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August 6, 1991
Ray Gomez SUBJECT: GREENPEACE/CHLORINE I am enclosing some comments on the document entitled, "Chlorine: The Product is the Poison".
___ Bob Hinderer cc: Carl Mattia (w/o attachments)
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GREENPEACE/CHLORINE COMMENTS
The document is not an assessment, but an effort to use mixture of fact and conjecture to support their position.
The author wants the reader to believe that because a number of chemicals in this class are well recognized as posing serious concerns, all chemicals in this class are the same.
Many of the author's positions and conclusions are supported by data which is frequently of questionable relevance and by major leaps in faith. In many cases, important logic steps and technical support are missing.
Some chlorinated organics resist breakdown and are persistent (paragraph 2, p. 2). However, VCM is degraded rapidly in air (1-2 days half-life) which route of loss into the environment.
Most living things have not evolved methods to detoxify or excrete them (para. 5, p. 2). This is a false statement. Most organisms have systems which can metabolize and excrete these chemicals. However, the efficiency of this process is chemical and species specific.
Many statements about chlorinated organics can be made for many classes of chemicals (i.e., cause many types of effects, can be detected everywhere, are a potential hazard to water resources).
(Para. 5, p. 6) The Great Lakes is a sink for CL-organics as far away as Latin America. Many classes of chemicals make their way into the Great Lakes. However, the prime contribution of pollutants are from local source. The suggestion that Latin America contributes to the Great Lakes is ludicrous.
The Great Lakes will take a long time to recover (Para. 6, p. 6). Lake Erie has recovered dramatically to pollution control efforts over the last 15 years.
(P. 7) The authors seem to have skipped a step. They do not explain why a ban is needed vs. a reduction in release. They do not consider the future impact that the implementation of existing regulations will have. They have not even considered that there are no effect or no significant risk levels.
(Para. 4, p. 19) The suggestion that the association of one with adverse effects means all are to blame is faulty logic. 10 They also fail to point out that associations are difficult to establish in population studies (humans, animals, or plants).
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While they note many chlorinated organisms have been found in man (p. 21), they fail to note that the presence of a chemical per se does not mean that there is an unacceptable risk. The same can be said for the presence of these chemicals in the environment.
(P. 26) The author would like us to believe that the reproduction failure was due to "a number of organochlorinsN. However, as one reads, it is clear that no one really knows. Many factors, physical and chemical can effect the embryonic and newborn stages.
(P. 29) (Jacobson, 1988) Because of numerous confounding factors in these types of studies, there is no way of knowing what the cause (inorganic, organic, or others) might be.
(P. 31) We agree that there has been an improvement in the concentrations of chlorinated organics in the Great Lakes. This is consistent with the improvement in the vitality of the Lakes. Although the authors concluded that diseases have flattened out, they fail to consider the impact of the continuing implementation of existing environmental regulations.
A few tables are attached comparing the uptake, BOD, bioaccumulation, etc., for various chlorinated organics. As you see, they can differ by more than an order of magnitude. Some chemicals like DDT are readily absorbed and metabolized, but are retained in the fat. Other chemicals like VCM are readily absorbed and metabolized and are rapidly excreted. Still others, like FVC, are relatively inert. They cannot be absorbed (i.e., are not biologically available) and therefore do not pose a toxic hazard in the environment.
The section on Environmental fate is provided from the EPA/ATSDR draft document on VCM. I have underlined some items of interest. Care should be taken in using any data not underlined, since it may be inaccurate/outdated.
Bob Hinderer
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6. ENVIRONMENTAL FATE
6.1 OVERVIEW
Effluents and emissions from vinyl chloride and PVC manufacturers are responsible for the majority of vinyl chloride released to the environment. When released to the atmosphere, vinyl chloride is expected to be removed by reaction with photochemlcally generated hydroxyl radicals (half-life - 1.2 to 1,8 days). Reaction products include HC1. formaldehyde, formyl chloride, acetylene, chloroacetaldehyde, chloroacetylchloranil, and chloroethylene. In photochemical smog situations, vinyl chloride has a half-life of - 3 _tO-_7--h. When released to water, volatilization is expected to be the primary fate process (halflife - 8.7 to 43.3 h). In waters containing photosensitizers, such as humic materials, sensitized photodegradation may also be important. When released to soil, vinyl chloride will either volatilize rapidly from soil surfaces, or leach readily through soil, ultimately entering groundwater.
6.2 RELEASES TO THE ENVIRONMENT
The major source of release of vinyl chloride to the environment is believed to be emissions and effluents from plastic Industries (primarily vinyl chloride and PVC manufacturers). Vinyl chloride released in wastewater is expected to volatilize fairly rapidly (on the order of hours to days) into the atmosphere. Other sources of release include disposal of vinyl chloride wastes in landfills, incomplete combustion of PVC, tobacco smoke, spills, and biodegradation of trichloroethylene, tetrachloroethylene, and 1,1,1-trichloroethane in groundwater (IARC 1979, HSDB 1987, Wakeman and Johnson 1978, Wilson and Wilson 1985, Smith and Dragun 1984). EPA estimated that prior to 1975, 110 million kg/year of vinyl chloride escaped into the atmosphere from PVC production facilities in the United States (IARC 1979). Worldwide emissions of vinyl chloride into the atmosphere during 1982 was -400 million lb (Hartmans et al. 1985).
6.3 ENVIRONMENTAL FATE
6.3.1 Air
Based on a vapor pressure of 2660 mm Hg at 25*C, essentially all vinyl chloride in the atmosphere is expected to exist in vapor form (Verschueren 1983, Eisenreich et al. 1981). Consequently, removal from the atmosphere by dry deposition is not expected to be an important fate process. Vinyl chloride has a relatively high partition coefficient between air and water (H - 50), which suggests that significant amounts of vinyl chloride would not be removed from the atmosphere by wet deposition (EPA 1985b).
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Reaction of vinyl chloride vapor with photochenically generated hydroxyl radicals is predicted to be the primary degradation mechanism for this compound in the atmosphere. The half-life for this reaction in the typical atmosphere has been -1.5 to 1.8 days (EPA 1985b). Products of this reaction are HC1, formaldehyde, formyl chloride, carbon monoxide, carbon dioxide, chloroacetaldehyde, acetylene, chloroethylene, chloroacetylchloranil, and H20 (EPA 1985b). In photochemical smog situations, the reaction half-life of vinyl chloride is predicted to range between 3 and 7 h (HSDB 1987). Reaction with ozone (half-life 4.2 to 33 days), reaction with oxygen atoms [O(-^P)] (half-life - 373 to 532 days), and direct photolysis are relatively insignificant degradation mechanisms in the atmosphere (EPA 1985b).
6.3.2 Veter
The primary loss process for vinyl chloride in natural water systems is volatilization into the atmosphere. The half-life for vinyl chloride volatilization from a typical pond, river, and lake has been estimated to be 43.3, 8.7, and 34.7 h, respectively. These values are based on an experimentally determined reaeration rate ratio of -2 and assumed oxygen reaeration rates of 0.008, 0.04, and 0.01 hour'^ for a typical pond, river, and lake, respectively (EPA 1985b). Predicted half-lives should be considered rough estimates since the presence of various salts in natural water systems may affect the volatility of vinyl chloride significantly (EPA 1985b). In waters containing photosensitizers, such as humic materials, photodegradation may be fairly rapid. This suggests that in some waters sensitized photodegradation would also be a significant removal mechanism (HSDB 1987, EPA 1985b).
Chemical hydrolysis of vinyl chloride does not appear to be environmentally important. The hydrolytic half-life for. vinyl chloride has been estimated to be <10 years (EPA 1985b). Vinyl chloride is not expected to oxidize chemically by reaction with photochemically generated hydroxyl radicals, molecular oxygen, or alkyl peroxy radicals in natural water systems. Limited available data on the biodegradation of vinyl chloride indicate that this compound is resistant to microbial degradation under aerobic conditions (EPA 1985b). Vlnvl chloride is not expected to adsorb significantly to suspended solids and sediments in water or bioaccumulate significantly in aquatic organisms (HSDB 1987).
6.3.3 Soil
The relatively high vapor pressure of vinyl chloride (2660 mm Hg at 25*C) indicates that this compound should volatilize quite rapidly from dry soil surface. The effective half-life (due to volatilization) of vinyl chloride placed 10 cm deep in dry soil is predicted to be 12 h (EPA 1985b). Evaporation from moist soil surfaces is also expected to be significant since this compound does not adsorb strongly to soil and appears to volatilize fairly rapidly from water.
Experimental data regarding adsorption of vinyl chloride to soil were not located. Based on the regression equations given by Lyman et al. (1982) and Sabljic (1984), the soil adsorption coefficient (Koc) for vinyl chloride has been estimated to range between 17 and 131. These Koc
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Based on data in aquatic media, chemical reaction of vinyl chloride In soil does not appear to be a significant fate process, and it appears that vinyl chloride would be resistant to biodegradation under aerobic conditions.
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7. POTENTIAL FOR HOMAN EXPOSURE
7.1 OVERVIEW
Anthropogenic sources are responsible for all of the vinyl chloride found in the environment. Most of the vinyl chloride released to the environment will eventually locate in the atmosphere while much smaller amounts will eventually locate in groundwater. Vinyl chloride has been detected in the ambient air in the vicinity of vinyl chloride and PVC manufacturing plants and hazardous waste sites. Vinyl chloride is expected to leach into groundwater from spills, landfills, and industrial sources.
Segments of the general population living in the vicinity of emission sources are exposed to vinyl chloride by inhalation of contaminated air. Average daily intake of vinyl chloride by inhalation for these people ranges from trace amounts to 2100 /ig/day. The average daily intake of vinyl chloride by inhalation is expected to be essentially zero for the remainder of the population. However, short term inhalation exposure to relatively high levels may occur during use of new cars. This is due to volatilization of vinyl chloride from vinyl polymers within the car interior.
The majority of the general population is not expected to be exposed to vinyl chloride through ingestion of drinking water. However, people who have PVC water pipes that have not been treated' adequately to remove vinyl chloride monomer may ingest ->0.06 to 2.8 pg/day of vinyl chloride from drinking water. The average daily intake of vinyl chloride through diet is predicted to be essentially zero.
NIOSH estimated that 27,000 workers are definitely exposed to vinyl chloride and that workers probably exposed may be as many as 2.2 million. Intake is expected to occur primarily through inhalation and less importantly by absorption through skin. Workplace air in some PVC manufacturing plants was found to contain 100 to 800 mg/m? (39 to 312 ppm) vinyl chloride with peak concentrations of up to 87,300 mg/m^ (34,000 ppm). A NIOSH survey of three vinyl chloride manufacturers reported a time-weighed-average exposure of 0.18 to 69 mg/m? (0.07 to 27 ppm) vinyl chloride in workplace air.
7.2 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
7.2.1 Air
Air in rural/remote and urban/suburban areas of the United States typically contain no detectable amount of vinyl chloride (Stephens et al. 1986; Grimsrud and Rasmussen 1975a,b; Harkov et al. 1984; Wallace et al. 1984; EPA 1985b). Limited monitoring data indicate that in areas near vinyl chloride and polyvinyl chloride manufacturers, the
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concentration of vinyl chloride in air typically ranges from trace levels to -105 jig/m3 (Gordon and Meeks 1977, Fellizzari et al. 1979, IARC 1979, EPA 1985b), but may exceed 2600 ftg/ra? (1 ppa) (Fishbein 1979). Elevated levels of vinyl chloride may also be found in the vicinity of hazardous waste landfills. Concentrations ranging froa below detection liaits to 5 to 8 ftg/m3 (0.002 to 0.003 ppa) have been monitored in the air above some landfills (Stephens et al. 1986, Baker and Mackay 1985). Homes near a hazardous waste site in Southern California were found to contain levels as high as 1040 /ig/m3 (0.4 ppm) (Stephens et al. 1986).
Typical values for the average daily intake of vinyl chloride by inhalation in urban/suburban and rural/remote areas have been estimated to be essentially zero. Assuming that the average intake of air is 20 m3/day, the average daily intake of vinyl chloride by people living in source-dominated areas has been estimated to range from trace amounts to 2100 pg/day.
7.2.2 Water
Vinyl chloride has been detected at varying concentrations in surface, ground, and drinking waters throughout the United States (EPA 1985b). Concentrations as high as 9.8 ftg/L in surface water, 380 ftg/L in groundwater, and 10 ftg/L in drinking water have been reported (Dyksen and Hess 1982, HSDB 1987). There was no report in the literature of vinyl chloride being detected in sediment.
The level of vinyl chloride in groundwater in the United States was determined during the 1982 EPA Groundwater Supply Survey. Water supplies from 945 sites geographically located throughout the United States were studied. Results indicate that vinyl chloride was positively identified in only 0.74% of groundwater supplies (detection limit 1 ug/L). The" maximum concentration detected was 8.4 ftg/L (Westrick et al. 1984). Other studies have also reported the occurrence of vinyl chloride in groundwater throughout the United States at levels at or below 380 ftg/L (Cotruvo 1985, Goodenkauf and Atkinson 1986, Page 1981, Coniglio et al. 1980, Stuart 1983).
The concentration of vinyl chloride in finished drinking waters in the United States was studied during the 1976-1977 EPA National Organics Monitoring Survey (NOMS). Only 2 samples out of 113 contained detectable levels (>0.1 ftg/L), and these averaged 0.14 ftg/L (HSDB 1987). Results of other studies also indicate that the majority of drinking water supplies in the United States contain no detectable levels of vinyl chloride (HSDB 1987, Coniglio et al. 1980). Based on these studies, it is assumed that the average daily intake of vinyl chloride by ingestion of drinking water for most persons in the United States would be essentially zero. Estimates provided in EPA (1985a) indicate that 0.9% of the United States population is exposed to levels of vinyl chloride in drinking water kl.O ftg/L, and 0.3% of the population is exposed to levels >5 ftg/L.
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7.2.3 Soil
Monitoring data for vinyl chloride in soil were not located in the available literature.
7.2.4 Other
In the past, vinyl chloride had been detected in various foods as a result of migration from polyvinyl chloride food wrappings and containers (EPA 1985b). Vinyl chloride has been found in vinegar at levels up to 9.4 ppm, in edible oils at 0.15 to 14.8 ppm, and in butter at 0.05 ppm when these foods were packaged and stored in PVC containers (1ARC 1979). At present, the Food and Drug Administration (FDA) regulates use of vinyl chloride polymers available for use in production of articles intended to contact food. These articles include foodpackaging materials, coatings, plastisols, gaskets, and parts for food processing (see Sect 9, Regulatory and Advisory Status). A recent study on the migration of vinyl chloride from PVC under conditions closely simulating actual food packaging and storage revealed that at very low concentrations of vinyl chloride in PVC packaging material, there was essentially zero migration of vinyl chloride (Kontominas et al. 1985).
It is reported that migration of vinyl chloride from rigid PVC water pipes into drinking water occurs, and that it is directly proportional to the residual level of vinyl chloride in the pipe itself. Under certain conditions, reaction with chlorine in the water may result in the complete removal of vinyl chloride from drinking water (Fishbein 1979, Ando and Sayato 1984). During one study, it was found that drinking water which ran through recently installed PVC pipes contained vinyl chloride at 1.4 jg/L, while water which ran through a 9-year-old system contained 0.03 to 0.06 ftg/h (HSDB 1987). This suggests that use of PVC pipe in water distribution systems contributes to intake of vinyl chloride through ingestion of contaminated drinking water. Assuming that the average daily intake of water is 2 L, the average intake of vinyl chloride from water contaminated with vinyl chloride from PVC pipes is expected to range from 0.06 to 2.8 jig/day.
The interior air of two new cars was analyzed and the level of vinyl chloride was found to range from 824 to 3120 /ig/m^ (0.3 to 1.2 ppm) (EPA 1985b). The source of vinyl chloride was believed to be volatilization from vinyl plastics found in the car interiors. Levels of vinyl chloride in the air in new cars may exceed estimates of minimal risk levels for acute and intermediate exposure.
Vinyl chloride has been detected in tobacco smoke (EPA 1985b). Cigarettes and little cigars have been found to contain 5.6 to 28 ng vinyl chloride per cigarette (IARC 1979).
7.3 OCCUPATIONAL EXPOSURES
NI0SH estimates definite worker exposure to vinyl chloride to be 27.000 persons and probable worker exposure to be 2.2 million (Sittig 1985). This includes -5000 workers employed in vinyl chloride synthesis, 5000 workers involved with polymerization processes, and as many as 350.000 workers associated with fabrication plants. Exposure is believed to occur primarily through inhalation and less frequently by absorption
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through skin (Sittig 1985). In the past, concentrations of vinyl chloride in workplace air in some plants producing PVC have been reported to range from 100 to 800 mg/m3 (39 to 315 ppm) with peak concentrations up to 87,300 mg/m3 (34,000 ppm) (IARC 1979). Currently, the Occupational Safety and Health Administration (OSHA) sets standards for occupational exposure to vinyl chloride (see Sect. 9, Regulatory and Advisory Status). A recent NIOSH survey of three vinyl chloride plants indicated that the time-weighted-average exposure to vinyl chloride varied between 0.2 to 70 mg/m3 (0.08 to 27 ppm) (IARC 1979).
7.4 POPULATIONS AT HIGH RISK
Data were not located specifically regarding subpopulations unusually sensitive to the effects of vinyl chloride. Individuals located near or downwind of production facilities, hazardous waste disposal sites, and landfills may potentially be exposed to higher ambient atmospheric levels.
Workers involved in the production or polymerization of vinyl chloride may constitute a group at risk because of the potential for occupational exposure. Since the mid 1970s, however, atmospheric levels in the workplace have often been reduced to Si ppm (Fishbein 1979, Kilian et al. 1975, Hansteen et al. 1978). Occupationally exposed men may represent a sensitive subgroup because occupational exposure in men has been associated with an increased incidence of fetal loss in their wives (Infante et al. 1976, Waxweiler et al. 1977). No threshold concentration has been determined for this effect. Women (or couples) of child-bearing age may constitute a group at risk, because data suggest that ambient exposure to low (but not quantified) environmental levels is associated with an increase in the Incidence of malformations at birth (Infante 1976; Edmonds et al. 1975, 1978; Theriault et al. 1983). No threshold has been determined for this effect.
Inhalation studies in animals demonstrated that exposure early in life resulted in greater risk of developing cancer than did exposure later in life (Drew et al. 1983). Although human studies that address the effect of age on cancer risk were not located, the animal data suggest that exposure during the younger years may result in increased cancer risk. Other animal studies suggest that prenatal exposure may increase cancer risk (Maltoni et al. 1980, 1981). Although human data were not located, the animal data may suggest that the prenatal exposure of humans to vinyl chloride may increase risk of cancer.
Animal studies have demonstrated that pretreatment with xenobiotics or drugs that induce mixed-function oxidase (MFO) potentiates the hepatotoxicity of vinyl chloride (Jaeger et al. 1974, Reynolds et al. 1975, Conolly et al. 1978). Although human data were not located, the animal data suggest that human exposure to environmental pollutants or drugs that induce MFO may result in increased sensitivity to vinyl chloride.
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