review of the original standar d, whfich would have made the standard more stringent. Neither these proposed amendments nor the requests for clarification of the definition of emergency were acted on. The other materials discussed in this section are not regulated by specific emissiob standards, but all of them, including VC, are affected by gen ral rules on volatile organic emissions, and thus come under the State Implementation Plans and New Source Performance Standards, which often require stricter control measures thfci n does this standard. The oxychlorination reactor in particul r has been subjected to additional controls (48FR40278, Septemb^ r 6, 1983), as have storage tanks. Most new volatile organ! chemical manufacturing facilities are subject to a leak d^ tection requirement similar to that for VC (48FR48328, October 18, 1983). Vinyl chloride, TCE and DCE are listed as priority pollutants under Sec. 307(a) of the Clean Water Act, and Water Quality Criteria Documents Ijiave been prepared for them (274). This subjects these mater ials to special considerations when discharge permits ar e Issued. A Health Assessment Document has been prepared for TC E (179). These documents summarize the evaluation by the Act ency of the health risks from these substances, and give some data on methods of waste treatment, Other sources of Age ncy data on VC, TCE, and EDC can be found in the "Treatability Manual" (262), the "Multimedia Environmental Goals for Environmental Assessment" (273), and "Fate of Priority Pci lutants in Publicly Owned Treatment Works" (273A). Vinyl acetate, DCE, and TCE also are subject to reporting requirements for spi 11s as hazardous substances under Sec. 311(b) of the Water Pollution Control Act and Sec. 102 of CERCLA. See 40CFR11 6, 117, and 302.4. Reportable quantities (RQ) of spills are 5 ,000 lb. for DCE, and 1,000 lb. for vinyl acetate and TCE. Vi nyl chloride has a temporary 1 lb. reportable quantity under CERCLA, pending designation of a permanent figure by the EPA. Reports are not necessary for releases at federal 1 y permitted facilities. The EPA has proposed to raise th e RQ for vinyl acetate to 5,000 lb. (48FR23552, May 25, 1983). The EPA issued a rul at 49FR5308 under which the distillation residues from the prle paration of EDC and VC are to be listed specifically as hazar dous wastes, rather than as the result of broader RCRA rules, This insures that all such wastes are to be disposed of'only cy RCRA-approved procedures. 37 SPI-00090 2. Water A11 of the substances di scussed In the previous section also are controlled under genieral discharge provisions to the extent that they produce convep tional pollutant properties, such as BOD. As would be expected, vinyl chloride has low water solubility, and is easily lost to the atmosphere from streams and discharges (268-9). Under one set of experimental conditions, the evaporative half-life of VC, TCE, and EDC are less than a half hour (269). In another experiment, a stirred beaker lost 96 of Its original 16 Dpm of VC in two hours, while an unstirred beaker lost 257., at 22*C. Plots of log concentration versus time gave straight lines, indicating volatility to be the only important loss mechanism. There was no difference in loss rates between distilled water, river water, or industrial effluent. It does not appear to be absorbed by microorganisms, as shown by tests with five mixed bacteria populations, three mixed fungal populations, two axenic bacterial cultures, and one algae. The mixed bacteria did not degrade the VC, nor was it toxic to the bacteri a at concentrations up to 900 mg/1, It does not bioaccumulate in the food chain (270). The EPA has reported (255) finding VC in the water supplies of some cities in the ppb range. The concentration was higher in the finished than in th e raw water, indicating that it may be produced in the chlorin ation step. Dressman and McFarren (271) have found VC in the ppb range in water from distribution systems using PVC pipe It is also present in the discharge of some VC-handling plants in the low ppm range (263). Banzer (272) states that no extraction of VC occurs from pipe containing less than 1 ppm residual by a test sensitive to 2 ppb. The EPA and the FDA have entered into a memorandum of understanding which assigns the EPA the responsibility for regulating exposure for VC extracted from plastic water distribution pipe (274A). No specific action has been taken in this regard, possibly because of the rapid decline in detectable amounts in qrinking water after new piping systems There is in place a voluntary industry standard limiting residual VC in the finished pipe to 10 ppmw. This program appears tc have been successful in eliminating the leaching of VC into water. Compliance is being monitored by the National Sanitatior Foundation (NSF), whose stamp of approval is required b) most codes before pipe can be sold or installed for potable ijater use. A recent report (274C> described a test for chlorinated organics in water extracts of p'astic pipe which is sSe ensitive to 2 Dpb, and the President of NSF has stated (274D) tnat VC s not found in tne extract at this 1imit of detectior . 33 SPI-00091 ( ( Similarly, TCE and DCE are found In streams and water supplies In low concentration s (179.262,273-4, see also 47FR9350). These seem to be pre sent because of a combination of waste discharges, formatlon during chlorination of water supplies, and, In the case of TCE, use by Individuals as a degreasing treatment for home sewer systems. Some state legislatures are considering a prohl ition of this last use. A relationship betw|e en vinyl chloride and chlorinated ethanes in groundwater has been established by recent work at Florida International Unlv e' sity for the EPA (274E). Analyses in the outer perimeter of tri- or tetrachloroethylene-contaminated groundwater showed larger than expected decrease in the original contaminan ts and the presence of vinyl and vinylidene chloride and 1,2--d1 rhloroethylene. Experiments with anaerobic bacteria from Florl pa muck demonstrated that several classes of anaerobic bacteria, Including the ubiquitous E_;_ col i, can biodegrade the more highly chlorinated ethylenes to the monoand dichlorinated di rlvatives. Their work also conf irmed the resistance of VC to further biodegradation, and reported a half-life of greater than 60 days under their experimental conditions, as compared to 43 and 34 days, respect ively, for the tri- and tetra-substituted ethylenes. They dev eloped a spray aeration system which attained greater th^n 951 efficiency for removal of VC per stage. Vinyl acetate would not be expected to be persistent in water because of its rapi hydrolysis, which is reported to be 8.57./day at room terniperature and 47./day at 4C in tap water (166A). The EPA has in progr ess two rulemakings which will regulate the allowable emission cf VC, TCE, and EDC beyond that of the general emission sta ndard. On March 4, 1982 the EPA published an advance notice of proposed rulemaking (47FR9350) requesting public input on work underway to limit volatile synthetic organic chemicals u nder authority of the Safe Drinking Water Act. It stated that it was considering establishing Maximum Concentration Limits of 1-100 ppb for VC and EDC, and 5-500 ppb for TCE. The Health Assessment Documents prepared as a part of this initiative sti1 are undergoing scientific review. On March 21, 1983 the EPA published a proposed regulation (48FR11828) containi ng effluent limitation guidelines for the organic chemicals and plastic industries which would place 50 ppb maximum for tie VC content of plant effluents. The limit for TCE i s pro}dosed as 75 ppb maximum for any one day, and 50 ppb for the a /erage of any four consecutive days. The EDC 1imits are 150 a d 100 ppb, respectively. The 'standard for EDC would apply to b th direct discharges and those whose effluent is treated urther at public treatment works; those for TCE and VC apply only to direct discharges. 39 p|.00092 3. Solid Wastes Vinyl chloride is list ;d as a hazardous waste under the Resource Conservation and Recovery Act (RCRA), as toxic and ignitable. Vinyl acetite and EDC are ignitable wastes, and TCE is a toxic waste under these rules. See 40CFR261. Any disposal of these substances is subject to permits under RCRA. The EPA recently incluJed the distillation wastes from the production of VC and EpC as hazardous wastes, as was noted earlier. 4. New Product Manufactur The EPA also adminis;te' s the Toxic Sustances Control Act (TSCA) which establishes heal th and environmental regulations for both new and existing subst^i nces. No one may manufacture or use a substance which is not on the Agency's official inventory, unless the EPA has ac cfepted a Premanufacturing Notice (PMN). Polymers containing mo re than 2X of an incorporated substance are required to be on this inventory, in contrast to European rules which do not cov|e r polymers. Incorporation of less than 27. of a substance i s ot deemed to be a new polymer, and a PMN is not required for ma tufacture. Producers have the choice of making these resins of low comonomer composition without a PMN, in which case they are not placed on the inventory and future variations are 1imi ted to less than 27., or of filing a PMN, in which case future vari ations may contain any desired amo.nt, but ful1 disclosure of all processing ingredients and conditions are requii red See 40CFR720, 48FR21722, May 13. and 41132, September 13, 1 983, for more details on this regulation. The EPA has proposed ( 47FR33924) procedures for exempting certain classes of pol|ymers from the PMN rule, but the conditions for this ex emption are so rigid that industry has opposed the proposal, and asked for a blanket exemption for all structural polymers si ilar to the European rules. IV. General Safety Procedures Extensive changes have occurred in the work practices and procedures in monomer and polymer plants in t"he last few years as the result of concern for the health effects of VC. These have been amplified by efforts to comply with the OSHA and EPA standards on vinyl chloride (248,252,275-6), and the broader volatile organic emission rules. There is no doubt that these compliance efforts have made the industry a safer place to work. The VC/PVC industry always has been a relatively safe industry from the standpoint of major disasters a nd fatalities due to the innerent nazards of the processes, even when the ASl cases are considered. Nevertheless, there have been several major i ncidents that resulted in fire ana loss of life (276A) one of which ra nked among the hundred largest losses of the last thirty years (2766). able 8 contains a listing of major 40 SPI-00093 ( ( incidents in the past few years. Thus, the basic considerations of the flammability and the need for careful control of polymerization still remain the controlling facto'S in efforts to protect life and property. Efforts to Improve plant saf| ty and to develop more effective means of compliance with health regul atlons has been aided signficantly by voluntary participation in t:-ade associations. The Vinyl Chloride Safety Association has been Especially productive, but substantial developments have come from :he Compressed Gas Association, the Chemical Manufacturers Association, a ipd the Vinyl Institute and its predecessor organization, which was an ar m of the Society of the Plastics Industries. The industry ha$ been very generous in exchanging nonproprietary information re lating to safety and health. A formal Process Hazard Revi <w (PHR) is used by many organizations to identify, evaluate, and plan remedial actions for potentially hazardous situations which may arise i plant operations. The PHR is in many ways an outgrowth of accident 1nv stigation, the difference being that the study is made before an even , with the intention of preventing it (287A.290E). Emphasis usual ly centers on the reactor and its attendant systems. A team with broad experience conducts the PHR. The skills included should cover plant operations, safety engineering, environmental engineering, and experts in the process involved, and also any particular special problems posed by the process. This usually involves 4-7 persons for all of the study, and others for portions. The initial phase may occupy 3-10 days at the plant sites, after gathering the initial background documents and data which will help identify the concerns to be addressed. Much of this first phase cons ists of a line-by-line examination of the process flow diagrams, but fi Id inspections and interviews are important also. If the Revi e h is for an operating plant, plant operating and support personn^ 1 should be interviewed. If the plant is in the design state, the desi jners and the future operators should be included. Each section or unit operati 01 is discussed by someone familiar with the design concept and operating ahi1osophy. A person familiar with the fault tree concept then leads in an examination of each major piece of equipment for potential fail u - e modes, determining (or speculating on) conditions which could cause prevent, or modify such failures. The results can be depicted m a fault tree, which show those conditions necessary to cause particular result-as an "and" branch, and gathers those various groups which ma cause the same result into "or" groups, Figure 1 is a generalized fau t tree for the failure under pressure of a monomer storage tank, such as a recovered monomer vessel, and Figure 2 is a more detailed analysis of one of tne branches of the previous figure, the probability of an external fire in the process area. The result is a description of th events necessary and sufficient to cause the potential incident (234). 4 SPI-00094 TT ( I T Figure 2 Feult Tree fo r futerne) F ire In Are< A second phase of the PHR is to attempt to quantify the probability of each contributing event, and of the postulated end result. This usually is done by a specialist in risk assessment, who often is the leader of the team. Where available, acti al experience for failure rates should be used, but publications glvinc predicted rates or rates for similar situations are available (290F, O . In this way those conditions or combinations of conditions whicl are unlikely to occur or to lead to a dangerous result can be fdentlfi ed and more attention paid to more probable scenarios. The third phase consists of the preparation of the PHR report, which contains specific recommendations by the whole team, for preventative measures for the serious consequence conditions, with appropriate priorities and the assignment of responsibility for implementation of each action. The final phase is a progress review of the Implementation steps Further change or revisions may ube~ -r-e--q--u-i-r-e--d----a--s---t-h--e----r-e--s--u**lt --of new data or cost estimates, or further exam nation of the interaction of the changes made. For new plants, the Operational Readiness Inspection (ORI) before start-up should inc ude a further review of compliance with the PHR report. A major uncertainty in the quanl: ification analysis is the weight to be ascribed to operator error. Th s factor often is enough larger than the other factors that errors in es imation of its value overrides the other uncertainties in the estimate ( 90G). This emphasizes the value of the thorough operator training in tli e prevention of accidents. Another fact apparent from such an experience is that an accident seldom results from a single event, bu that a combination of failures and errors is necessary in most casis. This is because of the redundancy and diversity of design safety buiIt in to most facilities. The use of the PHR to identify likely fault paths influence both design and operating philosophies so as tofreduce the probability of undesirable combinations. A. Raw Material Handling and S corage 1. Vinyl Chloride The shipment of vinyl chloride is regulated by the Coast Guard (46CFR40.151) and the Department of Transportation (DOT) <49CFR172,-173). In a ddition, 0SHA has specific rules for in-plant labeling of v nyl chloride containers (29CFR1910.1017), and equires that all shipping packages or containers of PVC carry a warning that PVC contains VC. The principal method o shipment for vinyl chloride is by ra i 1 car , in Type 105A nd 112J tankers, with capacity of up to 30,000 gallons. A few users are near enough to monomer suppliers to use pipe! ne transfer. Two suppliers can furnish 42 SPI-00097 T barge loads of monqimer and one of these maintains a terminal in the Northeast from which tank truck or rail transhipments can be made. International shipments are made by specially equipped tankers. Concern for the saffe disposal of the contents of derailed tankers has led to the development of a technique to pierce the car shell with shapb d explosive charges (276C.290H). The escaping material 1s then ignited. Leaking cars not already on fire also are Ignit ed. This is a general rule for leaking vessels in which thle leak cannot be stopped. The danger of an explosive vapor cloiid is far greater than that of the combustion products and point source flames should never be extinguished unless the source can be stopped. Reports of some recent transportati on accidents involving VC can be found in the references list ;d under 276C. The Compressed Gas Association, Arlington, VA 22202 has developed a field rupair kit that can be applied to leaks which have developed In the loading dome in valves or at welds. Two sizes are available which will fit most of the cars now in service. The Department of Tr ansportation has required that all new cars put in vinyl chlori die service be equipped with spade couplers, head shields, and ha s set minimum body insulation and relief valve specification;; A schedule has been set for retrofitting of all existing car; (49FR3468). An analysis of rail accidents since this change ha s been required indicates that it has reduced sharply the severity of such incidents (276D). The Society of the plastics Industries, New York, has organized a mutual assistance program between VC producers and users that can supply an Emerge ncy Response Team for assistance from nearby participants in case of a transportation emergency, This is coordinated through the CHEMTREC emergency number, (800)-424-9300, whi ch should be the first contact point. A principal source cf information on the safe handling of VC is in the data manuals provided by the manufacturers. The National Fire Protec tion Association (NFPA) codes specify the electrical and fire protection standards which are recommended (277). Insurance ca rrier requirements and local building cooes vary, but general ly require as a minimum the standards of the American Society of Mechanical Engineers (ASME) for pressure vessel construction Many of these factors were summarized (278) a few years ag o, and the following discussion is drawn from this source Vinyl chloride is $ t|able in the absence of oxygen, water, ana light and may be ha n j 11ed safely in iron, steel, or stainless steel if those substla nces are excluded. The use of phenol or other inhibitors to stabilize against spontaneous polvmerication of tn pure monomer was stopped more than 15 43 SPI-00098 T years ago. Inhibitors are still used in recovery systems to prevent polymerization of the recycle monomer under conditions which favor peroxide formation. Oxygen reacts readily wi th VC to form a variety of cyclic and linear peroxides by simple addition (279-83). These peroxides are shock, sensitive, decompose violently on heating, and can initiate polymerizatlop in either the monomer or the water be a major safety hazard in any manufacturing system which Involves water and has the possibility of the entrance of air and has caused serious damage in industrial accidents (283-4). The peroxide formation is accelerated by the presence of acids and aldehydes, but can be prevented by the presence of a base (234,283). Careful warming with 5-10t sodium hydroxide in water, or preferably methanol if polymer residues are present, is adequate for removal from process vessels. The EPA standard establl ishes specific rules for vinyl chloride unloading and handling (40CFR61.60). These are in addition to the general unloading rules prescribed by the Department of Transportation in 49CFf* 174.67(i). Unloading systems must be designed to minimize e release of vinyl chloride when the 1ines are disconnected and "slip gauges" no longer are allowed. Pumps must equipped with double mechanical seals, or the equivalent. Rub ture disks are required under the relief valves on storage tanks to prevent leakage through the valve. Storage tanks should be provided with adequate deluge systems to protect against local or adjacent fires. Efficient deluge systems which provide an effective water curtain sometimes can he i p prevent the spread of a vapor cloud, or the flame from its ignition. Saturation of the air with moisture also reduces the ignitabi1ity of the va Dor. Drainage area within a dike is recommended which is s jfficient to allow any spillage to run away from under the ta nk. The relatively high heat of vaporization of VC wi1 1 cause large liquid spills to pool for several hours, thus in creasing the potential for heat damage from fire. Fireproofi ng of supporting steel is required by most authorities. Cri tical valves in liquid service should have firesafe seats and automatic closing devices. Relief valves should be desig ned for at least the capacity required by a pool fire. Redundan t level control systems are desirable to prevent overfi11ing. Insulation and/or reflective coatings are recommended to reduce heat input. All piping sections which can be isolated by val ves should be provided with protection from thermal expansion damage. Earlier prohioitions against the use of brass or copper instruments or tubing were due to the concern for formation of copper acetylide from the acetylenic i mpurities in monomer made by the addition of hydrogen chloride to acetylene. This does not seem to be a prop em with VC from the oxychlorination process. 44 SPJ-00099 Consideration of th 3 ignition temperature and energy of vinyl chloride suggests t iat "spark-proof" tools are not necessary, and this practice no longer is customary (284A). Small fires can be xtinguished with carbon dioxide or carbon dioxide-generating solid extinguishers, but care should be taken for reignitioi of the flame if vapor remains in the area of hot surfaces. Larger flames should be allowed to burn if the source cannot ba closed off. Water Is not effective on liquid fires because it Is heavier than VC, and, of course, freezes upon contacjt with the liquid, and only serves to faster. Air-supplied respirators should be used by fire fighters that will protect against both the carbon monoxide and hydrogun chloride that are produced. Water spray or curtains should be used to protect adjacent equipment, reduce the spread of the fire, and, to some degree, absorb the combustion gases (2'r8A). Conventional gas di ^pension models of the kind used by the EPA for studying diffus on effects (2788) can be helpful in preparing rough est mates of the size and concentration of vapor clouds for re atively small VC releases, particularly when no pool of 1 iqt|i id is involved. These small releases do not cause significa nt changes in the density of the gas volume. However, 1 4rge releases, and especially those which involve evaporation from liquid pools, should be estimated by use of di spers ion nxj>dels designed especially for heavy gases. It is necessary to Consider the effects of changes in gas density and the coo ing which result from such large releases (2780 . A11 equipment shoulc be properly bonded into a common grounding system to prevent s tatic accumulation. This is especially important in flangec equipment, rail or truck unloading systems, and polymer air conveying systems. Continuity of the grounding system she uld be checked on a regular basis. It should be noted ijhat there are no cartridge-type respirators available for VC ser vice which have effective end-of-service indicators. Therefc re, as a general rule such respirators should not be reusec and should be reserved for short-term service where the VC concentration is known to be low. Airline pressure-type respi r|ators are used more widely than other types for this reason. A respirator programs must comply with QSHA regulation 29CFR191C 134. Vinyl Acetate Stainless steel cons truction should be used for storage and hand 1ing of viny1 ac etate because of corrosion from tne acet'C acid Dotentially pre sent from hydrolysis. Innibition with a few pom of hydroquin one or an equivalent still is practiced, The f1ammaoi1ity of the vapors requires exclusion of air in the headspace, and nitro|<gen padding is a usual oractice. In 45 SPI-00100 addition.fill and rec:ycie lines should return to the bottom of the tank, and not geneirate a spray in the vessel. Hydrocarbon emission rules vary wi1th the locality, but some type of emission control is required by most authorities. Coast Guard and DOT rules apply to) shipping, and EPA spill control rules apply to storage. DCE and TCE Carbon steel equipment is satisfactory for dry pure material; stainless steel is ne eded for wet or recycle streams. The same general type of rules for vinyl acetate applies to transportation, emissi on controls, and storage. Aluminum is not a satisfactory ma te rial of construction. Initiators The search for greater productivity in the polymerization cycle has led to the use of more reactive peroxide initiators. Most of those in use now require storage well below ambient temperature. The oxygen content of these materials is such that they often need little external oxygen for combustion. This reactivity has led to the classification of initiators by their self-acceleratirg decomposition temperature (SADT), the temperature at which the decomposition is self-sustaining and becomes violent, usual ly with self-ignition (285). Table 7 presents the SADT and recommended storage temperatures for several commonly used materials (286-7). Dilution with inert solvents or making a suspension of the initiator in water decreases the danger of handling these materials, while storing in a reduced oxygen atmosphere lessens the danger of fire. The most commonly usee storage method is in commercial top-opening freezers v h ich have been adapted to reduce the ignition hazard from the light and thermostat. These usually are arranged in an ops n shed with fire-resistant partitions between each unit and remote internal temperature alarms. General safety rules i'or the use of initiators include: Mark each type of initiator with a distinctive label and store only one type in each location Remove only enough for immediate use from storage and keep it at the proper temperature on the operating floor. Try to arrange the packag-ing so that only full shipping containers are used. Use extreme care in dividing packages, especia'ly those which are solid at storage temperature. Use only clean , d$ dicated containers if an intermediate container is nece sary. 46 SPl-00101 Table 7 SADT and Recomme nded Storage Temperatures _________for Typ t cal PVC Initiators_______ Name t-Butyl Peroxyplvalate t-Butyl Peroxyneodecanate (pure) 75X solution bis (2-Ethyl hexyl) Peroxydicarbonate di-n-Propyl Peroxydicarbonate di-iso-Propyl Peroxydicarbonate alpha-Cumyl Peroxyneodecanoate, 75X Azobisisobutyronitrile Lauroyl Peroxide SADT, *F 80 65 75 34 20 30 59 >70 123 Recommended Storage Temperature, F 40 0 32 0 -10 0 0 60 80 SPI-00102  Never return material to a shipping container. Remove empty contal ners promptly and dispose of separately, not with other trash. Use proper protecti ve clothing. The most critical peri o|d in initiator handling is when the proper charge for a bat ch has been weighed and is placed into the charging device, A|ny delay in the batch, or leakage of vinyl chloride or other materials into the charge device, can initiate a violent rea dtion. Cooling of the charge device with a jacket or by addition of cold water can be of some assistance, but only i the SADT is above 32*F. Decomposition is catal yzed by any organic reducing substance and many metal ions su ch as iron. Thus dust, rust, concrete, and many such common cc ntaminants have caused problems, Leaking cwov'nl ktWai'n"e rI sa may be the single most prevalent problem, a--nd care cshhmouillHd hbae +ta*akke, n to see that all containers are stored upright and that the ca*p s are tight. Any spilled material should be absorbed in an inert solid such as vermiculite and destroyed immediately. Manufacturers provide plroper disposal directions for each product (287), but in the absence of specific instructions the material can be added cautiously to glowing charcoal embers in a ditch or hole at a s a|fe distance from any flammable material. B. Monomer Production In addition to the general hazards of handling, storing, and shipping large quantities ofJ VC, the production plant must deal with a potential explosive mixtur > in the oxychlorination reactor. Flow control failure for any of th e three major streams ethylene, hydrogen chloride, or air (cx ygen) can produce a reaction mixture in the explosive range (287A) In addition to being a necessary reactant, the hydrogen chlor de serves to dilute the oxygen content of the mixture below the exp 1<osive range. Therefore, considerable effort must be made to assu rle that flammable concentrations cannot occur. Another hazard is the danger of overheating the reaction vessel by loss of the cooling system f low or excessive rates of reaction, This is particularly true whe n fresh, active catalyst is in use, and is a greater problem for fix ed tube reactors than for fluid beds. C. Polymerization The major safety and health hazards in the polymerization section have been from the danger of uncontrolled reactions and the exposure to vinyl chloride, especia y from reactor cleaning. Methocs to control these hazards and ot hers are discussed in this section. An 4a SPI-00103 T ( EPA report is available which presents the results of a brief industry survey by a con tractor concerning some of the causes of emergency releases (2481 , one of the contributors to safety problems in this area. 1. Reactor Control The heat of polymeiji zation of vinyl chloride is about 660 Btu/lb (Table 1) a rd this heat is not released uniformly during the batch unless $c ecial initiator blends are used. The heat release tends to be less at the beginning of the cycle, and accelerates unti1 just before the pressure drop begins in the case of homopolymerjs (282). There is a tendency to design the reactor batch chargje so that there is a small but adequate margin of control left at the time of the peak exotherm. However, because all of the batch is charged at the beginning, there is no easy me|thod for making adjustments during the cycle for unforeseen condiitions. The standard method of temperature control is to add cooled water to the jacket circulation system. The heat transfer values of a clean sjystem (Q value) range from 50 to 110, with the lower figure obt ained with glassed steel, and the higher with polished stai nless steel. The value decreases during the cycle as the viscos ity of the batch increases (234), and also can be decreased dr i stically by fouling on either the water or process sides. If that should happen unexpectedly during a batch, or if the c oo ling water supply or the agitation is lost, a runaway batch can result. Control of a runaway batch depends on the successful removal of the heat of polymeri zation. This can be done by several means such as additional cooling, addition of a chemical to stop the polymerization, rem^val of the unreacted monomer, or in the last resort, relief of the pressure by manual venting or by activation of the pi' essure relief devices. Most faci1ities use mechanical pressure relief valves on reactors and VC stor age and handling vessels, preceded by a rupture disk, as is required by the EPA standard. A few faci1ities, however use only rupture discs, usually two in series, as the protf ctive device on reactors. Mass polymerization syste ms must use rupture disks rather than relief valves. There are no real 1 y satisfactory means of calculating the required venting ar 6 a of a polymerizing system. Theoretica calculations have be en made (288-90), but the situation is complicated severe!) by the mixed flow regime which occurs, the p1ugging tendency of the spongy, partially polymerized mass, and the fact that tt e rate of increase of the reaction with temperature is a fu n|ction of the sloDe of the initiator half-life. Meither the amount of initiator left at a particu1ar point nor the slope of the decomposition rate at very high temoeratur es is known with any degree of certainty. 49 SPI-00104 TT This has resulted In an empirical approach to relief valve sizing. Nozzles on whl ch the relief valves are placed range from 4 in. on the sma er vessels up to about 4,000 gals, to as much as 16-18 in. on 25 ,000 gal. reactors. Relief valve sizes range from a single 4 x 6 in. valve on the smaller reactors to multiple 8 x 12 in. val ves on the larger sizes. This appears to have be en a satisfactory approach, for there are no known reports of reactors having exploded because of relief capacity design, One case is known where a reactor exploded after an enorntous overcharge of initiator, perhaps as much as 30 times normal was pumped in as the result of an instrument failure, but this can hardly be ascribed to the relief valve design. Iso, there are anecdotal reports of one glass-lined reactor havli ng been stretched sufficiently to spall off much of the lining, but not falling. The size of the relief system for that reactor is not reported. The American Institute of Chemical Engineers has formed a Design Institute for Emergency Relief Systems which has been working for several years to improve the design basis for relief systems. The results of this effort are expected to be released in 1985 (290A). Installation of a rupti re disc below a relief valve requires reduction of the valve capacity to 80* of its original rating, unless that specific c combination has been tested for capacity, There must be a pressur e gauge, vent, or other suitable telltale device betweer the valve and disk to indicate if the disc has leaked pressu re into the volume under the valve (2908). Many other fac tors also must be considered in rupture disk design and instal ation, and final choices of materials and type should be made only after consultation with suppliers (2900. Both redundancy and d versity in control instruments are used to assure proper inforiAlation on the internal temperature of the reactor. Dual temperat ure probes plus at least one pressure check are the most cominton forms. Reflux condensers can pe used on some types of processes, These can offer a signi ficant reserve cooling capacity, and often are connected to the emergency cooling circuit that is activated by high tempe rature or pressure alarms on the reactor. One company has descri t ed an emergency monomer remova1-cooling system which connects t'h e reactor to a large external condenser and tank. In the case of an emergency the monomer is then conaensed outside of tr e reactor, botn cooling the reactor and removing the source of any further heat. This has been used successfully on reactor up to 50,000 gallon capacity (2300). 50 T 'T SPI-00105 f Agitation failure sually results in a relief valve discharge because of the redi ced heat transfer in an unagitated vessel, Current flow or ue monitors can be used to confirm proper agitator action, bu t greater assurance results from detectors which measure the rjotation of the agitator shaft itself, Routine vibration easurements and visual inspection of the drive motor, gear coupling, and seal are Important preventative maintelinance items. A polymerization Inhibitor (short-stop) is effective in controlling or slow|ing overheated batches if enough Is added is truly out of control, and there is adequate agitation |to assure good mixing. Organic monomers which do not copolynerize well with vinyl chloride, such as butadiene, styrene, or alpha-methyl styrene, have been used, as well as straight imibitors such as phenol, t--butyl catechol or similar substances. Sodium nitrite is effective if the pH is low enough to assure formation of nitrogen oxides from decomposition of thu nitrous acid. This requires a pH of about 5 or below. Nitrogim or steam sparging through the bottom valve can sometimes supply the needed mixing action if the agitator is not operating, and if sufficient monomer venting rates cannot be ach eved. Short-stop addition systems should have a means of injection that is independent of the plant utility systems. A dedicated nitrogen pressure system or manual charge pot systems can be used. All nozzles cm the reactor head should be inspected frequently to be sure that they are not plugged with polymer. This is especially true, of course, for those leading to the emergency relief anc short-stop systems. Where there is room in the reactor, such as near the end of a batch, the injection of cold water sometimes can provide sufficient time for other systems to overcome an incipient runaway reaction. The EPA has accepted manual venting to the atmosphere as a last resort step to avoid the usually irreversible action of the relief valve system [40CFR61.64(a)(3)]. Venting to the recovery system, flare, or a gasholder may be helpful in marginal cases, but great care should be taken that foam and polymer are not cam ied over and plug the system. It is not feasible to build a gasholder large enough tc hold all of the vapor froin a large reactor, or more than one smal' reactor. Limitation;; on the rate of movement of the piston control the speed wi :h which vapor can be added. Thus, gasholders are not to be considered emergency devices except to a 1imited extent. It^proper attempts to control or de'ay emergency releases y cause more total release than if not used, if there is a general plantwide emergency. SPI-00106 Relief valve assemblie should be anchored firmly to resist the thrust which develops on activation. Tail pipes should be short, and if curved u ijjward for better dispersal, a weep hole or easily removable pi as tic cap should be used to prevent ice blockage in the winter An effective rain shield can be made from a short length of larger size pipe supported by standoffs on the tail pipe. Insurance provisions and local codes establish relief valve Inspection and test schedules, which should be no longer than one year, and after every activation. Instrument failure dur ng charging can result in overfilling of the reactor (or other vessels) and cause hydrostatic pressure on the rupture disk as the temperature increases. Level control Instruments in ide the reactor have not proven effective because of t e fouling problems, and external devices such as radiation mete s are not sufficiently sensitive or reliable. Diligent in ;trument maintenance, redundant metering, and visual inspection ire the most reliable means of prevention for overfi11ing. Premature rupture disk failure has been a problem in compliance with EPA rules (248). Fatigue from pressure-vacuum cycling during the batch or frbm vibration or swaying of the vent system, mechanical damage during installation, corrosion, and distortion by polymer formation are among the most frequent causes of this failure Careful installation, frequent inspection, and routine replacement are necessary. Insurance and corporate safety codes usually forbid manifolding of reactor relief valve discharge systems. On the few occasions where this hk s been tried, it was abandoned quickly because of the near in stantaneous plugging of the system. The greatest safety in the long run is obtained by rapid dispersion of any vapors released by a discharge. Other relief valves not in polymer service may however, be manifolded to flares or other abatement devices (248). A survey of the major accidents involving the production and polymerization of VC i presented in Table 8. This table does not include transportailtion accidents, for none of those have been reported to have caused any loss of life, nor major property damage beyond the accident scene. Also not included are VC re. leases whic.h did not result in serious injury or major damage. Two recent events of major proportion which did not cause loss of life are described in references 290H and I. Worker Exposure Plant design, process procedures, work practices, surveillance equipment, and persona 1 protective devices all play a part in reducing worker expose res to potentially harmful concentrations of vapors. 'hese metf ods all are interwoven witn the efforts to protect tne workers ana equipment from fire and explosion. 52 SPI-00107 Table 8 Major Vinyl Chloride Accidents Year 1955 1964 1966 1967 1968 Place Mass. Conn. N. Jersey Louisiana Rhode Island Cause Broken gauge glass on a storage tank, ignited by nearby boiler. Attempts to tighten a reactor sight glass while under pressure. Failed. Ignited by nearly extruder operation. Operator open ed wrong reactor bottom valve, discharging contents where handle failed. Ignited by st atic or other source. Pump failure, Ignition course unknown. Manway gasket failed. Ignited by static? 1970? Japan Discharged contents of wrong reactor. 1970 Delaware 1973 Germany 1973 1 974 Japan New Jersey 1 977 Texas Head gasket fe.i led. Igni ted by nearby gas-fi red drier. Thermowell fai lure in bulk reactor. Igni ted in the recovery secti on. Broken valve y oke Manway not sec ured properly, ignition from static discharge. Initia tor over charge to bulk reactor due to in s trumen t failure. Result Major plant damage 7 killed, 22 injured. Plant destroyed. 1 killed. Plant destroyed. $830,000 damage Extensive reactor damage from falling roof members. 4 killed, 8 injured in plant, 2 outside. Major structural damage. 1 killed. Instrument and control systems destroyed by fire. 5 killed outside struc ture by flame front. Plant badly damaged. unknown Several weeks produc tion lost from wiring damage. 1 killed, 1 injured. Plant destroyed. SPi-00108 T Year 1977 Place Mexico 1978 Germany 1980 Mass. 1980 California 1981 Canada Tatle 8 (con inued) Cauv Workman serviced valve on storage tank 1mp|operly, discharged conte ts. Ignited at adjacent plan Buildup of peroxides in recovery system exploded during steam purging. Operator opened wrong bottom valve, discharged fresh batch. Vapor cloud ignijred above ground level. Use of improper |alve type allowed a bottom valve to remain partially open. Ignition at nearby switch box Buildup of vapor in a sewer line entered laborato-y building. Result 1 killed, 3 Injured, major damage. Major equipment damage 2 injured, damage over $1 million. Major damage 5 injured. Destroyed laboratory and control room. 54 SPI-00109 The production and polymerization of vinyl chloride are, of course, closed proc esses. Outdoor-type construction is used to the greatest extent possible, but the severe winters of 1979, 1980, and 1983 11 hi strated the limits to this feature, with even fad 1 ities in the Gulf Region suffering damage and production interrup tions. Area and local ventilation are used for those parts of the plant which must be enclosed. Reactor cleaning operations were associated with most of the AOL and ASL cases, and thus this procedure has been limited sharply. Additions Impetus came from the introduction of large polymerizatiqin vessels, which are not practical to clean by hand. Anti foul 1 ng treatments (291-2), solvent cleaning procedures (293), and improved suspension recipes have allowed closed reactor ope ratiion for many polymerization cycles, High-pressure water cleaning is a useful supplementary tool, and massive bui dups can be loosened by dynamiting rather than by hand cutting as in the past. The development of effective spray rinse valves has assisted in reducing worker ex pjosure by reducing the frequency of reactor opening for inspect ion and cleaning (293A). These valves can be used to improve the efficiency of application of antifouling agents or rinsing sol uI tions, and for better distribution of lent short-stop solutions * mr When vessel entry 1 s necessary, careful adherence to detailed vessel entry and lo ckout procedures, the use of mechanical or human standby systepi s, the wearing of a proper safety harness, forced ventilation of the vessel, and proper monitoring of vapors and oxygen cb ncentrations can help insure the safety of the worker. The OSHA regulation for VC requires the use of respirators and prot ective clothing and prescribes the type to be worn under variola s circumstances such as monomer loading/ unloading or mechan cal repairs, as well as vessel entry. Extensive stripping of the unreacted monomer from the polymer slurry has made a mi jor contribution to reduced worker exposure. Emissions from the slurry vessels, centrifuge raffinate, and drye outlets are controlled to less than 10 ppm by the EPA standard either by direct emission controls, or by stripping of the si firry before transfer to these systems. This is an example where an expenditure for EPA rules has assisted in meeting the OSHA standard. Another example is the requirement for pre surized double mechanical seals on pumps, compressors, and ag tators. The OSHA requiremen for an area monitoring system to warn operators of concen rations requiring the use of respirators was adopted by the PA as a leak detection device. Overall correlation between area concentrations and personnel exposure can be shown if adec: uate attention is put on a time-motion study, but short-te rm conformance is poor (234, 2933). It has been observed that me chanics and senior operators - foremen SPI-00110 A major reason for the trend toward rising computer-controlled arge reactor operations is the increased safety which comes from fewer units, and thus fewer connections and fewer systems to control. This imprvement has been realized, but brings with it some hazards of Its own. It has added another level of Interface, and It requ res a higher level of technical sophistication for mai utenance. In addition, If total reliance is placed on electronl : systems, manual recovery from disaster c__o_n_d_it_io__n_s is l_o_s__t. I is normal to install sufficient analog systems to allow at least an orderly shutdown in case of necessity. Tunkel (32;!) has reviewed the design criteria to be considered in protecting vital equipment from blast damage. Computers with dual, automatic switchover processing units have demonstrated on-line service of well over 99X. However, operators have reported rare, unexplainable "GREMLINS" that either cause loss of control or issue random uncontrollable signals. Thus, specia attention should be paid to the computer Installation and its maintenance program (323). Careful attention shou d be paid to the failure mode of critical valves not on y for loss of operating power, but also for loss of operating signal. In addition to emergency analog control, the most cri ti cal valves should have an independent hardwired signal to thi control room. D. Stripping Prior to 1974 unreacted monpmer was recovered from the PVC batch on an optimized economical bas s. The reaction mass was transferred from the reactor to a blowdown tank, or the pressure was reduced on the reactor by venting, at the point where conversion rates no longer justified uttiilliizzation of reactor time, and further conversion was likely to reduce ddeesiraple properties of the resin such as porosity (282.294B). The s urry was then subjected to a short vacuum exposure (30 minutesj-1 hour) at temperatures of 160--195*F, depending on the residual heat stability of the product. This procedure left upwards of Z't by weight of vinyl chloride dissolved in the resin. Much of this was lost during subsequent transfer and drying operations, but the finished product usually contained 1,000-2,000 ppm of VC at thp time of shipment (294C). The EPA standard set a limi t of 400 ppm VC in suspension resin (2,000 ppm for emulsion prop ucts) at the time the slurry was released from a closed syst em as an alternative to placing abatement controls on the VC in the d ryer discharge air stream. The time to achieve this level by the c onventional means is excessive, and puts the resin through a harmfu heat history, resulting in yellowing. Most producers of suspension resins have adopted some variation of a continuous stripping system in which tne slurry is passed down a tray tower against a counte rcurrent stream of steam. Short residence time at elevated temperature and good agitation results i n lower final VC content, and 'ess heat stress tnan did the older metnod ( 294D). 53 SPI-00113 General purpose resins of average porosity generally exit the column at a few ppm residual VC, which is reduced to well under 5 ppm by time of shipment. Lower molecular weight resins, which generally have lower porosity, give somewhat higher figures, and very low molecular weight resins (bottle grald e) and copolymers have difficulty meeting this standard on a 100% basis, although the long-term average is well within the requirement (248). Emulsion resins are more difficult to strip because of their strong foaming tendency and sensitivity to coagulation with heat. A variety of falling film or spray dev ices have been developed which allow meeting the 2,000 ppm standarp (294E). These and other less useful devices are discussed by Burg ess (294F). The theory of VC migration in PVC his been developed by several workers. The monomer is quite soluble in the polymer, although the contrary is not true. The final solubility depends on the pressure and the temperature, and the rate or equilibration is a function of temperature, particle size, and morphology (294G). The rate is diffusion-controlled, and can be described by classical thermodynamic equations (294C.H). Diffusion rate is more important than temperature at higher concentrations, but temperature is the controlling parameter for the final interphase partition coefficient (2941). There is a discontinuity in the controlling constants at the glass transition temperature (T<|) of the resin (294C.J), and above this temperature the rate of diffusion increases sharply. In practical terms, these basic data show that stripping consists of movement of the monomer molecule throiugh the body of the resin and across the solid/liquid or solid/gas interface, through the pores of the resin into the larger body of the suspending water, through the water to the liquid/gas interface, and eventually out of the vessel. Any condition which can shdr ten or speed this movement assists in the stripping rate. Small er particle size, greater porosity, absence of a pericellular membrane on the resin, good agitation, and temperatures above the Tg all assist the progress of the monomer. Lack of porosity and especially the presence of glassy beads or gels hinder the rate greatly and even a small amount of such particles can prevent proper st(r ipping. Low molecular weight resins tend to be less porous, and this offsets any advantage of the greater mobility that might be expec ted within shorter molecules. Application of these concepts has re suited in successful equipment design for the stripping step, and a 1 lows prediction of the migration of monomer under many condf ions (294K , L). The latter reference contains a procedure for stimating the potential exposure to workers in warehouses and other s :orage areas, for example. Even further reduction in residual mo nomer can be achieved cy applying these principles in the pro<f essing and compounding steps also (294M), and levels can be obtai hed which near the limits of detection. It has been proposed on both theoretical and experimental bases that a -esipual 1 dve 1 can be reached beycnc which no further diffusion wj i i occur (2941* 0 > . c SPI-00114 Each mechanical stage of air transfer, unloading, or processing represents a disturbance of the establi shed equilibrium between the dissolved VC in the polymer and its sur oundings, and thus will cause some release of VC, and the begin ng of a faster rate of release of the monomer until equilibriu is reestablished, Therefore, caution should be exercised in opening and entering railcars, storage silos, or other closed storage areas unless it has been established that the free space is below the allowable concentration. Even moderate venti1 ati bn will assure that this has been achieved. Downstream Operations The PVC process changes from a pressuri zed batch operation to a generally open, continuous system after the blowdown/stripping step, and the safety hazards change to those (related to material handling procedures. The exception to this generalization is in the monomer recovery section, which is of necessity closed, and is pressurized after the compressors. Partial vacuum can occur upstream of the compressors in the blowdown/stripping section, and provides the opportunity for air to enter the system. The oxygen ca|n react with vinyl chloride and other olefins at the temperatures encountered in the compressor to produce peroxides, as discussed abov These peroxides can cause extensive fouling and plugging of the recovery system, and are shock sensitive. Dilute caustic can be used to control the formation or to remove these products. However, careful maintenance to prevent leaks in vacuum lines, together with proper inhibitors and pH control, can prevent their formation. Entry and cleaning of blowdown tanks, stripper vessels or towers, and recovered monomer tanks present the same potential hazards as does reactor cleaning and the same precautions should be observed. There are anecdotal reports of workers being asphyxiated by the inert atmospheres which may be maintaired in these vessels Thorough work entry procedures, including oxygen monitoring, and the use of color-coded air and nitrogen hos es with noninterchangeab1e fittings can reduce these dangers. The more thorough stripping required by the EPA standard and by commercial considerations has reduced reatly the exposure to VC which occurred in the past in this sec ion of the plant. Many of the manufacturers have found that the rying and shipping areas can be deregulated under the OSHA standard Fabricators. and processors generally find their operations are be ow the action level for the OSHA standard if they have even rudimei} tary ventilation systems. The "half-life" of residual VC in oagge a resin is about one week, sc there is some possibility of exposure n large unvent i 1 a tec warehouses for bagged resin. BuU sto age presents a higner probability of monomer accumulation in the air space, so that silos and bulk cars should be ventilated and tested before entry. SPI-00115 This extended stripping has caused a n additional hazard, however, The higher operating temperature at longer times has accelerated the formation of hydrogen chloride in th e slurry, which has resulted in accelerated chloride-induced stress corrosion near the welds in stainless steel equipment. This ap p|ears to be caused by chromium depletion in areas near carbide predipitates, and is especially pronounced at pH below 5 (294P). Cr acking has been seen in reactors, especially those also usee for stripping, and particularly near nozzles which may have some pol ymer deposition, in blowdown tanks, continuous stripping towers c n the trays and support rings, and occasionally on centrifuge scroll s. Routine removal of polymer deposits, additional buffering of the treated slurry to avoid the autoaccell eration of decomposition by acid, and avoidance of excessive loc alized temperatures can help alleviate this situation. Clad ves sels will be less prone to catastrophic disintegration than wi 11 solid stainless vessels. The use of proper grades of construction materials, such as low-carbon 316 stainless steel or high nickel all loys (295), and careful adherence to good welding practices also are of assistance. Dye tests of suspect areas sometimes can reveal the problem before it becomes a serious threat to safety. Dust exposure is a common problem in the bagging and shipping areas, more so with the fine emulsion and dispersion resins than with the coarser suspension resins (296). A1 so, the problem exists more with the total dust levels than with the respirable fraction. Operators are reluctant to wear respirators or masks in these work areas because of the greater exertion neces sary, and the higher ambient temperatures often are encountered, so careful equipment design and good local ventilation are required. Slips and falls from bulk cars and tr ucks can be a hazard, especially in wet or icy weather, Safety harnesses have been designed for this purpose, and accesls platforms can be provided avoid much of the climbing that woulj otherwise be necessary. to Strong static charges can develop dur ing the air conveying of PVC, especially during dry, cool weather, Static discharge in a conveying system is suspected as bei ng the source of ignition for ai least one major explosion following vinyl chloride release. Various methods have been tried to p 'event or dissipate this static buildup, but the most effective seem^s to be control 1ed humidification of the conveying air Waste Streams A. Water The EPA standard recuires that water reams whi :r, have tee" in contact with v;nyl chloride be Strip bed to telow io ppm before they are released or mixed with other str ^ams. Tnis ic because vi nyl chloride degasse: readily from water at a tmespne'-i c pressure, and would therefore become an air contam nani na s observed 6l SPI-00116 that In the past the centrifuge waste streams provided a significant contribution to worker exposure if the were transported in open trenches. This is no longer true for slurries which are stripped in accordance with EPA rules. All of the substances discussed here undergo biodegradation or removal in biological effluent treatmejnt systems (262,297-301 ). Somewhat surprisingly, one EPA report states that EDC is said to be removed more readily In some cases by air stripping than by biodegradation in comparison to the o ther substances (301A). Another EPA report (301B) states that EDC is relatively difficult to air strip, and that performance can be predicted by the Henry's Law constant of the substances. The value stated are 180 for VC, 0.5 for TCE, and less than 0.1 for EDC. The data of Dilling and of Roberts and Dandlicker (269) suggest that all these substances should air strip easily. However, all of these substances showed ready biodegradation in activated slu dbes, as they did in 24-hr. batch tests (3010. Air stripping and steam stripping are reported to be economically viable alternatives to biodegradation, The EPA has calculated that six theoretical trays are required to reduce EDC to 50 ppb from a saturated feed when using reflux, whil e only four are needed for TCE or VC (301A). Without reflux eight trays gave the same results for EDC and required 5g steam per kg of fe ed. Under the same conditions, TCE needed seven trays and 3g/kg of steam, and VC only six trays and 2g/kg, to obtain 100% efficiency. This same document gave examples of a ct ivated carbon removal efficiencies of 997. for TCE from very dilute streams, but did not show examples of the application of th is technology to the other substances. The Dade County water system found air stripping to be effective in removing VC from contaminated groundwaft:er (274G). A recent paper by Zhu, et al. (30ID), describes a pervaporation technique for removal of EDC and other chlorinated hydrocarbons from dilute aqueous solution by permeation through a polymeric membrane against a vacuum. The organic solutes permeate preferentially and may be collected in a concentrated forfri Some success has been seen in reuse of wastewater, especially as makeuc to cooling towers, provided that adequate fi1tration of residual solids is performed. There h as been 1imi ted success in reuse of centrate in the polymerizatioh batch because of potential cross-contamination by residual suspen ing agents. It das been shown to be feasible in pilot runs, hoW'ever, and could be possible in a s;ngle-product plant. Very thorop gh fi'tration is necestdry, and a o'owdcwn stream may be requires to purge dissolve: (234,233) SPI-00117 B. Liquids and Gases There are few nonaqueous liquid s tre ams from polymer production, but still bottoms and by-products are f o rmed in monomer production, These can be incinerated, provided that the chlorine formation is minimized by careful combustion air control and the hydrogen chloride Is removed from the stack, gas. Processes have been developed for redistillation or cata lytic decomposition of these substances which permits substantial recovery of the chlorine values <302-4). The EPA has listed the li quid wastes from the production of VC and EDC as hazardous wastes, which will restrict the disposal of these by-products to RCRA-permi tt ed facilities. The EPA also classifies spent TCE f om degreasing operations, and bottoms from TCE manufacture, as hafc ardous wastes C40CFR261.31 and .32). The commercial substances vi nyl chloride, EDC, and TCE are themselves hazardous wastes (40CFR2 i51.33) and may not be discarded without following RCRA regulations. Incineration has become the process of choice for abatement of the collected vent and purge gases from polymerization operations, Carbon absorption processes have be$ n developed which recapture the vinyl chloride, but various operati i|ig problems have prevented widespread adoption of this process One problem with copolymer operations is the difficulty experi 4nced with desorbing the vinyl acetate. In addition, there is a n qed for a purge stream to remove the nonreactive methyl chloride fro4 the recycle stream (304A). This occurs in monomer at 25-75 ppm but as it is concentrated about tenfold each cycle, it can soon bui d up to an unacceptable level as an inert diluent. It is necessary o have a small incinerator to destroy the purge stream containing this contaminant, and economics often do not justify any additional equipment. Incinerators must be equipped with s|crubbers to meet local and federal limits on hydrogen chloride and particulates (47FR27520). Incinerator design is based on the requirement for less than 10 ppm in the stack gas; actual performance is much better, with concentrations usually below 1 ppm. Vinyl chloride is readily combustible, and the calculated comb ustion chamber temperature for 99.997. destruction at 1 sec. residen ce time is 1 3710F ( 305). Vinyl acetate requires a temperature of 223F under the same conditions. Studies have shown (305A,B) that flares and industrial boilers can give greater man 997. destruction of organic wastes, but the EPA will not permit these to be used for routine removal of hazardous air pollutants without further demon stration of their efficiency. Solids Polyvmyl chloride is biologies1 iy i nert, anc ; ; u ' t a c' s disposal in any properly maintained andf i 1 l . 'here was statemen: by tne EPA M5ER331 IS May 19, 1 9301 that it intended to promulgate RCRA rules for "batch residues from :he batch polymer izaron of chlorinated pc1 ./men:" Put no r t n e r 3 C T on ug f [jeon rarer. 63 SPI-00118 A Presumably, this was to have been done because of reports that vinyl chloride had been detected in very low concentration around some pre-1975 landfills. Current operating procedures preclude the probability that any significant amoun of vinyl chloride will find 1ts way to a landfi11. Water from the centrifuge in suspension processes contains a small amount of fine polymer. This settles rapidly in clarifiers or sedimentation ponds. In fact, it is a good substrate on which other suspended materials gather. Together with the larger particles resulting from the cleanup of spills aid from washdown operations, this material, or sludges in which it may be present, may be disposed of in any convenient fashion. Solids recovered from solvent cleaning operations are free of vinyl chloride and thus also are not restric ted for disposal. The only problem concerns large unstriqped particles, such as those from "BB" batches, filters ahead of th stripper, and equipment cleaning. These are not now regulated by RCRA, but prudence would dictate that the residual monomer content should be reduced to prevent either employee or environments! exposure. This can best be done by weathering in some isolated locale. Solid PVC wastes can be incinerated if mixed with an adequate quantity of a combustible material. T here is little reason to do this, except for the disposal of used consumer items. The generation of hydrogen chloride from to usehold trash containing PVC articles has been a matter of controver sy in the past, but several studies have shown that the present con sumption rates of PVC in consumer goods add little to the normal chloride content of wastes (306-7). VI. Analytical Methods The EPA prescribes the analytical methods 106 and 107 of 40CFR61, Appendix B, for the analysis of gases and pf water or sol ids, respectively. Method 106 uses a 2 m. Chro nosorb 102 chromatographic column followed by a flame ionizing detect or to analyze an integrated gas bag sample. A secondary column of Chr omosorb B is required if acetaldehyde is present. The method is sa id to have an absolute sensitivity of 1-4 x 10'7 mg. of vinyl chi oride. Collaborative tests indicate that the repeatability is about = ppm at 10 ppm concent'ations and =10 ppm at 50 ppm (308) Method 107 uses the headspace method (309) in which an equilibrium is established in the free space above the sample in a vial , and an a 1iquot is injected onto a 2 m. column cf Carbowax 1500 on arbopak A. Poropak 0 is used if methanol or acetaioenyde are present This is stated to have tne same absolute sensitivity as meth od 106. equipment :s available which performs tne entire analys is automa:ica11y once the sample vials are filled (3094). r < SPI-00119 I Revisions to test methods 106 and 107 w* re published at 47FR39168, September 7, 1982 and 47FR39485, Septeml) er 8, 1982, which permit alternate columns to be used, and impost certain quality assurance requirements. OSHA requires that an analytical method be used for personal monitoring that has a 95% confidence level of s35X at 1 ppm of VC. A procedure generally based on NIOSH Methods 127 and 178 has come into broad use for this application. Air is drawn over gr^ nular carbon at a known rate for a known time. The carbon is extracted ith carbon disulfide and an aliquot is analyzed by gas chromatograph y (310). A variation on this procedure involves the use of other comnercial absorbents (Tenax or Spherocarb) and/or desorption by heat ri ther than by a solvent (311). These procedures have been developed so that under ideal conditions they are capable of detecting as little as 0 2 ppb, (312) but under average field conditions are reliable at about 0 ppb (41FR46560). Instrumental procedures such as infrared or ultraviolet absorption, or decomposition of the vinyl chloride fol owed by measurement of water conductance caused by those products, he ve been used in the past (276). These are limited generally to the ppm ange, and are not as versatile or portable as the carbon tube or bag cd 1 lection methods. The absorption/desorption method also is applicable to a wide range of substances, and can be used to determine the concentration of many different substances from the same sampl e. Unless the constitutents are well known, it is necessary to use a coinb ined GC/mass spectrometer to identify the peaks with certainty. This combination has been used to measure the ambient concentrations of vi nyl chloride, trichloroethylene, ethylene dichloride, and many other sub Stances in several areas of the country (260-1). If this method is used for vinyl acetate analyses, special precautions must be taken to avoid hydrolysis or poly1merization of the absorbed acetate. Kimble (313) has described a procedure which answers these requirements. The EPA has developed "purge-and-trap" (Methods for determining trace constitutents in water which are useful to 0.2 pg/1, and claims a detection limit of 0.01 pg/1. The same problems of interference exist in this system or any chromatographic me thod (313A). Several helpful manuals have been pubiis hed describing practical application of the analytical procedure described aoeve (314-17). Ref. 317 contains an extenaed discussion of interferences and alternate column packing. Bromination of VC in water samples, foil owed by exfaction into hexane and analysis with an e'eefon capture cn -omatcgrsDh, is reported to have a limit of detection cr 0.3 pg/i, cn 0.3 ppo. 7rs method has teen used to analyze surface arc prink, ing wat a r supplies >3174;. 65 SPI-00120 Portable vapor detectors have come into g eneral use as "leak detectors". They are used in conjunction with the fixed-point or area detectors for vinyl chloride, which are r squired by the OSHA standard, to locate the sources of excursions, and they are used for patrolling areas outside the area detector coverage, The EPA has promulgated a requirement that all new "volatile organi :s" processing facilities use these as a part of an emission control pr pgram (40CFR60, Appendix A, Method 21), thus extending their applicatfi on to all of the substances discussed in this chapter. These may have short chromatographic columns attached to provide some selectivity for /arious materials, but most often they are used in the nonselective ro>de as simple combustible vapor detectors. They have a wide range of sen$ itivity for different substances, and usually come calibrated fo r methane. The EPA has published tables of response factors for other compounds (318). Numerous problems have been described in the actual field use of these instruments (319) and they are not suitabj e for precise work, but they are a useful adjunct to a leak detection ind preventative maintenance program. One additional type of device has come in :o limited use in Great Britain as a fence-line monitor (320). Based on :he reaction of vinyl chloride with potassium permanganate-impregnated p per, it is not sensitive to concentrations much below 1 ppm, and is s bject to a number of interferences. Similar limitations apply to the Drager tube procedure, For these reasons, these devices are not particularly valuable at present conditions. Passive personal monitors have come into ider use because of the bulk of the electric pumps, and the cost of ma ntaining them in operation, These have exposed absorbent cartridges wli ich can be "developed" and analyzed by a variety of means, and can s <t>metimes be regenerated for reuse. The accuracy of such devices is a equate to meet regulatory needs (320A) for long-term samples, but g nerally do not have sufficiently rapid response times for 15- ifiinute tests. Experience has shown that process sampling and analysis of VC can result in high personnel exposure if adequate pn cautions are not taken (117). One of the European ASL cases is reported to have received his primary exposure as the result of sampling activi ify, by what must have been a very unsatisfactory procedure. Laboratory analysts must guard against inadvertent direct or indirect exposure, specially when conducting some of the evaporative tests on the monomer. Sampling systems have been developed which use essentially closea piping loops (320B). A aouble-ended sample tank is placed in a bypass system at the sample point and a flow-through .pr cess allows purging and filling the container with a minimum of re lease. This procedure also disposes of the unused sample safely. The EPA reauires that all VC samples be taken with a system eouivalen to the one descriDec . Vinyl Acetate Copolymers Tn? manufacture of VC/VAc copolymers is me re difficult than . K: I 0* *L (-*J. 71 homcpolymers. or of some other copolymers 'ncreaseo : ff; :j results in addit'ona 1 hazards not seen in other c'ocesses SPl-00121 One spectacular hazard is that of aggl cmeration of the reactor charge, or a "set-up". This results from fail ujre of the suspending system, and its effects are enhanced by the plasti izing effect of the unreacted VAc. The reacting mixture shrinks in voliume (increases in density) as the polymerization progresses, and at the same time the unpolymerized monomers are enriched in VAc because of the relative reactivity ratios of the two monomers (321). The unreac ted VAc swells and softens the precipitated PVC in each droplet, incr easling the tendency toward agglomeration If the suspending system is not performing correctly. Set-ups occur very rarely in homopolyme|r systems, and usually occur in copolymer batches after the density of the organic phase has increased to more than one. This is well into th e polymerization cycle, at about 60-757. conversion. Severe mechanical damage can occur to the agitator, shaft, baffle, and drive units. Releas e of VC is not usual, because of the relatively low amount of unreacted monomers at that stage. The primary hazards result from the di ff iculty of removing the rubbery mass from the reactor in the presence otf VC and VAc. The most satisfactory method appears to be to c opk the mass under vacuum to remove as much monomer as possible, the reduce the mass to workable size by many small explosive charges ( 234). This has been found to be both quicker and safer than manual remo val, and results in less damage to the equipment. The residual unreacted VAc also causes problems in the stripping step because of its plasticizing action. Copolymer is inherently less heat stable than homopolymer, and the greate^ tendency to adhere to vessel walls adds to the probability of produc ing burned resin. This results in more potential worker exposure from cleaning operations. The presence of VAc in the recovered mon omer stream presents several potential hazards. Acetaldehyde, which is formed readily by hydrolysis accelerates the formation of VC peroxi da s (234,283) and polymeric sludges in the recovery equipment. It jsually is necessary to add more inhibitor in the recovery systems for c o polymers and to maintain better control over the pH of the system in an attempt to control both the hydrolysis and peroxidation reactions a Td to reduce corrosion of the equipment. Limitation of the oxygen con tent of the recovery streams becomes more important, also. Careful jesign is necessary to avoid polymer buildup on instruments, relief /a 1ves, and outlet lines. Liquid and solid waste problems increas with copolymer production, There will be increased BOD loads on tn waste treatment system from the vinyl acetate and its hydrolys;s produc :s. Solid waste- inc-ease and are more likely to have entrapped organ c materia!s. The recycle streams are more corrosive because of the presence of higher cnlor 316L stain'ess steel is recommended for be given to prevention of corrosion at nan those de levels use here, elds. in ncmoDclyme- systems and acetic acid. Type and attention snould Thus, considerably more attention to oe ign and oroper operation of reactor and recovery systems, in pa-tic 1 ar, are necessary in tne manufacture of copolymers in order to c fset the additional nazards present. the 67 SPI-00122 VIII. Acknowledgemunt ireful acknowledgement is due to my many fellow employees in the VC-PVC '"'3u5try who have encouraged and assisted me in the gathering of data, in retaining obscure references, and in offering helpful comments on the original 3ocu<nent from which this chapter is drawn. Any remaining errors or omissions ` are. of course, my own responsibility. Acknowledgement also is due to Air Pr:*Jucts and Chemicals, Inc. for permission to publish this work. 68 SPI-00123 *::gh *cl *sl ASME BATF CDC CEFIC CERCLA CFR COC CPSC DOT DNA EDC EPA FDA FR GGTP rrr u<ji I ARC IGC IX. Glossary of Acronyms American Conference of Government and Industrial Hygienists, Cincinnati, OH 45211 Acroosteolysis Angiosarcoma of the liver American Society of Mechanical Engineers, New York Bureau of Alcohol, Tax, and Fi earms, a section of the Treasury Department Center for Disease Control, a part of the Health, Education, and Welfare Department European Council of Chemical Manufacturers' Federations Comprehensive Environmental Re ;ponses, Compensation, and Liability Act of 1980 (Superfuh d) Code of Federal Regulations, a compilation of promulgated rules. OSHA rules are in Chap :er 29, those for the EPA in Chapter 40. Cleveland Open Cup, one method of testing for flammability Consumer Product Safety Commis ion Department of Transportation Deoxyribonucleic acid, the constituent of chromosomes 1 ,2-dichloroethane Environmental Protection Agency Food and Drug Administration Federal Reqister . The official daily publication of the federal government. The number before the letters give the volume, the fo1lowing numbers a re the page. Volume 48 was published in 1983. gamma glutanyl transpepsidase - a liver enzyme same as GGTP International Agency for Resear Ch on Cancer, Lyon, ^ar,ce Indocyanine Green Clearance - a test of 1 i ver function SPI-00124 LD s 0 NAS NFPA NCI NIOSH NSF NTIS NTP OSHA PB number PHR ppb ppm PPt PVC RCRA SADT TCE TLV TWA VAc VC Lethal dose for 507. death of the experimental animals within 14 days National Academy of Science Nation Fire Protection Association, Quincy, Massachusetts National Cancer Institute National Institute of Occupational Safety and Health National Sanitation Foundation, A|nn Arbor, Michigan National Technical Information Selrvice, Springfield, VA 22161 National Toxicology Program Occupational Safety and Health Administration Document identification number used in ordering from NTIS Process hazard review Parts per billion. Units are per volume for gases, by weight for sol ids or 1iquids. Parts per million. See ppb for u nits. Parts per tri11 ion. Polyvinyl chloride, homo- or co-pblymer Resource Conservation and Recovery Act Self-accelerating decomposition temperature, at which peroxygen compounds decompose violently Trichloroethylene Threshold limit value - a guide t|o allowable exposure, set by the ACGIH Time-weighted average of exposure to substances in air, usually for 3 hours Vinyl acetate Vinyl chloride I 'j SPI-00125 L References F. A. Patty, W. P. Yant, and C. F. Wait e, Pub. Health Reports. 45 1963 (1930). S. A. Peoples and S. D. Leake, J^ Pharm acol. Exptl. Theory, 48 284 (1933). 0. Schaumann, Medizln ik Chemie 2 132 ( 1934). 0. Schaumann, Arch., Exper. Path. 18[1 , 144 (1936). R. H. Oster, C. J. Carr, J. C. Krantz, and M. J. Sauerwald, Anesthesiology, 8 359 (1947). E. Mastromatteo, A. M. Fisher, H. Christie, and H. Danziger, Am. Ind. Hyq. Ass. J^, 21 394 (1960). 7. L. Prodan, Ann_, Acad. Sci., 246 154 ( 1 975). 8. H. Kuebler, Aerosol Age, 9 (14) 44 (1964). 9. L. B. Lehman and F. Flury, "Toxicology and Hygiene of Industrial Solvents," translated by E. King and H. F. Smyth, Jr., T. H. Williams. S. Wilkins Co., Baltimore, 1943. 10. T. R. Torkelson, F. Oyen, and V. K. Rowe , Anu Ind. Hyq. Assn. JL, 22 354 (1961). See also T. R. Torkelson, Stat ment before the Senate Subcommittee on Environment, Aug. 21, 1 974. Committee on Commerce, Serial No. 93-110. 11 . D. Lester, L. A. Greenberg, and W. R. Adams, Am^ Ind. Hyq. Assn. J^. 24 265 (1963). 12. American Conference of Governmental and Industrial Hygienists, "Documentation of the Threshold Limit Vi lue," 1963. 13. V. K. Rowe and T. R. Torkelson, Am. Ind Hyq. Assn. J_ 38 A-25 (1977) 14. H. Danziger, Can. Med. Assn, J., 82 828 (1968). 15. R. Spiritas, A. J. McMichael, J. Gamble and M. Van Ert, Aitk Ind. Hyq. ,L, 36 729 (1975). 16. J. Cole, "Inside Story on Vinyl Chloride at B. F. Goodrich in Avon Lake," The Journal, Lorain, Ohio, March 26, 1975. 17. J. Klein, "The Plastic Coffin of Charlie Arthur," Rolling Stone, Jan. 15, 1976. 17A. W. K. Le1 bach and H. J. Marsteller, in Advances in Internal Medicine and Pediatrics," Vo 1. 47, Springer-Verl alg, New York , 1981. ) SPI-00126 18. Union Carbide, unpublished data (1974). 19. M. Hori, Y. Kobayash, and Y. Ota, Plast. Irid. News, 18 (11 ) 164 (1972), 20. Dublin and Vane, 1935, cited in K. B. Lehman and F. Flury, "Toxikol. u. Hyg. d. techniochem losungs mittel," J. Sprjinger, Berlin, 1938, p. 130-143. 21. E. D. Baretta, R. D. Stewart, and J. E. Mutfch 1 er, Anu Ind. Hyg. Assn. J^, 30 537 (1969). 22. 0. Schaumann, quoted in K. B. Lehman and F Flury, Ref. 9. 23. F. P. Guengerich and T. W. Strickland, Mol. Pharmacol.. 13 993 (1977). 23A. R. J. Laib, "Specific Covalent Binding and Toxicity of A11phatic Halogenated Xenobiotlcs", in Reviews on Dng Metabolism and Drug Interactions, A. H. Beckett, J. W. Gottod, eds., Freund Pub. House, London, Vol. IV, no. 1, p. 1, 1982, and L. M. Gwinner, R. J. 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