Document 2a50pypwrGxZ1QwdgBq8Q86g

DRAFT TECHNICAL SUPPORT DOCUMENT PROPOSED IDENTIFICATION OF VINYL CHLORIDE AS A TOXIC AIR CONTAMINANT Part A Report State of California Air Resources Board Stationary Source Division July 1989 PRELIMINARY DRAFT TECHNICAL SUPPORT DOCUMENT PART A PUBLIC EXPOSURE TO, SOURCES, AND EMISSIONS OF VINYL CHLORIDE IN CALIFORNIA REPORT TO THE AIR RESOURCES BOARD ON VINYL CHLORIDE Principal Author Richard Corey Contributing Authors Tom Parker Chris Nguyen Paul Allen Steve Hui Reviewed and Approved by: Joan Denton, Manager Substance Evaluation Section Robert Barham, Chief Toxic Air Contaminant Identification Branch Peter D. Venturini, Chief Stationary Source Division July 1989 CMA 0105 ACKNOWLEDGMENTS a\ i\a \ The authors wish to acknowledge the valuable assistance of the following people who contributed to the preparation and review of this document: Pacita Ayala, Technical Support Division/ARB; Rich Miller, Technical Support Division/ARB; Lynn Baker, Stationary Source Division/ARB. Gary Yee, Monitoring and Laboratory Division/ARB; Barbara Fry, Stationary Source Division/ARB; July 1989 (This report has been reviewed by the staff of the California Air Resources Board and approved for publication. Approval does not signify that the contents necessarily reflects the views and policies of the Air Resources Board, nor does mention of trade names or commercial products constitute endorsement or reconmendation for use.) CMA 010528 PRELIMINARY DRAFT PUBLIC EXPOSURE TO, AND SOURCES OF ATMOSPHERIC VINYL CHLORIDE IN CALIFORNIA 5U3 Q ft A h CT i3 Table of Contents Page LIST OF APPENDICES .................................................................................................... ii LIST OF TABLES ............................................................................................................ ill LIST OF FIGURES .......................................................................................................... Hi I. II. Ill- IV- INTRODUCTION .............................................................................................. A-l EXPOSURE TO VINYL CHLORIDE ................................................................. A-3 A. AMBIENT MONITORING IN CALIFORNIA ........................................... A-3 B. ESTIMATING AMBIENT CONCENTRATIONS .......................................... A-10 C. POPULATION EXPOSURE ...................................................................... A-13 D. INDOOR EXPOSURE TO VINYL CHLORIDE ......................................... A-16 E. EXPOSURE THROUGH OTHER ROUTES .................................................. A-19 F. REFERENCES ......................................................................................... A-22 PRODUCTION. USES AND EMISSIONS ......................................................... A-24 A. PRODUCTION ....................................... A-24 B. CURRENT AND PROJECTED USES ........................................................ A-25 C. LANDFILLS: A MAJOR EMISSION SOURCE ........................................ A-26 D. OTHER KNOWN EMISSION SOURCES .................................................... A-33 E. OTHER POTENTIAL EMISSION SOURCES ............................................ A-36 F. REFERENCES ......................................................................................... A-38 PROPERTIES AND PERSISTENCE IN THE ATMOSPHERE ............................ A-42 A. PHYSICAL PROPERTIES ...................................................................... A-42 B. ATMOSPHERIC PERSISTENCE .............................................................. A-42 C. REFERENCES ......................................................................................... A-48 CMA 010529 LIST OF APPENDICES APPENDIX I - SCAQMD'S ANALYTICAL METHOD FOR SAMPLING AND ANALYSIS OF ATMOSPHERIC VINYL CHLORIDE APPENDIX II - DESCRIPTION OF GLEIT'S METHOD APPENDIX III - ESTIMATE OF TOTAL EXPOSURE TO VINYL CHLORIDE FROM INDOOR AIR APPENDIX IV - INFORMATION REQUEST LETTER WITH ATTACHMENTS AND RESPONSES APPENDIX V - HEALTH EFFECTS REQUEST TO DHS AND LETTER OF RESPONSE -i i- l05 30 LIST OF TABLES AND FIGURES TABLES Page II-l SUMMARY STATISTICS FOR THE JANUARY 1987 THROUGHDECEMBER ............ A-7 1987 MONITORING DATA FOR VINYL CHLORIDE NEAR BKK LANDFILL II-2 SUMMARY STATISTICS FOR THE JANUARY 1986 THROUGHDECEMBER ............ A-8 1986 MONITORING DATA FOR VINYL CHLORIDE NEAR Oil LANDFILL 11-3 UPPER AND LOWER BOUND ESTIMATES OF THE ANNUAL MEAN ..................... A-10 CONCENTRATIONS OF VINYL CHLORIDE AT BKK AND Oil LANDFILLS 11-4 ESTIMATED EMISSION RATES OF VINYL CHLORIDE FROM BKK .................... A-1Z AND Oil LANDFILLS I1-5 RANGE OF CUMULATIVE POPULATION EXPOSED TO ........................................ A-14 VINYL CHLORIDE NEAR BKK LANDFILL I1-6 RANGE OF CUMULATIVE POPULATION exposed TO ........................................ A-15 VINYL CHLORIDE NEAR Oil 11-7 ESTIMATED VINYL CHLORIDE EXPOSURE THROUGH ........................................ A-20 DIFFERENT MEDIA III-l VINYL CHLORIDE LANDFILL EMISSION ESTIMATES ...................................... A-30 III-2 SUMMARY OF VINYL CHLORIDE EMISSION ESTIMATES .................................. A-33 FOR OTHER SOURCES IV-1 PHYSICAL PROPERTIES OF VINYL CHLORIDE ................................................. A-43 IV-2 ATMOSPHERIC LIFETIME AND REACTION RATE CONSTANT ESTIMATES .... A-45 FOR VINYL CHLORIDE FIGURES II-l BKK LANDFILL AND THE SURROUNDING AREA ................................................ A-5 11 -2 Oil LANDFILL AND THE SURROUNDING AREA ................................................ A-6 III-l NATIONAL VINYL CHLORIDE PRODUCTION, IMPORTS, EXPORTS...................... A-25 AND USE III-2 ANAEROBIC BREAKDOWN SEQUENCE VIA REDUCTIVEDEHALOGENATION .... A-28 III-3 LANDFILL GAS COLLECTION SYSTEM ............................................................... A-32 -m- CMA 010531 DRAFT I. INTRODUCTION Part A of this report is an evaluation of vinyl chloride's uses, emission sources, ambient and indoor air concentrations, and population exposure in California. Also included are discussions of the physical properties and atmospheric persistence of vinyl chloride. California Health and Safety Code Section 39655 states that substances listed by the U.S. Environmental Protection Agency (EPA) as hazardous air pollutants (Section 112 of the Clean Air Act) shall be identified as toxic air contaminants (TACs) by the Air Resources Board (ARB). Therefore, because the EPA has listed vinyl chloride as a hazardous air pollutant, the ARB is directed by statute to identify vinyl chloride as a TAC. The ARB is the state agency responsible for the identification of TACs in their non-pesticidal uses. The California Health and Safety Code Section 39655 defines a TAC as "an1 air pollutant which may cause or contribute to an increase in mortality or an increase in serious illness, or which may pose a present or potential hazard to human health." The findings of the Part A report are considered with the health effects findings (Part B report) of the Department of Health Services (DHS) to determine if a compound should be identified as a TAC by the ARB. In 1978, the ARB adopted an ambient air quality standard for vinyl chloride of 10 ppb for a 24-hour average. The standard represented the limit of detection for vinyl chloride at the time it was adopted. Vinyl chloride is an extremely volatile compound that is primarily used for the production of polyvinyl chloride (PVC). PVC is fabricated for use in several products of which many are used by the A-l CMA 010533 construction industry, In California, the ident fied sources of vinyl chloride emissions are landfills, PVC production and fabrication facilities, and sewage treatment plants. Available information indicates that landfills are the largest source category of vinyl chloride emissions in California. Vinyl chloride has been measured in the ambient air near hazardous waste and municipal waste landfills. Numerous studies have documented the presence of vinyl chloride in the landfill gas of these and other landfills, and have shown that vinyl chloride can be formed in landfills where chlorinated organic compounds have been disposed. Therefore, because disposal of such chlorinated compounds is prevalent, the staff recommends that all landfills (hazardous and municipal) in the state be regarded as potential vinyl chloride emission sources. In this report, ambient monitoring data and meteorological data are used with an atmospheric dispersion model to estimate population exposure to vinyl chloride near two California landfills. The modeling results show that people living near these landfills are exposed to elevated levels of vinyl chloride. The results also imply that people residing near other landfills in the state may be exposed to elevated levels of vinyl chloride. In addition to estimating ambient air exposure, this report also evaluates indoor air exposure to vinyl chloride. Based on limited monitoring data, indoor air exposure to vinyl chloride is probably not significant for the majority of the population. However, for people residing near landfills, inhalation of indoor air may represent the most significant source of vinyl chloride exposure. This is because vinyl chloride can migrate underground from landfills and accumulate in nearby structures. The concentrations of vinyl chloride measured in homes located near landfills have been reported to be several times greater than the corresponding ambient concentrations. A-2 CHA 010534 II. EXPOSURE TO VINYL CHLORIDE A. AMBIENT MONITORING IN CALIFORNIA Vinyl chloride is frequently detected in the ambient air of California. However, detectable levels are limited to locations near identified emission sources. Previous monitoring throughout the South Coast Air Basin (SCAB), as part of the ARB's ambient monitoring network, has failed to detect vinyl chloride above the ARB's limit of detection (LOD) of 0.5 ppb. In recent years, the only known emission sources in California near which vinyl chloride has been frequently detected in the ambient air are two landfills in the SCAB: BKK and Operating Industries Inc. (Oil). For both of these landfills, the South Coast Air Quality Management District (SCAQMO) has frequently measured ambient vinyl chloride concentrations above the SCAQMD's LOD of 2 ppb. The analysis in this report estimates ambient concentrations and population exposure to vinyl chloride near BKK and Oil because they are the only landfills in the state where vinyl chloride has been routinely monitored on a long-term basis. In response to the lack of monitoring data for o'ther landfills. Health and Safety Code Section 41805.5 requires hazardous and municipal landfills throughout the state to conduct monitoring for several contaminants that include vinyl chloride. As these monitoring results are evaluated, they will be helpful in identifying which landfills could be expected to emit vinyl chloride and warrant further monitoring studies or mitigation measures. A more detailed description of the requirements of Health and Safety Code Section 41805.5 is provided on page A-31. The SCAQMD's monitoring program for vinyl chloride at BKK and Oil has consisted of six monitoring stations. Three stations have been A-3 010535 located on the southern borders of each landfill. Previous monitoring around both landfills has indicated that the southern borders are generally where the highest concentrations are detected. All samples are collected in Tedlar bags over 24-hour periods and subsequently analyzed by gas chromatography employing a flame ionization detector. Details of the SCAQMD's sampling and analysis procedures are provided in Appendix I. Topographical maps of the BKK and Oil landfills are provided respectively in Figures II-1 and II-2. These figures show the approximate perimeter of the landfills, the approximate locations of the monitoring sites, and proximity of streets to the landfills. As indicated by the maps, the southern borders of BKK and Oil are adjacent to a network of streets. However, the maps do not show that the area served by these streets consists of single-family residential housing. Ambient air samples used to estimate population exposure near BKK and Oil were collected from January through December 1987 and January through December 1986, respectively. When the exposure analysis was performed, these sampling periods represented the most recent calendar years of monitoring data that were available. For BKK, 337 to 345 samples were taken at each of the monitoring sites; of those sites, a range of 55 to 90 percent of the samples are below the LOD of 2 ppb. For Oil, 128 to 264 samples were taken at each of the monitoring sites; of those sites, 32 to 100 percent of the samples are below the LOD. The ambient vinyl chloride monitoring data for BKK and Oil are summarized in Tables II-l and 11-2, respectively. Each table provides the number of samples taken at each site, the percent of samples below the LOD, an estimate for the values below the LOD, the estimated mean concentration, and the maximum 24-hour concentration that was measured. Calculation of mean concentrations for stations is complicated by the presence of concentrations below the LOD. The concentrations below the LOD must be somehow included in the calculation although their exact values are not known. ARB staff has used a method proposed by Gleit (1985) to calculate the means. Gleit's method assumes that the sample of concentrations is a random sample from a normal distribution. Data that are judged not to be normally distributed may be transformed to approximate normality. Inspection of the vinyl chloride data suggested that they were lognormally distributed, and Gleit's method was applied to the logarithms of these data. The calculated means were then transformed back to the original units. Gleit's method accounts for the concentrations below the LOD by setting them equal to the "below-LOD mean," the mean of the portion of A-4 CM* 010536 FIGURE II-l BKK LANDFILL AND THE SURROUNDING AREA Boundary Line W SanplIng Sites j - 1 Kllometer A-5 CHA 010537 FIGURE II-2 Oil LANDFILL AND THE SURROUNDING AREA Boundary Line Samp IIng Sites i - 1 KIloaeter A-6 CMA 010538 the normal distribution below the LOD. Setting the unknown concentrations to their average value seems intuitively reasonable, and the simulations reported in Gleit's paper show that his method is more accurate than other commonly used approximations. A detailed description of the method used to estimate the concentration of data below the LOD is provided on Appendix II. The estimated values for samples below the LOD range from 1.0 ppb to 1.1 ppb for BKK and from 1.0 ppb to 1.2 ppb for Oil. As previously indicated, the specific value for each station is shown in Table II-1 for BKK and II-2 for Oil. Because all samples for site 1 of Oil are below the LOD, Gleit's method could not be used to estimate their concentration. Therefore, a value of one-half the LOD (1.0 ppb) is assumed for these samples. TABLE II-l SUMMARY STATISTICS FOR THE JANUARY 1987 THROUGH DECEMBER 1987 MONITORING DATA FOR VINYL CHLORIDE NEAR BKK LANDFILL (Concentrations reported in parts per billion (ppb)) Number of Samples Percent of Samples Below the L0Da Estimated Concentration forb Samples Below the LOD Estimated Mean b Concentration Maximum 24-Hour Concentration0 . Station 1 337 73 1.0 Station 2 337 90 1.0 Station 3 345 55 1.1 1.7 1.2 2.6 7 8 15 a - The SCAQMD's limit of detection (LOD) for vinyl chloride is 2 ppb. b - Gleit's method was used to estimate the concentration of samples below the LOD. c - California's Ambient Air Quality Standard for vinyl chloride is 10 ppb for a 24-hour averaging period. A-7 CAM 010539 The estimated mean vinyl chloride concentrations, as provided in Tables II-1 and II-2 range from 1.2 ppb to 2.6 ppb for the monitoring stations at BKK, and 1.0 ppb to 2.0 ppb for the monitoring stations at Oil. For all stations, except station 3 of BKK, the estimated annual mean concentration is equal to or less than the SCAQMD's LOD for vinyl chloride. Tables II-1 and II-2 also list the maximum 24-hour concentration of vinyl chloride for each monitoring station at BKK and Oil, respectively. For BKK, the maximum 24-hour concentration is 15 ppb (measured at station 3); for Oil the maximum concentration is 9.8 ppb (measured at station 3). These concentrations can be compared to ARB's ambient air quality standard for vinyl chloride of 10 ppb for a 24-hour averaging period. The standard was TABLE II-2 SUMMARY STATISTICS FOR THE JANUARY 1986 THROUGH DECEMBER 1986 MONITORING DATA FOR VINYL CHLORIDE NEAR Oil LANDFILL (Concentrations reported in parts per billion (ppb)) Station 1 Station 2 Station 3 Number of Samples 264 220 128 Percent of Samples Below the LODa 100 41 32 Estimated Concentration for*5 Samples Below the LOD 1.0 1.1 1.2 Estimated Meanb Concentration 1.0 2.0 2.0 Maximum 24-Hour Concentration0 d 8.3 9.8 a - The SCAQMD's limit of detection (LOD) for vinyl chloride is 2 ppb. b - Gleit's method was used to estimate the concentration of samples below the LOD. c - California's Ambient Air Quality Standard for vinyl chloride is 10 ppb for a 24-hour average, d - All samples are below the LOD A-8 CMA 010540 adopted in 1978 in response to information which associated vinyl chloride with the development of cancer in humans. However, the standard is not necessarily health protective; it simply represented the LOD at the time it was adopted. For the monitoring periods presented in this report, BKK exceeded the state standard for vinyl chloride 11 times (all exceedances occurred at site 3) while Oil did not exceed the standard. Based on previous years of monitoring data, the number of exceedances at BKK and Oil has decreased substantially. In fact, due to the lack of exceedances of the standard, the SCAQMD discontinued monitoring for vinyl chloride at Oil in early 1987. The reduction in ambient concentrations of vinyl chloride near BKK and Oil has been attributed to the installation of gas collection and flare systems. In an effort to represent the uncertainties associated with the estimated mean concentrations of vinyl chloride, the staff developed a statistical treatment for calculating upper and lower bound estimates of the mean concentration at each monitoring station. This method takes into account factors such as sample size, variance of the data, and an estimate of the uncertainty associated with the sampling and analysis method. Table II-3 shows the estimated mean concentration as well as the upper and lower bound estimate of the mean concentration for each monitoring station at BKK and Oil. The following text discusses the statistical treatment that is used: a) After reviewing the ambient vinyl chloride monitoring data for BKK and Oil, the staff observed that the data appear to be lognormally distributed. Because available software analyze data that are only normally distributed, vinyl chloride monitoring data were first converted from a lognormal distribution to a normal distribution. This was done by using the logarithms of the data for the analysis. The statistical analysis system (SAS, 1982) was used to calculate the standard error about the mean. The standard error calculated from the logarithms of the data is then converted back into concentration units by taking the anti logarithms. b) The upper and lower bound estimates reported for the mean represent two standard errors. For the error associated with sampling and analysis, ARB staff used an overall uncertainty factor of 20 percent to calculate the upper and lower bound estimates of the mean. This is in agreement with the actual error which is estimated to be 1 ppb in the range of 1 ppb to 50 ppb. The lower bound estimate represents two standard errors for the data with each sample concentration reduced by 20 percent. The upper bound estimate represents two standard errors for the data with each sample concentration increased by 20 percent. Upper and lower bound estimates for each station are shown in Table 11-3. Because all values for station 1 of Oil are below the LOD, the upper and lower bound estimates represent 20 percent of one-half the LOD. B. ESTIMATING AMBIENT CONCENTRATIONS Annual average vinyl chloride concentrations were estimated for a 41 x 41 grid of one square kilometer cells surrounding each landfill with the use of the Industrial Source Complex Short Term (ISCST) Gaussian model. In order to predict the annual average concentration of vinyl chloride in each of the 1681 square kilometer cells, the ISCST model required the emission rates for each landfill as input. Emission rates were estimated for BKK and Oil using the range of estimated annual mean concentrations at each of the monitoring stations. The estimated emission rates were derived by ratioing estimated annual mean concentrations over modeled concentrations for each station. TABLE II--3 UPPER AND LOWER BOUND ESTIMATES OF THE ANNUAL MEAN CONCENTRATIONS OF VINYL CHLORIDE AT BKK AND Oil LANDFILLS Lower bound Estimate Annual Mean Concentration Upper Bound Estimate BKK Landfill Station 1 Station 2 Station 3 Oil Landfill Station 1* Station 2 Station 3 1.2 0.9 1.9 0.8 1.4 1.4 1.7 1.2 2.6 1.0 2.0 2.0 2.1 1.4 3.4 1.2 2.8 2.6 * - A11 samples are below the LOO of 2 ppb. A-10 CMA 010542 The modeled concentrations were determined by assuming a landfill emission rate of 1 gram per square meter per second (gram meter' second-1) in conjunction with historical meteorological data. Each landfill was represented as an area source. Based on review of topographical maps as well as information concerning the landfills disposal history, BKK was assumed to emit vinyl chloride from an area of approximately 1,700,000 meters* while Oil was assumedjto emit vinyl chloride from an area of approximately 330,000 meters'1. These assumed areas approximate the area where wastes have been disposed. Meteorological data for 1981 at the SCAQMD's Walnut and Upland stations were used for BKK and Oil, respectively. Meteorological data from these stations were used for this study because Walnut was considered the most representative station for BKK where processed data were available while Upland was considered the most representative station for Oil where processed data were available. These data were entered into the ISCST model to calculate the annual average modeled concentration at each monitoring station. Because one year of meteorological data is used, one modeled concentration is obtained for each monitoring station at BKK and Oil. For each site at BKK and Oil the modeled concentration was divided into the estimated mean concentration (from Table 11-3) of its respective monitoring station. The resulting factors or ratios were, then multiplied by the assumed emission rate (1 gram meter-* second-1) to estimate a landfill emission rate for each monitoring station that will result in an exact match between estimated and modeled concentrations. Equation (1) illustrates the procedure that was used: Estimated Assumed Estimated Modeled Emission Rate = Emission Rate x (Concentration / Concentrati on) (1) The estimated landfill emission rates for each monitoring station at BKK and Oil are given in Table 11-4* The emission rate derived from the estimated mean concentration for each monitoring station and the emission rates derived from the upper and lower bound estimates of the mean concentration for each monitoring station are listed. The greatest rangeqf estimated emission rates for BKK is from 0.75 micrograms . meter second-1 (lower bound at station 2) to 3.32 micrograms meter-* second-1 (upper bound at station 3). For Oil, tbe estimated emission rates range from 0.31 micrograms meter-* second- (lower bound at station 1) to 4.42 micrograms meter-*1 second-1 (upper bound at station 3)- Using the full range of emission rate estimates (0.75 to 3.32 micrograms meter-* second-1 for BKK and 0.31 to 4.42 micrograms meter-* second-1 for Oil), a range of estimated annual average vinyl chloride concentrations was derived for the 41 by 41 grid of one square kilometer A-11 CMA 010543 TABLE II-4 ESTIMATED EMISSION RATES OF VINYL CHLORIDE FROM BMC AND OII.LANDFILLS (micrograms meters'6 second'1) BKK -landfill Lower Bound3 Averageb Upper Bound Station 1 Station 2 Station 3 Oil Landfill Station 1 Station 2 Station 3 1.36 0.75 1.88 0.31 0.52 2.69 1.80 0.97 2.55 0.38 0.74 3.46 2.30 1.20 3.32 0.46 1.04 4.42 a - These emission rates were derived from the lower-bound annual mean concentration b - These emission rates were derived from the annual mean concentration c - These emission rates were derived from the upper-bound annual mean concentration cells. Each landfill was located in the center of the grid and was represented as an area source. As previously stated, SICK was assumed to emit vinyl chloride from an area of approximately 1,700,000 meters6 while Oil was assumed to emit vinyl chloride from an area of approximately 330,000 meters6. These areas approximate the area where wastes have been disposed at each landfill. However, because subsurface migration of landfill gases has been observed at BKiC and Oil, it is possible that emissions of vinyl chloride occur over an area substantially greater than where wastes have actually been disposed. The ISCST model used the range of estimated emission rates assuming no plume rise in conjunction with historical meteorological data to predict A-12 CMA 010544 , ** n A f" jWj fI k4 M if i 2f a range of annual average concentrations for each of the 1681 one square kilometer cells. The annual average concentrations of vinyl chloride predicted for the one square kilometer cells within the grid centered on BKK, range from less than 0.1 ppb to approximately 22 ppb. For Oil, the range is from less than 0.1 ppb to approximately 3.8 ppb. In order to obtain these modeling results, several assumptions are made. These assumptions may act to elevate or reduce the estimated annual average concentrations of vinyl chloride predicted for the cells surrounding BKK and Oil. The primary assumptions are as follows: 1) Vinyl chloride is assumed to be emitted from an area of . approximately 1,700,000 meters^ for BKK and 330,000 meters*" for Oil. Although these areas approximate the area where wastes have been disposed, data are not available to demonstrate that these areas actually represent where vinyl chloride emissions occur. Emissions of vinyl chloride may occur over an area which is either larger or smaller than that assumed. 2) Emissions of vinyl chloride are assumed to occur continuously and uniformly over a given area of each landfill. In reality, vinyl chloride is not likely to emanate uniformly over the surface of the landfills. However, the data required by the model to take this into consideration are not available. If emissions of vinyl chloride vary over the surface of the landfills, the annual concentrations estimated for some cells would be expected to be underestimated while others would be overestimated. 3) This study does not use meteorology for the same year as the vinyl chloride measurements. Because there is not a great deal of variation in meteorological data from year to year, the degree of error from using a meteorological year different than the vinyl chloride measurement year is estimated to be less than 50 percent. Because the emission rates were derived by model calibration to known vinyl chloride concentrations, the uncertainty is at a minimum near the monitoring sites. Alternatively, as the distance from each monitoring station increases, the uncertainty associated with the estimated concentration increases. C. POPULATION EXPOSURE The population exposure to vinyl chloride near BKK and Oil was estimated by using the grid cell concentrations estimated from the ISCST model in conjunction with 1985 updated census data. Estimates of the A-13 01054 cumulative population exposed to various concentration levels of vinyl chlor-ide near BKK and Oil landfills are shown in Tables I1-5 and II-6. The 1985 residential population estimates were determined for each 1 kilometer grid cell with the concentration determined at the center of each cell by the ISCST model. The 1,681 grid cells, with their associated populations, were sorted from high to low by concentration. The grid cell populations were then sunxned to determine the cumulative population exposed to a certain level of vinyl chloride. For Tables II5 and 11-6, a lower bound of exposure is estimated. This range of* Vinyl Chloride Concentration (DDbl 0.01 0.05 0.1 1.0 2.0 3.0 4.0 5.0 6.0 7.0 TABLE II-5 RANGE OF CUMULATIVE POPULATION EXPOSED TO VINYL CHLORIDE NEAR BICK _________________ Ranoe of Cumulative Population Exposed Lower-Bound Estimate Upper-Bound. Estimate 2,026,000 - 2,154,000 732,000 - 1,970,000 374,000 - 1,431,000 17,000 - 131,000 0- 54,000 0- 28,000 0- 20,000 0- 14,000 0- 0. 7,000 2,500 a - The exposure estimate is based on a vinyl chloride emission rate of 0.75 micrograms meter"* secT1 b - The exposure estimate is based on a vinyl chloride emission rate of 3.32 micrograms meter"* see?1 A-14 CMA 010546 TABLE II-6 RANGE OF CUMULATIVE POPULATION EXPOSED TO YINYL CHLORIDE NEAR Oil Vinyl ChToride Concentration f DDb) ...... Ranae of Cumulative Podu'lation ExDosure 0.01 0.05 0.10 1.0 1.5 2.0 3.0 Lower-Bound Upper-Bound Estimate, Estimate0 272,000 - 3,111,000 33,000 - 1,073,000 12,000 445,000 6,000 22,000 6,000 12,000 2,000 6,000 0 6,000 a - The exposure.estimate is based on an emission rate of 0.31 micrograms meter"* sec'1. b - The exposure,estimate is based on an emission rate of 4.42 micrograms meter' sec . exposure represents the range and upper bound of concentrations predicted for each of the one-square kilometer cells. Table II-5 shows that approximately 732,000 to 1,970,000 people are exposed to an annual average concentration of at least 0.05 ppb of vinyl chloride from the BKK landfill. Approximately 17,000 to 131,000 of these people are exposed to an annual average concentration of at least 1.0 ppb from this facility. Table II-6 shows that approximately 33,000 to 1,073,000 people are exposed to an annual average concentration of at least 0.05 ppb of vinyl chloride from the Oil landfill. Additionally, Table I1-6 shows that a range from 0 to 12,700 people are exposed to an annual average concentration of at least 1.0 ppb vinyl chloride near Oil. A-15 CHA 010547 In addition to estimating the cumulative population exposure to vinyl-chloride for people living near BKK and Oil, the populationweighted exposure results were calculated. The population-weighted exposure is calculated by multiplying the estimated annual average concentration for each cell by the population represented by the cell. The exposure results for the 1681 cells are subsequently summed and divided by the total population represented by the 1681 cells. For BKK, the population-weighted exposure results show that 2,154,000 people are exposed to an annual average vinyl chloride concentration ranging from 0.08 ppb to 0.34 ppb. For Oil the population-weighted exposure results show that 4,287,000 people are exposed to an annual average vinyl chloride concentration ranging from 0.004 ppb to 0.06 ppb. The model was also used to estimate the annual average concentrations for the maximum exposed individual at each landfill. For BKK, the maximum exposed individual is estimated to be exposed to an annual average concentration ranging from 2.3 ppb to 10.3 ppb. For Oil, the maximum exposed individual is estimated to be exposed to an annual average concentration ranging from 0.6 to 8.7 ppb. The population exposure results for BKK and Oil suggest that other landfills in California that emit vinyl chloride may expose the nearby population to elevated concentrations. However, because monitoring data for other landfills is limited, we are unable to estimate population exposure near other landfills in the State. Chapter III of this report discusses other vinyl chloride monitoring data that are available as well as existing programs intended to provide more information concerning vinyl chloride emissions and exposure resulting from other landfills in California. 0. INDOOR EXPOSURE TO VINYL CHLORIDE With the exception of some homes located near landfills, indoor concentrations of vinyl chloride are not expected to be substantially greater than outdoor concentrations. Although data are limited, the above statement is supported by the following facts: I) few indoor sources of vinyl chloride have been identified; and 2) most studies that have monitored for indoor concentrations of vinyl chloride fail to detect it. However, landfills have been identified as a source of emissions that contributes to elevated indoor levels of vinyl chloride in nearby residences. Homes situated near landfills can accumulate vinyl chloride resulting in indoor concentrations that may be several times greater than general outdoor concentrations. In some houses located near landfills, vinyl chloride has been detected at concentrations up to 100 ppb. We estimate that people living near landfills may be inhaling up to 2600 micrograms of vinyl chloride a day (see Appendix for III A-16 CMA 010548 assumptions). For these individuals, inhalation of vinyl chloride indoors is expected to represent the most significant source of exposure. A more detailed discussion of indoor exposure to air contaminants is presented in Appendix III. 1. Potential Sources of Indoor Vinvl Chloride There are several potential sources that can contribute to elevated indoor concentrations of vinyl chloride. These sources include landfills, polyvinyl chloride (PVC) products containing residues of vinyl chloride, water that contains residues of vinyl chloride and cigarette smoke. For most homes, these sources are not expected to result in substantially elevated indoor levels of vinyl chloride. However, for some homes located near landfills, staff believe that landfills may represent the most significant contribution to indoor levels of vinyl chloride. Vinvl Chloride From Landfill Gas. There are at least two ways that vinyl chloride emissions from landfills may contribute to indoor concentrations of vinyl chloride in nearby residences: 1) homes that are located downwind from landfills can receive vinyl chloride through direct outdoor air influx into indoor environments; and 2) landfill gases containing vinyl chloride can migrate underground and enter homes through substructures. The rate of accumulation of vinyl chloride indoors depends on several factors including soil permeability, source strength, air exchange rate, and structure of the home. In addition, higher indoor concentrations may occur because vinyl chloride is more rapidly destroyed in outdoor air than indoor air because of direct exposure to sunlight. Plastic Materials and Consumer Products. Plastic products made of PVC and other vinyl chloride polymers are ubiquitous in most homes. Because vinyl chloride monomer can remain in the PVC resin for an extended period of time, an indirect source of indoor vinyl chloride emissions may come from the release of unreacted vinyl chloride monomer from these plastic products. Emissions of unreacted vinyl chloride monomer have been substantially reduced due to improvements in monomer stripping technology (Wheeler, 1981). In the past, residual vinyl chloride concentrations in PVC resins at the time of shipment, were as high as 2000 ppm. Currently, PVC resins contain about 10 ppm residual vinyl chloride at the time of shipment and may lose vinyl chloride at a rate of 20 to 50 percent per month during storage. In addition, most of the vinyl chloride will vaporize and escape during the high temperature processes in which PVC resins are melted and made into final products. Thus, consumer products made of PVC resins no longer contain elevated A-17 CMa 010549 mArinJ**V A r residual levels of vinyl chloride monomer and, therefore, are not expected to be an important contributor of indoor levels of vinyl chloride. Vaporization from Water Sources. Because activities such as using water for cooking, heating and showering can promote rapid vaporization of vinyl chloride from water, contaminated surface or ground water may increase indoor vinyl chloride levels. In California, surface water is generally free of vinyl chloride (Sharrp, 1987). In assessing ground water quality, the California Department of Health Services reported, based on a limit of detection of 0.5 micrograms/1iter, that one out of the 2,947 wells for large public water systems that were sampled had detectable levels of vinyl chloride (DHS, 1986). The maximum concentration found in that well was 23 micrograms/1 iter with a median value of 20 micrograms/1 iter. Vinyl chloride has not been detected in wells used for small public water systems (DHS, 1987). Therefore, vinyl chloride in the water supply is not believed to significantly impact indoor air concentrations of vinyl chloride. Cigarette Smoke. A minute amount of vinyl chloride has been identified in the smoke of cigarettes (1.3 to 16 nanograms/cigarette) and of little cigars (14 to 27 nanograms/cigar) (IARC, 1985; Hoffmann, Patrianakos and Brunnemann, 1976). The vinyl chloride level in the mainstream smoke may be estimated by the total inorganic chloride content of the tobacco. However, the contribution from tobacco smoke does not appear to have a significant impact on the indoor concentration of vinyl chloride. 2. Indoor Monitoring Data Indoor air data can be obtained either by personal air sampling or by fixed-site air sampling. In personal sampling, the sampling equipment is carried by an individual and air samples are taken wherever the individual may be. In contrast, fixed-site air sampling refers to air samples taken at fixed locations. Personal air sampling data generally provide a more realistic estimate of individual exposure. Because most people spend 80 to 90 percent of their time in indoor environments, personal air sampling data are strongly weighted by indoor air exposure data. Personal Sampling Data. Based on limited personal sampling data, it appears that Indoor air exposure to vinyl chloride is apparently low. In monitoring nine subjects in New Jersey and three from North Carolina for several days on three separate occasions, all of the 138 air samples taken were below the LOD (Wallace et al., 1984). The LOD was reported to range from 0.25 ppb to 1.11 ppb (0.63 to 2.84 micrograms meter"J). A-18 CMA 010550 n) \ * Ci" V i \3 i Fixed-Site Sampling Data. For a study conducted in California, fixed-site monitoring stations were installed to monitor indoor and outdoor air concentrations of vinyl chloride. Based on the analysis of 32 indoor samples taken in eight homes during summer season for two twelve-hour sampling periods (daytime and nighttime), concentrations of vinyl chloride are all below the LOD. The samples were analyzed by two analytical methods with LODscanging from about 0.21 ppb to 55 ppb (0.55 and 140 micrograms meter ) (Pellizzari, 1989). A similar study was conducted in Baltimore where indoor air concentrations of vinyl chloride in about 160 homes were monitored by fixed-site sampling stations. Based on partially analyzed results, vinyl chloride was not detected in indoor air environments. The LOD was reported to range from 10.2 ppb to 15.7 ppb (26 to 40 micrograms meter-0) (Pellizzari, 1987). Special Situation Air Monitoring. In 1981, the SCAQMD collected 24-hour bag samples in the vicinity of BKK landfill. Over 500 air samples were taken at two outdoor sites and at four indoor sites downwind of the landfill (SCAQMD, 1982). All of the samples (approximately 120 samples) that equaled or exceeded the state vinyl chloride standard of 10 ppb (26 micrograms meter-0) were taken inside the residences. The highest recorded indoor vinyl chloride concentration was 50 ppb (130 micrggrams/meter-0). The LOD was reported to be 2 ppb (5.2 micrograms meter-0). In 1985, the SCAQMD collected grab-samples inside some residences adjacent to Oil. The sampling study was prompted by the SCAQMD's finding of elevated levels of vinyl chloride in several water meter boxes in homes adjacent to Oil. Indoor sampling results show vinyl chloride concentrations ranging from 8 to 100 ppb (20.8-260 micrograms meter-0) (SCAQMD, 1985). Presently, indoor concentrations of vinyl chloride in these residences are believed to be substantially lower because routine monitoring of water meter boxes has not detected significant levels of landfill gases. This has been attributed to improvements in the Oil landfill gas collection system (Coy, 1987). E, EXPOSURE THROUGH OTHER ROUTES While the main objective of this report is to estimate exposure through the air, exposure to vinyl chloride may also occur from the ingestion of food and water that contain residues of vinyl chloride. The Health and Safety Code specifies that the ARB shall identify the relative contribution to total exposure to the contaminant from indoor concentrations, taking into account both ambient and indoor environments (California Health and Safety Code, 1989). The inclusion of these data provide a useful perspective of the overall exposure to vinyl chloride through environmental media. The estimated daily dose of vinyl chloride A-19 CMA 0105^1 from different environmental media are presented in Table II-7. From the table, exposure to vinyl chloride from the indoor air of homes not located near landfills, food, and water appears to be minor. However, for people living in houses located near landfills, indoor exposure to vinyl chloride may represent the major source of total vinyl chloride exposure. The need for total exposure assessment and some of the issues and concepts involved in total exposure estimates are discussed in Appendix III. TABLE II-7 ESTIMATED VINYL CHLORIDE EXPOSURE THROUGH DIFFERENT MEDIA3 Media Daily Dose Reference AIR Ambient Air < 104 to 780 ugb Indoor Air Homes not near landfills < 11 ug3 Homes near landfills up to 2600 ug Table II-l Wallace et al.. SCAQMO, 1982 ingestion Drinking water: Surface/Ground Water Food including beverages 1 ug < 0.025 ug DHS, 1986; 1987 FDA, 1986 a - The assumptions that were used for Table II-7 are provided in Appendix III. b - ug Micrograms A-20 CMA 010552 1. Water Ingestion The major source of drinking water for California is surface water which, because of vinyl chloride's high volatility, is not expected to have detectable levels of vinyl chloride, Ground water used for public water systems is also relatively free of vinyl chloride with concentrations typically below 0.5 ug liter'1 (DHS, 1987, 1986). Based on this information, staff bel ieve that exposure to vinyl chloride through drinking water is not important under ordinary situations. 2. Food Ingestion Vinyl chloride is not routinely monitored for in U.S. food products. However, before 1973, vinyl chloride was found in food and beverages packaged in vinyl chloride polymer materials (IARC, 1979). kg'1 (ppm) of vinyl chloride monomer were present in alcoholic beverages packaged in this material. Vinyl chloride was also found in edible oils, butter and margarine at concentrations ranging from 0.05-14.8 mg kg'1. When cleaner PVC resins became available after 1975, vinyl chloride polymer containers typically contained less than 10 ppb of residual vinyl chloride monomer. In its recent rule-making proposal, the Food and Drug Administration (FDA) estimated lifetime-averaged individual exposure to vinyl chloride from food and beverages packaged with vinyl chloride polymer materials would not exceed 25 nanograms per day. A-21 CMA 010553 0i*5 REFERENCES TQ CHAPTER.II draft California Health and Safety Code, 1989., Section 39660.5 (d). Coy, C., 1987. Personal communication between Richard Corey of ARB staff and Carol Coy of SCAQMD. February, 1987. DHS, 1986. California Department of Health Services. Final report on a monitoring program for organic chemical contamination of large public water systems in California. DHS, 1987. California Department of Health Services. Status report- AB1803 small system program: Summary of results. FDA, 1986. Proposed uses of vinyl chloride polymers by the Food and Drug Administration-Proposed rule. Federal Register 51(22):4177-4188. Gleit, A., 1985. "Estimation for Small Normal Data Sets with Detection Limits," Environmental Science and Techno_laav. 19:1201-1206. Hoffmann D.; Patrianakos C.; and Brunnemann K.D., 1976. "Chromatographic determination of vinyl chloride in tobacco smoke," Analytical Chemistry. 48(1):47-50. IARC, 1979. "IARC monographs on the evaluation of the carcinogenic risk of chemicals to humans-some monomers, plastics and synthetic elastomers and acrolein," Volume 19. International Agency for Research on Cancer, World Health Organization. IARC, 1985. "IARC monographs on the evaluation of the carcinogenic risk of chemicals to humans-tobacco smoking". Volume 38. International Agency for Research on Cancer, World Health Organization. Pellizzari, E., 1987. Personal conmunication between Steve Hui of ARB staff and Dr. E. D. Pellizzari of Research Triangle Institute on December, 1987. Pellizzari. E.D.. et a!.. 1989.__ Development and implementation of exposure assessment orodedures for toxic air pollutants in several Los Anaeles Countv. CA-Comnunities. Research Triangle Park. SAS, 1982. SAS Institute, Inc. "SAS User's Guide: Statistics 1982 Editor", Box 800, Cary, North Carolina. SCAQMD, 1982. "Vinyl chloride in the South Coast Air Basin", Report by the South Coast Air Quality Management District. A-22 CMA 010555 SCAQMD, 1985. Internal Memorandum between S. Levy and Edward Camarena of the South Coast Air Quality Management District on September, 1985. Sharrp, C., 1987. Personal communication between Steve Hui of ARB staff and Chris Sharrp, staff of California Department of Health Services on December, 1987. Wallace, L.A., et al. 1984. "Personal exposures to volatile organic compounds1. Direct measurements in breath-zone air, drinking water, food, and exhaled breath," Environmental Research. 35(10):293-319. Wheeler, R.N., 1981. "Poly(vinyl chloride) processes and products," Environmental Health Perspective. 41:123-128. III. PRODUCTION. USES AND EMISSIONS Although vinyl chloride is not produced in California, several thousand tons are used each year in the State for the production of polyvinyl chloride (PVC). The PVC which is produced is primarily used by fabricators for the production of materials used by the construction, packaging, electrical, and transportation industries. Based on the emission estimates for two landfills in California (BKK and Oil), landfills are the largest identified source category of vinyl chloride emissions in the state. The information necessary to estimate vinyl chloride emissions for the hundreds of other landfills in California is not available. However, without monitoring data which shows otherwise, all of the state's landfills should be regarded as potential vinyl chloride emission sources. Other known emission sources of vinyl chloride in the state include PVC production and fabrication facilities, and sewage treatment plants. A. PRODUCTION Commercial production of vinyl chloride in the United States began in 1936. During the first year of production, two thousand tons were produced (CEN, 1984). With a reported annual U.S. production of 3.8 million tons, vinyl chloride ranked 21st on a list of the most produced chemicals in the United States in 1984 (CEN, 1985a). Figure 111-1 shows the production, imports, exports, and use of vinyl chloride from 1974 through 1984 (CEN, 1985a; US DOC, 1985a; and US DOC, 1985b). During this 10-year period, vinyl chloride production increased at an average annual rate of 31 (CEN, 1985a). More recent estimates for U.S. vinyl chloride production are 4.7 million tons and 4.2 million tons for 1985 and 1986, respectively (CEN, 1987). A-24 CMA 010557 r\ FIGURE III-l NATIONAL VINYL CHLORIDE PRODUCTION, IMPORTS, EXPORTS, AND USE A ooo-^ 1.300 + i. I.OOQ+- 2 rv 0 Z.590 f \ - z <0 73 2.000 +h 3 0 i ,500 fp- P i.ooof t 500 ^ f \// \ / '/ V -'-OOUCT.CM Imoons Exoorts 1 Use 1974 1975 197G 1977 1970 1979 1980 1981 1982 1983 1984 Year Two facilities in California currently use vinyl chloride to produce PVC. Two other facilities in the State that were producing PVC ceased production, one in 1982 and the other in 1985 (Personal Communication, 1985a, 1985b, 1985c; and Zwiacher, W. et al., 1983). B. CURRENT AND PROJECTED USES About 96 percent of the vinyl chloride produced in the U.S. is used to manufacture PVC. The remainder is either exported or used to manufacture 1,1,1-trichloroethane (methyl chloroform) (U.S. DH&HS, 1978; and McPherson, W., 1979). Sixty percent of the PVC is used for fabricating various plastic materials used by the construction industry. Specifically, PVC is used by the construction industry for pipe fittings, flooring, paneling, and roofing. PVC is also used by the packaging, electrical, furnishings, transportation, recreation, apparel, and medieal industries. The growth of the vinyl chloride industry is closely tied to PVC use. Historical data for California show the number of housing units in the construction industry increased from approximately 1.0 million units in 1981 to 1.8 million units in 1986 (U.S. DOC, 1987). If this growth A-25 CMrt 010558 in the construction industry continues, the PVC use by this industry is also expected to increase. Data are not available to forecast the use of PVC in other sectors. However, the total United States demand for PVC has been forecasted to increase by approximately 3 to 5 percent annually from 1985 to 1990 (CMR, 1985). C. LANDFILLS: A MAJOR EMISSION SOURCE Landfills are estimated to be the largest source category of vinyl chloride emissions in California. However, because landfills vary in the amount and composition of wastes they accept as well as the waste disposal methods used, estimating total vinyl chloride emissions for the state's hundreds of landfills is not possible. To better understand why all landfills are potential vinyl chloride emission sources, this section presents information on the types and number of landfills in California, the disposal methods employed, the causes of vinyl chloride emissions from landfills, vinyl chloride emission estimates for landfills, and some methods used to control landfill emissions. 1. Types of Landfills There are three types of landfills in California: Class I sites (e.g., BKK, located in West Covina) which accept all types of wastes including hazardous materials; Class II sites (e.g.. Operating Industries Inc. (Oil), located in Monterey Park) which normally accept only "non-hazardous" wastes but can accept certain types of hazardous wastes (ARB, 1982b); and Class III (municipal or sanitary landfills) sites which can accept only household wastes. In California, there are fourteen Class I sites (includes two open and twelve closed facilities), 210 Class II sites, and approximately 2000 Class III sites (ARB, 1982b; WRQCB, 1987). 2. Land Disposal Methods Landfarming, surface impoundments, and landcovering are often used as waste disposal methods in California. These disposal methods may be practiced by more than one type of landfill. For instance, any of the three types of landfills may employ landcovering as a disposal method. However, only Class I and II sites may contain surface impoundments. In addition, the same landfill may employ more than one disposal method. For landfarming, heavy oil sludge is spread several inches thick over the land. The sludge is then cultivated into the soil at frequent intervals. This cultivating process ensures a better aerobic decomposition of the wastes (Thibodeaux and Hwang, 1982). Surface impoundments, often called evaporation ponds or lagoons, are used to dispose of certain types of liquid wastes. As the name implies, surface impoundments allow the wastes to be evaporated into the atmosphere. A-26 CMA 010559 Landcovering is most often used at Class III sites or municipa I andf_i 11 s. In landcovering, wastes are spread over the land, At the end of each day, the wastes are covered with approximately six inches to 12 inches of cover. Ultimately, the wastes are covered with a layer of cover material that is at least four feet deep. 3. Landfill Emissions Emissions of vinyl chloride from landfills mainly occur by two mechanisms: 1) direct vinyl chloride emissions from disposed wastes which contain vinyl chloride; and 2) the formation of vinyl chloride from the biodegradation of chlorinated hydrocarbons. Other minor mechanisms by which vinyl chloride emissions may occur include chemical reactions such as pyrolysis, surface photolysis, and hydrolysis of trichloroethylene and other chlorinated hydrocarbons, and off-gassing of PVC (Molton et al., 1987). Direct Emissions. Direct emissions of vinyl chloride can only occur at landfill sites where vinyl chloride containing wastes were previously disposed. Because vinyl chloride containing wastes cannot be legally disposed in Class II or Class III landfills, Class I landfills (e.g., 8KK) at which vinyl chloride has been disposed are probably the largest source of direct emissions of vinyl chloride. However, because vinyl chloride containing wastes may have been illegally disposed. Class II and Class III landfills may also emit vinyl chloride directly. Formation of Vlnvl Chloride. Because vinyl chloride can be formed from the biodegradation of chlorinated wastes, emissions of vinyl chloride may occur from any landfill site including Class II and Class III sites where no vinyl chloride has been disposed. Of the three landfill disposal methods, it appears that landcovering and landfarming are most likely to produce the conditions necessary for the formation of vinyl chloride. Results of an ARB sponsored study demonstrated the formation of vinyl chloride when soil samples from two municipal landfills were incubated with chlorinated hydrocarbons (Molten et al., 1987). Similar results were obtained when sludge samples were incubated with chlorinated hydrocarbons. The evaluation of the biological mechanism showed that vinyl chloride production occurred predominently under anaerobic (without oxygen) conditions. Subsequent experimentation with carbon-13 labeled chloroethanes and chloroethenes yielded carbon-13 labeled vinyl chloride as well as other biodegradation products. These results are in agreement with other studies which evaluated the biodegradation of chlorinated hydrocarbons to produce vinyl chloride (Kleopfer, 1985; Beeman, et al., 1978; Wood et al., 1980; and Parsons et al., 1984). Figure III-2 illustrates the pathways by which vinyl chloride is formed from the dehalogenation (chlorine removal) of A-27 CMA 01054.0 FIGURE II1-2 ANAEROBIC BREAKDOWN SEQUENCE VIA REDUCTIVE DEHALOGENATION Chlorinated Ethenes C; \ / Cl C =C / (1) \ Cl Cl Tetraenloroetriene Cl 4- CI \ H / C=C / C2) \ HH Chlorotthen* (Vinyl ctilonae) 1.1 - Dichlonoetnene Chlorinated Ethanes Cl \ / C 1 Cl /, H / C I C\ /H M --C-C--H C 1 / (2) \ H / (1) \ Cl H H^ 1,1-Trichloroattiana 1,1-Oichloroetflana Chioroatllane (1) - Substantial degradation (2) - Slow degradation Source: Cline and Viste, 1984. chlorinated ethenes and ethanes. In addition, the figure indicates the relative rate by which the various compounds are degraded. Not all of the compounds presented in this scheme have necessarily been unequivically demonstrated to form vinyl chloride. However, given the current state of information, they should be regarded as vinyl chloride precursors. Although the disposal of halogenated wastes from industrial operations is now substantially restricted, for decades these materials were disposed in Class I landfills as well as some Class II landfills throughout the state. The halogenated wastes are composed of many of the chlorinated compounds which can lead to the formation of vinyl chloride. However, the amount of halogenated wastes previously disposed in these facilities is unknown. Therefore, without monitoring data that A-28 CMA 010561 shows otherwise, all C ass I and Class II facilities (th s includes open and closed facilities) should be regarded as potential v nyl chloride emission sources. Industrially generated halogenated wastes were never permitted to be disposed in Class III facilities. However, many of the chlorinated compounds which can lead to the formation of vinyl chloride are used extensively in consumer products, which after use typically end up in Class III landfills. The amount of chlorinated compounds remaining in consumer products and disposed in landfills is not known. However, because of the widespread use of these compounds in consumer products, all Class III landfills (this includes open and closed facilities) should be regarded as potential vinyl chloride emission sources. Methods of Estimating Landfill Emissions. Several models have been developed to estimate volatile organic gaseous emissions from hazardous waste landfills (Thidobeaux, 1981; Hwang, 1982; Shen, 1981; and Hartley, 1969). The models usually apply to specific landfill operations such as landfarming, surface impoundments, etc. However, these models are difficult to use because they require a number of input parameters such as waste composition, wind speed, and ambient conditions which are not conmonly known. These models involve the use of Fick's law (Fick's Law describes the diffusion of a species through a layer of fluid) and may be appropriate for estimating direct emissions of volatile compounds such as vinyl chloride. However, because the models do not consider factors such as formation, they may not be appropriate for estimating vinyl chloride emissions where formation is occurring. A method to estimate vinyl chloride emissions where formation may be occurring is to establish monitoring stations around landfill sites to measure the ambient concentrations of the compounds of interest. The ambient concentrations along with appropriate meteorological data can then be used in dispersion models to back-caleu late the emission rate from the landfill site. This is the method that was used to estimate vinyl chloride emissions from BKK and Oil. Landfill Emission Estimates. As previously stated, the largest source category of vinyl chloride emissions in California is landfills. Table III-1 summarizes vinyl chloride emission estimates for the state's landfills. As indicated in the table, vinyl chloride emissions have been estimated for BKK and Oil landfills. Although other landfills (Classes I, II, and III) throughout the state may emit vinyl chloride, the information necessary to estimate emissions is not available. Thus, total vinyl chloride emissions from landfills may be significantly greater than estimated in this report. The vinyl chloride emission estimates for BKK and Oil make several assumptions. These assumptions are: 1) vinyl chloride is emitted from A-29 CHA 010562 U a r\ iHi -7) h l Source TABLE III-l VINYL CHLORIDE LANDFILL EMISSION ESTIMATES* Source Emissions Type (tons/vearl Inventory Year Rfll. Class I Landfills BKK, West Covina Other Sites Class II Landfills Oil, Los Angeles Other Sites Class III Landfills Area Area Area Area Area 44-197 NA 4-51 NA NA 1987 1986 ARB, 1988b ARB, 1988b * - These emission estimates assume that the vinyl chloride emission rates are uniform throughout the year over the area of the landfill that is estimated to emit vinyl chloride. NA - Not Available2 an area of approximately 1,700,000 meters 2 for BKK and 330,000 meters ? for 011; 2) annual average emission rates of vinyl chloride from BKK and Oil are within the ranges estimated in Table II-4; and 3) emissions of vinyl chloride are uniform over the entire area of the landfill that is estimated to emit vinyl chloride. Although these assumptions add uncertainty to the emission estimates for BKK and Oil, ARB staff believe they are sufficient to infer that landfills represent the largest identified source category of vinyl chloride emissions in California. Based on 1987 monitoring data for BKK, ARB staff estimate a vinyl chloride emission rate ranging from 0.75 to 3.32 micrograms meter-11 second"* (see Table I1-4). For BKK landfill, this translates to estimated vinyl chloride emissions ranging from 44 and 197 tons per year. Over BKK's history it is not known how much vinyl chloride containing or halogenated wastes were disposed at the landfill. However, in 1984, BKK received approximately 136,000 tons of volatile or toxic wastes. An unknown portion of these wastes were halogenated solvents (ARB, 1982b). For Oil, ARB staff estimated a vinyl chloride emission rate ranging from 0.31 to 4.42 micrograms meter- second-1 A-30 CMA 010563 (Table II-4). For the Oil landfill, this translates to estimated vinyl chloride emissions ranging from 4 and 51 tons per year. The amount of halogenated wastes disposed at Oil over its history is unknown. However, in 1982, Oil received 9,200 tons of volatile or toxic wastes. As with BKK, an unknown portion of these wastes were halogenated solvents (ARB, 1982a). Other than for BKK and Oil, vinyl chloride emissions have not been estimated for any of the state's landfill sites. However, based on test results from several Class II and Class III landfills, it is expected that many other landfills in California are vinyl chloride emission sources. Monitoring results available for several other landfills are as follows: Flux measurements on the surface of the Scholl Canyon sanitary landfill (a former Class II landfill located in Glendale, California) showed vinyl chloride concentrations ranging from non-detectible to 180 ppbv (parts per billion by volume) at various locations (Todd and Propper, 1985). In addition, tests conducted by the SCAQMD at several other Class II landfill sites from 1981 to 1985 confirmed the presence of vinyl chloride in landfill surface gas or gas collection system (Coy, 1985). To partially address the lack of monitoring data from other landfills throughout in the state. Health and Safety Code Section 41805.5 (AB 3525 and subsequent amendments by AB 3374) requires the development and implementation of landfill monitoring guidelines and the reporting of monitoring results. The law requires the ARB to establish guidelines to monitor gas migration, gas constituency, and the ambient air at many of the hazardous and municipal waste landfills in California (ARB, 1986; ARB, 1987). The testing guidelines identify vinyl chloride as one of the compounds requiring monitoring. Landfill operators were required to report their results by July 1, 1987 with provisions for an extension of not later than January 1, 1989. Presently, results for 386 municipal and hazardous waste landfills have been received by the ARB. Of these 386 landfills, 288 performed landfill gas testing with vinyl chloride detected in the gas of 136 sites. Concentrations of vinyl chloride in the landfill gas of the tested sites ranged from below detection to 120 ppm. As these monitoring results are evaluated, they will be helpful in identifying which landfills could be expected to emit vinyl chloride and warrant further monitoring studies or mitigation measures. 3. Sas Collection Systems For many landfills emissions are required to be controlled to reduce odors as well as emissions of methane and toxicants. However, A-31 CMA 010564 DRAFT gas control systems have been installed at some landfills as a resource recovery and/or energy conservation measure. For example, BKK transmits collected landfill gases to either one of two flare stations and/or to a five megawatt gas turbine for use as a fuel in generating electricity. Both well (vertical piping) and trench systems (horizontal piping) are used to collect landfill gases. In 1983, BKK installed a number of wells and gas collection lines to help control gaseous emissions. Although there are still potential sources of gaseous emissions such as cracks at the landfill surface, pipe connections and valves, and burner exhaust, ambient concentrations of vinyl chloride near BKK have been declining. Since installing their gas collection system, BKK has continued to expand the system by adding wells and trenches. Since installing a gas collection system at Oil, ambient concentrations at the perimeter of the facility have continued to decline. Due to the lack of violations of the state standard for vinyl chloride (10 ppb), ambient monitoring at the perimeter of Oil was discontinued by the SCAQMD in early 1987. A well system consists of a network of wells drilled vertically into the refuse to collect the generated gases. These wells are connected to collection pipelines where gases are withdrawn from the buried layers of waste. In general, a vertical gas well is constructed by drilling a 30-inch diameter hole 50 to 100 feet deep into the wastes. Perforated PVC pipes are then placed inside the hole. The space between the pipe and the hole is backfilled with uncrushed gravel (Sanitation Districts of Los Angeles County, 1984). A typical gas control system showing both well and trench systems is shown in Figure III-3. FIGURE III--3 LANDFILL GAS COLLECTION SYSTEM FLARING STATION OR GAS COLLECTION TRENCHES Source: Sanitation Districts of Los Angeles, 1984 ~ A-32 CMA 010565 n w a ci tJ i ii 11 3 In the trench system, a network of perforated pipelines is laid in trenches within the waste at approximately 200-foot intervals horizontally and 80-foot intervals vertically. To support the pipes and to allow the migration of the generated gases, approximately 2 feet of uncrushed gravel are packed around the pipelines. These pipelines are then connected to a main collection pipe where gases are withdrawn (Sanitation Districts of Los Angeles County, 1984). D. OTHER KNOWN EMISSION SOURCES Other than landfills, emissions of vinyl chloride emissions occur from: PVC production and fabrication, publicly-owned treatment works (POTWs), ethylene dichloride production, vinyl chloride production, methyl chloroform production, caprolactam production, and incomplete incineration of chlorine containing materials (Sittig, M., 1981; Zwiacher et al., 1983; and Lamorte, M., 1978). In California, the identified sources of vinyl chloride emissions that can be quantified are PVC production, PVC fabrication, and POTWs. Table III-2 provides estimates of vinyl chloride emissions for identified sources. Currently, there are no known vinyl chloride, ethylene dichloride, methyl chloroform (TCA) or caprolactam production facilities operating in the State. TABLE III-2 SUMMARY OF VINYL CHLORIDE EMISSION ESTIMATES FOR OTHER SOURCES Source Source Emissions Ivoe Tons/Year Inventory Year Reference PVC Production Point P-VC. Fabrication Point POTWs Point Qn^i-ite- Wastewater Treatment Plants Point Waste Incinerators Point Transportation and Accidental Spillage Area NA - Not Available <0.5 0.75 1.7 NA NA NA 1988 1982 1985 ARB, 1988b Zwiacher, et al., 1983 Chang et al., 1987 A-33 CMA 010566 lJ 3'1A F T 1. Polvvinvl Chloride (PVC1 Production Three PVC producers reported emitting a cumulative total of 3 tons of vinyl chToride in 1984 (Personal Communication, 1985a, 1985b, and 1985c). In 1982, vinyl chloride emissions from these producers were estimated to be 1.4 tons (Zwiacher, W. et al., 1983). All three producers reported that they were in compliance with South Coast Air Quality Managment District's (SCAQMD's) Rule 1163. This rule requires that vinyl chloride emissions from designated plants not cause ambient vinyl chloride levels to exceed 10 ppbv (parts per billion by volume) during any 24-hour period when measured beyond the plant's property line (Personal Comnunication, 1985a, 1985b, 1985c; and AR8, 1980). Rule 1163 was adopted by SCAQMD as part of their program to control vinyl chloride emissions to 10 ppbv. In 1984, the PVC producers operating in the State reported using closed systems, incineration, routine leak surveys, and maintenance programs as control technologies to comply with existing standards for vinyl chloride emissions (Personal Communication, 1985a, 1985b, and 1985c). The primary control method used by the two PVC producers currently operating in California is incineration. One facility (facility A) uses an afterburner with an operating temperature of approximately 2000F while the other facility (facility B) uses a catalytic type incinerator. Both facilities have a monitoring system that continuously measures the vinyl chloride concentration within various areas of the plant. Portable hydrocarbon (HC) detectors are used to pinpoint leaks detected by the area monitoring system. These plants are also inspected at least once a year by the SCAQMD Enforcement Division to ensure compliance with district rules (Personal Communication, 1985d). The SCAQMD periodically conducts ambient monitoring for vinyl chloride near the two PVC producers in-California. In addition to the SCAQMD's monitoring program, the SCAQMD requires one of the PVC producers (facility A) to monitor the ambient air for vinyl chloride at the perimeter of their facility on a daily basis. The other PVC producer (facility B) is not required by the SCAQMD to conduct ongoing offsite ambient monitoring for vinyl chloride. This is because: 1) historically, the facility has not exceeded the Ambient Air Quality Standard for vinyl chloride; and 2) the process that is used to manufacture latex emulsions is not expected to result in vinyl chloride emissions as great as those associated with the other facility which produces PVC resins. Generally, 24-hour average concentrations near these facilities are below the 10 ppb standard. However, in October of 1988, the SCAQMD reported concentrations as high as 20 ppb for facility A (Molita, 1989). As a result, the SCAQMD plans to conduct ambient monitoring more frequently at this facility to ensure compliance with the ambient air quality standard for vinyl chloride. The SCAQHD's A-34 CMA 010567 m monitoring results indicate that this PVC producer may contribute to the public's exposure to vinyl chloride. Therefore, this facility should be investigated in more detail when considering control measures to reduce the public's exposure to vinyl chloride. Table III-2 lists the cumulative vinyl chloride emissions estimates from the two PVC producers in California at less than 0.5 tons for 1987. This estimate is substantially lower than the 1984 estimate of 3 tons when three PVC producers were operating in California (Personal Communication, 1985a, 1985b, 1985c). 2. Polwinvl Chloride Fabrication Polyvinyl chloride (PVC) can be fabricated into several products such as PVC pipes, pipe fittings, plastics, etc. Some major fabrication processes are extrusion (to shape by forcing through a die), calendering, molding, and bonding. PVC contains the vinyl chloride monomer as a residual from the PVC production processes. Residual vinyl chloride (RVC) in PVC ranges from 0.002 ppmw (parts per million by weight) to 10 ppmw (U.S. EPA, 1982). When PVC is fabricated into final products, vinyl chloride is emitted. The SCAQMD identified 33 PVC handling and fabrication facilities under its jurisdiction with an estimated usage of 75,000 tons of PVC in 1982. The SCAQMD staff assumed that all vinyl chloride is emitted from the fabrication processes. Using this assumption and a maximum RVC of 10 ppmw in PVC, the SCAQMD estimated that these handling and fabrication facilities emitted approximately 0.75 ton of vinyl chloride in 1982 (Zwiacher, 1983). This estimate represents an upper bound condition because the maximum RVC was used to estimate emissions, and because all RVC from the incoming PVC was assumed to be emitted from the fabrication processes. The vinyl chloride migration studies conducted by the Environmental Protection Agency (EPA) indicated a much smaller percentage of monomer is released during fabrication (U.S. EPA, 1982). A typical release of vinyl chloride in the extrusion process was only 10 percent of that in the PVC (U.S. EPA, 1982). 3. Publicly-Owned Treatment Works Publicly-owned treatment works (POTWs) are wastewater treatment plants that are owned by public entities, and which consist of wastewater collection systems, wastewater and sludge treatment facilities, and effluent and sludge disposal systems. Users that discharge wastewater into POTWs are normally classified as commercial, industrial, and residential. The two primary mechanisms that result in emissions of organic gases are volatilization and biodegradation. Because POTWs treat wastewater which can contain vinyl chloride and A-35 CMA 010568 halogenated compounds from industries, vinyl chloride can be volatilized during the treatment processes. In addition, chlorinated hydrocarbons such as trichloroethylene and 1,2-dichloroethane could be biodegraded to vinyl chloride. Halogenated hydrocarbons including vinyl chloride have been measured at wastewater treatment plants throughout the nation, including California (U.S. EPA, 1980). A preliminary study of two wastewater treatment plants, one in Los Angeles and another in the Sacramento Valley, indicated that vinyl chloride is present in the anaerobic digester tanks. Concentrations of up to 2.6 ppmv have been measured (ARB, 1985). These digester tanks are equipped with pressure/vacuum (P/V) valves to equilibrate the inside and outside pressure of the tanks. These P/V valves are potential sources of vinyl chloride emissions along with fugitive emissions associated with pipe fittings and valves. In a study performed by the University of California at Davis (UCD), researchers used a mass balance approach to estimate that approximately 1.7 tons of vinyl chloride were emitted by POTWs in California in 1985 (Chang et al., 1987). Specifically, the difference between the concentration of vinyl chloride in the POTW influent and effluent was assumed to be emitted to the atmosphere. This approach may be useful in assessing which POTWs constitute a threat to public health. However, because this approach does not take into account the formation or degradation of vinyl chloride within POTWs, the resulting emission estimates should only be considered rough approximations. In response to the need for more information concerning emissions of toxicants from POTWs, ARB is currently funding a research contract. When the research is complete, the resulting report will contain the most recent information concerning the estimation of emissions of toxicants from POTWs and POTW collection lines. The report will also address the efficacy of POTW odor control systems on reducing emissions of toxic compounds. E. OTHER POTENTIAL EMISSION SOURCES Along with the sources discussed in Section D, there are several other potential sources of vinyl chloride emissions in California. These include on-site wastewater treatment plants, incineration of PVC materials, and transportation of vinyl chloride. 1. On-Site Wastewater Treatment Plants As presented in the discussion on POTWs, wastewater treatment facilities are sources of vinyl chloride emissions. At several industrial facilities such as oil refineries, chemical manufacturers. A-36 CMA 010569 DRAFi etc., industrial wastewater is normally treated before being discharged. These wastewater treatment plants are also potential sources of vinyl chloride emissions. 2. Waste Incinerators Vinyl chloride has been identified as a combustion product in the flue gas of an incinerator burning plastics (Boettner et a 1., 1973). It has also been hypothesized to form upon the combustion of PVC materials (Ahling et al., 1978). PVC materials are used extensively in automobile's upholstery, bumper parts and floor mats; when these materials are incinerated, vinyl chloride is a likely pollutant in the incinerator exhaust. Hospital waste incinerators are another potential source of vinyl chloride emissions since much of the hospital waste such as syringes and plastic bags are PVC-containing materials. 3. Transportation and Accidental Spillage Another potential source of emissions is the accidental spillage and/or leakage of vinyl chloride that is being transported either by rail car, tank car, or marine vessel. Vinyl chloride is transported by rail cars to the two PVC producers currently operating in California. As far back as records are available, there have been no reported accidents involving vinyl chloride in the State (Office Of Emergency Services, 1985; California Highway Patrol, 1985). A-37 CMA 010570 REFERENCES TO CHAPTER III Ahling, 8.; Bjorseth, A., Lunde, G., 1978. "Formation of Chlorinated Hydrocarbon During Combustion of Polyvinyl Chloride," Chemosphere. 1(10): 799806. Air Resources Board (ARB), 1980. "Response to Petition Pursuant to California Health and Safety Code Section 40451 to Review Adoption of Rule 1005.1, Control of Vinyl Chloride Emissions by the South Coast Air Quality Management District," Sacramento, CA. ARB, 1982. "Suggested Control Measure to Reduce Organic Compound Emissions Associated with Volatile Organic Waste Disposal," Stationary Source Division, Sacramento, CA. ARB, 1982. "An Assessment of the Volatile and Toxic Organic Emissions from Hazardous Waste Disposal in California," Stationary Source Division, Sacramento, CA. ARB, 1985. Memorandum from Ken Jones to Dean Simeroth on "Source Tests for Vinyl Chloride and other VOC at Sewage Treatment Plants" dated October 1985, Engineering Evaluation Branch, Stationary Source Division, Sacramento, CA. ARB, 1986. "Testing Guidelines For Active Solid Waste Disposal Sites," Prepared Pursuant to California Health and Safety Code Section 41805.5, Stationary Source Division, December 1986. ARB, 1987. "Hazardous Waste Disposal Testing Guidelines," Prepared Pursuant to California Health and Safety Code Section 41805.5, Stationary Source Division, January 1987. ARB, 1988a. Memorandum from Andrew Ranzieri to Joan Denton concerning "Updated Vinyl Chloride Expsure Results for BKK and Oil Landfill," Modeling Support Section, May 1988. ARB, 1988b. "Survey of California PVC producers," January 1988. Beeman, C.P. et al., 1978. "Survey of Trihalomethane Distribution in Various Potable Water Supply Sources in the State of Florida," Final Report to the State of Florida, Department of Environmental Regulation, Tallahassee, FL. Boettner, E.A., et al., 1973. "Combustion Products from the Incineration of Plastics," U.S. EPA, Report No. 67-12-73-049, Cincinnati, QH. 8SK & Associates, 1987. "Solid Waste Assessment - Air: City of Clovis Landfill," Job No. 87147. Fresno, CA. A-38 CMA 010571 Chang, D.P.Y.; Schroeder, E.D.; Corsi, R.L., 1987. "Emissions of Volatile & Potentially Toxic Organic Compounds from Sewage Treatment Plants and Collection Systems," U.C. Davis, Department of Civil Engineering, Davis ,CA. Chemical and Engineering News. 1984. "Additives Sales Buoyed by PVC Recovery," June 18, 1984. Chemical and Engineering News. 1985a. "Production by the U.S. Chemical Industry," June 10, 1985. Chemical and Engineering News. 1985b. "Product Report," June 3, 1985. Chemical and Engineering News. 1987. "Facts and Figures for the Chemical Industry," June 8, 1987. California Highway Patrol, Operational Planning Section, Sacramento, CA. Chemical Marketing Reporter. June 24, 1985, pp. 3, 5, 24, and 27. Cline, P.V., and Viste, D.R., 1984. "Migration and Degradation Patterns of Volatile Organic Compounds," Municipal and Industrial Waste, Annual Madison Waste Conference, 102(26): 14-29. Coy, C., 1985. Attachments of the letter from Carol Coy of the South Coast Air Quality Management District (SCAQMD) to Ralph Propper of the CARB on September 25, 1985. SCAQMD, El Monte, CA. Eljumaily & Butter Associates (EBA), 1987. "Air Quality Solid Waste Assessment Test Report for Will its Solid Waste Disposal Site," Santa Rosa, CA. Hartley, G.S., 1969. Evaporation of Pesticides - Formulation Research, Physical, and Colloidal Chemical Aspects, Advance Chemical Series. 86, pp. 115-134. Hwang, S.T., 1982. Toxic Emissions from Land Disposal Facilities, Environmental Progress. Vol. 1, pp. 46-52. Kleopfer, R.D.; Easley, D.M.; Haas, B.B. Jr.; Deihl, T.G. 1985. "Anaerobic Degradation of Trichloroethylene in Soil," Environmental Science and Technology, 19(3): 277-280. Lamorte, M., 1978. "National Emission Standards for Hazardous Air Pollutants - Inspection Manual for Vinyl Chloride," prepared for U.S. Environmental Protection Agency by Research Triangle Institute, PB 289778, Research Triangle Park, NC. A-39 CHA 010572 McPherson, W., et al., 1979. Hydrocarbon Processing, "Vinyl Chloride Monomer - What You Should Know," March 1979. Molita. D., 1989., Telephone conversation between Richard Corey of ARB and Dave Molita of SCAQMD, April 1989. Molton, P.M.; Hallen, R.T.; Pyne, J.W., 1987. "Study of Vinyl Chloride Formation at Landfill Sites in California," Prepared for the CARB under contract # A4-154-32 and 2311206978. Battelle, Pacific Northwest Laboratory. Richland, WA. Office of Emergency Services, Planning Division, Sacramento, CA. Parson, et al., 1984. "Transformations of Tetrachloroethene and Trichloroethene in Microcosms and Groundwater," Journal of the American Water Association. February 1984. Personal Communication, 1985a. Telephone conversation between Pacita Ayala.of ARB and PVC producer A, September 1985. Personal Communication, 1985b. Telephone conversation between Pacita Ayala of ARB and PVC producer B, September 4, 1985. Personal Communication, 1985c. Telephone conversation between Pacita Ayala of ARB and PVC producer C, August 28, 1985. Personnel Communication, 1985d. Telephone conversation between Pacita Ayala of ARB and Karen Haaclc of SCAQMD, October 1, 1985. Sanitation Districts of Los Angeles County, 1984. "Spara Landfill and Resource Conservation Project," State Clearing House # 84053011, Whittier, CA. Sarokin et al., 1985. "Cutting Chemical Waste - An INFORM report," INFORM, Inc., New York, NY. Shen T.T., 1981. Estimating Hazardous Air Emissions from Disposal Sites, Pollution Engineering. August 1981, pp. 31-34. Sittig, M., 1981. "Vinyl Chloride and PVC Manufacture," Noyes Data Corporation, Park Ridge, N.O. Thidobeaux, J.J., 1981. Estimating the Air Emissions of Chemicals from Hazardous Waste Landfills, Journal of Hazardous Materials. 1981(4): 235-244. Todd, D. and Ralph Propper, 1985. "Method to Determine Emissions and Possible Health Effects of Organic Compounds from California Landfills," California Air Resources Board, Sacramento, CA. A-40 010573 CM* U.S. Department of Commerce (U.S. DOC) - Bureau of Census. U.S. Fynnr^, FT410 and FT 446. Annual 1974-1984. U.S. DOC - Bureau of Census. U.S. Imports for Consumption and General Imports. FT 246, Annual 1974-1984. U.S. DOC -International Trace Commission. Construction Review. Bi-monthly Industrial report. Washington, DC. U.S. Department of Health and Human Services, 1978. "Vinyl Chloride: An Information Resource," DHEW Publication Ho. (NIH) 79-1599. U.S. Environmental Protection Agency (U.S. EPA), 1980. "Fate of Priority Pollutants in the Publicly Owned Treatment Works - Final Report, Volume I and II," EPA 440/1.82/303, PB83-122/88, Washington, D.C. U.S. EPA, 1982. "Vinyl Chloride - A Review of National Emission Standards," Prepared by TRW Inc., for U.S. EPA, EPA-450/3-82-003, NTIS no. PB-114-354, Research Triangle Park, N.C. Water Resources Quality Control Board, 1987. Data retrieved from computer database consists of information as required by the Caledron Bill (AB 2535)Jonathan Mulder. Sacramento, CA. Wood, P. R., et al., 1980. "Removing Potential Organic Carcinogens and Precursors from Drinking Water," EPA Report, EPA-600/2-80-130a, U.S. EPA, MERL, Cincinnati, OH. Zwiacher, W.; Yuhas, L.D.; Fakhoury, J.S.; Whittacker, J.L.; Grisinger, J., 1983. "Emissions of Potentially Toxic/Hazardous Air Contaminants in the South Coast Air Basin," Engineering Division, South Coast Air Quality Management District, Los Angeles, CA. A-41 CMA 010574 IV. PERSISTENCE IN THE ATMOSPHERE A. PHYSICAL PROPERTIES The chemical structure of vinyl chloride (chloroethene, chloroethylene) is CH2CHC1. Vinyl chloride is a sweet smelling, colorless gas at ambient temperature and pressure. It polymerizes in light or in the presence of a catalyst. Vinyl chloride is readily flammable and forms explosive mixtures in air. Upon combustion, it is degraded mainly to hydrogen chloride gas, carbon monoxide, carbon dioxide and traces of phosgene. Vinyl chloride is expected to volatilize rapidly from water systems. Experimental data indicate that for an initial concentration of 1 ppm at a solution depth of 6.5 cm and a stirring rate of 200 rpm, the average evaporative half-life of vinyl chloride at a temperature of approximately 25C is 27.6 minutes (Dilling, 1977). Another study determined that distilled water spiked with 16 ppm vinyl chloride lost 96 percent of the vinyl chloride within two hours (U.S. EPA, 1974). Although it is soluble in ethanol, industrial solvents, and a number of organic liquids, vinyl chloride is only slightly soluble in water. Vinyl chloride's physical properties are shown in Table IV-1. B. ATMOSPHERIC PERSISTENCE Reaction with hydroxyl radicals is the dominant mechanism removing vinyl chloride from the troposphere (1980; Atkinson, 1986a). Estimates of vinyl chloride's tropospheric lifetime range from 0.5 to 5.8 days. However, for reasons provided later in this section, ARB staff believe that a tropospheric lifetime ranging from 1.6 to 3.9 days is representative of typical atmospheric conditions. The rate at which this reaction proceeds depends on the temperature and the tropospheric A-42 CMA 010575 t=\ a r 5 I $*' JMi sTM U V\ i TABLE IY--1 PHYSICAL PROPERTIES OF VINYL CHLORIDE Prooerties Value Boiling point, 1 Atm -13.37 C Molecular weight 62.5 Vapor Pressure, 20 C Sol. in water, 25 C 2530 mmHg O.llg/lOOg H20 Partition Coeff.H20/air 10C 0.02 Octanol/HgO Partition Coeff. 20.7 Specific gravity, 20/4 C 0.912 Flash pt. open cup 3 Liq. Dens. -14.2 Cg/cm -77.8 C 0.969 Heat capacity, 27C 16.1 Reference Merck Index, 1983 Merck Index, 1983 Merck Index, 1983 Kirk-Othmer, 1980 McConnell ,G., et al. , 1975 Withey, 1976 Kirk-Othmer, 1980 Kirk-Othmer, 1980 Kirk-Othmer, 1980 CRC Handbook, 1985 concentration of both vinyl chloride and hydroxyl radicals. The temperature dependence of the reaction rate is incorporated in the rate constant for the reaction of vinyl chloride with hydroxyl radicals. The product of the rate constant and both species concentrations gives the rate at which vinyl chloride is being degraded (Finlayson-Pitts and Pitts, 1986). The tropospheric lifetime of a compound is an estimate of the time required for a given amount of the compound to decrease to 1/e (0.368) A-43 CMA 010576 of its original concentration (at time zero). The tropospheric lifetime (r) of vinyl chloride is related to the rate constant (k) and the hydroxyl radical concentration ((.OH]) by the equation (1): r = (k[.OH]) (1) In deriving the above equation, it is assumed that hydroxyl radicals are at a constant or steady state concentration in the troposphere. Estimates have been made for the rate constant resulting from vinyl chloride's reaction with hydroxyl radicals. Perry et al. (1977) estimated the absolute rate constants over the temperature range of 299 Kelvin (K) to 426K. The limiting high pressure rate constant^for a temperature of 299K.is estimated to be 6.60 - 0.66 x 10*16 crir molecule -1 second . Howard determined rate constants for the reaction of vinyl chloride with hydroxyl radicals at 296K over a range of pressure where the highest pressure employed had not reached the limiting high pressure regime (Howard et al., 1976). However, when data obtained by Howard are extrapolated to the highpcessure limit, the resulting rate constant is approximately 7 x 10"l cmJ molecules-1 second-1 (Perry et al., 1976). This is in good agreement with the value reported by Perry et al. Table IV-2 sunmarizes the rate constant estimates, atmospheric lifetime estimates, average temperature assumed, and the method used to estimate the rate constant for the reaction of vinyl chloride with hydroxyl radicals and ozone (Og). The 24-hour average hydroxyl radical concentration in thefi troposphere has been estimated to range from 3 x 10 to 3 x 10 molecules cm-3 (Hewitt & Harrison, 1985). Because hydroxyl radicals are only present during daylight, the actual range for daytime concentrations is twice the 24-hour averages given above while nighttime concentrations are essentially zero. Daytime hydroxyl radical concentrations vary depending on many factors including photolytic activity and the concentration of ozone as well as other pollutants in the troposphere. Using the rate constant determined by Perry et al. for an average tropospheric temperature of 299K and a rangefiof hydroxyl radical concentrations ranging from 3 x IQ3 to 3 x 10 molecules cm , the estimated tropospheric lifetime for vinyl chloride ranges from: C* 0.6 days for [.OH] 3 x 10 molecules cm to C3 5.8 days for [.OH] 3 x 10 molecules cm A-44 CMfS 010577 TABLE IV-2 ATMOSPHERIC LIFETIME AND REACTION RATE CONSTANT ESTIMATES FOR VINYL CHLORIDE Reactant Rate3 Constant Temperature (Kelvinl Method Atmospheric Lifetime (days) References OH 6.6 - 0.66 x 10~*12 * * * 2*99 3 2.45 - 0.45 x 10"19 298 3 2.3 x IQ'19 NR 3 6.5 x 10"21 295 FP-RFC S-FTIR S-FTIR s-uv3 1.6 - 3.9d 47f 50 4.9 years Perry et al., 1977 Zhang et al., 1983 Gay et al., 1976 Sanhueza et al. 1976 a - Rate constant units are cm3 molecule-1 second-1 b - The atmospheric lifetime is defined as the time required for a given amount of the compound to decrease to 1/e (0.368) of its original concentration (at time zero). c - FP-RF = Flash photolysis, resonance flourescence. d - Assumes a 24-hour average hydroxyl radical concentration ranging from 0.5 x 10 to 1 x 10 molecules cnfJ (Cupitt, 1980). e - S-FTIR = Static system, Fourier transform infrared absorption spectroscopy. f - Assumes a 24-hour average 0- concentration of 1 x 10 12 molecules cm-3 (Singh et al., 1978). J g - S-UV Static system, ultraviolet absorption. NR- Not Reported A-45 CMA 010578 As previously indicated, the concentration of hydroxyl radicals in the troposphere can vary considerably. However, several researchers recommend 24-hour average hydroxyl radical concentrations which are between 0.5 x 10 and 1 x 10 molecules cm~J (Prinn et al., 1987; Winer, 1987; Singh et al., 1983; Cupitt, 1980; Cox et al., 1976; Davis et al., 1976). By using this range of 24-hour average hydroxyl radical concentrations (0.5 x 10 to 1 x 10 molecules cm"J) in conjunction with the rate constants determined from Perry's rate constant at 299K, the resulting range in atmospheric lifetimes is from 1.6 to 3.9 days. Using Howard's adjusted rate constant derived by extrapolating to the high pressure limit, and,the same range of hydroxyl radical concentrations (0.5 x 10 to 1 x 10 molecules cm J), the atmospheric lifetime estimates for vinyl chloride ranges from 1.6 to 3.3 days. The initial step in the reaction of vinyl chloride with hydroxyl radicals proceeds by the addition of hydroxyl radical to the carboncarbon double bond. Although subsequent steps in the reaction mechanism are unknown, reaction products have been identified (Atkinson, 1986b). The major product resulting from hydroxyl radical attack on vinyl chloride is formyl chloride. An ARB sponsored study demonstrated that the yield of formyl chloride from the reaction of hydroxyl radicals with vinyl chloride is unity (one molecule of formyl chloride for each molecule of vinyl chloride) within the experimental error of the study (Pitts et al., 1984). The observed unit yield of formyl chloride implies a corresponding unit yield of formaldehyde and shows that the reaction of vinyl chloride with hydroxyl radicals proceeds by essentially 100 percent cleavage of the double bond. Equations (2) through (6) summarize the overall reaction scheme which seems most likely (Pitts et al., 1984). .OH + CHg.CHCl--------> hoch2chci (2) 2 0-0. HOCHjCHCl ------ ------- > hoch2chci (3) 1-0. H0CH. HC1 + NO ---------------- > 9H0CH2CHC1 + no2 (4) hoch`2hci ---------------- > L .CH-0H + HC0C1 (5) (formyl chloride) .CH-0H 0--------------> HCH0 * (formaldehyde) .HOL. (6) A-46 CMA 010579 Under atmospheric conditions, the reaction of vinyl chloride with ozone-is not expected to be important compared to its reaction with hydroxyl radicals (Atkinson, 1986a; Atkinson and Carter, 1984). Several rate constant estimates have been made for the reaction of vinyl chloride with ozone. Based on these rate constants, atmospheric lifetime estimates range from about 47 days to approximately 5 years (Zhang et a 1., 1983; Sanhueza et al., 1976). Table IV-2 summarizes the atmospheric lifetime and rate constant estimates along with other pertinent information for vinyl chloride's reaction with ozone. Due to the variability among the estimated rate constants, a review publication made no recommendations as to the rate constant for the reaction of vinyl chloride with ozone (Atkinson and Carter, 1984). Furthermore, because the reaction of 0. with vinyl chloride can be complicated by secondary reactions, the rate constants provided in Table IV-2 should be considered to be upper bound limits. Products resulting from the reaction of ozone with vinyl chloride in the absence of scavengers are formyl chloride and formic acid (Zhang et. al., 1983). Other products resulting from the reaction of ozone with vinyl chloride include carbon monoxide, carbon dioxide, formaldehyde, and hydrochloric acid (Gay et al., 1976; Zhang et al., 1983). As stated, the most important atmospheric removal mechanism for vinyl chloride is its daytime reaction with hydroxyl radicals. Vinyl chloride does not absorb in the actinic ultraviolet region, hence photolysis need not be considered. Reaction with nitrate radicals (.NO.) may participate in the atmospheric removal of vinyl chloride. However, no kinetic data for .NO. are available, and studies of .NO. reactions are not yet sufficiently advanced that lifetime estimatesJcan be made (Finlayson-Pitts and Pitts, 1986). Little is known about the formation of vinyl chloride in the atmosphere. However, under experimental conditions, vinyl chloride has been shown to be a photodissociation product of 1,2-dichloroethane (Yano and Tschulkaw-Roux, 1980). In the study, 1,2-dichloroethane photodissociated when irradiated with ultraviolet light at 147 nanometers (nm) under pressure and in the presence of NO and CF4 additives. Although it was not the purpose of the study to identify vinyl chloride formation pathways, vinyl chloride was one of the photodissociation products. Since wavelengths of ultraviolet light below 290 nm do not reach the troposphere, this formation pathway is not important for vinyl chloride in the atmosphere. A-47 010580 REFERENCES TO CHAPTER IV Atkinson, R., 1986. Personal corimunication between Richard Corey of ARB Staff and Dr. Roger Atkinson of UCR. May, 1986. Atkinson, R., 1986. "Kinetics and Mechanisms of the Gas-Phase Reactions of the Hydroxyl Radical with Organic Compounds under Atmospheric Conditions," Chemical Reviews.. 6:69-201. Atkinson, R. and Carter, W.P.L., 1984. "Kinetics and Mechanisms of the GasPhase Reactions of Ozone with Organic Compounds under Atmospheric Conditions," Chemical Reviews.. 84:437-470. Cox, R.A.; Derwent, R.G.; Eggleton, A.E.J.; Lovelock, J.E., 1976. "Photochemical Oxidation of Halocarbons in the Troposphere," Atmospherir Environment. 10: 305-308. CRC Handbook of Chemistry and Physics, 1985. 66th Edition. Cupitt, L.T., 1980. "Fate of Toxic and Hazardous Materials in the Air Environment," Environmental Protection Agency, EPA-600/3-80-084, Research Triangle Park, North Carolina, August 1980. Davis, D.D.; Machado, G.; Conaway, B.; Oh, Y.; Watson, R., 1976. "A Temperature Dependent Kinetics Study of the Reaction of OH with CH,C1, CH,C1,, CHC13, and CH^Br," Journal of Chemical Physics. 65(4): 1268-1269. 3 22 Dilling, W.L., 1977. "Interphase Transfer Processes. II. Evaporation Rates of Chloromethanes, Ethanes, Ethylene, Propenes, Propylenes from Dilute Aqeous Solutions, Comparisons with Theoretical Prediction," Environmental Science and Technology. 11(4): 405-409. Finlayson-Pitts, B. J. and Pitts, Jr., J. N., 1986 " Atmospheric Chemistry: Fundamentals and Experimental Techniques," John Wiley & Sons Inc., 1986. Gay, B.W. et. al., 1976. "Atmospheric Oxidation of Chlorinated Ethylenes," Environmental Science and Technology. 10(1):58-67. Hewitt, C.N. and Harrison, R.M., 1985. "Tropospheric Concentrations of the Hydroxyl Radical - A Review," Atmospheric Environment. 19(4): 545-554. Howard, C.S., 1976. "Rate Constants for the Gas-Phase Reactions of OH Radicals with Ethylene and Halogenated Ethylene Compounds," Journal of Chemical Physics. 65(11).*4771-4777. IARC, 1979. Vinyl Chloride, Polyvinyl Chloride and Vinyl Chloride-Vinyl Acetate Copolymers. IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans. 19:377-438. A-48 % CMA 010581 Kirk-Othmer, 1980. Encyclopedia of Chemical Technology. 3rd Edition, Volume 23. John Wiley and Sons, Inc., New York. Lillian, D.; Singh, H.B.; Appleby, A.; Lobban, L.; Arnts, R.; Gumpert, R.; Hague, R.; Toomey, J.; Kazazis, J.; Anteil, M.; Hansen, D.; Scott, B., 1975. "Atmospheric Fates of Halogenated Compounds," Environmental Science and Technology. 9(12): 1042-1048. McConnell, G.; Ferguson, D.M.; Pearson, C.R., 1975. "Chlorinated Hydrocarbons and the Environment," Endeavour. 34 (121): 13-18. Merck Index, 1983. An Encyclopedia of Chemical, Drugs, and Biologicals, Tenth Edition, Merck & Co., Inc. Perry, R.A.; Atkinson, R.; Pitts, J.N., Jr., 1977. "Rate Constants for the Reaction of OH Radicals with CH?CHF, CH-=CHC1, and CH?*CHBr over the Temperature Range 299 - 426K."^Journal Of Chemical Phbsics. 67(2): 458-462. Pitts, J.N., Jr.; Atkinson, R.; Winer, A., 1984. "Formation and Fate of Toxic Chemicals in California Atmosphere," Final Report to California Air Resources Board Contract No. A2-115-32. Prinn, R.; Cunnold, D.; Rasmussen, R.; Simmonds, P.; Alyea, F.; Crawford, A.; Fraser, P.; Rosen, R.t 1987. "Atmospheric Trends in Methylchloroform and the Global Average for the Hydroxyl Radical," Science. 238(13): 945-950. Sanhueza, E.; Hisatsune, I.C.; Heicklen, J., 1976. "Oxidation of Haloethylenes," Chemical Reviews. 76(6): 801-826. Singh, H.B.; Ludwig, F. L.; Johnson, W. B., 1978. "Tropospheric Ozone: Concentrations and Variabilities in Clean Remote Atmospheres," Atmospheric Environment. 12:2185. Singh, H.B.; Salas, L.J.; Stiles, R.E., 1983. "Selected Man-made Halogenated Chemicals in the Air and Oceanic Environment," Journal of Geophysical Research, 88(C6): 3675-3683. U.S. EPA, 1974. "Preliminary Assessment of the Environmental Problem Associated with Vinyl Chloride and Polyvinyl Chloride," Office of Toxic Substances, Washington, D.C., EPA/560/4-74-001. Winer, A., 1987. Personal conwunication between Richard Corey of ARB staff and Arthur Winer of UCR. October, 1987. A-49 CMA 010582 Withey, J. R., 1976. "Pharmacodynamics and Update of Vinyl Chloride Monomer Administered by Various Routes to Rats," Journal of Toxicology and Environmental Health. 1: 381-394. Yano, T. and Tschulkaw-Roux, E., 1980. "A Reexamination of the Photodissociation of CHjCICHjCl at 147 nm. Test for Chlorine Atom Reactions," The Journal of Physical Chemistry. 84(25):3372-3377. Zhang, J.; Hataheyana, S.; Ahemoto, H., 1983. "Rate Constants of the Reaction of Ozone with Trans-1, 2-Dichloroethene and Vinyl Chloride in Air," International Journal of Chemical kinetics. 15:655-668. A-50 CHA 0*0583 CMA 010584 APPENDICES June 1989 CKA 010585 APPENDIX I SCAQMD'S ANALYTICAL METHOD FOR SAMPLING AND ANALYSIS OF ATMOSPHERIC VINYL CHLORIDE CMA 010S86 5"'3 4-7 t?.1\ rum: .,.- -AMBIENT AIR -SAMPLES AT LANDFILL PARIMETER - ~ - TREQULRED BY SUBPARAGRAPH (C) {4) CD) OF RULE ,1150.1)* " *' 7; ft SAMPLING FREQUENCY r-... .... ' - r'T t" Once per month or at less frequent intervals to be determined by the Executive Officer. The landfill owner/operator must file a written request with the Executive Officer if be wants to sample at intervals less frequent than nonthly. Such a re-guest must be supported with previous sampling results and ott^er documentation. In determining if the requested sampling frequency is appropriate, the Executive Officer will consider previous ambient air sampling results, landfill'surface sampling results, landfill gas composition and other pertinent data. The Executive Officer will notify the landfill owner/operator of his decision in writing. NUMBER Of-SAMPLES * -- . **. -T% * -/ ~^.l 7 . . . ' - - ' "*L > < The number of ambient-ear, samples required vill" depend -upon. the ;- -topography and the, sire .o-f the' tLandfiTi -:: - Jrty-g-jajtrinm^ . ^-n^-errs.;:t?jL. will be sited to provide good -meteoxological -exposure to.tbe ; < . . predominant offshore (drainage land breeze l.-and onshore (aea breeze) wind f1 ow patterns.' In 'area^ with -significant.aiopesy j; ^32- CMA 010587 * sampling locations roust be approved by the Executive Officer prior to sampling. SAMPLING CONDITIONS Ambient air sampling will be conducted on days when stable (offshore drainage) and unstable (onshore sea breeze) meteorological conditions are representative for the season. Preferable sampling conditions are characterized by the following meteorological conditions: 1. Clear cool nights with wind speeds tvo (2) miles per hour or less. 2. Onshore sea breezes with wind speeds 10 miles per hour or less. No sampling will be conducted if the following adverse meteorological conditions exist: 1* Rain 2. Average wind speeds greater than 15 miles; per hour for any 30 minute period. 0 3. Instantaneous wind speeds greater than 25 miles per hour. Continuously recorded on site wind speed and direction /. measurements will characterize the aicrometeorology of the site and' serve to verify that the meteorological criteria .have fceei^l -33- CHA 010588 met during sampling^ . EQUIPMENT DESCRIPTION An ambient air sampling unit consists of a 10-liter Tedlar (Dupont trade name for polyvinyl fluoride) bag, a DC operated pump, stainless steel capillary tubing to control the sample rate to the bag, a bypass valve to control the sample flow rate (and mimimize back pressure on the pump), a rotameter for flow indication to aid in setting the flow, a 24-hour clock timer to shut off the sampler at the end of the 24-hour sampling peri d, and associated tubing and connections (made of stainless steel, teflon, or borosilicate glass to minimize contamination and reactivity) . The^ physical layout of the sampler is shown in Figure 5 (see Appendix A). EQUIPMENT SPECIFICATIONS A. Power -- one 12v DC marine battery The marine battery provides 12V DC to the pump and the clock. B. Pump -- one 12V DC pump The diaphragm is made of non-lubricated Viton (Dupont trade name for co-polymer of hexafluoropropylene and vinylidene t- fluoride) rubber. The maximum pump unloaded flow rate is -34- CMA 010589 4.5 liters per minute. C. Bag -- one 10-liter Tedlar bag with a valve TEDLAR BAG IS ENCLOSED IN A LIGHT-SEALED CARDBOARD BOX TO PREVENT PHOTOCHEMICAL REACTIONS FROM OCCURING DURING SAMPLING AND TRANSPORTATION. The valve is a push-pull type constructed of aluminum and stainless steel, with a Viton o--ring seal. D. Rotameter Rotameter is made of borosilicate glass and has a flow range of 3 to 50 cubic centimeters per minute- The scale is in millimeters with major graduations (labeledJ every 5 nun and minor graduations every 1 mm. E. Air flow control orifice -- 316 stainless steel capillary tubing F. Bypass valve <S. Fittings, tubing, and connectors -- 316 stainless steel or teflon H. Clock timer Accuracy should be better than 1%. I. Wind speed and direction monitor with continuous recorder 1. wind speed -- 3 cup assembly, range 0 - 5*0 miles per hour with a threshold of 0.75 mile per hour or less. 2. Wind direction Vane, range 0 -- 540 degrees with a threshold of 0.75 mile per hour or less. -35- CMA 010590 SAMPLING PROCEDURES DRAF Ambient air samples will be collected at the perimeter of the'-^ll .... . . -T| landfi 11 over a 24-hour period beginning between iq a.M. and .'K 11 A.M* using the above described self-contained port*frle sampling units. The samplers will be placed at the approved locations as described previously. One or more wind speed and direction monitors with continuous recorders will be ins-tailed and operated in areas approved' by the Executive Officer to measure wind speed and direction throughout, the entire sampling period. The wind direction transmitter must be oriented to true north using a compass. QUALITY CONTROL PROCEDURE The following quality control procedure is required for the ambient air sampling operation: A. Assign an identification number to each sampling bag. E. Clearly mark sampling locations on a landfill topographic map which is drawn to scale. C. Document the date and time that the bag was put into operation, the sampling location, and the date and time that it was pulled from service. D. Check the clock timer. The clock tine and the actual time t should agree within + 3 mijiutes. 36 CM* 01059i r* v' r* iw O I U' 1 V **m *w E. Check whether or not the pump is running. \ u F. Check the rotameter reading. The float (measured at the middle) should be within +3 and -6 minor graduations of the marked setting for 6.0 cubic centimeters per minute. If the rotameter setting exceeds the above limits adjust the bypass valve to correct the flow rate. Make sure that the flow has stabilized (at least three minutes at constant flow) since there may be a lag time between the adjustment and final flow. G. Check whether the bag valve is in the open position. If the valve is in the closed position open the valve and and record the time on the quality control sheet. H. Remove the bag for analyses at the end. of the 24-hour period. KEP THE BAG IN A LIGHT-SEALED CONTAINER AT ALL TIMES. Data for each sample collected must be entered on a quality control sheet_ as shown in Figure 3 (see Appendix A) . Prior to use, the Tedlar bags should be evacuated and filled with purified nitrogen three times to flush out the old sample. Before sending the bags into the field, they should be checked to make sure that the vacuum has been maintained. Remove .from service any bag that has experienced any leakage. -37- 010592 ANALYTICAL PROCEDURES DRAFT1 Bag- samples collected must be analyzed within ?T hours of collection, or shorter period if notified fay the Executive Officer, for total organic compounds and toxic air-Contaminants using analytical methods identified in Tabie 1 (see Appendix A) or equivalent methods approved by the Executive Officer. NOTE THAT ALL BAG SAMPLES MUST BE KEPT IN LIGHT-SEALED CONTAINERS TO AVOID PHOTOCHEMICAL REACTIONS. REPORTING OF THE RESULTS The following data must be submitted to the Director of Engineering within A5 days after the end of the quarterly reporting period for the -landfill or 4 5 days after the analytical results are available whichever is sooner. A different submittal time may be implemented upon approval of the Executive Officer. A. Volume concentration of total organic compounds (reported - as methane and total non-methane hydroca rbons) . B. Volume concentration of toxic air contaminants identified in these guidelines. , C. Barometric sea level pressure (inches of mercury) on the d. the samples were collected. If a barometer is not availab at the landfill site, use the National Weather Service dat at the nearest station. -38- CMA 010S93 : ;O ; 9 *- i ' ~ r - i ,-it C VW J D. Wind speed and direction data. E. A drawn to scale landfillV topographic map with sampling locations clearly marked and numbered. F. Quality control data sheets. V -39- CMA 010594 t-. .t VINYL CHLORIDE ANALYSIS -- METHOD^ *i \ jj i i | ' Instrument: Hewlett Packard 5700A Gas Chromatograph Detector: Flame Ionization Injection System: Two Carle valves, a lO-port and a 4-port, are plumbed to contain a 4 ml, 1/4" stainles steel sample loop with pre-column, back-flus and pressure balance. See Figure D for valve plumbing. GC Conditions: Detector Temp. - 200C Oven Temp. - " 60C V Analytical Column - 6? x 1/4" ss, Chromosil 310, 60/80 mesh Pre-Column - 6' x 1/8" ss, Durapackm-octane/Porasil 100/120 mesh Carrier Gas - 80/100 ml/min nitrogen Data Gathering: A Hewlett Packard 3388A Integrator is used to calculate concentration by peak area comparisi to an external standard. Valve Timing: Timing and switching events are performed by th , integrator. 1.4 minutes after injection both 'v are switched to the back-flush or initial posit -64- 010595 RESTRICTION VALVE HusR\AniFT* MAIN COLUMN CARRIER IN SAMPLE LOOP - SAMPLE INJECTION PORT PRE-COLUMN AUXILIARY CARRIER FIGURE D: Valve Pi umb i r : -65- CMA 010596 "A Standard: Approximately 1 Ppm vinyl chloride is prepared by ScotEnvironmental Technology and certified to 2% analysis. Range: 2 ppb to 1% vinyl chloride Accuracy: i 1 ppb in the range 2 - 50 ppb, * 2 in the range 50 ppb to 1% \ -66- CMA 01059? u T\ CMA 010598 APPENDIX II DESCRIPTION OF GLEIT'S METHOD ORAFi CMrt 010600 APPENDIX II DESCRIPTION OFGLEITS METHOD Gleifs method accounts for the concentrations below the LOD by setting them equal to the "below -LOD mean" PBLOD* cf the portion of the normal distribution below the LOD. Setting the unknown concentrations to their average value seems intuitively reasonable, and the simulations reported in Clefts paper show that his method is more accurate than other commonly used approximations. The below-LOD mean of a normal distribution of a variable v/sth a limit of detection L is given, in terms of L and the mean n and the standard deviation a of the distribution, by equation 1: HBLOD - P- * M f((L-jiVd) / F((L-ji)/c) ] (1) * In equation (1), f and F are, respectively, the probability density function and cumulative distribution function of the standard normal distribution. The "Estimated Concentrations for Samples Below the LOD" reported in Table 11-2 are the below-LOD means of the assumed lognormal distributions of She concentrations. These below-LOD means are computed from equation (2) in terms of parameters of the associated normal distribution: the LOD L, the mean concentration from Table 11-2, and the estimated standard deviation (which is not tabulated). exp (p.+0.5* o2)* F((L-p.-o^)/o) / F(L-p/o) (2) We now describe how Glefts method estimates the mean and variance of the assumed normal distribution. The mean and variance cannct be estimated by merely substituting into standard formulas, if below-LOD concentrations are to be set-to the below-LOD mean. On the one hand, the mean and variance must be known in order to calculate the below-LOD mean from (1); on th oth r hand. CMA 010601 -1- the below-LOD mean must be known if it is to be used in the calculation df the 4 mean and variance. Statistical theory, by asserting that a "best -fitting * mean and variance for the distribution exist, provides a way out of this dilemma. Gteit uses a simple iterative procedure to compute these best fitting parameters. Since his procedure can be simply described in words, a written description is given, supplemented where necessary by equations written in a notation more convenient than Gleitis. Starting with initial guesses p.(0) and 0^(0) for the mean and variance, the procedure repeatedly generates new estimates of the mean and variance by the two-step computation described below until successive estimates of the mean and variance converge sufficiently (The K-th pair of estimates are denoted by *i(K) and c^K).). The two steps are: (a) The K+1 -st below-LOD mean pbLOD(k+`i ) is computed by substituting p(K) and a(K) (the square root of c^K)) into equation (1). (b) The K+1-st estimate of the mean, p(K+1), is computed in the usual way with HBLOD(K+1) substituted for the sample values below the LOD. The K+1-st estimate of the variance, o^(K+1), is also computed in the usual way, with an analogous substitution for sample values below the LOD: the squared deviations from the mean of concentrations below the LOD are set equal to the average squared deviation from the mean of the below-LOD portion of tine distribution. Let the N sample items be X(1),....X(N), and let p be the number of sample items below the LOD. p.(K+1) is computed by: *i(K+1) - (1/N) Z Y(J), where Y(J) - X(J) if X(J) * L and Y(J) HBLOD(K+1) otherwise. cp2(K+1 ) is computed by: o2(K+1 )- (1 /N) I D2(J), where D2(J) - (X(J) - n(K+1 ))2 if X(J) i L, and D2(J) c2blod(K+1 ) otherwise. CMA 01060 The quantity o23i_qd(k+1)* the average squared deviation of the below-LOD portion of the distribution, is computed from the following equation: ^BLODtK+U - ' 200* (K)) / F(Z(K))) ], where Z(K) - ((L-ti (K)) / <r(K)). Gleit's method nearly always converges in a few steps unless there are only a few distinct values above the detection limit, in which case it may converge very slowly. Gleifs method and closely related methods appear to be the best available estimators of the mean when the sample includes values below the LOD, as is demonstrated by the simulations reported in Gleifs paper. * 0i63 APPENDIX III ESTIMATE OF TOTAL EXPOSURE TO VINYL CHLORIDE FROM INDOOR AIR CMA 010604 * INDOOR AIR EXPOSURE/OTHER ROUTES OF EXPOSURE ASSESSMENT FOR VINYL CHLORIDE I. BACXSRQUNQ Health and Safety Code Section 39660.5 directs the Board, In its toxic air contaminants identification process, to assess exposures to toxic air contaminants in indoor as well as outdoor environments. Indoor exposure assessment has become increasingly important as an integral part of air exposure assessment because (ARB 1987, 1989): 1. people spend a predominant proportion of their time indoors; and 2. personal and indoor air monitoring data indicate that some pollutant concentrations are regularly higher indoors than outdoors. Indoor air exposure data, combined with outdoor air exposure data, can provide a realistic estimate of personal exposure through the air environment. A more detailed discussion of indoor air exposure is contained in Appendix A. Indoor air data can be obtained either by personal air sampling or by fixed-site air sampling. In personal sampling, the sampling equipment is carried by an Individual and air samples are taken wherever the individual may be. In contrast, fixed-site air samplings refer to air samples taken at a fixed location. Personal air sampling data generally provide a more realistic estimate of individual exposure. Since most people spend 80-902 of their tim in indoor environments, personal air sampling data are strongly weighted by indoor air exposure data. While the main objective of this report is to define exposure through the air, this report also presents personal exposure data through other media. The inclusion of these data will provide an useful perspective of the overall exposures to toxic air contaminants through environmental media. The need for total exposure assessment and some of the issues and concepts involved in total exposure estimates are discussed in Appendix B. II. INDOOR AIR EXPOSURE TO VINYL CHLORIDE A. PERSONAL AIR SAMPLING Personal air sampling data for most organic compounds come from the Total Exposure Assessment Methodology (TEAM) studies conducted by the Environmental Protection Agency (EPA) during 1980-85 (Wallace, 1987; USEPA 1987a,b; Wallace & Clayton, 1987; Wallace ei_a.l.. 1986; Pellizzari et al.. 1986). Although vinyl chloride was included in the initial pilot study (Phase I) of the TEAM project, vinyl chloride was deleted from the subsequent main studies (Phase II and III). The deletion of vinyl chloride was due to two -1- CMA 010605 factors (Pellizzari, 1987). First, Tenax, the most cost-effective sampling medium which could collect a number of compounds of concern, was not suitable for vinyl chloride collection. In addition, the alternative sampling method used to collect vinyl chloride in the pilot study did not provide the required reliability for detecting low vinyl chloride concentrations. Consequently, the pilot study provides the only available personal air sampling data for vinyl chloride. Based on this limited information, indoor air exposure to vinyl chloride is apparently low. In monitoring nine subjects in New Jersey and three from North Carolina for several days on three separate visits over a 6-month period, all of the 138 air samples taken were below the limit of detection (Wallace et al. 1984). The range of the limit of detection was from 0.63 to 2.84 ug/m . B. FIXED-SITE AIR SAMPLING As part of a recent follow-up TEAM study in California, fixed-site monitoring stations were installed to monitor indoor and outdoor air concentrations of a number of organic compounds (Pellizzari, et a!.. 1989). Specially designed stainless steel canisters were used for collecting vinyl chloride air samples from homes in the Los Angeles area for two seasons. Ten homes were sampled in the Winter season and eight of the original homes were sampled in the Summer season. Canister air samples were collected indoors and outdoors at each home during two, 12-hour periods. Samples obtained in the Winter season did not provide reliable data due to technical problems. All outdoor or indoor samples, a total of 32 samples, obtained in the Sumner season indicated that vinyl chloride air concentrations were below the limit of detection. The samples were analyzed by two analytical methods with limits of detection at about 0.55 and 148 ug/m , respectively. A similar TEAM study was conducted in Baltimore. Indoor air concentrations of vinyl chloride in about 160 homes were monitored by fixedsite sampling stations. Based on partially analyzed results, vinyl chloride was not detected in indoor air environments. The limit of detection was quoted by the researcher as 26-40 ug/nr (Pellizzari, 1987). C. SPECIAL SITUATION AIR MONITORING In 1981, the South Coast Air Quality Management District (SCAQMD) collected 24-hour bag samples in the vicinity of the BKK landfill (a Class I site) in West Covina. A total of more than 500 air samples were taken at two outdoor sites and at four sites inside downwind residences (SCAQMD, 1982). All the samples (24% of the total sampled) that equaled or exceeded the state vinyl chloride air quality standard of 10 ppb (26 ug/nr) were taken inside the residences. Ihe highest recorded indoor vinyl chloride concentration was 50 ppb (130 ug/nr). The limit of detection was 2 ppb (5.2 ug/nr). In late 1984, the SCAQMD staff took about ten grab-samples inside the water meter boxes of residences adjacent to the Operating Industrial Inc. -2- CMA 010606 (Oil) landfill (SCAQMD, 1985a). Vinyl chloride with other landfill gases, had migrated-to and accumulated in water meter boxes at concentrations ranging from 13 to 36000 ppb (31.2-93600 ug/mJ). In 1985, the SCAQMD (1985b) conducted further monitoring by grab-samples inside some of the residences and found indoor vinyl chloride air concentrations at 8 to 100 ppb (20.8-260 ug/nr). Present indoor concentrations of vinyl chloride in these residences near Oil landfill may be lower since recent routine monitoring of water meter boxes have not detected significant levels of landfill gsses due to improvements of Oil's landfill gas collection system (Coy, 1987). C. SUMMARY Except for houses near landfills, the vinyl chloride concentration in indoor air appears to be low. However, this conclusion is based on the evaluation of a very limited database. In addition, the sampling and analytical procedures for vinyl chloride indoor air monitoring are less than satisfactory as evidenced by the wide range for reported limits of detection. The limit of detection, 0.55 ug/m, reported in the latest California TEAM study appears to be the most reliable. This limit of detection will be used to estimate the upper limit exposure for house not adjacent to landfills. For houses near landfills, the measured high indoor vinyl chloride air concentrations may indicate the potential impact of nearby emission sources to indoor environments. A more detailed discussion of landfill emissions as a source of indoor vinyl chloride is presented in section III(C). III. POTENTIAL SOURCES OF INDOOR VINYL CHLORIDE A. PLASTIC MATERIALS AND CONSUMER PRODUCTS Vinyl chloride has not been used in any consumer products since 1974 when vinyl chloride was banned as a propellant in household aerosol products and as an ingredient of drug and cosmetic products (IARC, 1979). Because of Its versatility, plastic products made of polyvinyl chloride (PVC) and other vinyl chloride polymers are ubiquitous in any household. Before being made into different products, PVC polymer is in the form of a resin that is made by chemically linking the vinyl chloride molecules. Individual vinyl chloride molecules are also called vinyl chloride monomer (VCM). Unreacted VCM can remain in the PVC resin for some time depending on the initial amount of the unreacted VCM. Therefore, an indirect source of vinyl chloride Indoors may come from the release of unreacted VCM from these plastic products. For example, during 1975 to 1976, low VCM concentrations, ranging from below 2 ppb to 1.2 ppm, were measured in autonobile interior air space under experimental conditions (U.S.EPA, 1976; 1977). Emissions of unreacted VCM have been greatly reduced due to improvements in monomer stripping technology (Wheeler, 1981). In the past, residual VCM -3CMA 010607 concentrations in the PVC resins at the time of shipment ranged as high as 2000 ppm. Currently, PVC resins contain about 10 ppm residual VCM at the time of shipment and may lose VCM at a rate of 20 to 502 per month during storage. In addition, most of the VCM 'will vaporize and escape during the high temperature processes in which PVC resins are melted and made into final products. Thus, commercial products made of PVC resins do not now contain significant residual vinyl chloride for later emission. 8. VAPORIZATION FROM WATER SOURCES Water can serve as a medium to carry pollutants from outdoor to indoor environments. Once in contact with air indoors, volatile chemicals such as vinyl chloride can leave the water and enter the air. Human activities such as using water for cooking, heating or showering can promote rapid vaporization of vinyl chloride from water. Industrial solvent contaminated surface or ground water may, therefore, bring outdoor vinyl chloride indoors via the water supply. In California, surface water is generally free of vinyl chloride (Sharrp, 1987). In assessing ground water quality, the California Department of H alth Services (C0HS, 1986) reported that only one out of the 2,947 wells for large public water systems was contaminated with vinyl chloride. The maximum concentration found in that well was 23 ug/1 with a median value of 20 ug/1. Vinyl chloride has not been detected in wells used for small public water systems (CDHS, 1987). The limit of detection of vinyl chloride in water is 0.5 ug/1. Based on this information, vinyl chloride in the water supply will have an Insignificant impact on the indoor vinyl chloride air concentration. C. VINYL CHLORIDE FROM LANDFILL GAS Homes built on or near landfills containing vinyl chloride or related chlorinated hydrocarbons may have high indoor air concentrations of vinyl chloride. Vinyl chloride emission from landfills can be caused by the vaporization of vinyl chloride that was originally disposed there. Class I landfills that are designated for toxic waste are likely to contain vinyl chloride waste. In addition, microbiological conversion of chlorinated hydrocarbons can produce and emit vinyl chloride in situ (Molton, Hallen and Pyne, 1987). Wood and Porter (1987) reported their evaluations of over 20 Class II landfills that are designated only for municipal waste. Ninety percent of these landfills contained measurable amounts of vinyl chloride and the concentrations at half of these landfills were above 1000 ppb. These high concentrations were measured by grab-sampling, an instant filling of a twoliter evacuated flask, at ground levels or at landfill gas collection points. For five of the landfills, 24-hour bag sampling was also conducted. Only one of these five landfills produced measurable 24-hour concentrations of vinyl chloride off-site. -4- CMrt 010608 DRAFT There are at least two ways that vinyl chloride from landfills may contribute to indoor vinyl chloride concentrations of nearby residential houses. First, houses that are located downwind from larrdfills can receive vinyl chloride through direct outdoor air influx into indoor environments. Secondly, landfill gases, carrying vinyl chloride, can migrate underground and enter houses through substructures. The rate of accumulation of vinyl chloride indoors depends heavily on the soil permeabi1ity, source strength, air exchange rate and structure of the house. Higher indoor than outdoor vinyl chloride concentration may occur because vinyl chloride is more rapidly destroyed by direct exposure to sunlight. Another contributing factor is the trapping of migrating, subterranean landfill gas by the house. As discussed in Section 11(B), houses located near Class I landfills had higher indoor than outdoor air concentrations of vinyl chloride. The accumulation of high vinyl chloride concentrations in the water meter boxes indicated that landfill gas containing vinyl chloride can migrate underground and enters nearby Indoor environments. Controlled release or combustion of landfill gas on site may slow down vinyl chloride subterranean migration. D. OTHER FACTORS THAT MAY INFLUENCE INDOOR CONCENTRATIONS A minute amount of vinyl chloride has been identified in the smoke of cigarettes (1.3-16 ng/cigarette) and of little cigars (14-27 ng/cigar) (IARC, 1985; Hoffmann, Patrianakos and Brunnemann, 1976). The viflyl chloride level in the mainstream smoke may be determined by the total inorganic chloride content of the tobacco. The contribution from tobacco smcfce appears to hav insignificant impact on the indoor-air concentration of vinyl chloride. E. SUMMARY In general, there are very few, minor emission sources of vinyl chloride Indoors. However, houses that are situated near landfills may accumulate vinyl chloride in the indoor environment due to subterranean gas migration and direct air infiltration. Some of these houses may have indoor air levels of vinyl chloride higher than the State of California Ambient Air Quality Standard for vinyl chloride. The results from SCAQMD's five hundred 24-hour bag samples can be used to estimate the upper limit of indoor air exposure to vinyl chloride In houses near landfills (SCAQM0, 1982). The results obtained by grab-sample monitoring, however, are not useful for estimating long-term indoor exposure to vinyl chloride. IV. OTHER ROUTES OF VINYL CHLORIDE EXPOSURE A. WATER INGESTION The major source of drinking water for California is surface water which does not have detectable vinyl chloride concentrations. Ground water used for -5- CMA 010609 DRAF public water systems is also relatively free of vinyl chloride (CDHS, 1987, 1986). The detectable limit of vinyl chloride in water is 0.5 ug/1 (0.5 ppb). Based on this information, vinyl chloride exposure through drinking water is judged to be insignificant under ordinary situations. B. FOOD INGESTION Vinyl chloride is not one of the compounds that have been monitored routinely in U.S. food and food products. However, before 1973, vinyl chloride was found in food and beverages marketed in vinyl chloride polymer containers or packaging materials (IARC, 1979). At that time, levels as high as 20 mg/kg (ppm) of vinyl chloride monomer were present mn alcoholic beverages packaged in this material. Vinyl chloride was also found in edible oils, butter and margarine at 0.05-14.8 mg/kg. When cleaner PVC resins became available after 1975, vinyl chloride polymer containers contained only about 10 ppb of residual vinyl chloride monomer. In its recent rule-making proposal, the Food and Drug administration (FDA) (1986) estimated vinyl chloride exposure from food amd beverages packaged with vinyl chloride polymer materials. These materials include liquor bottles, wine bottles, oil bottles, vinyl chloride bomopolymer film, and materials made with vinyl chloride-vinylidene chloride copolymers. Based, on a conservative approach, the FDA's estimated lifetime-averaged individual exposure to vinyl chloride would not exceed 25 nanograms per day. V. ESTIMATES OF TOTAL EXPOSURE FROM INDOOR AIR AND OTHER ROUTES The estimated daily dose of vinyl chloride from different environmental media are presented in Table l. From the Table, exposure to vinyl chloride in indoor air, food and water appears to be insignificant. However, exposure to vinyl chloride indoors in homes near landfills may be the major portion of total vinyl chloride exposure. A. AMBIENT AIR EXPOSURE The 24-hour average concentration of vinyl chloride oajtdoors ranges from below the L0D of 2 ppb (5.2 ug/n) to the maximum 24-hour average concentration of 15 ppb (39 ug/trr) as measured near BkK in 1987. B. INDOOR AIR EXPOSURE The average concentration of vinyl chloride indoors in houses not near landfills is estimated to be below the limit of detection (0.55 ug/nr or 1.4 ppb). For homes that are located near landfills, the highest observed daily average measurement, 50 ppb or 130 ug/m , is used for a conservative estimate. C. FOOD INGESTION The estimate of daily dose reported by FDA (1986) is directly used. -6- CrtA 010610 D. DRINKING WATER The relative contribution of drinking water to daily exposures of vinyl chloride appears to be insignificant. The average concentration of vinyl chloride in drinking water is estimated to be below the limit of detection (0.5 ppb or 0.5 ug/1). E. ASSUMPTIONS Some of the assumptions used for making the daily dose estimates from different environmental media are: 1. The average person ingests 2 liters of drinking water per day; 2. The average person inhales an average of 20 cubic meters of air daily; 3. Dermal exposure is negligible; and 4. lOOt of the pollutant ingested or inhaled is absorbed. -7CMA 010611 Table 1: Estimated Doses Of Vinyl Chloride Exposure Through Different Media Media AIR Daily Dose Outdoor air < 104 to 780 ug Indoor Air Homes not near landfills less than 11 ug Homes near landfills up to 2600 ug FOOD Including beverages less than 0,025 ug MATER-DRINKING PURPOSES Surface/Ground Water less than 1 ug Ref s. Table II-l Pel 1izzari et aT.. 1989 SCAQMD, 1982 FDA, 1986 CDHS, 1986; 1987 -8CMA 010A12 REFERENCES: ..j ARB (Air Resources Board) 1989. Staff report on reducing exposures to indoor air pollutants in California: existing authorities and recommended actions. ARB (1987). Staff report on indoor air quality and personal exposure-- briefing paper. CDhS (Calif. Dept, of Health Services) 1987. Status report- AB1803 small system program: Summary of results. CDHS (1986). Final report on a monitoring program for organic chemical contamination of large public water systems in California. Coy (1987). Personal communication between Richard Corey of ARB staff and Carol Coy of SCAQMD. February 10, 1987. FDA (Food and Drug Administration) 1986. Proposed uses of vinyl chloride polymers by the Food and Drug Administration-Proposed rule. Federal Register 51(22):4177-4188. Girman, JR, J Wesolowski and P Jenkins (1987). The role of total exposure in air pollution control strategies. In: Indoor Air '87 Volume 3--Developing countries, guaranteeing adequate indoor air quality, control measures, ventilation effectiveness, thermal control and comfort, policy and strategies. West Berlin, Germany, pp.515-520. - Hoffmann D, C Patrianakos and KD Brunnemann (1976). Chromatographic determination of vinyl chloride in tobacco smoke. Analytical Chem. 48(1):4750. IARC (International Agency for Research on Cancer) 1979. IARC monographs on the evaluation of the carcinogenic risk of chemicals to humans-some monomers, plastics and synthetic elastomers and acrolein. Volume 19. IARC, World Health Organization. IARC 1935. IARC Monographs on the evaluation of the carcinogenic risk of chemicals to humans-tobacco smoking. Volume 38. IARC, World Health Organization. Molton, PM, RT Hallen and JW Pyne (1987). Study of vinyl chloride formation at landfill sites in California. Battelle, Pacific Northwest Laboratories report prepared for the California Air Resources Board, Contract No. A4-15432. Pellizzari, ED (1987). Personal communication between Steve Hui of ARB staff and Or. E. 0. PelliZ2ari of Research Triangle Institute on 12/28/1987. Pellizzari, ED et al. (1986). Comparison of indoor and outdoor residential levels of volatile organic chemicals in five U.S. geographical areas. Environ. International 12:619-623. -9- 010613 DRAFT Pellizzari, ED et_ al. (1989) Development and implementation of exposure assessment procedures for toxic air pollutants in several Los Angeles county, CA community. Research Triangle Institute. SCAQHD (South Coast Air Quality Management District) 1982. Vinyl chloride in the South Coast Air Basin. Report by the South Coast Air Quality Management district. SCAQMD (1985a). Letter from Edward Camarena of the South Coast Air Quality Management district to Angelo Bellomo of the California Department of Health Services on 1/5/1985. SCAQMD (1985b). Internal Memorandum between S. Levy and Edward Camarena of the South Coast Air Quality Management district on 9/18/1985. Sharrp (1987). Personal communication between Steve Hui of ARB staff and Chris Sharrp, staff of California Department of Health Services on 12/12/1987. Wallace, LA (1987). The total exposure assessment methodology (TEAM) study: Summary and Analysis: Vol. I Final Report. (EPA/600/6-87/002a) Wallace, LA and CA Clayton (1987). Volatile organic compounds in 600 US Homes: Major sources of personal exposure. In: Indoor Air '87, Volume 1-- Volatile organic compounds, combustion gases, particles and fibers, microbiological agents. Berlin, West Germany, pp.183-187. Wallace, LA et_al. (1984). Personal exposures to volatile organic compounds1. Direct measurements in breath-zone air, drinking water, food, and exhaled breath. Environ. Research 35(10):293-319. Wallace, LA et al. (1986). TEAM study: Personal exposures, indoor-outdoor relationships, and breath levels of volatile compounds in New Jersey. Environ. International 12:369-387. Wheeler, RN (1981). Poly(vinyl chloride) processes and products. Environ. Health Perspective 41:123-128. Wood, JA and ML Porter (1987). Hazardous pollutants in class II landfills. JAPCA 37(5):609-615. U.S. EPA (Environmental Protection Agency) 1976. Sampling of automobile interiors for vinyl chloride monomer. EPA-600/2-76-124. U.S. EPA (1977). Organic emissions from automobile interiors. EPA-600/7-77149. U.S. EPA (1987a). The total exposure assessment methodology (TEAM) study: Elizabeth and Bayonne,New Jersey, Devils Lake, North Dakota and Greensboro, North Carolina: Vol. II Part 162, Final Report. (EPA/600/6-87/002b) U.S. EPA (1987b). The total exposure assessment methodology (TEAM) study: Selected communities in northern and southern California: Vol. Ill, Final Report. (EPA/6Q0/6-87/002C) -10- CMA 010614 APPENDIX A INDOOR AIR EXPOSURE DRAFT Prediction of health risk from pollutants depends upon knowledge of total personal exposure to the pollutants. For direct exposure to air pollutants, the dose of pollutant received through the respiratory system is the basic quantity needed for risk assessment. In general, that dose depends on: a) the pollutant concentration in the environment occupied by an Individual (exposure concentration); b) the length of time spent in that environment (exposure duration); c) the rate of breathing in that environment; and d) other physiological factors. Exposure through air can be estimated by using only the first two parameters, exposure concentration and exposure duration. Historically, outdoor air concentrations of an air pollutant have been used as a surrogate for estimating personal air exposure. However, studies of indoor environments and of personal exposures to pollutants have revealed that indoor concentrations of some pollutants are regularly higher than outdoor concentrations of those pollutants. In addition, human time-activity pattern studies show that people spend most of their time in non-outdoor microenvironments such as in their homes, work places, transportation vehicles and public buildings. On the average, people spend 80-90 percent of their time indoors. The California Legislature recognizes the importance to risk assessment of considering both indoor air exposure and outdoor air exposure. The current statute requires the Board, when identifying toxic air contaminants, to assess exposures in indoor, as well as outdoor, environments (K&SC Sec. 39660.5). This combined indoor plus outdoor, or total air, exposure assessment permits more accurate public health risk estimates for airborne toxics. Indoor air exposure information can also provide direction for the control of many toxic air contaminants. An even more realistic estimate of total air exposure would be the sum of the products of the pollutant concentration in each microenvironment and the fraction of time people spend in that microenvironment. However,, time-activity and indoor/personal monitoring data are limited and insufficient at this time for quantifying the concentration of most air pollutants in each microenvironment. Based on this limited database, indoor air exposure assessment of most of the toxic air contaminants will be crude estimates. Risk assessments, based only on outdoor air concentrations, may greatly underestimate health risk to the public. For some pollutants present in high concentrations indoors, ventilation with clean air is the only feasible method of reducing exposure. The Board must, therefore, manage outdoor concentrations of toxic air contaminants, not only to reduce significant outdoor exposures where they occur, but also to preserve a clean air supply for controlling indoor exposure to these substances. -11- CMA 010615 APPENDIX B TOTAL EXPOSURE FROM ALL MEDIA DRAFT The concentrations of some pollutants have been measured in different environmental media such as air, water, food, pesticides and drugs. Ideally, these measurements can be integrated to estimate the total exposure to those pollutants through all the environmental media. Total exposure data are critical for setting priorities and formulating regulatory actions that can best achieve overall personal risk reduction. While one of the main objectives of this report is to define exposure through the air medium, personal exposure data through other media are also included. Exposure data are presented according to three basic routes of exposure which are inhalation, ingestion, and skin absorption. The combination of exposure data from all media will allow the determination of the total human exposure to a toxic air contaminant through the environment. To determine the added risk caused by a particular exposure, both the shape of the dose-response curve and the previously existing exposure level must be known. Although the exposure through a particular medium may besmall, its addition to exposures through other media could provide a total dose in excess of a postulated "safe level". In addition, the pathway of pollutants in the environment is dynamic and complex. Pollutants emitted into the environment in one medium can remain in that medium, transfer to another medium, and/or disperse into a number of media. This results in different routes of exposure. For example, solvents emitted as water pollutants can become airborne and cause exposure through inhalation. Airborne lead particles can be deposit onto food and result in exposure through ingestion. Thus, inclusion of exposure through all media will provide a more accurate exposure estimate for each route of exposure, including inhalation, which is the Board's primary concern. Documenting exposure to toxic substances through different media can serve as a stimulus for coordinated risk reduction efforts among different regulatory agencies. Other regulatory agencies are more likely to increase their efforts in reducing the overall exposure through other media if they are made aware of such exposure data. -12- CMA 010616 DRAFT APPENDIX IV INFORMATION REQUEST LETTER WITH ATTACHMENTS AND RESPONSES CMA 010617 STATE o' Cai^C'nia AIR RESOURCES 1101 Q STRjn PO. SOX 2B13 SACRAMENTO. Ca >73812 BOARD GEOG DEUKMEjIAN. Gowne Apn`1 4, 1985 Dear Sir or Madam: Subject: Request for Information Regarding Vinyl Chloride I am writing to request information on the health effects of vinyl chloride as part of our toxic air contaminant program. This program is based on Health and Safety Code Sections 39650, et se. which require the ARB to identify ' ~ compounds as toxic air contaminants and once identified to develop ana adopt control measures for such compounds. After consultation with the staff of the Department of Health Services (OHS), we have selected vinyl chloride as a candidate toxic air contaminant to be evaluated in accordance with the provisions of Health and Safety Code Sections 39650, et seq. During our evaluation of vinyl chloride, we will consider all avatlaETe health information regarding this compound. Additionally, we are soliciting information regarding possible biological production of viiryl chloride. Eefore the ARB can formally identify a compound as a toxic air contaminant, several steps must be taken. First, the ARE must request the Department of Health Services to evaluate the health effects of candidate compounds. Second, the ARB staff must prepare a report which includes the health effects evaluation ana then submit the report to a Scientific Review Panel for its review. The report submitted to the Panel will be made available to the public. Information submitted in response to this request will be considered in the ARB report to the Panel. Although any person may also submit information directly to the Panel for its consideration, I urge you to submit all information at this time for our consideration in the development of the report for the Panel. The Panel reviews the sufficiency of the information, methoos, and data used by the DHS in its evaluation. Last, after review by the Scientific Review Panel, the report with the written findings of the Panel will be considered by the Air Resources Board and will be the basis for any regulatory action by the Board officially to identify a compound as a toxic air contaminant. Prior tc formally requesting the DHS to prepare a health effects evaluation of vinyl chloride, we are providing, pursuant to the provisions of CMA 010618 -2- April 4, 1985 Section 39660(e) of the Health ana Safety Code, an opportunity to interested parties to subir.it information on the health effects of vinyl chloride which he or she believes would be important in DHS's evaluation of vinyl chloride as a candidate toxic air contaminant. In March 1985, we received a reference search on vinyl chloride health effects using the MEDLINE ano TOXLINE Information Services. These information services include material available to the public in late 1984. The attach d bibliography lists the references from this information search. We are requesting pertinent information on vinyl chloride health effects, including any material that may not be available to the public, that is not included in the attached bibliography. Pursuant to the provisions of the Public Records Act (Government Code Sections 6280 et seq.), the information you provide will be a public record and subject to puBTic disclosure, except for trade secrets which are not emission data or other information which is exempt from disclosure or the disclosure of which is prohibited by law. The information may also be released to the Environmental Protection Agency, which protects trade secrets and confidential information in accordance with federal law, and to otner public agencies, which are also required to protect such information. To expedite the review process, we ask that any information which you believe should be regarded as "trade secret" be clearly marked and separated from other information. You may iaentify portions of the information you submit as "trade secret" in accordance with Health and Safety Code Section 39660(e). The claim of trade secrecy must be supported upon the request of the Air Resources Board. Other information claimed to be trade secret and information otherwise claimed to be exempt from disclosure may be identified as confidential in accordance with Section 910)1, Title 17, California Administrative Coae. Section 91011 requires that the claim of confidentiality be accompanied by specified supporting information. I would appreciate receiving any relevant information you wish to submit by May 19, 1985. Your help in expediting our review will be greatly appreciated. Please send the information to the attention of: William Y. Loscutoff, Chief Toxic Pollutants Branch Re: Vinyl Chloride California Air Resources Board P. 0. Box 2815 Sacramento, CA 95812 If you have any further questions regarding health effects information, please contact Mr. John Batchelder at (916) 323-1505. For any other questions, please contact Mr, Don Ames at (916) 322-8285. 01061? April a TORS If you are not the person to whom this request should be addressed, please forward it to the appropriate person in your organization. Also, please let us know whether you would like to continue to receive information inquiries for other candidate compounds, and if not, if there is anyone in your organization to whom such requests should be sent. Sincerely, o ia i* i who r j vuu iwc uniaiwu cc: Alex Kelter, DHS Lori Johnston, DFA Wayne Morgan, President, CAPCOA Jan Bush, Executive Secretary, CAPCOA David Howekamp, EPA Region IX Assemblywoman Sally Tanner, Chairwoman, Committee on Toxic Materials Senator Ralph Dills, Chairman, Committee on Governmental Organization Senator Art Torres, Chairman, Committee on Toxics and Public Safety Management Emil Mrak, Chairman and Scientific Review Panel Members APCOs Attachment CMA 010620 Vinyl Chloride Refs. (3/1.'5) U3 = C 'I?-:', The p r s d i c t ab i 111 y of bioassays Frog Clin 3ioi Res. 109:149-41 Andersen, D end Richardson, C R. (19 8 1) Issues relevant to the assessment of ihtr.izs.il)- induced chromosome damage m vivo and their relationship to chemical rout agenesis Hut at Res. 90 ( 3 ) . 2 4 1 -72 . Andersen, D , Richardson, C 'I'll' Chromosomal analysis `. = ndi.:d `erhntcue w;th the : l' -0r R , Purchase, I. F., Evans, H. J. and Q'Riordan, H. m vinyl chloride exposed warier*: comparison of the s i s t e r-Chr ona t i d exchange technique. Mutat Res. L. Anderson. M V Hoel, D. G. and Kaplan, -N L (19SC) 1 general scheme for the . r. a *. i or. :l pharaacek met i cs m low-dcse risk estimation lor chemical ::*:;t:ssis ex amp I e--vinyl chloride Toxicol Appl rharmacol 55(1)134-41 k-.- : ~ 8 C ; The Carcinogenicity of Vinyl Chloride ar.d Related Compounds (HTIS/PB80T r t Reports Announcements S Index (GKASI). 11 *:n-;m:us le7i' Editrrial: Vinyl chloride the car r mcgemic risk.. Br Med J p: 2 4 - 5 2 Ar.twsiler, H (19751 Studies on the metabolism of vinyl cSloride.. Environ Health Perspert 17 p2l?-9 Apfeldcrf, R ar.d Infante, P. F (1931) Review of ep i demi ol 05 i c study results of vinyl chloride-related compounds Environ Health Perspect. 41:221--4. Sahlman, L J. , Alexander, V., Infante, P F., Wagoner, J, K, Lane, J. K. and Bingham, E. (1979) Vinyl halides, carcinogenicity Vinyl bromide, vinyl ehtorid , an vinylidene chloride. Am Ind Hyg Assoc J. 40(4):A30,32,34. 10 Earbin, A , Eartsch, H., Leconte, F. and Radmtn, M. (19313 Studies on the miscoding properties 0f.1,Ni-ethenoadenine and 3 , N4-ethenocytosine, ONA reaction products of vinyl chloride metabolites, during in vitro DNA synthesis.. Nucleic Acids Res. ?(2 ) 375-87. EARTSCH, H. ( 1 976 ) MUTAGENICITY TESTS IN CHEMICAL CARCINCCENESIS. IARC (I NT AGENCY RE :an:e?.)Sci publ. 13 229-240. EARTSCH, H, , MALAYS! LIE, C.. BARB IN, A., PLANCHE, G. ar.d MONTESANO, R. ( 1974 ) ALKYLATING AND MUTAGENIC METABOLITES OF HALOGENATED OLEFINS PRODUCED BY HUMAN AND ANIMAL TISSUES. PROC AM ASSOC CANCER RES. 17:17. 1 2 Sartsch, H , MalaveiHe, C , Camus, A M , Marte1-F1anrhe , C , Erun, G., Ke f`ef eu i 11 e , A , Sabadie, H. , Barbin, A Kuroki. T Ere von C , Piccoli, C. and Mcr.tesano, F. ii'EC' Validation and comparative studies :r. :IC chemicals with S. ryphimcrma s'.rair.s ar.d V7* Chinese hamster cells : r. : he presence of various m * *. t r 1 : r : r. o s v s t 4 m s M u t a t Res " 1 ! - IC . 4 i: * s c h , . h . '. r : ; e and Mor.tesir.c F. (1'7S) hr.igenic ar.d : a r : i - ;e tr. i c effects of vinyl Mutat Fes 32 '2' p93-1 14 EARTSCH, H , TQM.ATIS L and MALAVEILLE C ( 19 2 QUALITATIVE AND QUANTITATIVE comparisons setvsen mutagenic and carcinogenic activities of chemicals, mvtacek-new CMA 0 1 Easier, A end Rohrborn, C < 1 ? E 0 ) V i r. y i chloride: in example for evaluating mutagenic effects in mammal* in iv: after exposure to imhalation.. Arch Toaicol . 41C 1 > 1 --7 i / Becker , C and Coye, M J Toe i : o l Cl in Toxicol . 22 0 13 Binghaa, E. and lane, J. M. Toxicol . 22( 1 ) : 31-3. 1? , Bolt, H. M. (1978) Pharsacok metics of vinyl chloride.. Sen Pharmacol . 9 <2>:p9l-f 11 Bolt, H. M. , F i I s e r, J C a r.d Euchler, A (1981) Inhalation pharmacokine t ice based :r. ; i i uptake studies III A pharmicokinetic assessment in man of "peak concentrations: of vinyl chi 21 5GLT, H. M. , FUSER, J C , laie, s 2: "INYL CHLORIDE AND VINYL ?. 1 S K ASS E52KENT IN CHEMICAL ar.d OTTENVAELDER, H. < 1980> BINDING KINETICS .`ERV LCV 0C5ES, IN. QUANTITATIVE ASPECTS or IS ARCH TOXICOL SUPPL. 3:129-142. 2 ;.l : , H . M., La i b , R J . Ka chloride in the rat , Toxics 7 (2) p 1 79-88 . 2 3 E r i r. d , K G . Eusen, L. C a chi:ride vinyl acetate copcl Cancer 1 nst 34 (!) p!2 79-42 . 2 M ER.V.N. P , , 3CHCSIIEICH, J . MUTAGENICITY OF SELECTED CKE CKE'tl CAL MUTAGENESIS ENVIRO TOR, M = MC ORECOR , D. 6. and KOHN, C. E- < Z 981 > ACS IN THE HOST-MEDIATED ASSAY, IN: COMPARATIVE Cl RES. 24 333-392. 9* r V S a : h *. e r. A , F 11: r , J G , Fite:, K ar.d Eolt, H. M. (1980) Phiaraaeokiaet ice of vi-./l chloride i^ the Rheiur monkey Toxicol Lett . 8 '3 ) :p33-4. U e / c: kowska, Z. ( 1 9 3 2 ) (Carcinogenicity of vinyl chloride!. Pol Tyg Lefc (BOLAND) 3 7 3) p93-7 , 27 California Air Resource* Beard (1977) Effects of airborne vinyl chloride. ARB Staff Deport! 73-1-1. 127pp 22 Chu, K C and Milman, H A '1-31) Review of. experimental carcinogenesis by e xpounds related to vinyl chloride Er. vircn Health Perspect . M:211-20. 27 Clemmesen, J (1FE2) International Commission for Protection against Environmental "He gens and Carcincgeni 1CFEMC working paper TG1/2/79. Mutagenicity and teratogenicity of vinyl ihl:::ds monomer 'VCM' epidemiological evidence. . Mutat Re -ran:* r a : : c s of vinyl chloride Cletterl. * m\ _a *m a 19 < ^ ita*0 :'v:`5 vied in the pharmaceutical - * p; 1 1 : " " L:r. fid.rce intervals and test :r.` .nferr ~i from. tn:si`. CMA 010622 .r.. r.i : . t Tazhurrc, C H ;sr. 'h '7 PP A FT and "az, L 7 f .* ? 8 i ) 0 ccupa t i ona^*4a4 A no j^snes is r yl ah Itride-assceialed hepatic angiosarcob*.. Am * - r ir.d seam, f. . : lstkal assay. :i'Su mutagenicity ct selected chemicals comparative chemical mutagenesis, envirc ielorze, " ,`~l' fAijGaiatton of angiasarccaa of the liver and hepatoma in vinyl : h I ::. f s a : r L * r I A. r. r. A n a t F 11 h o 1 (Paris) . 23 f 2 ) : p 1 0 5 -1 4 . is Visits:, I , E r e r ; * ; - v s n Eogaert, V . laatot U-Vandepaer, H. . Hc&orfroid, M. , crisis*.. " and Marais:, V (1**:: Mutagenicity of vinyl chloride in the Arne* test : * i is f t: s:: p e : 1:. s r. t a I conditions . K-j * a t "es 77(2) 175-7. . 2 . Psr.cslit, F . "cfcerfroif. M. nd Mereier, M Cl?7?) Vinyl chloride: and::*:1. zu t s g sn !;:: a * s d i r.; s I Arch In t Physiol Eiechim 87 (3> :p620- ..St. L . (#Ia'.:3m7) -m IS0r ilmncs cl experimental : I Z ar.d Cihring, Sr, J. (1981) Translation oi - - - ` , siiisici-i A-t E = ; Med Biol. 134 Pt *r * *f". Z E and v =: a s r.. C "in y I chloride-induced hopatic a with transition to ahrtn.ia hepatic porphyria.. Klin Vochensehr . Z A , Hasezan. J if , McConnell, E E-, Susey, V. H. and Ths sfleat :f a;s :.( exposure duration on cancer induction by .r. rats. z..e ar.i hac.it s:s Tozi.o! Ap p I Pharmacol. 48(l):120-3fl , Ltzbitte, V . Malvj-sin, S 3e Meester, C , Poncelot, F. and Kereier, Met =.; . I . _ acti.it ::r, ini zutagen.oity of 1 vinylic monomers Cvinyl ft a a r y I : n 11: i I e . butadiene! Toziaol Sue Res. 3 < 3) : 1 31-40 . I ;; s: t, M , Lazho 11 e-Vjnde; aer, M , "e Meester, C , Kereier, M. and t -12 ' Vinyl tVtt.ii and acrylonitrile activation mechanism and czt a ah . A x --.i .` TENVAILCEE, H l-'S;) MUTAGENICITY OF .37 as inzicatds organism. haunyn- ;d St :a :;f . V t t?7d) Vin7i ana and chloroacetaldehyd> and tvepat oce Hula: .2 chemicals. pesticid* ;a n y I ah to tide CMA 010623 * Vinyl chloride dependent i* i it a radicals.. ns* at Res 36 (2) : p 81 irpit'jrt indices I c ; tp i des i o I o g i ea l '* i'-f'. r -. 1 chemical * r.r i r onnent . . J Qceup Sti Publ . <22>:j3 I LT.i ; ; I' . K . H '! * S 3 > Iv idence of . i j : I : 1 chloride t ow* r d DNA : :. i ". h /1 * i h e r Carcinogenesis. 4(11): 1483-4. F:j!j to `.hi offspring frcn parental Crafstrjs, S anil Same I, C. (1981) Th* .i.'.iiei sufccellular friction* of Drosophila. .'..-.Hi, C-ncinointtraceno and bansotalpyrene i Iyph ircc-r jua. Chon Biol Intonct I < nst > Sea* prictical problons C 0 d * i for risk estimation.. J Toxicol Environ ir.yl chloride careinogon i ci t y/not agoniei t j . lih intervention and not da for now research cr :t'.ic policy perspective.. Environ Health stents and the epidemiology of eancer. J J., Villigan, 0 A , Sierbower, G. xnc Mowing single and multiple exposures to ; Environ Health Perspect. 41:13-72 tit: sen, k M5B41 Incidence of cancer among v. or hers. Hr J !nd fled 41 ( i 25-30. i:. 7 and Viiiuo, K fI?B4 5 ilepr oduc i v e 11 ; t. I i o 1 Res 141 79-87 CHA 010624 rets, R ( 1 9 78 ) Carcinogenic effects cf chronic 11 7 tciic subitanees Environ Health Ferspect 22 : pI5S-9 . DRAFTto diflow levels of ns PRESTON, R J , ADLER I-D, , LEONARD, A end LYON, M`t Clcl) MUTAGENICITY OF SELECTED CHEMICALS IN IN VIVO CYTOGENETIC ASSAYS. IN COMPARATIVE CHEMICAL MUTAGENESIS, ENVIRON SCI RES. 24:549-632 1 1 9 Preussmann, R. ( 1 9 7 8 ) Toi i co 109 i ct I aspects of food safety - carcinogenicity and nu tagen ic i ty , . Arch Toiicol tSuppl) U):p6?-s4. 120 Preussmann, R. ( 1 9 76 ) Chemeal carcinogens :n the hunam environment; problems end quantitative aspects.. Oncology (Switzerland) 35 C23 :jc51 -- 7 . 12 1 Purchase, I f ( 1 980) Appraisal of the merits and short comings of tests of mutagenic potential. Dev Tosicol Environ Sci. 3:113-18. 122 P.adike, M J., Steamer, K. L. and Bingham. E. (1981) Effect cf ethanol on vinyl chloride carcinogenesis.. Environ Health Ferspect. 41:59-;. 113 SANNUC. U. (1978) SHORT-TERM MUTAGENICITY TESTS ON SALMDilELLA TYPHIMURIUM. STUDIES VINYL CHLORIDE, ETHYLENE DICHLORIDE AND OTHER COMPOUNDS BELATED TO THE VINYL CHtORI INDUSTRY ACTA UNIV UPS AB3TR UPPSALA DIES "AC SCI 467 3E ?P 124 Rannug, U, Cothe, R and Va chtme i s t er , 0 A. (:9?t > The meet a. gtnici t y of ch I or oe t hy I ene oxide, chloroacetaldehyde, 2-chlcr oethar.sl and chloroacetic acid, conceivable metabolites of vinyl chloride.. Ches Biol Interact. 12(3-43:251-63. 125. Rice, J. M. (1981) Prenatal suscep-t-ibi 1 i ty to carcinogenesis by xenobiotic substanc including vinyl chloride.. Environ Health Ferspect. 41'1T'?-9S. 126 Richardson, C. R.. Styles, J. A. and Ber.nett, I. P. CI'83) Activity of vinyl chlori monomer in the mouse micronucleus assay Mutal Res. 122(21:139-42 127 . Rinfcus, S. I. and Legator, M. S. ( 1979 ) Checi.cai char act ei nation o* <63 known or suspected carcinogens and their correlation with mutagenic activity in the Salmonel typhimurium system.. Cancer P.es . 39 (9) :p3289-31 8 . 12 6 Robinson, J. S., Thompson, J. M., Belcher, R. and Stephen, V I. (19763 Vinyl chloride: the carcinogenic risk tletterl.. Hr Med J (England) . 2 (6039) ,p8 15 . 12 9 . Rowan, C. A., Connolly, V. M. and Brown, K S. (1964) Evaluating the use of occupational standards for controlling toxic air pollutants. U Environ Sci Health 183 . 19 (7) : 6 11-48 . 130 . Sabadie, N. , Malaveille, C., Camus, A. M. and Eartsch, H. (19B03 Comparison of the hydroxylation of bent0(a)pyrene with the metabolism cf vinyl chloride, N- m t :o somor ph 01 i ne , and N-ni t roso-N'-me thy 1 p : pera : :r.e tr mutagen* by human and rat liver microsomal fractions Cancer Res 42(!) 119-26 13 1 Shubii, ? <1*75) Potential car cinogeni:: y of feed additives and contaminants Cancer Res 35 (11 Ft 2) p347l-:I :ms, P < 1 - 3 D j The metabolic activation :: chemical c a r c : n r g er.s . . Sr Med cull 36:1)11-8 = m:th, A H (19:3) Problems in doee 'response epidemiology Sangyo Ika Daig.aku Zassh: 1 Sup; I I 6-- . occupational D s:. J tdrychowski, R. A , Sokal, J. A and Chmelnieka, J. (1984) Influence of expos tcit on vinyl chloride action. Arch Toxicol. 55(3)p 1:1 95- 1 98 . B3 Jehn, J A ,-Snith, F A end Schweti, 3, A. (1981) Vir.yl chloride: inhalation teratology study in nice, rats end rabbits""'. Environ Health Ferspect. 41:171-7. SB . Kelmet, E E. end Kalnas, Z. 3 ( 1 9 84 ) Carcinogenicity and epidenioIog i ca 1 profile analysis of vinyl chloride and polyvinyl chloride. Regal Toxicol Pharmacol. 4(l):t: 27 . 85 HILEEY, 8. J. (1981) COMPARATIVE MUTAGENICITY OF AFLATCIIN 81 AND VINTL CHLORIDE, I! COMPARATIVE CHEMICAL MUTAGENESIS. ENVIRON SCI RES. 24:857-882. Si Roller, L. D. (1980) Public health risks of environmental contaminants: heavy metal: and industrial chemicals J Ad Vet Med Assoc. 17&(4):525-9 . 8? KVRCF.I . T., AESONDANDOLO, A., DREVON, C., HUBERMAN, E. and LAVAL. F. (1910) MUTAGENESIS ASSAYS VITH MAMMALIAN CELLS, IN: LONG-TERM AND SHORT-TERM SCREENING ASSAY3 FOR CARCINOGENS A CRITICAL APPRAISAL. IARC MONOGR SUFPL . 2:107-133. 88 Langauer-Lewowicka, H , Kurxbauer, H. , Eyerkowska, Z. and Vocka-Marek, T. ( 1983) Vinyl chloride disease-neurological disturbances.. Int Arch Oceup Environ Fealth. 52(2) : 151-7. 89 Lassiter, D. V (1974) Recent approaches to the control of carcinogenic exposure*. Case etudy 3: vir.yl chi or i d e--bes t available technology. Ann NY Acad Sei ' 271 ;p17 4-8 . 98 Let, C. C., Bhandari, J. C., Vinston, J. M., House, V. 8., Dixon, R. L. and Voods, S. (1978) Carcinogenicity of vinyl chloride and vinylidene chloride.. J Toxieol Environ Health . 4 (1) :p 15--30 . 91 . Li, F. P. (1977) Clinical studies of cancer etiology.. Cancer :7445-7. 40 (1 Suppl) 95 , Lilif, R. (1981) Review of pulmonary effects of polyfvinyl chloride) and vinyl chloride exposure.. Environ Health Ferspect. 41:147-9. 93 . Lloyd, M. H., Cauld, 5., Copland, L. and Soutar, C. A. (1984) Epidemiol gieal study of the lung function of workers at a factory manufacturing polyvinylchloride.. Br J Ihd Med. 41(3>:32S-33 *4 . Lotw, G. H., Kurkjian, E. and Rebagliati, M. (1983) Metabolism and relative carcinogenic potency of chI oroethy1 ones a quantum chemical structure-activity study.. Chem Biol Interact. 43(l):33-44. 95 Loprieno, N, Barale, R., Saroncelli, S , Bauer, C., , Sronsetti C, . Cammetlini Cercignani, G., Corsi, C , Gervasi, G., Leporini. C., Kieri, R., Rossi, A. M., Etretti, G. and Turchi, C ( 1 974 ) Evaluation of the ger.etic effects induced by viny chloride monomer (VCM) under samnalian metabolic activation- studies in vitro and i f;v: Mutat Res 4C (1, 1 p 8 5 - 9 6 Icuagie, Y A G ; a r. e . ; : r Kef', e n s ? Eon bled, r and Kaot, J G (1914 Vir.yl chT or i de-i r.du c ed hepatic angiesaerona Er J Surg 71.4) 3 22-323 . Magnus sen , J Halls*.: ion o ! " : n y i wi:: pfceneSarb ; ta 1 a cG ?"-96 ! and Panel, C ( 1 9 7 9 ) Studies cr, metabolic h.::iie in Droscphila me 1 ano; a *. er alter pi a r ea tn*s* ;:iy,chlorinated bipher.ylr Ghee Sic! Interact 24 CMA 0 1 0 6 2 6 010627 * h a * .* * , L and Susanne, C (1978) Mutagenicity of E.l; Med See 9(2) .91-55. If... a.. e ; . - j. - s;ns*i 3 (1977) Metabolic activation of chlorinated ethylenes: .: n.. agaric effect on electrophilic reactivity of the metabolically * r - Arch Tested (Eetl ) 39(1-2) .7-12 :* 0 , ":r.se, C end Dekant, V f 19 8 3) Mechanisms of formation and reactions of electrophilic ir.t ermed i a t es of halegtnated olefins.. Prog Clin Biol Res. 132B.175 S3 . d . Kenschler, Q., Eons*, C. end Greim, H. ( 19 7 6) Carcinogenic: potential of chlorinated ethylene* tentative molecular roles.. I ARC Sci Publ (13):pl71-5. s? Ke:r.ir.iei Branched. I4.. (1984) Toxic oil syndioat and vinyl chloride disease tletter: Lancet. Z(S4QS>:931. 70 Hineno, S., Okuda, K. and Suiuki, T. (1983) Lack of dominant lethal effects in malt CD-I a: t! after short-tern and long-term exposure* to vinyl chloride monomer.. Tax re o 1 Lett. 1 i 1 -2 ):47-53 . 71 Hsinberg, 3 (1954) The toxicology of monomers of the polyvinyl plastic scries.. Pro Cl in B rol Res t 41:99-112 . -- 72 Hong, C 5., Vinstcn, J. M. , Thornburg, L. F., Lee, C. C. and VSoods, J. S. 1981) Follow-up study on the carcinogenicity of vinyl chloride and vinylidene chloride in rat* and mice tumor incidence and mortality subsequent ta exposure. J Toxicol Environ Health 7>i) .909-24 . 73. Hopkins, J. (1930 Vinyl chloride -- part 5: mutagenicity ia mac.. Food Cosmet Toxicol 18(2) 200-1. 79 HOPKINS, J . ( 1 979 ) VIKYl CHtOR1DE. 2.MVTAGENICITY. FOOD COSMET TOXICOL- 17:542-344 75. Huberman, E,, Bartsch, H. and Sachs, L. (1975) Mutation induction in Chinese hamster V79 cells by two vinyl chloride metabolites, ehloroetbylent oxide and 2- chloroacetaldehyde.. Int J Cancer 14 (4):p439-44. 74 I ARC ( 1974) Some anti-thyroid and related substances, nitzofuram and industrial chemica 1 --viny1 chloride. 1ARC Monographs on the Evaluation of tfhe Carcinogenic Risl of Chemicals to Human*. 7:291-318. 77 !ARC (1 979 ) Sosa monomers, plastics and synthetic elastomers end acroIein--v iny 1 chloride, polyvinyl chloride and vinyl chi oride-viny1 acetate copolymers. IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans. 19:37; 438 71. Infante, P. F < i 9 7 7 > Mutagenic and carcinogenic risks associated: with halogenated olefins Environ Health Ferspect II pZIl-4 7 v Infer*, e, P F : ; 'll : Observations of the stie-spaeifie carcinogenicity of vinyl chloride to humans viron Health Ferspect 41 89-94 3 C I n f a r. *. t , r T (!--:> Gene::: c ,'i: c h a e 1 , A J , wagoner, J K . Va k we tier, F. . J and Falk, H. sks :: vinyl chlcridt Lancet f 734-735 e r a t :en i c K and Vaywaller. R 197c-) Carcinogenic, mutagenic -ted wi*h vinyl chloride Mat at Res 41 '. t spel no i DRAFT* 98 Makarov, I. A and Fedotova, I. V. (1?83) [Mechanisms el the carcinogenic efflVr of vinyl chloride (literature review)}. Gig Tr Prof Zabol (USSR) (4) :p4Z-S 99 Maltoni, C. ( 1 977 ) Recent findings on the earcinogen:city o chlorinated olefins.. Environ Health Perspect 21 : p1 - 5 . ICO Maltoni, C (1978) Predictive carcinogenicity bioassays an industrial oncogenesis.. Prog Biochem Pharmacol 14:p47-56. 101 Maltoni, C. (1974) Occupational chemical carcinogenesis: new facts, priorities and perspectives. IARC Sci Publ (FRANCE) (13>:pl27-49. 102. MALTONI, C. (1977) VINYL CHLORIDE CARCINOGENICITY:EXPER1MENTAL MODEL FOR CARCINOGENESIS STUDIES. COLD SPRINC'HARBOR CONF CELL PROLIFERATION. 4:119-144. 103. MALTONI, C. ( 1 976 ) CARCINOGENICITY OF VINYL CHLORIDE : CURRENT RESULTS. EXPERIMENTAL EVIDENCE, ADV TUMOR PP.EV DETECT CHARACT. ,3 2 1 6-237. 10 4 Maltoni. C . Ciliberti, A and Carretti, D. (1982) Experimental contributions in identifying brain potential carcinogens in the petrochemical industry.. Ann NT Acad Sci . 38 1 : 2 1 6 -49 . 105 . Maltoni, C. and Lefemine, C. (1975) Carcinogenicity bioassays of vinyl chloride: current results Ann NY Acad Sci . 244 : p 195-21B . 106 Maltoni, C., Lefemine, C., Ciliberti, A., Cotti, C and Carretti, D. (1981) Carcinogenicity bioassays of vinyl chloride monomer: a model of risk assessment experimental basis.. Environ Health Perspect. 41:3-29. 107 . MOHN, G. R. (1981) MUTAGENICITY OF SELECTED CHEMICALS IN ESCHERICHIA COLI TEST SYSTEMS, IN: COMPARATIVE CHEMICAL KUTAG EN*E*S IS. ENVIRON SCI RES. 24: 108 MONTESANO, R. and BARTSCH, H. (1974) MUTAGENICITY AND METABOLISM. OF VINYL CHLORIDE. ADV TUMOUR PREV,DETECT CHARACT PRO!* INT SYMP 5THU973). 3:342-44 5. 109 Nicholson, V. J. ( 1 984 ) Research issues in occupational and anvlzonmental cancer.. Arch Environ Health. 39(3) : 19 0-202. 110. Nicholson, V. J. (1977) Cancsr following occupational exposure to asbestos and vinyl chloride . Cancer . 39 (4 Suppl) :pl7?2-80l. 1 1 l Nicholson, V. J., Henneberger. P. K and Seidman, H. (l?84> Occupational haiards in the VC-PVC industry.. Prog Clin Biol Res 141:155-75. 112. Nicholson, V. J., Hennsbsrger, P. K. and Tarr, D. (1984) Trsnds in cancer mortality, among workers in the synthetic polymers industry.. Prog Clin Siol Res. 141:45-78. 113 Oesch, F and Doerjer, C. (1982) Detsction of N2,3-thanogaanins in DMA after treatment with ch! o r oa ce t a I dehy de in vitro. Carcir.oger.es is 3 ( 6 ):443-5. CMA 0 1 0 6 2 8 1 4 Oser, J L (1980) Extent of industrial tape sure to epichlorahydtin, vinyl fluoride vinyi bromide and ethylene dibromide. Am Ir.d Hyg Assoc J 41(7 ) 463-8. Ottenw alder, H Kappus H ar.d Bolt, H M ( 1 9 6 3' Covalent protein binding of via' chloride metabolites during to-incubatton of freshly isolated hepatocytes and hepat smuspidal cells of rats Arch Toxicol CSuppll 4 2 4 4-70 . tier and Uncvary. C ^ I960) Lack of mutagenic effect oi vinyl chloride monomer `it* M j ` j * 8e 7 7 ' * 1 1"_< si 13 4 Smith, A H , Vaxweiler, R J and Tyroler, H. A. ( 1 9 8 0 ) Zf i deal ^ySg J c o( occupational car c i nogtnes 1 s using * serially additive expected doss Zpldealol_ 1 1 2 ( 4 ) : 7 87- 97. 135 Spirtis, R , Beebe, G., Bister, P., Dicey, Z , Fiber, M , Falk, H., sin Kaick, G. ame Stafford, J ( 1 9 8 3 ) Angiosircorn, is i code! (or cocpirttiTt carcinogens* i s (letter?. Lince t. 2 ( 8 3 47 ) . 4 3 4, 136 . Sloretvedt Heldns, S., Ling'ird, S. L. *nd Andersen, A. 11964) Incidence of caneec among vinyl chloride and polyvinyl chloride workers.. British Journal of Industrial Medicine 4 1 <1 ) : 25-3Q . 127 Styles, J A. (1977) A method for detecting carcinogenic organic chemicals using minnalim cells in culture.. Br J Cancer 34 (5) :pS5-A3. 13 8 . Suzuki, Y. (1983) Neoplastic effeet of vinyl chloride in xsuse lung--lower doses and short-term exposure . Znviron Res. 32 (1) :> 1 -103 . 13 9 Tamturr o, C. H. ( 1 9 7 8 ) Heilth effects of vinyl chloride.. Tea Rep Biol Ked . 37:pl2t 44 . 140 . TAKBURRO, C. H ( 1 9 78 ) KZPATIC ROLE IN CARCINOGENESIS AND STS EARLY DETECT!ON-THE VINYL CHLORIDE MODEL YALE J BIOL MED. 31 47-80. .,, 14 1 Tamburro, C H. ( 1 9 84 May) Relationship of vinyl monomers, and liver cancers: angiosarcoma and hepatocellular carcinoma.. Semin Liver Dis. 4(23:138-49. 14: Tamburro, C H and Greenberg, R A ( 1930 ) I den t i f i ca t icn of human ton'eity and carcinogenicity by ethylene derivatives Dev Toxicol Environ Sci. 8:317-33. 14 3 Tamburro, C H., Maick, L. and Popper, H ( 1 984 ) Early hepatic histologic alteration* among chemical (vinyl monomer) workers. Hepatology. 4(3>:413-6. 14 4. Th:eriault, G, Iturra, H. end Gingras, S (5983) Evaluation ef the association between birth defects and exposure to ambient vinyl chloride.. Teratology. 27(3):33f- 70 14! V.S.E.P.A (1*34) Draft Criteria Document for Vinyl Chloride. (NTI5/PB84-177538) . EPA Report. 109pp. 144 U.S.E.P.A. (1981) Ambient Water Quality Criteria for Vinyl Chloride (NTI5/PB811 1 7 8 8 9 ) EPA report EPA 400 / 3- 80-7 8:9 9pp 147 Ungvary, G., Kudak, A., Tatrai, E., Lorinci, M and Folly, G. (1771) Effects of vinyl chloride exposure alone and in combination with trypan blue--tppl ied systematically during til thirds of pregnancy on the fetnses of CFY rats.. Toxicology . 11 (1) p43-S4 148 . Vtinio, H. ( 1 9 7 3 ) Vinyl chloride and vinyl btmene (styrene)--metabolism, mutagenicity and carcinogenicity Cher B;oI Interact 22 (1) :pil7-24. 6 S 9 0 W VW3 14 * Vtn Duuren. B L (1973) On the possible mechanism of rtrcinogenic action of vinyl chloride Ann NY Acad Sci 244 p23S-47 150 Wagoner, J K ( 1 9 8 3 ) Toxicity of vinyl chloride and polyivinyl chloride): a critica. re "iew Environ Health Perspeet. 32 o'.-4 VAG011EF. , J K and INFANTE, P. F. (1978' QUALITATIVE EXTRAPOLATION FROM LABORATORY -- u"W`i;c >c ;rr>; T-"EVCJ ""JE 2 i r 7 I N'CCZN I C TTY MVTAGENT CITY OR TIE ATOC ENI C ITT n v#H9 OiivJd Uhl iJLbck WlMllllQ c*lrioty irytii,iN It irtviitvinj h iNhluf MlH dilutes k IkBilyuf 111 ttifciruli). h |4<u Ijw m Itwj UnMud Vaiyl dh Fust vmyJ lAjslic hilo Anieiican h ffu t>is tri \ lluoujlt e* plU.llK.IS S of II mi vast looted. eval DRAFT CM/S 0 1 0 6 3 0 I The Law and Policy ol` Toxic Substance? Conlml A Case Sludy of Vinyl Chloride 1 UAVIt> a IMNIflKR NWilwtf lor Rimhkii lor Ik# Ftfm r Thr fohm Ilu|ilihn UoJvcrahjr hw IlkilMtl ml ImhIm l-J ( Till TO CC AC flnvl IllV til toixk* udiuri leijtiii ivuK'i urulcf '.l.ihih I ll<IKji IAh* |At l, * Oi V*r I I ii.i.I* n*v t>* rMltk .1 iiw i. lit II M Mimaivi Cnm-of u. iIjiiJi, however. give viomlly t*o ini llw iclulivc ci|N It* 1<e juiiHikil beilili hhI vumiihih kin ill jiiicit'sh in 4inii}imImm in ntHHinw one*. ttihl lo it.iif, llw u|;mk!k' aiiiom idku (dnnickv'x Ul ol vmiiwK IHl llw iliW lM iK'CC| Hill'll' tisk A measure of giiMjin* fu dcifcioN nurUw iftflkr fait of umtit*U*y ami Uk nf t ttiic* K provided hy ilw observation Him rcgiMklory dccl- vi.Hii invithe iihiIaI ik ucll as ccmKimtc vahwi. Wc uiuy kgm wiili Hie ntndvaiion Itul ifo sainfkc nf an ImiivMuil fm ihe benefit 14 * |UW|i h iat|HahFc if llw kitcfii wived h llw group*! iMvivalut Hie fulfttlmriH of Kinie oilier ImsIc need llw KKtifke k morally unHceptilile, however. If ll U for no tiHMc iotpoHam Iwnefil Ilian llw provision nf llw liumwi of out tmisiioiing society Thai some must rite mi ibaa idl can cal is iwc thing; ihaa sihoc mihi die mi ihal all can Imve seC'lhfOttgh food packaging is aitoHtrr IVilimtoily w\w\e mini^wwUI pnnlmn * comihUfil, llw long Him goaf of Imie siilisliiik'O vmMrol anti ibe long-term clleil of tacb rcgulailun should W lo channel economic growth away frotis iiMhhliics ha/aichna% hi lieahh aotl lowanK s-det podsM'ii awl forms of employiiwttl. As rite case Kutly in I'ail II sIkiws. Hie pmbiems of ikcaliog uodei nncetiamly and of lulancing mcomnwiisuiiftble imprests have jwvaJcil ihe icjtolrttiim nf VC KilmiaiMe lo face Hie sc difficult problems accounts in |Ufl fnt Hie fac| Hiat in more Hum four yc:ws Hie agencies ti.ive sti siamUfih lor only iwo nl Hie itiiijnf sooiics of exposure lo VC. Wink; llw slatulaids llial luvc lccn scl ami llw proposals Hut have been fmi Imwaol aic by nu meant loially dclickrtt, Hwrc have been Kgnifkaut instance* in which llw .igemics have made fmtually <h logically insuppoiliihk tonclotliNtt, or In which Hiey have ignored evidence ami tailed to draw conclusion* Hie cvhlcme virtually demands In all instances, iIk agencies have Iwtd hack loins imposing standards ibai would fcrjuiie any cigmlicanl economic change in Hie regulated imlusiriec Ibe tmfusiric*' profile, volume o| proHut liun of Hie regulated substances, and future growth prospect* have Iwrrs virtually unaffected. Oik may ipwsHon wheiher llw benefits of VC piuduclion anil inc are siihslaniial ciHHigh lo juslily such cNlrenw dcleicncc hi ihe m* *1(1*1* p'<i*nKHtt Mt< Ht >W Cdtllt t lh ihtlHH tKW l*4wrc ItNld m*4 IihuI fji.1 Agtug I>|*h jMf. tJkr ihr |Hi%iiun4lMi wurdhi n aNtioK*n Out IwiMivf ul the <Mlkt*lir mikinf w mmh|> vi ihrwr * Hgiwiih Sti. t g , hiTwiofi .>/ I.J/r mnJ Limk. t+pr* ihhc It. hi 1 H. Ul) lot llw kO*ttilr tf nulif* ih fcjrJ iluci (hM Mifune lit t Htuif Rtwlmf ftw iwt AW ii*m tarril mH ifw * Uiai llw * alu i*T * tiM-irtir mi a h* r< giw Jcit MVHihlr I i h-o*r * * cumt* r tutlf HMltrtiiHMl, hui itMiijnlf cm fire Iium ih* mllutnr' t4 |i*Hift^, will at Hw ln*iiiwtt toiiuiiiHiifg. wiili Mmih* ItiuiKial wtottlt mi ^toiwiliiif iltc hmIcimIimh CiMtuitniHf 1 llw pulilk Ath|fiHiiTMlK|'witil `(^k ' mnH wmity atvwnt iNjI cwtl t'lcJ imiIi wficit fcunfM*tn| l(w amtc ^uctH>H nf wkcihcf *t *hi* h* i MJicn. ml iScar clHlJfCM'r thtUtrii. 1 kvc |t1*%lk imU " Inhc. W*ti NtH fit IAmiS (huu ft*j#fr Iiffi in Whui Vii tiOiwi Kt tl. TIMI. lnhc.C S^hrltMtf. A i VmnA liaurmflwMi ui mf|iivih W chu IKufnwt Am ficcMcr Vl|iri muf f'cunxiMrcurfiVutfiMi. icir wi Mill "7}Wr7T~r' "* yrfy -iffllfr It 7. 7 HwMft Dmfear II tmhMlrir*' iihkLcI (hKhimi. 'THK ^ncsHitHl If (Hhmk-iI in llw wilkiuf HmI MIi>w. tatli llir many llw IcfifirtKiy fCwiiiM) will, .cgai<1 *it ikk <k nimr ivl .4 huiium ci|nme t> VC VWVI. flNiWIIC (AW. SllitlV 4. . A* l*tr,ntm llim lo (hkoiift In llw fcclhm rt>c |HMi;nn li tkt'Ming untlcf nntviiniiily nil Ilelcimining Wh i.llly lk'tc|il*t>lc riskt wcic iKhiksoI ii they (|>|4y in link' iiibsIMXcs irfftlnltiwi gcnriatly In (tiii can? (Iwfy, Uicw |HnMim ( cumiikied *f riwy have nllfi tiH agency ilcciciiaf making with iccjvcl m llw legulatHin <4 vinyl ctihnnk llw caw omly lagini will, mmiil hxt IiumiM mainlal im llw ii^tOcaiinnf cf VC, mi Hw imliiMiief wliUh ucaic, tiamliHili. ami uvr h, and n ilc deadly pd^wniei. Suliwtiiiw I cmveys llw tkinkd', uves and itie Inlmnid twclMol wiili Ihm Siilifrillnn 2 twvcyv VC, limkiiy and ,lar Maine, nf human cpniix In it f.( Vinyt CMraiilr i din nmf it. AtiorimeJ fabiinn Tlw wiiwfca vinyl cMnciife k Ihe hack. <>( *V wtmnl iwhi widely uu-U |4a\lW In llie tinned Klafe,."1 VC, a gav. if ni.nle linn, |*clin*lieniii al, and thimiiw When pidynic,i/cd inln |aityvhiyl clihaidc. a mM. a is Ulnicaicd into a |dieniiirnat array nf (antiil, VC was fiisi iiM<iiiflins'd ciHimwicially in lie llulled Stale, in I'l.l1!;*1 hy I'lTh, VC |iinilticiinn ciceeilrd 15 hillinn jaiumli *' TV wide variety nf mn rtf l`VC if icfliiWMiy Hi ils iHla|aahilily TV inaint iim; uf i'Vf' if in CHiMiuCiun ptalwls; ihIhli un,Hi,lni use, ate packaging ami ciniMunr, (hihIikIs nf all limlf I'igurc I Mnnnnniri's llw ^plkninni nf I'VC in 1974. Wiaak., nwlals. glass. hIki ,IjsIks. ami idliei malrriah can siilisiiinlc Iih iKaily all nf I'VC's uses, Ina I`VC is |aclenrd hecaiivc nf Vtlrr |vffianiaiKC ia lnwci cnsl '* Ihnvcvci. ihere a'C imly a few use, Uh which rar dried ftdnlinHes ells, 11 Several lined use, uf VC gat Ml uucc ecisltd. tail lltese lsc V*n discunliniwd In die tale lUh. VC wa, levied for use a, an auaesiV iii-, Ihit 11 Wv ffevmtiffAftrHf rSwirrf ft* 4i***4 Put Irwi. ('him A I'M.f till, M IS hdiitihkM ii Ar iMflkrU i4imk |4avu< M Nt.a I iKIH fwmmmrmt tfuuArirfur Vi*. Wftf ** I, l IS |W 11 fffii F%nutiit(i' VfU|rfnrfMW(.(*iii5i A |-.i'iiNMkV Aug JV Wk m 1 94 &Maur IUMi m', Cwuu i With. toH M Wl 41 II IS IIS I uuiMMutal Kmnlwii Afeufy, tuffun wtl t uvtttmmct pmet SidffwrM I WK5UM Stmubir Urn Vimft lUisiA t 4 |(M. tH| (hiruhiliff , H*.S l.0|. OS I uvHOHMfMdl hofrrlMt AfrMhf. lulmuumy AkwiHWM ul ih I nhiitu-Iim< wviMmI PiililiM' AcvtiuHiii Will Vyl ( Umulr Mil l*nlj rWaniAr K,|vhi iIk Artwrt*5 mn* I A4ma5 4 At Vmyl thiifulf f5t huvi M Ihicitulkf wiv-4 t V.S l%L Inttt Rir)uf| f I uN,- ? (Sn-|4 |74| ' 1lJI|ggy!gl!l*CTy^l">T;,'|w ynyrara'Wn ' #.-!s i* ^fiw.r! -,.t 4 ......... CMA 0 1 0 6 3 1 Tin TC e< AC Oavi * dt wulif ChUtMl rcyi^J Mtvoiv* innlut *ljM< OunKJi 4t**K |4t; la M.U ih Van 1**1.' (rtaslic ArikU*i B*e Q* Bwong jnmJiji *4 IttO I'-'JCll Tntk Suhuacti CtiMmt 14 iw I ni Ivorm Vim11 (iihuuoi pun wnw Cmuaii* u ru Itirfai if r,Utkmk$\ H* * I MmiIm | milrUiwM'#***** L'VC|jhfi>tuiltHIHtkvtlffl (V( f4ttu4|Mt| , 1 *Jll4uku#<- V( Iinrtil ptm4fU |wi >tm'UlHt')| [ |Vr t^af*** *inlpt*ci all hit AlHlIlll J|4 {aiftiorati drink tag **> fW*** i** VI" Ib* ? (mhikVI (tiMwIfit'lia'I T f *fctkMU piuU |*V( muf* ihio tanked ffJHtcriwcdlMt flatitc |H4hIiuh (uuwVC icwdual rut^i, ion* ii*untMi fiMnkrd plJMh.il I IhiilJ'iitf #mI t*nn**u\ ikwi |<*irr p*f*. IliMHtdrl............................... Iluiw tumiitimfl tfmnkiiirt, vhowt* ** IIS I'm,!J(h* llutidi. drutt, tmiwlkt. arlioifmOwtMtKtify(fHcooJiMvmtiHt fdiici-tirdt, lorn 1l44tl4MMtMwn J*M)I Hmfl. WfdwHMIft . . Appairl|lf*t>rpi*ii.fifi|<*t|. . .. MiiuDiikmi Imedh tl fr>nrt, rrrM r J| taJHMil ..................... {man V( rcikhva) ttcapetf m *S IS . IS IS IS rw tMp nntUtn* *U frkAlfl| iih orlp**tclr jndikfft ak * wmlplicr I tnicilof Mr fit ImI Nig wait) Iwd), diwff. fariilr M tinnian Mr _ l*u viMiKjn* pv^n? ;^rv,**L I f)ari4 i). t>0rttfer 1% il wv (I'jci'fKil hrcuut il iijivel i'MitiiKL (unctiim.** Hu'ic me ulvn jiiilknliiMt Nia* VC wuv iincc tiled as a rcfiigtianl in cnnliug ci|iii|mKnt " linlil late 117.1, a tm;ill percentage ol the VC (umhucd wat lived at n ac until (UntieHaul in tnme cuiiuetici. dingt, pevllchki, and iulvt etumiinti jnnd uclt. In 1974, when VC'i catcinugcniciiy became generally known, mil linns iif VC' imifwIIni kiihiiH wen Hill im Hie market m in onmimci hamlt. Tlw UK id VC In aetmnlt hut lime leca pttdiilrilcil " l:i|n I itWMiMei the tjtle t Vf'ificnk*, Itans lot iiial'inn, tic, and elivfMtvnl, and the ttwtei n( In........e|*tnc Hiece me lime imluvliifv n| wulral linjitHlaiae. Tl* VC' Imlncuy |ilcci VC from pcitociKiiifculi. Hu- l*vt: klll'lf* I(if ( im ihc srditl Iilaiik, Lmiwn in in * (mm us levin, ihc lalnkullnM indnsliy iimtuh l`VC icvirn jnld linitli- eil |H<hIikis Italy {< iiHnuiiw use in (in monpiMaliuii inm ihikIucIv ul iHltt'f kiniliin, Il jt is Ill'll' lime imlihitin Hun tin muicit me mmi iHravlly eijdiMi lu VC* jhmJ ihM ilw fciiown Ihmiiuii tamrii Imvr miniini tMsiiW irf plants iitlilkiHKwl |*ci|ilc tc cHjMiwd * VC lit fwii nujiN ways, 1`iisl* VC eluiuittiK esca^K (ftcliHiL'N to ||ms winmncliiig ir r* Sccowl, tfiKT Ihc fwilyMicfi/alMiii ihihc^ K utifvHcii, mhiic VC* rewirtm a pi frajrpcd ht f*VC malrnah I hit rciiM cwa|vi htwi itic lilattit in laicf |unthlfon In fnlrlcttihin |ilnl* grnt licjiNiit, mul hi mine- i|nciil om; mill ifj^fMisal. As ihh* moves Ihtongh iIk cycle ol VC* ami I*VC, (Ikt miffltici of plmiis ami com|Mmct incursset, amt |tfiints Ivtisnc \mallcf ami tunic Ulna hiteiislvc *flac VC tmftivliy is cotii|fnvctl ol III cotii|imic* iifk'ialhig M plans; in 1*171, Sliell, l)nw, iiml (itimhicli together IkIiI V* percc m n#tfl|Mcity wln 197^, 23 tmnpanks n|Hrrafing l7pViuitsaHii|HiM'il the l*VC imluslry. Gnmlrich is ihc major PVC puHliH'Cf wiih 15 fieueut; Ftfcslone, Comico* UniiHi Carbide, flimlcn, OiMitoml Shaiwixk, ami Ten itcco each imidnce Ictwccn five ami nine perccm.*1 IVie me afxiui H.CVIU fahfkalhm cHiif>anics <rf all sires.*1 Ileyond ihis poiai tialusiries cea>e lo he McmilH fHinwrily by their use of VC a* (Ishri, Kontir, A WiwU, VVIYf M\i**upui wirli Vm*/! *!*.k lANisimvi^d Ht, W.I|tIT| If J| |*Uh,lMH*h(l| IlMiHM 4XH{4MIH|lltl Ml IIh* l.iir(be*arm'Hoh is ilttkMsvrdin ik* Ui.Ki*htt|*>uvnf nK%set .'Mitsui at khm Iff*ocimi Atei`if)i inwik <w Vm* Irxm itr figMi m (NIwm wart, ninti *1 lift* VI" *h .(< WMwtt* atl >Wtl*A IdllttKt arptitl. fva iho* It. hi S. Ap(*mIh'*% m M: IIwikhihmi mm Pfiirn i**if Ai.ivt ANSI IN*** H* * WlllH I'hHMMH.tm IM t>*IM*.IM. Wild |Hri4l *41 Oi'M.Hiwi f Jilt, ll It limi Ibtiriiufitf (kJ i* FfA Tail 1*1-4 sh> KihiMim lat-iMi, aMIlflh HMdMl <nI Mint * i a* 11 im ii mi Ik im ivvi vi H % Fwt m %t Ihnif* < imi Ai-i i * i. Si hnimh imii Tl* I*** il AimsuMM Kinai mm Vou i ihihiih imi fit* muil ( dMMiif *H|t*Hii> If f'||thteMMl|f titrd 40 I f \ S* a vino iviiIumsh* Hi*i| 91 M HI .'I ?t 9* | t*A t IS iNf*M 4Mf M a I !' C4 CMA 0 1 0 6 3 Davti Hid (111 rlnii tcgntjl* HIVOIVUI IMHhK i .i.ihtim IKvh^Oi tlA tmli tw IIk? Ur* Vu.yl tiu.1. vt 14.1 ,hC I Ajll(t*ICI IIM* <j.l$ (ftHMNjft hmAk-I i4 IlkU V I* Id. draft O lO ^3 H Tonk Snhtnittl C\ As iIk iilMM- h|!iircs indkalc. die VC mul I1VC Imhi^rkK Me iuIhcImidaily cnmcniiaud Htcy jic also wiiiiuily iMcgnttcd In 1*)t2, .VI |kkcm VI VC pioJuccd was sotil iii I'VC plums owned by VC comp(niei, tlliii<i|h hit Iigore li.nl tbopywil Jhhii 61 |kikM in l%3 as the IndiMilei IIh1 fact that IIn' VC mul I*VC imlucuics cmtlain only small nUMtfccf ul rclalicely i'ihkcihijiciI uni Imc|iiKiI linns Hus mk It easy lur the imhislrirs k> speak wilh mw voice in rcgnlaioty proceeding* tcj>ar(ting flic biuils of (heir Icthinilogical rad teamimic capdhiiitlet ID euMiut VC tifomih'I 11k mkInvii i.il nuitcl snncimr also mule* k ikf'kuk In KHifly/e fbe lioc costs ul iiown it mc.isuic'c nntl to dctcimioe flir iitCMk.`ike of Ibosc finll mi inuilwi'i pikes, prutlit. wages, and other irtfiuis. Moil VC plaoli ore open-air. tesendding nil refineries. They arc Incaicd in |Kt)iu(i*ci1 area* la warm Kale*--principally I milliard, Ttau, ki'tiniily. ted CulHmiiia " PVC planii are enclosed, (mi iiift emit VC, and hey ton ait hKMed mostly fat populated uni. In addiikm to Hie above stale*. New knty, (Dun, ami Massachusetts ate ma|ot PVC-ptmlocing units" Only ahuwt one ihiitl ul Mat VC prodnetimt Is ptdymetiied al the ibe at tvhkti h is puhn'il Most VC mml he lmtti|KHlnl lielwet-n VC and I'VC plants, mainly hy tail tank car, ami also hy lank liucl ami barge. In addillon, I'VC KWH must Ik transported Iwtwccn the PVC ami lalaiealiim plant*; this is illmw |ninh'Hfly hy Irani uml Ifml * VC ami PVC plants ate highly mcchani/cJ ami rni|i|y a iclatlvely small mimlwr of woikers. Al any one lime, iIkic aie only tlaM 1,1*10 eniphiyees in ihe VC iniliislty, ami only altool 3,3(11 in tlw I'VC indnslry.*' Tuliug into annum iIk mwiuai mi novel <il wmkers, alDiut 30,0M> employ ees me estimated lo have wwttil in llwse intimities since Htfl." I'shikatiam plants ate mine lalnx intensive. The numbei of labitcatkm workers It estimated al 130,01111" I Itese woflets are subject to nmefi hiwct cx|Hisutet ul VC llum llw wiHkets In VC ami PVC plants, as site etpniite of the luluicuiimi tun lets comes tmly limn esea|ting VC icsubial.1TM Ihe sire ul llw pinup, however, fives lise tu Ic.ui 11, si even a low imiitcnee nl cancers may claim a laigc minilwf id lives. St I (holer |l Jhh'H, Iih . Ihtrl* I m.tl Hc|hn| 1 uflwum thy.nl SiwW* ul llw I Ifttfihdl lSst)Mcr4 IISIIA Skjdld4t|N lid V(rt|4 t Mmuk. art III 1 |S*|rt II, IIMf |tiri(Mjltit di(4 < Sjk IlfciHkrtlH IrtifiiH t Nhisl) I si M n ill j, t r\ i is. tflfmi fit n. it i n. w Vt | |'S S* H Mh NH llirirwcl SMr*l. ikyred fhflr < dl .'I Ji STi I |rA Iflki luite Nr|tnt|, ittptt *artr IV j| 1 SI SmN I oimhhK li*fi.*it StwJ|r. wyifl SI. M til 4. N S* K A'liloid rt ut tufirfl mrtc V j* VH. "It iTHhrMniy VC ic|iib|jM m if*r wmlftLihfll llw MDihri l miwm liRMhl m Ifcese tntrii, dink n. Ijip ( rfnotmt >c|HCNmN mi,%icMrty MhMfctod in ilw |*pMLrtNi * f M ld>i Isitsi Kv|hni t*ftett Hpe Ut. m If * - a - .a --------- . J.. I d 13 Or! fll ^JP*"r*!Tp *1* I Itand It. Omdffi II The VC and PVC wmleii me leptetented pintatily by llirtc uninns: Ibe OnileJ Huhber Wmkm, die linked Sleelurmkm, and the Oil, Chemical ami Ammk Wnrkcri. Oft Iheb own and rhnnifh llw Imhislriat linhia 1V|iiintern nl ihe AP1. CK), these imkmt weie mt|n( pliel|iai|ir in veiling IIk VC iktnpiliiimd eapnsme CldaJanl. Ih* fahtkalhm wmkm are tepresemed hy a variety id tmhnts, and some ate md tmhmi/id at afl. The trchmdngieil and economic capability* id the VC, PVC, and labticaihm indtnrirlea In lower the release ul VC--in plant*, lo ihe rwriuOfki ilip air. and thnm^i Intel tsea)dii| leibhial in PVC - have (wen cmniamly M Issue In Ihe legulMmy actiont dciuihcd in lubsctpKnl aeclkmt Ihe ddlkuti)1 id |nedkiin| flic Irtw* tec1imdo|kal and etummttc timiti to changes in these bnlniliiel ll discussed elsewheie,1** but hetc It h uselut In give unite imlicadon ol Ihtk elewly dcinmntfaled past and prctenl cnpdMHlki. Wifhmd neeil Im any signtlicanl leihankifkal Inealtliriwghi, in rite Inor ycata time VC'a carcinogenkily became dear, rite VC, PVC. and labfirMttm imlutUici have signilkaiuly icduced their ichases id VC. In lespaptsc IIk icgnlathma w Ihe thical ol tcgiilalimu, (lie VC ami PVC imhistilet have been shown hi be able hi reduce wwk|dacc aolMnne imnenIratliMis td VC limn almul 131) |>mis pet niillhm (|>pin) lo abmn one jiyMii,'*1 hi reduce VC emissions lo flK outside by about 95 percent,1*' and lo ieduce llw VC tcsiihial content ol hmd packaging hy several mtk-is id mag nmle ,,M New plains laic tat ilillkulliet imrling iIksc htwcicd levels.wn liiiltKiiiHiic, lltetc is mi sign that Ibe limits td cmtcM tcchnohtgies have been reached and llw |nnsihility teinains Ihat lundanwmal tediiMikigical bteaillatmghs cmihl mcui these ledueihnu have been aeldcvcd wirlnwl any significantccmHunic sitaio tin ihe companies or damage to PVC's ntarlct |msithm and lutoie growth pcns|wets. Ihtooghiwl the 19Mk and early I'Wlk, PVC ............. lion grew m a tlaggeriitg rale as ptices declined ami tlw numlwi td uses Increased.M* In 107.1, ihe business analysis Inrccasl uniirtcont'inl giowih; tlw mayor |niriitcni capettemed at that time was the light supply td pci rwledt il taw matctials.1*' Iat Sn macs SI ft myra IMJ tr Mb* dnumUhdwpim fldtii Ilf, MVMI Nfifl ll ITA I IS, Hfid trt M.il M, M** ai K(ni, imt* mht |im % Mf' S*-r y*i MtuMfhfldtfawf lit t*ft* rw ffdffi tk4 *4U+fAtifrtdwm. 1'rrt hw ai Wiu, Stfk it, IfN, * M. lUs W WN I ciHmnih IflipMl uyw mrtt tl. it Ilf I, thluM III I. FfA Kit. Hftd fliflf IV tfg J-1 U*f Itght Ifwwflw Stiffh Huf** fW' Hmdmnrt. Cmn A l-wcl'* Mini, U|r II. I**'.** _ X. ^ Dili IUK lUhkl -tul I' .|i<ft s-i .4* , 1.1. f l^i*| i M < |-. . It l'* iU |^-.l n ** <-> 4im-' i ft'l' a\* It'Msi J| Omsk m wh- iij.ii u TomIc X*tb*t*nc<t Canfjvf hi Wl ;iinl W7V Vt' ,mdfVt4dinniedhhut(dy,utuifc iujr lltc hr4 Kcsil in iIk lieml of |diciiiHtk'n.d (irowtli Ik' sfuwft, iHiwvK'f, was IM i^tscd |) it 0^11111**1 *s|wiiim' iii Ik* rmd.ritoit ii| VC'stviiibHi* lankily nihf Ui ilic insti of iiihi|)(}iiig v\illi *M* buds M;hIh*I. Ilu ^utH|iIv m1 illin\k'tihim s: (If ulfc'tiffirs hr ihv early 1 ">>(K m jMvs mi in unMiiiK'b i)k lising uhts i4 (tivilshnU; and 17) the gimiat ffomniiir leccssiim in |974 h) 11173. which was |urfi irbily wvt-w in lk huihhtig vmslruith** intimity, 9 major Ui of lihisiiiv m I ho shnnji tuft sh.io'd I'ljiiiilly hy nil d*- tiuyK jdasltLs Willi iIk` fml n| lilt' it'U'^imt and i|h* u'vKiil til lltc Ik Hiving imhrvny, fdeiih* p'lki.ifl) muf W in fttflh iita hliHikil u> lln* ftiiiir iwwf if )Di)iilnltli' 0> IVseiill), ww |i|Mtlh me King Imitl In luo l *ntH't|iiift:il ih iiMml. wiilimn <my i^utcm Imuhiincv hn*n imicnt Mini pnptsedtvgtfki- limis m Ifcmv, ll uppem llwi vmieuliw jnoiK'f icdiiriliHis in VCrktHfcUfc uwM Iv iltiHMitli'il til tin* JiiilijhliJtih wiltmiil ii'itili'iiiin iMIh'i filin'id i|tcia- Minis m i iinjitiififMlilc' As ilw InllitniN)] sinvcy of Vl'\ hnkitjr veil) show, lK*iu is no Imsii Ini ilnuMiii? Ik Vr Im/not Iyen diiiiiiitik'il by Ik iiHMMiirs already I.ill'll, mi it will Ik' t'lwHHHlt'tl by lk wltlllinnal liictoiiii's .MiHnWit by lltc nulmlMi's ii) Ik hmlt k'ijiniitit|;ii,illy and ccimhhids ally wiihiii their ic.nh limber toe jiMditd b> the metfk af evidence Ik jarird aJ wliti It ihc tmlitstihrs would Ik; sctinovly lutltlcrn'tl cuMHonicully is, bnwcvci, iiii|Hi%sililc in imuliti icliiddy. 2 Health WitjU ami Sotatrt t*f t:\futfttti* ta Vinyl (`Himnit I tic inoc i lfciis of VC mic tnw immii IcHcr Ittmt tlhiM' *# nearly my dilicr iinliisiii.il iktttkitl VC"s carcinogenicity has liccti well c.Mablisbot by human cAjiciictKC. unitnul cutHiimcnis, ami other lalKHMlivy tests The hiliei cx|KiiciKV til iK'cti|rfuiit;il e|Nivme has imifWmcil VC'v M>ilily l uuse latKcrs iiiul m hml of lesser elicits in knuin The lists raieixl Inryoml ihc woilcrs; niillinns oC tHlwr |n'ii|ilc me cjt|Misc(f hi V(* Tins ii|>vccititt vuivcys the evidence of VC's huieMy Mint lltc cHlem nl Iiuiiiih ck|misiic lo llnr ihciititat n At tat tun! * krtwtir human htsii riy Mclttic I'>7-I, svIk'm VI' hail ihh yci Ken cmiiKid'il in Imtii.intaiKYf, idki ifinif'cis ol die iltcMiKMl 'sere well lmtwit. VC is I'slrcnicly flttM* niaHe, mihI comcnliiilhins in nil ciceding -111,111)11 jijini arc csj4osive.**# ItIM l i^kt, |V?f MwtUJ. jn If 1 t **,ifH*n (IinmmiI fwiftriO/ri. (Hitt I l **i 1 t m- K Kl t . Af* 4 li.liUsV I *(*! f Af.vi>tr Mill t H f Vk.ffiHiri H* 19ft, V,I 111 ^ AS * Ni *v w 1'tJV Ml N iin nnr.A riw ! ir.fvirii. fn*i> fnkkto. t*n no. m '< 11 Ik ||.k|, 1'wiff UiriA H(#n Sf,jm h I t |*sn A 1 nvf'l III | ill If niUiljs W #f.> Urikr (Vi*)friNi '| i |i I Dm*-lrf /J Oflttigrr 79 Sdvo| unfU'ts ktve died (tiuli hthultiifi ekuonely Ingli ittitn'iinnlinits f:ft|NrKtc |o iniHviifrrHhMK gfCiilcr fhiirt K.fKNt |t|ini VI* umscs ihh1 lo tenm* dir/) ihnwvy, iIImhii'iMuI, uml c^cmiidly unuMiuHtus 1,1 Ktw.ii ditscs iolmkd itwt it (H'liml of n woil dhfl mule one intmc lo <lci-|t, dn.*um1i*ss diY|t,M 2.VIIkliMi' l(lM, VC ctHkCiKfiiliutts til id .fOtl)i|Hii woe umiinmi hn many job caicgmh's in tlic VC uml l*VC onhiMfks 114 Aiming wwUo t*pn*d in ihest t'limrmniiinfh fi>r ptriuih id onmills r*r yeau u niiinhn id effects hmt.lk'L'11 ltlcttlifkd Many workers snlfcmti'iilarfi'incnl mid liKmrs id rite liver ami h|Mii'n.'n Malt) I'diitiflitl Kr>iiMml\ symliorth1, rltiii.H Ini/nl by I'lntiluhny ilcjfrWUilJihi in the cjthowik's wvl liy fcHnig or a freliug of jiins ami nerdtrs In (tie hands ami feci.11* Mnny lcvii'|<cd ki tculiHim, a skin vmHlitHtn, ami auimshrulysis, a laic disease ilMiusH iimt by tlie dinVii4' of ihr fast In Mies in die fjnjtm mh! toes OT AIiIhmii-Ii wntlri* ivlro wllmtl one of lieve cllccis did mr alwM)S snller i!k- (ilkn, 11k rffeiis writ fioujH'il iinth'r the runmr akvhyl thUitk dsra\e. Wkn VC\ ia|Knhy hi cause iwnci hi himiims K*ia*ne elfin in l*)H. (Jvc nktliyill esamlnuliim til VC mhI TVC wmleis Uhmilivd mnmtiHis acute mih) iIimhoc elicits of VC ihnl picvimisly Inn) pioic Ini yniivtl ativtial liunbiiiHi ami IIUmK of the livei ami \|tKcii isfie found in iNittr al a rnifriisc<t|ifc' level hnig lielirre iliey wete ihinYidf) oliseisMfdi' f,,f lit 5fmi^s. Mi SlthMt'l, rinntMc. A Vm# f, 1ft# 4ni**iri<Mi \f kht4t i *{*' HKfl U'tfft 4L(trfH,tal SvHl|4f*tltl, k) \M iKtllS A'S h 1 IWU'KH IU I PA 'riu itNii iin litirMi o ft*t>i. tK<M mite vi) m Mi 11 Wrm it,*m IShMmui \ ti^ini Hiilr till, |K M ll i'C ttrmtmg*. **?*+ nmM |,Ma(K*tHwMtfirilr M-ir*ws Kcj. Ikirci.M. lihlihiif hi* IkiNfulfcHtd Wil) mkI IIuNM 1)4 Kirftfwi A MnhWiri*. ?a# *4 taw at mtj t-'m*tr,>n*n**tnt $artt**ntmtntt P,w HWitM )ifsnnfM VtorlmMuft. II Sn Imim % Hii.ilM il`.% i t l1(IO.'j|lH'Hw.iliff viHl s Ktulft Isftimin m VC). ItA & n MH r ihiIihish m Niivo. in^hh n.tio jt 111 lifts. Amhl'iw*. NkMvHi, IImmi, IKM:m A VtW^l. |Snlnnr **| Ifcw.uc 4iMHy VMrffUwJftMNrArnwthhHhfr H'wlfrt, *aAhMM)t V Si n Si* ??I!*>( IftovwdNM imi-M.r. rs#nAm#i/ffti#lfi#|. | mh|c. Inftr. Si#ih. A flitANfiiH* HWIrfi, ia 1 N V .Si 'ii Nt * \M*J as I Mift#* ftridi) twlftc* ft.twluw III IVf.itlriK t >r fSmx/. iifwaW IO.M I.', t 9t*uH* Mr H' * IN IU IVfiitfttHf *H IJm#**#. w*e*a ai IU. h) 3!, tmtiktr ffnalri. Mf#4 hmiv II1. .it IK, Stlltlk- fftfar 1 #ii*mm 4mhn| fWtiMtl fftftfral# tlnvlHiturn H.tirr' *m itifwa IV. Awxi \ HV At m Stl tMlIVD*. IV-Wti. Mmi (MniiM tSfbhrm* *. *' I Hi lie Vv-anwa, | , !*#. Slna. A OftHMif JW^wfrOMfwHM itxl I Vijim# ,if CU#ift IJtiritv. .*a Sssii i N V A* mi S>t ft |IK*'I (It MiNhl t*>fttsm. ftbrHow. A icitii (nfiAirt lN<nwtiftlii ft* fi<f>int| (MmA ISnIiMiuit tfimmuttiM Bf laVtui MNfMnyr, ?aj Vi Ml u Aw h IViNiI'CM, tS*rt*ri A IhmiMs, ,4ft#fMO**Nl tff thftmml Sftrtn 4***. Vi*tt ?Wi NY An mi 5h 11! (Mill; IIhmus A Kh1*'1- * *f KiHtarifuiir <y rft# I ttft 4mm| tWriftvhft-IW^imiI (Mwiift H'inUm. !ft Am*h v CHA 0 1 0 6 3 4 V- s cj fi II, *M*"siu* JO fork' JabiMwn funnel Mieiinenfde eummalkm icvt-iilcil nthcr dla|tcs in liver etHs.,!* Surra: workers dis|4n)eil u nk t. uiii.ty' <4 ahnonoal User InnettoN and Mmnl lesls.'*' Sunk' sulli'lnl int|siliiiieiH td tong luntilo,,, The medhal researchers lu.l lliai itltse idrservahlt elfetls tsKihl lie nwd In liwlii'afc wtai is ai bn leased list ill ikvckiplng lamoi ami ho* VC (imkJih its eau inogrnir itllcil. lo llieit ililNf>tt>nUm'lri. however, none n( flu's,' illiili corribueil well ciHHifh with observed eases erf liver anginsaiiiHiiu hi ill iitlni eniK'm in imlitMe ikafly sshkh wnVris aic ai iiwieascii itsl. mif lias ilk- kiamledye id tlirse effects enabled teseafelieie In eijilam liuw VI' causes lancer1,1 fi Human faiti ftt ihiwghtttl Ite ti IWJ, itfift ft* ik*iIh ul if* lm (ImHtfkh wniltik ItcrKttiC Mhlwlt, iHliCt tiklllHMldt itcuihs mittmg VC mhJ |*VC Ilie !) lias ii^r Mcwllly tlmt Hm-h tliifiriii cast's v4 angiitowcoma ! Ihc five* had Iwck icwmccI iiwmi Amciuaft wiHkrls hy July aud a null uf 75 cases were known N V Amo $i < frJHUHMirJtik. Mofto.i Hri.Mflsslw*ci. iffhr* ttmmmgf .<tfNiiii| MyHHif ( httHfJ* tfirjmItrVI Hirtlfrf A Rr/n*t l| fdiri, A*fb ov N V At *11 So DMIVMI I'M )nFst>Htte'lli1lHII>M|' HVlKfiM I MfemniMahtWai IVudrAff fhiir. iwfwt*l!l IHihiJ ptatekl nMHt h-tv Kch ihiwo hi . hut WH iM. <klMs .4 *f>M i***rsaM- % I ifi fiHH iMiit id si i shiv* -* wnlc viuiei|r nl ot ihH( MV Imaltr ffdMfJbt, ih|in Mi llf,VrlimM.f tingr. Infer. Sirin. I itAorr, imp** omr III. Man iirlto, I tllsiih. UuMti, A tacahgl. flwintl Sfttmtmtgtiht I *\ tt HiMiMf an I a idrnr tj 0* |VnriN*robi t*pjr and finUrd I Tirr Jfoirtjr An**** t4i4r*in*i<hL*mff Ptt*4tn ffitm ?lf. Aijn*J\ N Y Atm Si l 0||*mi I.'? Imiibk, |.w, MsMhImvI. i Wavocikt. mf <X a mjn*ttnnS t\4 Wmowioni Im*h*if fd'fnri m iV ft/tftfutitf Si*t*m *$ I'm;!{"ftfeittdramf flfcrr Utolr*t, HI thM M* Iushai Mi h In p4iMt>ulg*rlint Itw (XHtMicM MMn.htf d Iih ataa*V|4*i**- OSH A nail'd ihc foitwre M faiial in Ifliiwl Irtit, lave* IwKlimiltjIv ond ttitaie ulh(l ttjnniiilinm m nh.iMa mhWjIsM ul ImkiviI Cihk<i list OMM Stumhtnl I'ttr VC. imp** ouir I, al IVH1 Siiwt iM t*lt ul Oil iulKfl iPSIIA's ulisu vaiHiK as ouJt, iKcie Ims ktH Milt iImho* in ihc Oair *t tiiiawleJ^r ul VI \ Mis iMftKsh Simic lH|*e ul uhVI* wulunJilwmit* m rh e*af> binge tt |HiaHHs<J Ok 1*M IdsCHl ICt-ltnb^itCS lid lt*M K MNlMSUHaitl J|4t|. * Wi ktafM fan ' intiasg |>k tuie" tf ImciimI aMgeah mk.Ii mi the Bvn Mmls|4rfl w!h*h \wgctk ll^UMflh j siM nl "vsHuif " I Mi ittMmui taeiiTtiil Manets mwluHtei gmnitiiuy > hold** iu|hk lo|M( lUtarH. WiKmims, SmhIi. 6 |VkI. f^rb*t***tf Af%utti rtf Href i*l* in ffrr IWfr. rnm */ 1`Mei I MmuIt ttihUrJ I hrt tiiml Xpttrtn fOtenir. fMSun Kim m Sa iMiit 1*1) Aoutho tc.|tM*fwr deles** Mi rats* ifH.' tltMHft * m It* bl*` daM) sf steniM ike Iwiro lr 4ai ecMsuned iIij* iltc Rcymml's syadunntf jimJ iKiiHislenlk'sIs nnuM W acircde4 Of suit Unn aI rAnO, 4 tf#f umU l |<wmI, n*wlil lx nn tadtown** td insi**ed Osh jkOitkif. Mmsan, Whthluiif, f cHuf, tmptm mill 111 OaHttct ul ihot uiIuikiiks, Iwwivh, vHrit mrtf imw4iHr <4 Ainiwf Vt'-imfmril ttuuirs Itrlmr ibr thnnfcs nl lit* hIMm level mIikIi CMMuaMy k.id h* CHuci luw MtfejJ)1 ncsMied 114 Otawf^lKWaf S^friji Mid lltmhh A<lmtmVim/It AltmA* P**1p*ued SlnnJ*ied, W 1 cd He| It.DWi llflll HkicomIici coed 4> OVfM rutpmuJ .Vtnwlnrd Av W'| IfA (t\'i44 Ptimtamemt **mmtmt4f*tr W`. tttptm mi( I, kl I4! PM IKvid li. wnrldwiffc oik Womb taler.*M Alltaaiidi die inajmily nf eases invnlvetl wihLcis al I'Ve ptaiMs, ndict anabets weic atsn tilte-iH'tl1,1 'lime sstie 1H eases wntlflwhle liy hint tOK,'" M Icasf SI cases liy lletenilki I'lTli,"* and *1 Vast Ml eases by die spting id ISI7*. Ahknsiels III atisiduK Mims these numheis ate ant lafgr, ihr late id liver anthismeiHisa In mims yinups ,rf I'VC snnlkeii si wiled langcs Ikhii 4MI nt J.laal limes Ilk cs|>eeicd Inebleme hi Ihc (tanil imfMlMiin1" Shut iIk lalerwy IhihhI ' the lime lielwccn inhial t|isme in VC ami die rUnhal t|S|eafam-e id fiver t amet~has been aveia|iin| ahnul 711 yews, mine eases can he es|k'ih'il as Ihe icsull td lilyh ea|aismea in ihc llUh, I'Hdh, and early 197th Many id the rirtdnyec* wtm have died <4 liver angbisavenriM win bed as thHKii id lha |ailynKi|ratkni naeha (tin tlHinhei Ih which VC hcimrcil td Its PVt`1 m sunbed hi area* midi shntlarly hiyh Vl' r*|ises "' lliese wurber* inrdmMy were Ihe nnMt lieavily ea|HKc<l. tn terms nf hub nnniwn- twy |icabs ami snsrained averaces The preeise levels are mn known Iwr arr cslimatcd in have iik'lnded pcab ca|aiswcs id several rhraisantl |i)mi amt an veci(c id J Ml lit.nal 1M Orhcr liver angimaremna viiiiiiis inesumatily hail lower, less susialnetl es|xismet in VC.'" I1A VC' HftoMyt, rwpfu mne t. n li l) (M<nmriit d IW lirs<|4i K W^hkii iff 1|mt*c jrffctlul twhdcd * at V4" pfjnd, n wmtri nVi CMr4 fi sln, tab k .hiv with V(`flMfcHftM iHtsi 4tt ;KO>tMld4 wtd 0 ntnkrt tt| fVC' ifinkf^tnnMing |>Lnl> fj I Ihk Wri tt me lit fcjvr bd *riy km tt|>iHtN(t ill 14 MM.l'PA SncoiMi tsolMiMti O IlfiMb Mpd ndr VH. n f!. IJ til H|M>*Kd (Vwv <4 AttfKtvMtcmkh 4 At I iv*t Annanf Vutyf('Mm*de< Fi4ynro74iim Wwlitb IIbar A. |4?M ttMnwiiMtd lniwAn Arht ent kivtd witk IclKt ta ikr mhImi Itrwn Hi*e KMWnaU, StMlNthM* illcilhl. hMnh SechrM, tVmntif ad fiurtciaiiid. HaMil |'voliHiinHi9b nn4 | whl SimW*, NrMaaaawt lninan< lm IHaatfaunmnl Sufcty nnr| H<.dlli Ilk v A, W IW PriwWal irmwiaaiwHinnt itk Note Al Kwindi, StaUMhiaN (lltnkhl. IHm * t fItclb SfirliaaK, Hbvlvnm %4 Satvvdkankt. |U*Mi hv*4nnUuv. ul tbnWl Ki*As. HaAKssMl InvMndtf fan IbtttfMnnwf Wd? mtd HcrAA. Af* fi. 4**i 111 Ike kawet fftn H ItMtt liiAb. I'rdlL. A ('irmli, I koriIvnafar i ufCditi i*f An|At*ereNM mfthf I hr* Amtmg Vt*gi t Mnddr Wrmtrrt la fht V*k4 .ifmtfi. J-to Ahh u + H f. At rMi %o J1I. )ll|t**H| Ihr ItigWr ltfm< 0 Ipmni I VA l VA. NaH***l t muum St#n*H4t JU IfufAikwi -dvr AdhtniM. f>rynv4 .WnwrAwd /w t'm^f t'klvatr. MttJ Hr* **l|f ||Ht| |ktitht4M tWrl nv KM Ihtayntird Si*mJa*4 f+ Vl*| Ihrx Itpuir r ihc itauh ad cntnf.Mtaa Ac laics nf jngki*niii*--i nf dir lint hi ntnlm ah lb* *Mdr n* ikt pemrtwt ftiftaafailnM. naMMMHf Ai the trnrinl.pnmfalk*o tiHt n* *4 rnrscJ h| VC' lha rl. n At ttMhdtf nf d\ wfolinn ong^rMw. mhw d At r*soin iW fcnciMl farrfHiLntattt ntray lx ennard ky Mwco^itdiiNut VC rwfbtMHC. dtrudbrsc (tganvv wnhUdH thi fantnif ot the vktmmj ttj V('ft^nmigt. nj**n raHir I, at t*iHttinrMutIh tomgl bcMdll.tlcnkJall.l Cdcchh. infir* nudr HI. 4 1*1 til. Nnhadvan. Il.wmntnd. Stwhun, A Vhfcntf. Mldhr faftwinr tf n IVlntt >f Vhtt4f*liJftUru*!i44U*t4fWm*trrt.!*A*mMiNY A* m* Stl C Mh !fll*| V nftn t in A 1 a4ko. llrHiuht Kwinvatmt vf tt'dwtrrc fifuidw VhdOAudr Mnwwitt hike tm*r nf ftdrtmti tAlmrtJt t*1Srrm Ihhado. M Rai* f fnn>v Mtt 11| Hiidr* t ifwiwt tm VC. mpt* m*r III III l:PA Sa h nin n imi I it iin* ti ilftniWf anr W. 4i D, T S 2 9 0 T 0 VW3 ,s u Tniir iNtiiMnt ('mitf IIh.' bmp Iviiii rW\ til VC CRpUMii* niiiy mil k liwlhyl to lim in^WHuHH.i < hie Mmt> til PVC wtifLriv htcmiftcd MallMbNjr signifi- ant fuvis tmhkihc' sd tiimeh il line liraiM intd t)c fr*piitM)T byvfrm''*1 ttady ttl ilk1 i'uiw\ nf ileiifli uimUig yiituriliih wuikm I'kntlfLcd imtlm itigiosarioiiu*, hm il did soggcM wi hictnttil Imilrmt of aimcri uf the igoiivc iyiitiii umimp Mil iika iml wumea rikJ flue btml widlltc uriiwy \ieiki in wodfcti l1T tivlikiwc of iHhci efftrtt fat ngyrurcd topiipularioiii o lhan wntkch One Minty has \tnmn a MMtukntiy ognititwil excess ttf biiih dcfccis ami central ikivomi system luruors iiimmg rise tbiMrrn of iiiilk-^ iii ilncc Ohio L'OMiiiMinilks ihiit luve Imslvd I'VC (ihnls fix tttlong 2i yems "* * - Anhnttl buiututyt tutti ttthsr trm fttr tun itutyettit fry VCi lurciuogcnkJly lutt Ittcil loufiniKil hy flic ICftUllt if tf Kplilmfffl OH aiiimuk liiul ly irflWt lilmtniiny k`M. VC Iws teen Omiwh lo cause cancel In aimnaU Mt wtien inhiN iwt when inpucJ Ik firs* hint (tort ihe ikniJciit cauui c ant'd came from line ptiMkalina in 1971 *4 Ihe lesuhi ol Inljan experiments |nnsoied by the 1:uiopc*n ami Amciican VC ami rvc |ntKhueii, In ikie loh ibis Inhaling high umceiHGHkMs of VC (1(f,U(Jil ppm) developed ana-riMi tumors of ific stln. fang, ami lHtne.,,t I uniter icms sponmwciI hy (tie producers were com.'Imlcd ami reported lotlie (ktipiiiiiM.il Safely and Ileatill Admin'Mutant (OS1IAI in early 197*1 As shall lie Mt'ii in ihe tiise study uf OSJIA's standmd selling, Hie data arrived ai a ciuciat lime On lehruaty 15, al OSJlA*i lad-finding hearing mi VC, die Ituhan jesciwcliers irporied llieir Ihen-iinpublislred findings iImm VC bad induced angiosarcoma nf ilie liver in tail inhaling ctmcenirulhms as low as I5U ppm *** On April 15, OSflA received repoils fiom icsis umducird in I Mi r.*tTiUw A Gal l jf. lt<*rtut*r Stoilf of ftWIeri m fir Httmtfitttntr ttf ViOft Otlvnjf II I Uuupapkhm Mhi MW<1*70 St* otto Mom***. Print, A tiiKflitiii. tittftmUty Amtmi Vtnyt CkU*roit Uiirlfii. Iih I imii. AMg |T, 1*14, Mi WJ III Nitkdt, A Wiwif. Aittrimtitf Amtutf fimphtfrtt of fW SoAtfrutori, 41 i (SiunU)HM Min 111, i?l 4I*1>1 uu< u *(**{<? FaHadm I mfthtftt11 Ik hiiibutt ihikJ * mimt'fr *4 IIh% n ih design hM J-pi* fm ibeir iibjf ib*t fKilaJrif Ji4*mg Inm imtlu'HHli frum tt In partHtiLw, a uuU k Wffl hi fuNna1 ik popuLatum uf fafemrltun Im turn* )caii mlo 'be IhHM< at a tulPhicnt SloMf (wituA nuy M vet Imk ebigved Iwt hiim clletls So mwI4 ibctntelvet 111 IhIimI, Om**f*mir u*4 htttfMgtttn Mitt u rnMwM(iri ii4 t\4ffbtft (lAifiAr 271 AnnuiKY At ah So n.)4|lfft| (/ InfMitf, McMkhnl. WagvAri. WjiHttkl. A I alL. iititrii* Mill l of Via if fhhHnleu till I %m M. Aft 1. |*M. M III tfuhkng iiKicatcJ ItiJ kitt among wives uT winter % caytoseJ to Vf'l IJ* VmiIh. Iligutli, A CarH,l|t' tbtruferiN' Http*'"** *4 *** ttm. iongt, *n4 Monti to Vtoft ( StunJt. IICituiiRi m mh lla (l*II| |lKTeioafir meJ as fki'trwr Uttfwnt* of Khii to Vt'| 14(1 IktufJthiiul tafetg ami tle.iNh Atbrnm'it athwi. ffmergem jr Ventptttmp StomJorJfm f ifHMH'r fir S'mrfflUhfp Ulril H<g I? tt' fl*74< |lwirmjflri iiuifjt I#C/I4 Fmrig/orf ttmfworf iinoJont fit* VC | v; rrj ~ qrvr 1 H:> r } ,v -r^TW! DirW p. Pmlirr )) iniimtl 4 ilmllw ic.tttlli Iii hhcc il lit Kiwtil level nf e>|iime ifien Ixrlnf leHetl, JO j^xh.*41 Aiwiml *eM letuhl iltmil hi IhK jxiiiil until enljr 1971. It nil t(|m(ti`il lh(* Ituu iitgttlkm Sy (til n( tl little i ipjiineliiiHety 17 mtlt!|ii\n pci llkifiam of hnaljr weight pnKlocet liver *(iui*(cunw tod other tenent."* hhtsi icceMly, In Stiucmlwi 1916. the tenilts nl wuihtt inum) ul InluUiltn capertruelilt iletmutMitletl llial VC rau^er tivet Migkiwivoim far rail al U plHtl. aiWI tint ta CMaea inaniinaiy Imntita at rote |ipiii, Itic kmetli tHKenliainn yet tcHril.11'111 Tilt) Injllliil (llwlitlViili alto IU|i||uil wt|iicliH Out VC eaawi hiimaa canceti ndier Ihaa anginurenm* id ilie liver. 11m c*|>ctinKMi have thtinvu ilaieawil eatO'er IneklriHe at iiwny trie* otlict than I|k tivei, iik liiitnie ilv lungs, spleen, luain, awl, a, already anul, breaM.,4< l*.a|iciiiiienlt ikiwMt illjiiiig llw Irufuctlun of ettnti III Inn ijirrlri olliei Hum mu - utke and kMiiltii-ImiIiu eunfkiH llial VC Is tafeiwigclc.M* In llw animal ca|)eil' WCMi lh* snli|eel> aetc e|His*-il Intumiimt, ptidongcif times nl VC Hr need was noted in aiM-lfll fin itiulies id Ihe effects nf single awl *|hmmIic tlnset, ly|iical nf many humans' ca|hisuie '* Sotli a stwly is nw iraiing couiptelion, hul Ihe results ate not yet avaHalde d AthlilUHttil kumant of rill to atklilkm In sevctal hmxhcd tlHinsainl win ten in VC awl I'VC piwind km ami in I'VC fahclcalinn, niillinns of Atnctkan liave Iren, and continue to he, caposed in VC. Tim, about 4 6 million |rnpte live within III OSIlA fftpotrd SiotJorO fm VC, topro rsulr |}4. Hi lA.HWi 1h rHihs uf Ik lukhfv ttsll, h>v >kwM| |b imlktibiii f Nvr Hngiutmt-msw a* Ml ppm. *rr fmbhtbcJ m 4lt)r 1*1} MjSwii A I riinr, Corfimfroitilf Atmui>ni/ IWfSftwufr ('uttrnt HttoUt. !4t AmnaM N V Af ais hi |*<tl*'1| |41 MAmi, CifikiH, ('t4mu, A (lutcv left Ff^it (knni|f (VI 0.nkfd IV VuhIi ImmImiWm hf Vfu Orok t4*t Mott* fCkrufmlr tff** ft of VCAJmimtftrtJ 1trmttfi**Mo*t MitUmiooty Htpottf, Or r OcrtnAi * Vtia. Dvr , 4*11 iHMfugjnattd iipmi u* filr la* uflkt * uf At (Vr4g; l.tuur (Jomrttftfl III (JtmonmAum (hm Cimf MAmt ik Mtwkf> nf ik 4 mi'ivmi fimpidiiit OfOkf lot Aw t-ipciimcmal Km atugt ha Vin|il ( MwidcCdM.mi>|nHirtr <HiaJ,netlH(Kt<mJ Kf ci*4a MAid MnwHfHwJHihl 144 Stl Hmctl Cfk4 k MNl (M 1 MfWd 141 ETA SnMflMH um Iii ihm m Askhh. iurwt m* A, mM kmUHiMi. mridlatKn uf VC kt kca Awmk HMMtkwMfii m*J yeulMnik "*uhI irtit" IwinHiaffwii' tp. Set. eg , I upfkm*. AmhV. rnmn^Ai, Umltck. VhuuMSSl, CtHMaeUim, t urn. Frrif.a, Nkff, l.tfnrifii. IiacKm, A Russs, Mwhm of tSrn* Xtototi*mt n4 lc*r (Wuuimi Sf Vtoft (Vivtilr NrftfMkJ A Ytott, SI Cmfr Riwmin IO 4l*lft mJ Jiwfiu Autis MMigtakkf s ntA4 w ik%c sctit comUitt *<44 *isb t,wtinugfimi)f St* Md'iM A Ames, wpa aafi |1` From MirroMtt to (fro. toy** ma< II 144 VC Iffdfkft. ipa I.ttllll Itlutmral 4 IV TkiAur I lutlrlwal 14} fekphuM miotic* *Mi IS Iwwfb Mel mtgMm. IbtetMt Oii*Mu( lut*uihgy af UtAiuae, CiMwiwf VmkIw.4 Suftijr Cmmktm. Feb *f. I*TM If '! rpr `w!) ^i* y7!w''* v....... CHA 0 1 0 6 3 4 ur )l U,k Jatilaneei CmtHtl five mile) ol VC ot I1 VC plain'4* Id 1974, about 110 milliim ftxiwb ol U- VC ttciptil into tltc ati suituundiiig tuch fhnls.1* 11 fta* tteiglibiui lo have been espoved tu mute Ihan ihw ppm leu than III percent (4 llw thne."** One ah (ample. hosvever, Mcatmcd JJ ppm new a plaid.0* Till TO CC AC suggesting ilat (here niiiji Ik kind I leim, liKilircil (teak *|nmhiic*. *** Id wkliliiHi. VC It lound in ihe sludge waste and walct tlUtscli* id iIkm plants.' VC lui iKen found in tlud|c al level] at high a) 1.000 ppm,1" and In water effluent ai high at 10 nmt.1" Mint id lliii VC escapes into Ihc air wrnitmdlug die plaids;'" sonic, hnwvvei, make* its wap lain dilaking walet.lw O lltcse VC emissions to iIk ainhient air liave been tio|dicatcd as llie mule of h messed tatet ul camel and birth iklevlt In IIk sun winding com- HHiniiki.1" Oilvi Amilhct large gimtptd prison) Is capoted to VC retraced In itampm la- litin, Only rtfxrul tmc-lliMof VC ptiHlucilnii It judpuieilicd al ihe (iff wlwfi 11 hi *i ll It puutmed. The letl most Ik std|i>ed Iwlwcca VC ami PVC latlotle) viHler picssuie at a Ikpiilied gaa. About M percent l this it tfM|*|ied In rail vviNh* |! ll Uff lu>p tffWlfV ttHkif il.lllll llUM^ ilihm l*(* I Hki U Vr I Mil Am mm tfw 0 H(W piiiji dt Mm IO'jIm lank cat), and the real In tank liwcki. lank vessels, and barges.*'* Thru tanks map leak, pnnctinc, or eaptode. sometimes In heavily populated aieas.1'* Ilclwcea IVII amt 1914, there were M least 14 accidental releases ol VC Iutm rail tank cam alone.1M* A* VC diffuse* from lire tltc ul a iplll nr an aicideiii, tiuiispmtulhifl wrnkeit, nearby ret idem!, Havelien, and mIki bptuntlcrt can receive abort-term esposmes to VC concentrationi ranging limn a lew pailt per billion (|>|ih) to ibonsamlt id nin. Trant|HKimbm wmkrrt and cinrrgcm'p pertoniKl well at llreinen ami police olliceit map III I M, NaUiwal FinOsim Sr.ardent Are Weie-J.H.1 Air IUMmi, SenWfe Wd ItlaiMr. 41 I ra tr|. M.tUMtVHI pmihnlln ched *1 IN JwdaJAr V('l tl i r* Sr n Mirra *nr In moral wl, nri< * *1. ' U DO U 1)1 td 1)1 to U IfI EM Pert Force Peporl. n on tl. M t. lit Id 1)1 Itl . Bppt . M 11)1- m Sitaukifitri HI Set IMIMI (Mi* MM HfM (II fcl*A latk I Wftrr M(|hmI, lft m tl, at 1. I?) Sfi Mil 1*4 tmfrm lie Moil tl riwM ktMmII KUHitila TMl awl l.ttiitMb, *t MtMt <"'** At Mpk*H tMbk<atiuliMi tl VC Mrf fVC iKliftt. Thera wot Mvotl Afi krUmt bwiltlti M itkiK. Dot M KiUtati ami itktfti ft Mt4 Nm CMffwtn liltilAt (fepwlMrirt at 1itnpotiMKWMtli iftoJiWUdriiof hamJuwt >ltii^tkili|f m KtUtOt4ow|lMt priioA. Mhl limit lW upffidii tollH Iti* No KM. 1M Cong , 14 $to M 14 (HMI Ott CkiJcnt, t FmI WifM, Mum. MttiMMil At tvKvolwat l,W people. IJ. at It. WVft * tank cae ptwcb. (Mcb it )0.OU gattowi at VC cbcafct wwlteiwm la In llkK ||w (t|w< lor At wdawiMi taak lilt cihmi Ii a* ioi*(tw wMt Maijr Oitmkel lfl|MMii, IkpuiMM of TcamparlJlhM. Office ofllaJMiltHib Mauiidlt Optiokwi, Iki It. 1111 M( 0. PI*II %* rr J] he lubjccl to repealed ei|iuitoei and, if accldcirii occur in tlw same pixel, to map rctlilcnlt and hyilamten. Iliete cipnatt) aie test sustained rhan ihote tufftied bp VC and I*VC winkers ami plaid otighlaiis. inn (vaV comenttarimu map reach llmse enpeikneed bp I'VCpnfpincrlraiiimtts.tiif cleaners, the mod heavily etposed wcnpadonal group 'third, |Ko|4e are ca|Hiud lo VC dnmigh roosomci lamhii rs, hmd, ami illinklag water, llmil Iale 191] at early 1914, VC was used at an acrottd |uii|Kllant in thug, cotmelic, pcMlchk. and other consumer |wm*ucls ,M The I VC as *user td |HH)flltd actinrd jmuhkl sml| hair S|nap in a |Kdiciile in a small, enchtted space such at a hatlumnii map have liccitt|*<rseilliislal term coaceniralltmt appioacbiag 4011 ppm, and persons map have hmI an average capotarc Inm all VC' pri>|*lled ptmlmli in ibrir Inmwt crjuiealein to an aveiagc eipuunc td alruat 16 p|no la Ihc lacllHict.,>, VC has been deieclrd In Ik ik of immii liolily iwimrif with miaiii latea pmnls, bui no VC endstirtnt have (wen detected in a limited tampllug id mlrei new I1 VC products or frenn amtanobile interiors.,M VC leMhci imn hanl ami Ik*ciagel horn Die more than 4X1 million pmindt of I'VC packaging and irllier rVC liMuJcontact mareiiali med amiaallp.**4 VC also rulerirlrhiking wxci bum raw water MppHei and bp leaching bom incrcasiuglp cmnnani I'VC plgK."1 One ttadp eslinlalei average American daily human inlake of VC IhriMgh loud, water, ami air al 14 micrograins *" Tlie haiardinunett of noii4>ccu|>ali(Hial capnsutes In VC it even less well understood than the risk lo tin wmkcri The danger limn inhaling ealiemelp h>w cuntcruralioui td VC, nr bum single or t|HHinlic ei|H>sinrs to high VC ciHU'ewrnltom, It unknuwn. Sindlailp, the relative risks of infest Ing and inhaling VC are unknown **' Ihut ihe tugem-p id ledociui: of eliininaling IIksc touted of el|Kisme It bu|Hissible to assess. 141 Set leal KCHfHfM| iHMei 111 1)4 tmfr* 141 tlay, I immmm, IihImmI, A Umm, UpdiwiwM of Vmpi fUmdr fram Attvut Sr**t*. 144 AMM*L N T Aca* Sit lt4. rM 141 CavitaiiMiilalfiMtctiua Apacy. Offki at Tik SatniMsii, *idmfliii| W Am)|!- ih at ?ak SiAmmv T*4 HI-- Vbyl tHmlft, Sfumdny SHMi*h. laMc 4, m || fApr **741 144 Fim* mmI Ding AMahltpiiiM, Wup* (IrirnWr fMiwuri (a CmHtI wM I ao4, Mtflri *4 a%t4 ttalMMUng, Mlf* Hag M.ltf, H,f1*tlVD||lKt(M4flii tM4 n IfH fhipM(V Jfefra far faad CamM | 141 KfA bKMHHi' *M VfdWiui Ithai. Mpd Mt . al **;1 l*A NuimimaIi Riiimi m IIbinkimu Wait* Cimtwx)| m. ntpr* mat* 11.al 40 44, LI*A 1 A Fwk< Rcimm, tafia matt II. at 1. 19. 144. tfA ScMMUHl' ami Tumnn ** NlMlt tafia wit W. at 41 *41 Sit WMhag A Caftai. A StaHiik at A1 tmatrml aftkr Qaaatitatiir Vftat* ttf Mayf CMmUr (fwtdNMr ftam Apwdw SaMam, 11. fiiunaiMk A *.nvr'i III aim II111*1 ; WMkg, Ik riidfxMiirf|ibiiafri al Itftati vf Hyf Dlvafr JftNhmtpr AJmnattrrrJ tp Vaiiaat Maatrt ta Bait, 11. Ttiwtn imiv A twrl'l IKa* lit III (l*N| laikfmmfiMiKlt, i4m anibOTa mm>m Ami fw alv, At f Vt" m iIk mAi mI am m tf)HOtHMUl|r ip| iw iafcalim 4 ppm bat dgRtlwawb Tkf cmnim ifAukl M| AfsltMupi Una la limua (pfiialxafri Wakp ll CmAnh, Mpk, # II* Jt s" Mifll kTMAi'p'a - 010637 r oc jr Chemicals T EL '^pc E-Jr -- V O/or-Alkaii Business Unit PPG Chemicals One PPG Place Praaursh, Pennsylvania 15Z72 May 13, 1985 Mr. William V. Loscutoff, Chief Toxic Pollutants Branch California Air Resources Board P.0. Box 2815 Sacramento, CA 95812 Re: Yinyl Chloride Dear Sirs: Relative to your request for healtji information on vinyl chloride, we have no information which was not covered in the MEDLINE and TOXLINZ information services. We thank you for asking for our input. Sincerely yours, Clete M. Smith Technical Service CMS/rs CMA 010638 PACIFIC GrJAS -A.3ST ID ELSCTRIC COMPANY 77 EEFLS STREET . SF'. r = i-;C:S '3F.\ st.vx : 5557 May 7, 1985 Mr. William V. Locustoff, Chief Toxic Pollutants Branch Re: Vinyl Chloride California Air Resources Board P.0. Box 2815 Sacramento, California 95812 Tear Mr. Loscutoff: Request for Public Health Information Regarding Vinyl Chloride Pacific Gas and Electric Company received your April 4, 1985 request for additional public health information regarding Vinyl Chloride. We have reviewed the bibliography attached to your request and concluded that we are unaware of any additional information which would be of use to you. Sincerely, CM(S 010639 V---------- ,-v r _rcef Dcicr-r Ci .-.C :. i-.c . -.-i. \ it ; i?r,ingror,. DC " >'/ l :e: m-no: To: William V. Loscutoff From: David D. Doniger Ditr: April 10, 19S5 Subject: Vinyl Chloride The attached is in answer to your recent, inquiry. j\ / CMA 0106-40 152 Wagoner, J . K , Infant*, P F and A p f * 1 d ; r f , F, B. and polyvinyl chloride as sen through epidemiologic observations Health 4<S-4> 1101-7 J Toxicol Eneiro 113 Valar.abe, P. G., Young, J. D. ana Gehrir.; ?. J (1977) The importance of non-linear ( dos-depndnt) pharmacokinetic* in hatard assessment. J Environ Patho Toxicol. 1(2): 14 7-5 9. 154, Waters. M D., Garrett, N E , Covone-DtS*rr*s, C. M., Howard, B. E. and Stack. H. (1933) Genetic toxicology of seme known or suspected hex an carcinogens. Chem Mutagens:Prin methods their detection. S 261--*41 . 155 Withey. J. R . and Collins, 3 T (197a) A statistical assessment of ths quantitative uptake of vinyl chloride n:-1: from aqueous solution.. J Toxicol Environ Health . 2 (2) p311 -21. 156. Zajdela, F , Croisy, A., Earbin, A , Kalaveille, C, Tsmitis, L. and Bartsch, H. 1 - 0 ? Carcinogenicity of eh 1 oro*thy1ent arid*, an ultimate reactive metabolite of vir.yi chloride, and b i s < ch 1 or :mehy I t her after sutcuraneous administration and in initiation-promotion experiments in mist Cancer Res. 43(2)352-4. OiO^Al CMA South Coast ] AIR QUALITY MANAGEMENT DISTRICT 8150 FLAIR DRIVE. EL MONTE. CA 91731 (818) 572-62DO April 22, 1935 Mr. William V. Loscutoff, Chief Toxic Pollutants Branch California Air Resources Board P.0. Box 2815 Sacramento, California 95812 Dear Mr---Losetrtorf: Vinyl Chloride In response to Mr. Venturis's request for information on the health effects of vinyl chloride, we are submitting several references which could be of use in your toxic air contaminant program. These references were not included in your bibliography dated March 1, 1985. Also, information regarding possible biological production of vinyl chloride may be obtained from Dr. Freeman Allen of Pomona College. .~ - We would like to continue to receive information inquiries for other candidate compounds and to be kept informed of your program's progress. Very truly yours JAA:cas Enclosure Oo Anne Aplet Director of Planning CMA 010642 Additional References on Vinyl Chloride Health Effects draf i Albert, R.E. Letter to R.S. Naveen, EPA, "Comparison of Vinyl Chloride Carcinogenic Risks with Risk From Other Pollutants," Washington, D.C., June 16, 1978. Edmonds, L. "Birth Defects and Vinyl Chloride," Proc. Conference on Women and the Workplace, Washington; D.C., 1976, also Teratology 17. 137 (19781. Equitable Environmental Health, Inc. "Epidemiological Study of Vinyl Chloride Workers, Final Report." Prepared for Manufacturing Chemists Association, Washington, D.C., January, 1978. Graniger, R.G., A.E. Walker, and A.M. Ward. "Vinyl Chloride Monomer-Induced Disease: Chemical, Radiological and Immunological Aspects," Chapter II in Induced Disease; Drug, Irradiation, Occupation, L. Preger, ed., Grune and Stratton, London, 1980. Kuzmack, A.M. and R.E. McGaughy. "Quantitative Risk Assessment for Community Exposure to Vinyl Chloride," U.S. EPA, Washington, D.C., December 5, 1975. National Academy of Science. Principles of Toxicological Interactions Associated with Multiple Chemicals. Exposures 1981, 207 p. AD-A093 809/2 PC A10/MF A01. National Cancer Institute (1978). Vinyl Chloride - An Information Resource, 112 p. HRP-0028012/3 PC A06/MF A01. National Institute of Occupational Safety and Health (1977). A Cross-Sectional Epidemiologic Survey of Vinyl Chloride Workers. 50 p. NIOSH Pub. No. 77-177, NTIS No. PB-274. Ziskind, R.A., Smith, D.F., and Spivey, G.H. Health Effects in Children Exposed to Vinyl Chloride. Final Report to U.S. Environmental Protection Agency, SAI-068-81-569, January 1981. CM* 010643 (A <^lt7^AcducS^ / INTEROFFICE MEMORANDUM To From L. B. Tepper J. T. Barr cc: G. Bays H. L. Watson Subject Surgical Removal of Angiosarcoma Corporate Medical Department (t-Oc*i>on, Orvu*lton, or Regulatory Response (Loutton, OffimuiiOA, or Dtp4#tmnt) The attached article is a report of an apparently successful surgical removal of an angiosarcoma from the liver of a PVC worker. It appeared at Br. J. Surg. 71 322 (1984). JTB:csb CMA 010644 Air Product* ind Chtmicalt, Inc. A' j-.-.c/..-.. pa *S105 Te-ec-c-f* (215) 481-4911 16 April 1985 DRAFT W. V. Loscutoff Chief, Toxics Pollutant Branch CARS Box 2815 Sacramento, CA 95812 Re: Vinyl Chloride Dear Mr. Loscutoff: We are happy to provide some information relative -to vinyl chloride in response to the April request of P. D. Venfcurini. This includes: 1. A paper by me given at the APCA, New Orleans meeting. 2. A paper presented at a CMA seminar in Washington, 9 December 1983. 3. An unpublished review by me on the safety and health aspects of vinyl chloride, which contains several references not in the bibliography with the Venturi ni letter. 4. A report from Br. J. Surg. 71 322 (1984) of are apparently successful liver resection on an ASL patient.5 6 5. An article from EST 1_9 277 (1985) on biodegradation of TCE to VC. Note especially reference 10, Parsons, et. al., for corroborating evidence. You may want to get the Dade County report "An Investigation into the Source of Vinyl Chloride Detected at the Preston and Hialiah Water Treatment Plants" by J. C. Balter, 1983, for more details. 6. A summary of a report on a 1934 bioassay by CIVO. I hope that these are useful to you in your evaluation of this substance. JTB:csb CMA 0106-45 Short notes and case report* Sa * '-X V - /' Vinvlchloride induced hepatipjG 2 1 b3^wenon^L-!trjd ` aTarge cfrrrsc tumour of the rig,1 av ng'iosarcoma r hepatic lobe with area olf neeccrroosseis. The **Tc hepatic tan confinm die presence of an ill-defined filling defect in the interior part of tl right lobe with two small delects at the level ofihe hilum. Y.A. Louagie, P. Gianello, P.J. Kestens. F. Bonbled and J.G. Haot Department of Surgery of the Alimentary Tract Louvain-en-Woluwa Medical School, and St. Luc Hospital, 1200 Brussels. Belgium Correspondence to: Or Y.A. Louagie, 20 Avenue d'Huart (bte 3), 1150 Brussels. Belgium The relationship between vinylchloride exposure and The liv cr computerised tomography confirmed the integrity oftf left lobe. A selective angiogmeshy of the cefiae artery revealed a hype vascularized tumour ofthe right hepatic lobe {figure It. At a right thoracopbecnolaparotomy the tumour was found to 1 confined to the right fetbe. An extended right lobectomy was the performed. The postoperative recovery was uneventful and tl patient was sent home,-with a monthly administration oTVincriair (I mg IV) and Adrianvein (150 mg m- IV) which was discontinm in June 1981. Repeated controls ep to September 1981 by liver scan ar computerized tomography remained normal. The patient is still good health 38 monthsarierthe resection. human angiosarcoma ofthe liver (ASL) received attention in 1973 when a case of this rare tumour was diagnosed at Pathology autopsy1. The resected specimen was 2050 f. On macroscopic*! exammado the main tumour (13-5 x 8 cm) was yellowish-and spongy ar contained cystic and haemorrhagic zona. A second small Case report A 39-year old man was first seen in July 1979 with pain in the right upper quadrant. The liver was palpated at the right costal margin. Oral cholecystography and barium swallow were normal and liver haemorrhagic mass was found at the inferior aspect of the right lot surrounded by numerous purple" Macroscopially. the main rumour showed large areas ofnecros and haemorrhagic psendscvstic spaces {Figure2). These spaces we surrounded by areas ofdense vascular proliferation. The sinusov function tests were in normal limits. From 1965 to 1970 he had were lined with variably sized Irregular sarcomatous cells we cleaned reactors used for the polymerization of the vinylchloride hyperchromatic nuclei. Elsewhere, blood-filled spaas we monomer in PVC and was thus exposed to high amounts. He was admitted 3 months later with persisting right upper surrounded by ssrcomccaus cells. The sarcoma cefls-epcoBipest adjacent liver cells as bile ductules and iaiiluaied the pace cuadrant pain, loss of appetite and fatigue. The liver edge was by then hard and 4 cm below the costal margin. The ESR was accele chyma. The pathotogaal diagnosis of multicentric angiosarcon was made. The rest of the liver was normal except for sac rated (80 mm/h) and alkaline phosphatases and CGTP were elevated. Carcino-embrvonic antigen (CEA) and a fetogiobulin moderately enlarged portal tracts. Progressive fibrosis scpamii hepatocytes at the mar-pros ofthe portal tracts from adjacent hepat Fifure 1 Sileetne anvioeruphy ol the eueltae unerr. The hyperluv. nlunzcit ii:imir i\ utppheil hv an anterior brum it lurrotei ol the Figure I Phi'tntmrri'-eriirhy </ the mum lum-ntr ik.mine AAi flle.1 *puee\ 'urrounji J hr *urcr,*itutuu\ *v/lv * /luemutuxxiin rhi * Ibis, Sheet notes arid case reports cord cell*. AnisoearvoMs and amsocytosis '`ere frequent. A erossseciion hiopvy of the left lobe showed normal tissue with slight hepaioe'iic anisocaryoM*. The lymph nodes taken Irom the liver hilum were hyporplaitie. The mam features of this tumour were its multicentricity and thc-prcsence of mild fibrosis. Discussion The occurrence of liver angiosarcoma in vinylchloride polymerization workers was reported in 1974'*. Prolonged exposure and long interval from initial exposure is required before liver disease becomes apparent The average interval is 12 years (range 6-29)*, Our patient was exposed for 5 years and became symptomatic 14 years later. It is a rapidly progressing fatal disease, especially in adults. The clinical features include rapid liver enlargement with haemorrhagic ascites, fast deterioration and cachexia usually with death within 6 months. The treatment is disappointing and chemotherapy and radiation of palliative value only. If the diagnosis is made early, the disease is localized and there is no associated liver fibrosis or portal hypertension, resective operation might prove to be curative. However, there are few reported cases of successful operative removal of hepatic angiosarcoma and ' the longest survival has been 16 months*. ! In our case the tumour was confined to the right lobe and ` there was no sign of the extensive fibrosis. So far the patient is apparently free of disease alter 38 months. This is. to our knowledge, the longest published survival. References 1. Creech JL Jr. Johnson MS*. Angiosarcoma of the liver in the manufacture of Polvunyl Chloride. J Occup Med 1974; 14; 150-1. 2. Block JB. Angiowrcorca of the liver foHow-in* vinyl chloride exposure. JA.\/A 197-4:229; 5$-4. 3. Heath CW, Flak H. Cmch JL Jr. Characteristics of eases of angiosarcoma ofthe frver among vinvl chloride workers in the United States. Ann .V >*. icudSei 1975; 246; 231-6. 4. Adam YG. Hu'os AGu Hajdu SI. Malignant vascular turnouts of the liver. Ann Surx 1972; 175:375-83. Paper accepted 27 July 1983 I I CHA 010647 Environ Set Tectvot. 1S8S, 19. 277-280 face morphology, there was no evidence that the surface nodules were composed of any special, unique element These particles from these particular collections seem to be quite similar to the micrometer size particles emitted in the ash (2), It is not clear, therefore, why the collected ash shows a bimodal distribution of micrometer size par ticles centered around 5 pm and submicrometer size par ticles centered around 0.5 >im. X-ray photoelectron spectroscopy (XPS) and depth profile XPS have been applied to these samples to determine surface composition. Results cf these analyses will be presented in the near future. Literature Cited (1)'Planning Studies for Measurements of Chemical Emissions in Stack Gases of Coal-Fired Power Plants'. Report pre- pared for EPtL^^P V*. 4by sluthera S insutute, Birmingham, AL Battalia Columbia Lab Columbus, OH, and Roth Associate*, Inc, Rocivi (EA-2392, Research Project 1776-1), March 1983. (2) Kiufherr. N.; Lucbtmas, D. Environ. Sci. Techno* 18, 544. (3) Valkovsd, V. Trace Element* in CoaT; CRC Press: P-fton, PL 1982; VoL l, pp 83-177. (4) Diamond, Su Lopes-FIorw, F. Proc. Symp. H. Mate; Soc. 1981. 34. (5) Rahn, XL Au Lowenthal, D. H. Science {Washington, 1984,223,132. P.eceivtd for rtzriew April 23,19S4. Revised manuscript rrce September 4.1384. Accepted Cctaber 30.1584. This work supported by Sleetric Power Research Institute Contract Anaerobic Degradation of Trichloroethylene Robert 0. Kleopfer,* Diane M. Easley, Bernard B. Haas, Jr., and Trudy Q. Delhi Region VII Laboratory, U.S. Environmental Protection Agency. Kansas City, Kansas 6115 David E. Jackson1 Ecology and Environment. Inc, Kansas CHy, Kansas 66101 Charles J. Wurrey Department of Chemistry, University of Missouri, Kansas City, Missouri 64110 d When trichloroethylene (TCE) isotopieally labeled with one "C atom is used and gas chromatography/mass spectrometry is employed to monitor the production of l^-diehloroethylene-^Ci (DCE), it has been demonstrated that reductive dechlorination of TCE takes place in the soil. Microbial involvement in this process is indicated since unsterilized soil samples yielded up to 73 ppb of labeled DCE while sterilized soil samples produced none. Isomer specificity was also found; only 1,2-DCE was produced--no 1,1-DCE was observed. Introduction Since trichloroethylene (TCE) is a major industrial solvent (234000 metric tons produced annually, worldwide (!}) used for degreasing and cleaning metal parts and electronic components, it is perhaps not surprising that TCE has found its way into the environment. In fact, TCE appears to be widely distributed in the aquatic environ ment (J). However, the environmental fata of TCE has not been well documented, and considerable controversy still exists concerning its behavior in environmental matrices. Early literature references have concluded that C* and Cj halogenated hydrocarbons are not metabolized by microor ganisms (2, J), More recent studies, however, are split on the issue of whether TCE is biodegraded (4-7), with one research group reporting both *no appreciable anaerobic degradation' and 40% degradation of TCE in similar methanogenic cultures (3, 9). In a very recent publication. Parsons et aL have dem onstrated that tetrachloroethylene (herein referred to as perchloroethylene, PCE) is reductively dechiorinated to ' Pretest addrrvc Depmaect of Civil Engineering, University of Illinois, UrLens. U. 61501. TCE, diehloroethylene (DCE), and vinyl chloride in Flo rida muck/surface water microcosms (10). Whether TCE. which was present as a L6% impurity in the PCE study, was similarly biotransformed wes not directly investigated but was implied by the results for PCE (10). Therefore, is order to determine whether TCE itself undergoes biodegradation, we have undertaken a study using TCE with single atom "C isotopic labeling, soQ from a TCE spill site in Dee Moines (11), and very sensitive gas chromatography/mesa spectrometry (GC/M5) analytical techniques. Since DC-aCj co uld only arise via a soil or soil-microbe-induced reductive dechlorination of TCE-^t, this experimental method should provide concrete evidence in support of such a pathway. The results of our inves tigation of this problem are reported herein. Experimental Section Materials. Since any microbes present had probably adapted to TCE soil samples went collected at the Des Moines site, st depths of 1-2 ("A' samples), 6-8 ("ET samples), and 15-17 ft ("C" samples), by using an 13 in. long by 2 in. o.d. split barrel sampler (11). These soil samples were analyzed by GC/MS for the presence of TCE and DCE In spite of the TCE sludge application having been discontinued in 1979 (11), all soil samples contained 6 ppb of 'native' (unlabeled) TCE No DCE's were found in any soil sample. (An analysis of the Des Moines TCE siudge itself by this laboratory and hy an independent testing laboratory showed very high levels of TCE (3000 ppm), but no DCE was detected.) TCE*lJCi was purchased from Merck Sharp ti Dohne Isotopes. Single llC Labeling was used to produce molec ular and fragment ion peaJcs which did not K?v mfz values as the "Cl,r'"' - Gr/*'e DRAFT 3 .. * \\ i4 a 1i i i____ i ir 1i; i i i .-a i i. j Figure 1. Representative mass specsa of rieMereethylene and 12-dlchlorolhykn*: (A) WieWtoroemyiene; Iff) tndVorpefriyteoe-^C,; {P) 3 1,2-Oiehioroethylene: (D) 1 ^-dfeh(ofo*8Tyio*-0C contamination. Volatile organic standards weir purchased from Supelco, Inc., and were diluted appropriately with methanol to contain 200 ppb of TCE and DCE. Soybean meal was obtained commercially. Methods. Five grains of soil from each depth was placed in 5-mL amber vials which had been baited at 150 *C for 3 h to remove any adhering volatile organic com* pounds. One gram of soybean meal was added to each vial to ensure anaerobic conditions, and the vials were then tilled with "organic-free* distilled water (which had been purged with nitrogen). (Organic-free water is distilled, passed through a carbon column, and checked for organics by using GC/MS methods.) The vials were sealed with Teflon septa. Samples to be sterilized were placed in an autoclave for 30 min at 15 psL Each vial was then injected with 10 ftg of TCE-uCj (2000 ppb. or Mg/kg). Duplicates of each sample were prepared. The sealed vials were transferred into CO^/Hj Anaerobic-Paks (SBL, Division of Eioquest), which were then placed in an incubator at 23 *C. As much as possible, the samples were kept in the dark to avoid photoiytic degradation of the TCE. Subsets of the vials were removed for analyses at 6. 17, and 41 weeks. Control and method blank samples were prepared as follows: (1) Vials containing only organic-free water, both with and without the Td&-nCt spike, were prepared to monitor volatilization losses and to check for cross-con tamination throughout the procedure. (2) Vials containing only soybean meal (both sterilized and unsterilfredl end TCE to DCE by the soybean meal itself or any "foreign* microbes and to monitor adsorption of the TCE onto ttrfa organic matter. (3) For the 6-week samples only, vials containing soils A-C.soybean meal, and water without the TCE-l3Ci *P>k were prepared as method blanks. For the analyses, the contents of each vial were trans ferred to a 25-mL vial by using organic-free water to eliminate headspace again, sealed with a Teflon septum, mixed, and allowed to settle. Five milliliters of the su pernatant liquid was then removed for volatile organics analysis using a Fmnigan Model OWA GC/MS and standard purge and crap methodology (12,13). Detecticn limits for TCE and DCE by this method are estimated to be 1 ppb. CMA 010649 Results and Discussion All compounds involved is this study were identified by their characteristic GC elution times and mass spectra. (Figure 1 shows the observed mass spectra of labeled and unlabeled TCE and DCE.) Both qualitative and quainrati* tative identifications were effected from several scliecmsL ion mass chromatograms for each substance. For examfl the ions at the listed m/s values were used for the intaalyl^ff of the following compounds: TCE (m/s (95.97. 130.132, 134); TCE-,3C, (m/x 96, 8.131,133,133); DCE (m/s SI,' 63, 97.99); DCE-l3Cj (m/s 62. 64,98,100). No confusion resulted from peeks having the same m/z values for these substances since each compound (exclusive of its iaoto- Tablt I. Amount* (mcAc) of lJ-Dickloroeihyleoe-^Ct Produced by Degradation of Triebloroethylene-,,C, La Uosterilized Soil* time, weeks 6 17 41 Mil A* S 28 78* m3 B* 7 31 27 *o3 C 11 8 25 * See text for m3 depth designation*. Result* are average* for duplicate lamplea; range* were 50%. `No duplicate value wa* obtained. for the 1SC and compounds were identical. This as sumption appears to be valid since we observed natural abundance peaks in the unlabeled TCE and DCE mass spectra having 2To of the intensity of the corresponding peaks (theoretical value 12%). The pertinent results of this study are discussed as follows: (1) In the water-only samples, no cross-contamination was observed at any stage of the experiment. Therefore, no exogenous substances appear to have entered the sain- pie vials. (2) The vials containing the water with the TCE-l3Cj spike showed considerable variability in their percent re coveries, indicating substantial and inconsistent volatil ization losses of the TCE. We were thus unable to obtain reliable quantitative data measuring the conversion of TCE to DCE by following the rate of loss of TCE. Any ex periment that measures only the loss of TCE appears to suffer from these volatilization problems and from ad sorption problems (to be discussed next). No degradation products of TCE-l3C, were observed in these water and TCE-l3Ct samples, so soil or microorganisms contained in the soil must be present to effect this conversion. (3) In the samples containing water, soybean meal (whether sterilized or not), and the TCE-13C, spike, no conversion of TCE-"Ci to DCE-^Cj was observed. Thus, these control samples eliminate the soybean meal as a potential source of TCE degradation. However, adsorption of the TCE on the soybean meal was significant. From 50 to 60% of the TCE spike was adsorbed after 6 weeks. As seen from the sterilized soil samples (where, except in one case of incomplete sterilization, no conversion of TCE to DCE occurred), another 10-15% of the TCE was ad sorbed on the sod. Thus, adsorption losses pose another major problem in a study like this. Experiments that monitor the loss of, for example, TCE and attribute it solely to degradation are potentially suspect, particularly if care is not taken to account for volatilization and ad sorption losses. (4) The 6-week method blanks (containing water, soil, and soybean meal with no TCE-llCt spike) showed no generation of any substance (TCE or DCE, labeled or unlabeled) not already present In the soil itself. (5) Conversion of TCE-t3Ct to DCE-^C; was noted in all unsterilized soils. Table I summarizes the amounts of labeled DCE produced. As seen from Table I, a general and gradual increase in the amount of DCE-13Ci produced occurs with time. (Of course, due to adsorption and vol atilization losses, the amounts of DCE-uCi actually pro duced are no doubt larger than those reported here. Actual amounts of TCE -- DCE conversion in 'real* soils may be even larger than those reported here, since the soybean meal added to ensure enaerobiosis may well have been a more attractive energy source for the soil microbes than the TCE. Indeed, breakdown products of the soybean meal were also noted in the unsterilized soil samples.) ff*' ____ __ ____________ -- - - . 1 -jl - -- J ^ e* * es/J soil samples shewed thns|nqe jfl p>b of *>CE-UC This may, however, be life result of an incomplete ster ,Iization since this was only observed for one of the longe: time samples. Since conversion of TCE-"Cj to DCE-uCi occuire almost exclusively in unsterilized soils, microbial partic pation seems certain. Some caution should be exercise in drawing this conclusion, however, since Kaufman (Ihas reported that autoclaving changes not only the bi logical properties of the soil but also its physical ar chemical properties. Nevertheless, on the basis of oi results for TCE and those of Parsons et aL (76) for PCI it appears that the degradation of TCE to DCE is the sc is indeed of biological origin. (7) Only lt2-DCE-nCt was produced whenever TCE-13* was degraded. No Ll-DCE-^C, (which elutes more rapid than 1.2-DCE) was found in any sample. Under our e perimental conditions, cis- and trsras-l,2-DCE coeluu (and cannot be differentiated on the basis of their ma spectra). Thus, we could not identify which geometric isomer was formed, or if a mixture of the two was pr dueed. (In their study of PCE biodegradation. Parso: et aL (70) were able to separate the cis and trans isome chromatographira lly. They found that cis-1,2-DCE significantly Cffrored over the trans isomer.) Summery By using TCE isotopically labeled with a single C atoi we have shown that TCE is definitely dechlorinated m t soil to 1.2-DCE. Isomer specificity was also observed; i 1,1-DCE was detected. The TCE -- DCE degradatii appears to be biological in nature, since soil samples whi had been sterilized exhibited no such conversion. Since it has been shown that microbes that have adapt to degrade one member of a homologous aeries have al simultaneously adapted to degrade ocher members of t same series (75). the possibility exists that DCE can further biotransformed into vinyl chloride in soils. Mo itcring data at the Des Moines site (71) end elsewhere (7t this work and the work of Parsons et aL (70) all strong: support this DCS -- vinyl chloride contention. Consic ering the well-known carcinogenicity of vinyl chlorid further research along these lines is definitely warranto Acknowledgment* We gratefully acknowledge John CaoOt (of Ecology a Environment, Inc:) for obtaining the soil samples and C Bailey and Angelo Carasea (of the Region VII Envirt mental Protection Agency Laboratory) for providi technical assistance. Registry No. TCE, 79-01-6; DCE saft-sa-O. Ul.ratur.CiMi CMA 010650 (1) `Ambient Water Quality Criteria I-Or i uwiuuivtuvttM, U.S. Environmental Protection Agency: 19SO. EPA 4< 5-80-077 (NTIS iPPSl-117871). (2) Peanon, C. Rj McConnell. G. Proe, R. Soe. London, B 1975, 759. 305-332. (3) McConaeU. Gj Feigusim. D. Pearson. C. R. Endcetx 1975. 34.13-18. (4) Van Dyke, R. A Environ. Health Pertpeet. 1977, 121-124. (5) WiUon, J. Enfield. C. G,,- Dunlap. W. Cosby. R. Foster, D. A; Baskin. L. B. J. Environ. QuaL 1981. 501-506. (6) Tabak. H. H.; Quave, S. A; Maahni. C. L; Barth. E- F r~\ Water P*_c*Lut. Control red. 1^951. 53.15 0T3. -~1518. 9 * Environ. Set reeftnot 1985, 19, 280-282 (8) Bower, E. J- Rinmaa. B. E.; McCarty, P. L Environ. ScL Ttchnol. 1981, 15. 596-599. (9) Bouwer, E. Ju McCarty, P. L. Appl. Environ. MicrobioL 1983, 45, 1286-1294. (10) Parson*. Ta Wood, P. Rz DeMaieo, J. J.--Am. Water Works Assoe. 1984. 76, 56-59. (11) Caoile, J. 'Field" Investigation* of Uncontrolled Hazardous Waste Sites*, 19S3, task report submitted to the Environ mental Protection Agency, Contract 65-01-6056. (12) Eaalev, D. M.' ICeopfer. R. D.; Causes, A. M. J. Assoe. Off. Anal. Chem. 19S1, 64, 653-656. (13) Lorgbotton, J. E4 Lichtenberg, J. J. 'Methods for Organic Chemical Analysis of Munidpal and Industrial Wastewater*; U.S. Environmental 4-82-057, Method 624. (14) Kaufman, D. D. In 'Pesticides in Soil tad Water*: c3__ W. D, Ed4 S5SA Publishers: Madison, WT. XS74* on 133-202. ' (15) Stanier, R- Y. J. Ezeierjsl 1947, 54.339-348. (16) Sprague. R, T, Post, 3uciteiy, Schuh and Jtmigan.Denver. CO, private communication, 1983. Received for revieu August 22,1983. Revised manuscript received May 7, 1984. Accepted August 9, 1984. Mention of products and manufacturers is for idensifieation only and docs not imply endorsement by tkm US. Environmental Protection. Agency. Gas-Phase Hydrogenolysls of Polychlorobiphenyis Jeffrey A. Marion. Peter Mulder, and Robert Louw* Gorfaeus Laboratories, The University of Leiden, 2300 RA Leiden, The Netherlands Chloroarenes in an a'taosphere of hydrogen are ther mally dechlorinated to yrtM HC1 and benzene as major products between 700 and 925 *C, with residence times of cl 10 s. Polychlorobiphenyis (PCBs) are both dechlo rinated and split into chlorinates, beczenaa, with splitting about twice as fast as dechlorination. Thermal hydrogenolysis, which occurs via radical mechanisms involving H atoms, may therefore be consideremas a useful method for workup of (toxic) chlorinated wait Following studies on thermolysis (1-3) inA on several free-radical gas-phase aromatic subsuurdons--hhlorinadon (4), cyanation (5), ntoation (6), and oxidation (/V--we are now engaged in thermal conversions of benzene and de rivatives with hydrogen. Within this category, "hydro cracking* of chlorinated arenas deserves special attention. In general, reaction 1 is of potential interest as a raethc Ar(R)Cl + H, -- Ax<R)H + HQ (1) for dechlorination of (highly) chlorinated industrial waste materials etc. Thermolysis of chlorinated benzenes in an excess of Hj (quartz flow reactor, atmospheric pressure, residence time 5-15 s) proceeds smoothly at 750 *C and shows very high degrees of conversion (HC1 formation) at ca. 900 *C (8). Sooting is unimportant'even at 900 *C provided that tha H^mrene molar intake rmrio is above 10. Aliphatic and olefinic chlorides, in general, react much faster than chlorobenzenes (5). Polychlorobiphenyis (PCBs) have found widespread application, especially as transformer oQ, its use and dis posal enLading considerable environmental problems. We therefore thought it worth whde to examine the behavior of PCB in hydrocracking (eq 1). Our observations, in cluding those on appropriate model compounds reported below, confirm our ezpectation that PCB can be com ino pletely converted into HC1 and non-chlorinated organic o products, mainly benzene- Hydroaadcing thus constitutes an environmentally clean alternative to incineration. Representative examples with Aroclor 1248 (Cl 487* o* wt) are outlined m Table I. That conversion of PCB is essentially complete and is illustrated by Figure 1. De chlorination of chlorobenzene (PhCl) is 97%; mono- chlorobiphenyls are seen in minor amounts only, biphenyl comprising ca. 0.7 % on the PhCl feed. This biphenyl stems from PhCl--or better, from benzene made jw f-rt ** *,*to*,\ V* * * - 1 o Table L Thermolysis of PCB ia CkJorobtutni with Hydrogen* r,*c *,s conversion* of PCB*. % PhCV-* It PhCl,,* % Ph**% ClPh*"* Ph&PbQ molar 1 I 715 83 <=*. 10) 44 L2 0.010 0453 0.059 run no. 23 4 760 14 28 U IS 0.034 0.13 (US 80S _ 878 8J 7S 70 >484* L5 OS _ 0.10 a04o o.sn 0.13 <003 032 33 SpiralLz*d quart: tabular flow reactor (34 m, 46 cm*); inflow (mmol/h): H* 221 * 4; PhCl. 102: Arochior 1248 (0.69V. duration, of runs 40-65 mi&4 product coDacsed in a temp cooled with liquid Nj. * By GLC with ?h3r ta internal standard; total of area from dichlorobipbaayt on (retention time > 27 min. Figure; 1), m- uming reaponae to be indepesdamt of chlorine coolant Thaea numbers parallel tboee for dtpeea of decblerination of PhCl, PhClj or PhCl, under the not condition* 'Mote percent am PCB 1 *n X 0J. * Mol* pcrcant on besmnaa oul *Isoaar diaaributioa ortho:mta.-p*ra. 9): m I, 40-25-35; ran 2. 3727:36; run 3. ia33:35. /I*omer distribution (onhonscta.-parn. %)z run 1. 31^35: run 2.32:35:33: run 3. 34:38-28. 'Confirmed by GC with electrhp capture detection The dl\and tzichlarobenzanes clearly stem from spHtxing of PCB and account .for cl 6% of tha Arochlor feed. Chlorobenzene is produced via. the same route but is ob scured by its use as diluent. Its amount can be estimated from what is knqwn about the composition of the PCB mixture. SpedfichUy, the identified portion of Arochlor 1248, cl half, is composed of the following ratios of phenyl units: PhJbCkPbCl-tPhCl, * O.02:lzUd).lS. If changes due to the small degreVof dechlorination are neglected, PhCl from PCB would mas be 1:(L3 + 0.16) X 6 a* 4%, so as to give a total degree of splitting of about 10%. PhCl alone yields cl 6% of HC1 thader these conditions so thia mode of hydrogenolysls is aohut twice as fast as dechlo rination. \ As we have reported elsewherh (8, 9), methane tj^o formed, ranging from 0.2% (run Dtp 1 % (run 4) on PhCl feed; small amounts of C-H4 and C-H and traces of C-H, are also produced. v Simultaneous splitting and dechlorination of PC3 will cause the yields of PbClj and PhCl* to pass through a maximum with increasing temperature. The same holds THE DOW CHEMICAL C October 5/ 1984 THE OOW CENTER MOLAND. MICHIGAN A8640 Document Control Officer Management Support Division Office of Toxic Substances (KH-557) U.S. Environmental Protection Agency 401 M Street, S.w. Washington, D.C. 20460 AIRBORNE Dear Sir/Madam: Attached for your information please find a copy of a summary of a report on a Lifespan Oral Carcinogenicity'Study of Vinyl Chloride in Rats which we recently received sad which I discussed with David Williams on Tuesday, October 2, 1984. ~ This study was conducted in Europe by' Civo Institutes TNO and was sponsored by Verband Kunstoffer2eugende Industrie E.V. IVKI). It is our understanding, from VKI that the SPA. will soon be receiving a copy of the final report. We do not have a copy. W Upon review of this summary, we have been unable to determin whether this study presents any substantial risk information under the EPA's Statement of Interpretation and Enforcement Policy. 43 Fed. Reg. 11110 (March 16 , 1978}. It appears from the minimal data presented in this summary that tile study is corroborative of effects already documented in the scientific literature. Sincerely, ______ -- 2030 Willard H. S17/636-0933 Dow Center Attachment Dec: F. D. Hoerger, 2020 WHDC H. Schumacher, Horgen CMA 010^52 sut 1. tin itil if vleyl cUarUf CTr (VOI) vaa uultta la llfaipa* *:u^r \fltl fli (ravp* af Ylitar fact, lac* (titlei af 100 ulti ! 100 uttfl far tha tap-daia inur v vfclch tatfrli*! 30 t-U. in! 39 ttulti. TOI v*a ililatitar*! by t*" cafpratlt( rdlyvf*Tl chltrlda (TTCJ yw<ir with a bl(h 7Q1 eBtr*C let* tha dlat. tti flit * ytavldad 4illr far parled if 4 eauactr* tin bnri, vtirtii food vltbdnwa dtrlxg tit ichtr 20 hiurt* Iti *a if till vay if nl fat Uildimtm ruiltif la t^ fiUnrfit trpeivta lavalti 0 (eatcral), 6.OH. 0.12 ttd 1.3 ax VOi/b-t Vady val(bt/day. *Ji ucti caactdl (taap a* 190 rttt/iax vaa bawaad la a ufm rao. Additional adttlllta traupa af it vaXa >! 10 {aula rata, uck > ciltlit tha tana ttiitut: at eba uda |tyi *art uit far (itital* aatleaa if (luutUisi lualt ta tit lint altar 9 tad II aiichi. Obtarvatltma vara aid* af (aural ipyutiaca trailty, irottb, fiad lnctka, throaaaeyte taunt, ;tatfniUa tin, tlutatfciaaa Laval* ta tba Hvar, (taia pittalety *d tleitiutfc pathalacy *f tha lint and af all (taaaly vlitbl* naauti ar |tiiuaab',i tuati la tha abdaalaal cavity, tbt (laada af fyibil lad (U atairy (land*. Z. Caaatal haalch, Wfcurtaur, badr -tt* *ad 1h< lataka vara aat dvartaly affactid by tba taat wbitiita. 3. la tba aaeaad half tf tbi axparlsacsal hHd, aartalley la tba act* eaacTtl (roup aa hi (bar that la all atbar (rawpa. TMi mi aaat ?r* ably dua u a U(b lulfiua af ebttslc raaylratary dliaaaa la tba aztta camtral paif. la tba final t*ft af tba atvdr. tba aattallty la tha tap-data (ranp mi tU(btly bltbat tha* la tba Invar data tfwpi ltd tba caatrala* 4, Tkraahcerta cyans. aratbr--bla claa aad llvar tlutitblna lavala <U mat ibtr tliaaittniliut flflanuai aaa*( tba |mupa. CMA 010653 c 5. a clearly Mthtt IkKimi { ;rc*ir iihit, twtwreue. liver eot- "i* fe^4 It Wet eelee fad fgil of thee tep-Cse* ttm than la *o? of the other troupe. it forntlee at the ter-*ee |rn nRAftiXo laeUteco of l*;ie ejiii ta conelterehly hither thoa^ trait. * Xlercotepl* lutiutlet of tie Liver reaWlei 1 OcreortA'iseltoiwea of liver-toll polrtorthlra. Ym^xzlz eyttt, fact of cellule t eXittetloo. tupUnle oe^ulee esc ttrelftt It t> ^<n'trwp tt tnpitti to cbi ciitrol frosy. St:rr, t Upttlt aotlaeoreowa fousi la oat ult tpd two imlit of tit coydoon trout, vhertto mo uch future nn eoeouateret It t*7 of xba ether {taupe. ^ wWt 1 Mlttli Wttlst foci of ttlltltt oltefotloo It ttt liter mi Ioo etttletlcelly (ItillUtitlT litfUMl la ijultt of the .ald-loeo trogp tt n;ittd to cetsnlt. ta itditlot, Is liulo hit eaVia ulti, the iaeidef-.es il lutpMUt Joel of tillaUr olcoftclnm la the llvtr vta etttlttfcolly t'.isJLitzxr-.z It hither .la he.d^ght..louy to4 che old--dote {toup thta la tit goatrol ttwi- 7. There vtt to evlPeace of TOt'ftttiif tffeetlat tbt Iwtdttn of ttr lutul mttitllati r tbt <77* tsl istldtut of attatry (Ittd tvp aur*. d# Zynhtl {load ttoeour vtt fcrust. - (. It vtt ceceluCed thet usier the deii ties* at the pretest uptebtett: - TOt at t level of 1.3 g/fc< body veliht/cdtT lafuent oeooltttle eel ooc-ncepleetic ehtsfee la the Uvtr at rate, VCK tc t level of 0.13 etAa Wr volihtiyfey tty loot to part fault tttt beoflsi foil of aUtitf oLterttla* lLtbt Urtt, ~ TQf tc levele of 0.01* or 0.13 t/V( body- eeLfftt/dsy eey reeolt la tt loereteed incideeet of ttniblllt fec.li of collultt titered** la (be lint of ftttlt rate, " 0.13 t VQl/if body velfht/dty It * *Mt;itwd*tfrirw<<fitt- level' with raepeec to the iedwerjoa of twteaurt to rata. CMA 010654 ~** * b tn tii*1: *f ttM iriuitc rat atuty tn4 UU"* *eeou th * tu liM.r .u.l * i,,J MQiltlTitj *f ^MUi ( tu c4tdM(utt actlm ( tot la CMHrtm with rt, Iftiltitti Oat the uiot tltk ti a Ulaly mzImjb atal tfally iettka if 0.1 pc VOt y*r f*ro Hr lay ui W practically M|llcti4, DRAFT CMA 010A55 DRAFTj^ RISK MANAGEMENT OF EXISTING CHEMICALS Proceedings of a Seminar Conducted December 8-5. 1933; Washington. D.C. Sponsored by: CM* 010656 Chemical Manufacturers Association tii avals for subIn each case, nplies a regulaacceptable to ial carcinogens, id EPA have all million ought not values represent phthalate esters, not be regulated. .*0 be subjected to significant popu?lcs to regulatory . "Review of Data Formaldehyde and ` 1982. rologv and Pharma- DRAFT CHAPTER 10 VINYL CHLORIDE AND TSCA John T. Bart .. Air Products and Chemicals, Inc.1' INTRODUCTION 4 The well-known regulatory history of vinyl chloride and its role as a bellwether of current regulatory philosophy makes it a useful paradigm for examining the relationship of existing laws end the Toxic Substances Control Act (TSCA) for control of chronic hazards. To this end, we will first review some of the highlights of its regulatory history, and then engage in some speculation as to the response these events might elicit today under TSCA. INDUSTRIAL AND COMMERCIAL USE OP VINYL CHLORIDE Vinyl chloride became of industrial importance about fifty years ago, approximately a hundred years after its discovery, when Semons discovered that its polymer could be converted into useful articles by plastization with phthalate esters. Commercial develop ment began first in Europe and then in this country in the late 1/ Air Products and Chemicals, Inc., 1S83. 129 CHA 010657  w k"' iva'*ts*" --'a3g.g`*ft i~~'^>. ,7- j.f-iri v-:--?. *,j,*^-TT'tr^r^; 130 / RISK MANAGEMENT OF EXISTING CHEJi thirties, lergely using existing rubber processing eruipment, for it was rubber which it initially replaced in the market. For the same reason, the use of polyvinyl chloride (PVC) was sequestered by the government during the war years, and it wras not until the early fifties that widespread consumer applications developed. PVC is now a mature product, and its growth rate falls in step with the Gross National Product. Presently, about six billion pounds are used annually in this country, and about four tines that in the world. Some of the broader toxicological attributes ci vinyl chi ride (VC) were recognized in the thirties. It was known tc be an anes-thetic, but problems with cardiac arrythmia prevented its use in that application.^' As pathological techniques iimproved, industry scien tists recommended in the early sixties that exposure be limited to 50 ppm. because of temporary liver enlargement in animals at that level,*' but the American Conference of Governmental and Indus trial Hygienists considered this overly conservative and accepted instead the 500 ppm recommendation of Ear-rand scientists.*/ This was the value adopted by the Occupational Safety and Health Administration (OSHA) in its formative days. Also in the early sixties, the European industry recognised among its workers a disease termed acrocsteolysis, AOL, which is a degenerative disease of the bone tufts, particularly in the fingers, that is accompanied by Reynaud's phenomenon.5/ An extensive epi- 2/ W. F. vcn Oettigin, "The Halogenated Hydrocarbons, Their Toxicity and Potential Dangers," Public Health Service Publication No. 414 (Washington, D.C.: U.S. Department of Health, Education and Welfare, 1955). 3/ T. R. Torkelson, F. Overs, and V. K. Sc-.ve, "The Toxicity of VC as Determined by Repeated Exposures of Laboratory Animals," American Industrial Hygiene Association Journal. XXII (1961), p, ITC . 4/ American Conference of Governmental and Industrial Hygien ists, "Documentation of the Threshold Limit Value, 1963" (Cincin nati, OH, 1963). 5/ S. Suciu, J. Drejman, and M. Valaskai, "Study of Diseases Caused by Vinyl Chloride," Medical Intern.. 1CV (1953), p. 957. CMA 010658 rocessing equipment, for it the market. For the same VC) was sequestered by the it was not until the early :at;ons developed. PVC is rate falls in step with the t six billion pounds are used mes that in the world, attributes of vinyl chloride was known to be an anesne prevented its use in that s improved, industry scien tist exposure be limited to gement in animals at that T Governmental and Indus:onservative and accepted Harvard scientists.*/ This tional Safety and Health ys. '?ean industry recognized >steolysis, AOL, which is a articularly in the fingers, enon. An extensive epi ted Hydrocarbons, Their lealth Service Publication lent of Health, Education `owe, "The Toxicity of VC of Laboratory Animals," Journal. XXII (1961), p, al and Industrial Hygienlit Value, 1963" (Cincin- :ai, "Study of Diseases XV (1963), p. 967. demiological survey here and in Europe round about a hundred possi ble cases which were associated closely with manual cleaning of reactor walls between polymerization batches, but neither the pre cise etiological agent nor the disease mechanism was identified- / An attempt was made to reproduce this disease in rats by the medical department of one of the European producers. An exact duplication of the human disease was not seen, but many of the rats developed tumors at numerous sites. The reporting of this finding by Viola ^ in 1970 evoked little interest in the regulatory community, possibly because of the very high doses used, several thousand ppm, which were frankly toxic to the animals, and the fact that the tumors were largely metastatic from the Zymbal gland, an organ not present in humans. Nevertheless, both the European and domestic producers formed consortia to perform bioassays at lower concentrations and also began epidemiological surveys of their employees. w Preliminary results of the European bioassay became available first in early 1973, and showed tumor development at much lower concentrations in organs which do have human counterparts. This result was transmitted to regulatory officials that summer, and industry screening of employee records was intensified.^ This re sulted in the recognition that winter by am industry medical director of a cluster of three rare liver tumors termed angiosarcoma, ASL, in the employees of one facility.9/ The reporting of this fact to 6/ W. A. Cook, et aL, "Industrial Hygiene Evaluation of Thermal Degradation Products from PVC Fetus in Meat-wrapping Opera tions," Arch. Environ. Health. XXII (1971), p. 74., Also, B. D. Diman, et al., "Occupational Acroosteolysis I, An Epidemiological Study,1* ibid., p. 61. 7/ P. L. Viola, "Pathology of Vinyl Chloride," Medicine del Lavoro. LXI(1970), p. 174. 8/ A. W. Barnes, "ICI Ends Its Silence cn Vinyl Chloride," Chemical Engineering News. (July 8, 1974), p. 21- 9/ J. L. Creech and M. N. Johnson, "Argiosare ma in Workers Ex posed to Vinyl Chloride as Predicted for Studies in Rats." Journal of Occupational Medicine. XVI (1974), p. 150. CMA 010659 ?s-S51>4S-s s^SSr!?^ government officials led to the current regulatory status of vinyl chloride. It elso led to a virtual explosion of research on the chronic toxicity of VC. The body of scientific literature on the oncogenicity of vinyl chloride is es large es that for any other substance. It is recognized that VC is a classical procarcincgto. Metabolism by the mixed function oxidase in the liver converts it to the ultimate car cinogen, an epoxide. Detoxification of this intermediate by the sulfhydryl group of glutathione or ether proteins removes the toxic potential.1`'7 Both of those mechanisms are saturable.**' An.overload of the metabolic step assures that the vinyl chloride will pass through the liver end some will be metabolized in other organs. An overload of the detoxification step allows escape of the toxicant into the sinusoidal passages of the liver where interaction with the chromosomal protein causes ASL to develop. An overload of both mechanisms can lead to tumor development cutside of the liver, as is seen in mice and rats at very high doses. Despite the Iazge data base, however, information on the precise mechanism of these vari ous steps still is lacking. Vie do not even understand why some per sons respond with AOL and some with ASL, but none with both diseases. REGULATORY STANDARDS OSHA proceeded promptly in early 1S74 to set an emergency temporary limit of 50 ppm for worker exposure, and later that year reduced the limit to one ppm, the current figure. Industry was given a grace period during which respirators could be used to meet this requirement, but now that level must be met by engineering prac tices.127 10/ W. K, Lelbach and H. J. MarsteLer, "Advance in Internal Medicine end Pediatrics " Sorincer-Verlez. XLV3 (New York, 1981). 11/ R. Hefner, P. Katanabe, and ?. Gairing, "Percutaneous Ab sorption of Vinyl Chloride Gas in Rhesus Monkey," Toxicology and Applied Pharmacology. XXXIV (1975), p. 19. 12/ OSHA Standard for Vinyl Chloride, 29 C?E 1910.1017. CMA 010&60 Jgulatory status of vinyl research on the chronic iture on the oncogenicity >y other substance. It is >gen. Metabolism by the S it to the ultimate carfiis intermediate by the Jteins removes the toxic ; saturable.11^ An over vinyl chloride will pass zed in other organs. An escape of the toxicant ere interaction with the p. An overload of both outside of the liver, as Despite the large data echanism of these variderstand why some per il*, but none with both 74 to set an emergency ure. and later that year ure. Industry was given id be used to meet this st by engineering prae- "Advance in Internal -Vn (New York, 1981). ng, "Percutaneous Ab>nkey," Toxicology and :R 1910.1017. The Environmental Protection Agency CEPA) promulgated a combined engineering and works practice standard in 1976 which has resulted in ambient concentrations in the fractional ppb range near producing or using facilities.13/ In the meanwhile, the Food and Drug Administration (FDA) and Consumer Product Safety Commission (CPSCJ established prohibi tions on the use of VC in aerosol or other consumer applications, a practice which had been discontinued is IS73. The Bureau of* Alcohol, Tobacco and Firearms of the Treasury Department (BATF) had already banned the use of PYC liquor bottles in 1973 because of concern for taste effects from migration, of residual VC into the contents. In 1975 the FDA proposed revocation of the generally regarded as safe (GRAS) status of rigid FVC packaging under the Delaney clause, also because of migration concerns, but that proposal never has been promulgated, and tie FDA has stated that It is considering withdrawal of the'proposal and recommending,, to BATF the reauthorization of plastic liquor battles In light f the current very low residual monomer levels in fabricated FVC articles. Other regulations have followed as new statutes and rules hav come into play. The Department of Transportation (DOT) and the Coast Guard regulate the transportation of VC, of course, and VC is listed as a priority pollutant and hazardous waste under various water and solid waste rules, and has a reportable quantity of one pound under Superfund. Did the existing laws operate satisfactorily at the tin of discovery of the chronic hazards of VC? it appears that they did. A leading medical authority who was deeply in volved in the w rker health evaluation in 1974 has termed VC a "suicess story." Reeval uation of the risk to employees under the cr > ppm standard by a conservative nonthreshold extrapolation methrr.'1"*' yields a lifetime estimate of less than 10 , a risk level which is not thought t be of concern. The comparable risk estimate for the general populace is 13/ EPA Standard for Vinyl Chloride, 40 CFE 61.60. 14/ P. J. Gehring, P. G. Watanabe, and C. K. Park, "Risk of Angio sarcoma in Workers Exposed to Vinyl Chloride as Predicted for Stud ies in Rats," Toxicology and Applied Pharmacology," XLEC (1979), p. 15. OlOA^ several orders of magnitude lower. EPA has stated on several occasions that it believes that vinyl chloride is regulated adequately. RISK ASSESSMENT Risk assessment has been a popular avocation among thos interested in VC, and more than a dozen have been performed.15/ These can be divided generally into two classes: those which rely solely on animal data; and those which attempt 10 incorporate the human experience. Those in the first class yield samiter results, and show the normal spread of estimates from the verious mathematical models in common use. These range from 1,50<J to 10"5 ppb for a lifetiro risk of 10-6, or. eight orders of magnitude. It is necessary to eliminate the high-dose data points, that is, those over 2,500 ppm from the Maltoni data1/ in order to get reasonable fits to most .models, because these doses show broad systemic toxicity. The lower doses, 500 ppm and below, as a group fall into a general pattern on a logprobit plot, but individual two or three cose experiments show tre mendous differences in slope when plotted separately. The popular multihit model predicts a lifetime risk of 10" at fractional ppb levels. The human factor was accounted for in two ways. The EPA used some preliminary emplovee epidemiological data to confirm its animal-based extrapolation.17/ Unfortunately, the human data were* 25 15/ J. T. Barr, "Risk Assessment for Vinyl Chloride in Perspec tive," (Paper 82-9.2 presented at the 75th Annual Meeting of the Air Pollution Control Association, New Orleans. LA, 1982), Lines 2025. 16/ C. Maltoni, et al., "Vinyl Chloride Carcinogenicity Bioassays (BT Project)," (Paper presented at rLe Club de Cancerogenese Chemique," Institute Curie, Paris, November 10, 1979). 17/ A. M. Kusmack and R. E. McGcughy, "Quantitative Risk Assessment for Community Exposure to Vinyl Chloride," (Washing ton, D.C.: U.S. Environmental Protection Agency, December 5, 1975). CMA 010662 stated cn several .5 regulated adequately. v'ac-.tjcn among: those ro 'fieri performed.*' ; those which rely er.'Pt to incorporate the r'rsj'iis, and show the 7,metical models in :vh for a lifetime risk ; icesssry to eliminate :i 2,SCO ppm from the : fits tn most models, '.loitv, The lower doses, oneral pattern cn a log- Imenis show tre'psrarely. The popular 20"' at fractional ppb in two ways. The EPA jicai data to confirm its the human data were Chloride in PerspeeA.mual Meeting cf the -is, LX, 19S2), Lines 20- :rcir.oger.icity BioassEys 71 us dc Cenceregenese 10, 1973). hv, "Quantitative Risk ;yl Chloride," (Washing- Agency, December 5j VINYL CHLORIDE / 135 selected from those locations known to have ASL cases, while other facility data were omitted. They also were in error on the past exposures by more than an order of magnitude. This resulted in an estimate of 20 cases per year from the estimated 1974 ambient concentrations for the population within five miles of production and processing facilities. The EPA seldom bothers to check its estimates against avail able data, so it sometimes comes up with results such as that made for arsenic a few years ago that would have predicted 18 million cases of skin cancer a year in this country if it had been applied to Agency data on the average arsenic concentrations in drinkingwater. Similarly, a survey of all known ASL cases in this country for the ten years before 1974 showed no cases associated with residency near such plants,18^ rather than the 200 predicted cases. It is rea sonable to assume that if any cases had developed since that time, the publicity associated with it would have brought them to light. Thus we have 110 million-person years of negative history for nearby residents. This places an upper limit on risk of less than 10"" per ppm-yr. Two studies applied pharmacokinetics in an attempt to obtain relevant human data. Gehring and coworkers estimated a lifetime risk of 10"8 at one ppm from the probit model, based on e biotrans formation of rat data. The unconstrained linear model predicted n risk at less than 99 ppm,19' Anderson, Hoel end Keplen carried this procedure one step further, and applied it to bound metabolic products, rather than to the total amount metabolized. Their results gave a lifetime risk of 10"7 at less than one ppm, with the probit model, or at less than two ppm with the linearized multistep model.2/ 18/ H. Popper, et aL, "Development of Hepatic Angiosarcoma in Man Induced by Vinyl Chloride, Thorotrast, and Arsenic," American Journal of Pathology, XCH (1578), p. 349, 19/ P. J. Gehring, P. G. Watanebe, end C. N. Park, Toxicology and Applied Pharmacology. XLIX (1979), p. 15. 20/ M. V,\ Andersen, D. G. Hoel, end N. L. Kaplan. "A General Scheme for the Incorporation of Pharmacokinetics in Low-dose Risk Estimation for Chemical Carcinogens, ibid.. LV (1980), p. 154. CMA 010663 ^ ^ - it C^" ' krj-VTcT.'-~i7----~~-~' ^~r^~i-i`"---AiSJP- "L. t -->rr ^`*svi?-lit- *" r-'Vw-.ViTr- ^ DRAFT 136 / RISK MANAGEMENT OF DCSTTNG CHEMICALS Thus we see that risk is in the eye of the estimat r, bat it is clear that estimates incorporating hu man data reflect the human experience for VC far better then do tthe direct application of ani mal data. There was understandable uncertainty on the part of both th regulators and industry in 1974. This aas the first commodity chem ical to be regulated under the relatively new statutory situation as the result of new information. Nevertheless, both the regulatory agencies and industry acted promptly to reduce exposures and emis sions to an acceptable level. The current count of occupational ASL cases is about 100 worldwide, with 30 of these In this coumtry.2^ All these cases had their first exposure in 1964 or earlier, jand there appears to be room for optimism that the steps taken in She mid-sixties because of the AOL information will have prevented! any significant number of cases developing from exposures commencing after that date. Cer tainly it is reasonable to expect that there have been no new cases initiated after the early seventies. Had TSCA been in place in the nicd-sirties, would it ha-'t made any difference in the course of eventsS? It appears unlikely that it would. Certainly the AOL discovery would have resulted in a series of 8(e) notices to TSCA. The probable outcome of that would have been either a recommendation from fee Interagency Testing Com mittee (ITC) for more tests, or a Section 4 testing requirement. It is possible that, because of its commercial importance, VC could have been placed on the ITC list before the AOL data became available. Additional data could have been called! for under Sections 8(a) and (d). The result of all this most likely would have been a negotiated testing rule, under which industry would ha ve initiated a series of studies which would have culminated in a bioassay, and the car cinogenicity of VC would have been discovered in due time. Yet, this is precisely what did happen in the absence of TSCA, except that the preliminaries were omitted, ar.d the bioassay was performed concurrently with the screening tests.. Thus it is possible that the 21/ J. Stafford, personal communication, Liver Angiosarcoma Cases, April 15, 1983. CMA 010A64 of the estimator, but it is n data reflect the human direct application of ani- iy on the part of both the the first commodity ehemnew statutory situation as si ess, both the regulatory *duce exposures and emis- ASL cases is about 100 y.21^ All these cases had there appears to be room Tiid-sixties because of the iv significant number of ing after that date. Cer- have been no new eases xties, would it have made t appears unlikely that it have resulted in a series come of that would have iteragency Testing Comesting requirement. It is portance, VC could have i. data became available. ' under Sections 8(a) and i have been a negotiated ive initiated a series of bioassav, and the earered in due time. Yet, jser.ce of TSCA, except bioassay was performed :s it is possible that the Liver Angiosarcoma final critical data were obtained earlier than would have occurred under present conditions. Bear in mind that most of today's powerful testing methods were not available twenty years ago. That fact would not have been changed by legislative fiat, and any decision made at that time had to be made in light of the available knowledge. If the data of Viola suddenly became available today instead, would there be any significant difference in the outcome, or the timing of that outcome? Probably so, but only because of thejmstly more powerful scientific tools which we have available to us now. Neither the speed of agency motion nor the rate at which Industrial facilities can be built or modified has increased. If anything, tfc|B latter has slowed, given the multiplicity of permits and approva^w now required. Overall, it is possible that if today we knew nothing more about VC than was known in 1970, we would arrive at a regu lated state a few months earlier than was achieved in 1974, but scientific progress, and not legislative or regulatory advancement, should get the credit. What if VC were to become a new product today? Would it run the same course in which it would be 40 years before there was full recognition of its chronic potential? Certainly not. Again, however, the reason is due more to scientific progress rather than statutory development. One change might be epparent. If VC were the subject of a Premanufacture Notification (PMN) today, rather than being the model to which all other aliphatic olefins are compared for struc ture-activity analysis, it would be judged by the others in Its family. This comparison would be less dogmatic than th reverse is now. Ethylene end vinylidene chloride ere not animal carcinogens; the relevance to humans of the carcinogenicity of high doses of . trichloroethylene (TCE) is equivocal and controversial; and vinyl acetate has only a preliminary "non-negative" report. Thus, this class of substances would heve lost its leader for structure activity * comparison, and a decision as to the need for further testing from that analysis would not be clear-cut, based on analogous compounds. Neither would a full minimum premanufacture data (MPD) set be of any great assistance. VC responds poorly to the classical i^t vitro tests, and only recently hes it become possible to btain rep^B ducible positive results in many of these. If the position were take* DMA 010665 140 / RISK MANAGEMENT OP EXISTING CHEMIC. "little lists" for the executioners apparently is too great to be re sisted, ' as Lester Lave pointed out recently. We believe that EPA can best obey its statutory mandate by developing a more efficient system for establishing priorities, and by implementing more effectively its Section 9 procedures. BIBLIOGRAPHY American Conference of Governmental and Industrial Hygienists. - "Documentation of the Threshold Limit Value, 1963," Cincinnati, OH, 1963. Anderson, M. W.; Hoel, D. G.; and Kaplan, N. L. "A General Scheme for the Incorporation of Pharmacokinetics in Low-dose Bisk Estimation for Chemical Carcinogens." Tcotioology end Aoolied Pharmacology." VoL LV (1980), 154. ~ ' ' Barnes, A. W. "ICI Ends its Silence on Vinyl Chloride." Chemical Engineering News. (July 8, 1974), 21. Barr, J. T. "Risk Assessment for Vinyl Chloride in Perspective." Paper 82-9.2, 75th Annual Meeting of the Air Pollution Control Association, New Orleans, LA (1982). Barr, J. T. "Establishing Regulatory Priorities." Toxic Substance Journal. VoL IV (1983), 290. Cook, W. A. "Industrial Hygiene Evaluation of Thermal Degradation Products from PVC Fetus in Meat-wrapping Operations." Arch. Environ. Health. VoL XXH (1971), 74. Creech, J. L., and Johnson, M. N. "Angiosarcoma of Liver in Manu facture of PVC." Journal of Occupational Medicine XVI (1974), 150. 26/ Lester Lave, "The High Cost of Regulating Low Risks," Wall Street Journal, August 19, 1983. CMA 010666 CHEMICALS y is too great to be re ly* is statutory mandate by Wishing priorities, and by procedures. d Industrial Hygienists, ilue, 1963." Cincinnati, . L. "A General Scheme 'cs in Low-dose Risk lexicology and Applied yl Chloride." Chemical ileride in Perspective." Air Pollution Control ities." Toxic Substance )? Thermal Degradation ig Operations." Arch. ^oma of Liver in Manudicine XVI (1974), ISO. iting Low Risks," Wall * DR/vn VINYL CHLORIDE / 141 Diman, 8. D., et al "Occupational Acroosteolysis I, An Epidemio logical Study." Arch. Environ. Health. Vol. XXH (1971), 61. Environmental Protection Agency. "The Ccst of Clean Air and Clean Water." Annual Report to Congress, Senate Document 96-38, December, 1979. Gehring, P. J., Wstanabe, P. G., and Park, C. N. "Risk of Angio sarcoma in Workers Exposed to Vinyl Chloride as Predicted for Studies in Rats." Toxicology and Applied Pharmacology, VoL 3CLIX (1979), 15. Hefner, R.; Wataneie, P.f and Gehring, P. "Percutaneous Absorption of Vinyl Chloride Gas in Rhesus Monkey." Toxicology and Applied Pharmacology. VoL XXXIV (1975), 529. Kusmack, A. M., and MeGoughy, R. E. "Quantitative Risk Assess ment for Community Exposure to Vinyl Chloride." U.S. Environ mental Protection Agency, Washington, D.C.; December 5, 1975. Lave, L. "The High Cost of Regulating Low IRisks." Wall Street Journal. August 19, 1983. Lelbach, W. R., and Marsteller, H. J. "Advance in Internal Medicine and Pediatrics." New York: Springer-Verlag, Vo'JU XLVH (1981). Maltoni, C., et aL, "Vinyl Chloride Carcinogenicity Bioassays (BT Project)." Paper presented at "Le dub de Cancerogenese Chemique," Institute Curie, Paris, November 10, 1979. National Research CouncfL "Regulating Pesticides." Environmental Studies Board, Committee on National Resources, Washington, D.C., 1980. Popper, H., et aL "Development cf Hepatic Angiosarcoma m Man Induced by Vinyl Chloride, Thorotrast, and Arsenic." American Journal of Patholorv, VoL XCII (1978), 349. Stafford, J. Personal communication, Liver Angiosarcoma CasesJ April 15, 1983. CMA 010667 CMA 0 1 0 6 6 9 82-9.2 Risk Assessment for Vinyl Chloride in Perspective John T. Barr Air Products and Chemicals, Inc. Allentohn, Pennsylvania For Presentation at the 75th Annual Meeting of the Air Pollution Control Association Now Orloans, Louisiana Juno 20-25,1902 ai-i.t roductlnn tMtliMilon of cfrcumstances which found the carcinogenic hazard vinyl chloride (VC) being discovered at about the sane time -as the ence of risk analysis was undergoing rapid development, and the at conmerrlal Interest and long history of use of the substance has ulted In a body of literature and pharmacological data greater than can expect to have for most substances. It Is therefore Instrue* e to review the many risk assessaents which have been prepared (or against (he available biological Information to determine If we can luate the extrapolation methods used, and to discuss the current ulations lor VC In light of this comparison. ards of Vinyl Chloride is necessary to decide Tlrst which of the hazards presented by VC uld he the basis for the risk estimation. The substance presents acute hazards ol frostbite from exposure to the liquid, ol anes* sia at concentrations over 8.000 ppm and suffocation at higher centratlons (von Ocltlnger, IMS). It also forms explosive mixtures air above 3.75 volume percent, and so the efforts to control the steal safety of operations generally preclude exposure to acutely lc concentrations. te control efforts were reinforced In the mid-1960's where It was overed (Suclu, 1963) that workers who had been exposed to very i levels of VC developed "vinyl chloride disease," the primary I reflation of which was acroosteolysls (AOl), a degenerative disease ihe hone tufls in ihe hands, and eore rarely of the reel end lubber Inn. Although crippling to some degree, this disease Is not fatal. Is at least partially reversible If exposure Is eliminated (Cranlger. <er and Ward, 1980). >st ten years later It was found that tome of the workers having lar exposure also were developing angiosarcoma of the liver (ASL), >pldly fatal disease. Oddly enough, there It only one possible of a worker developing both AOL and ASL (Stafford, 1981) among UO-plus cases of AOL and 90-plus cases of ASl now known worldwide, tough both are diseases of th* vascular system. Several large imlology studies were conducted on workers exposed to VC (Baxter fox, I9?6; Chime, I960; Duck. Carter and Coombu, 1975; Equitable ronmertal Health, 1978; fox and Collier, 1977; FrenUel-Beyme, ill, and Ihelss, 1976; Theriault and Allord, 1981), and ASt was only fatal disease found consistently to be In excess In these CMA 010670 * * >1 'vk persons. Animal studies have shown an excess of tumors at other sites, but the lowest exposures at which these occur are considerably higher than that for ASL. For example, Halloni (1979) reported the following data: Site Concentration For Significant Elevation Forestomach papillomas: Heiirohlastomas: Zymhal gland carcinomas; Nephroblastomas: Liver angiosarcoma male: female: Hammary adenocarcinoma: 30,008 ppm 10,000 ppm 10,000 ppm 250 ppm 200 ppm, SO mg/kg SO ppm, 16.7 mg/kg S ppm Ihe low concentration for onset of mammary tumors was of concern when a preliminary study of fabrication employees reported an excess of breast tumdrs (Chiazie, et al., 1979) but a follow-up case-controlled study (Chiazie, 1960) found no association between the cases and VC exposure. Ihe largest study of VC-PVC workers in the United States reported slight excesses of brain and lung tumors (Equitable Environ mental Health, 1978), but this was not seen In the other studies referenced above. The excess of brain tumors was small, and not doseor exposure-related. The overall excess of lung tumors resulted from an excess in one plant only, and reexamination of those cases also showed no association with VC exposure (Waxwefler, 1978). Vinyl chloride has been found to be active in several in vitro mula- genetic tests with bacteria and yeasts (Hopkins, 1979) and U appears to cause chromosome abnormalities in exposed workers, but these changes are reversible when exposure is reduced (tianstccnc, 1970) and several studies of neighborhoods around PVC plants have failed to show a supportable association with birth defects (Ldmomls, 1975, 1976). It Is not a teratogen in rodents (Johns, 1977). Therefore It appears reasonable to assume that If there Is any signif icant chronic risk other than ASL, It Is considerably smaller than that for ASL, and that an adequate risk assessment can be based on only the liver town. NOTE TO EDITORS O Under Ilia new taderal copyright law, publication right* lo 11*1* paper arm rolaliiod by Ilia aullior(t). --T1 -view of Wisfc Assessments 1. Sthnelderman, 1975 One of the first attempts to util lie ul*il dtli to estimate risks at very low exposures was that of Scimeiderman, Mantel and Irmn (1975). (hey used preliminary MaUonl results to compare the estimates obtained frto three possible mathematlcet Models. Th|,99I assurance level of a "safe* dose at * Ilfeltoe risk of 10 b was estimated froa several extrapolation Models as fellows; tog Problt (slope = 1) logit (slope 3 3.05) Logit (slope 7.3, one-hit) 7] ppb 119 ppb 2.1 ppb (hr author's discussed the recogntied difficulties of extending these rat data to humans and of providing animal experlnents that could answer satisfactorily the question of huaan risk ot very low doses. 2. Kuimack and HcGaughy, 1975 (he ifA was the first group to attempt a human risk assessment for vinyl chloride (Kuimack and HcGaughy, 1975). Ihls pioneering effort attempted to use both animal and human data, and to show comparative results fron both Use linear and log-probtt ngdels. It concluded that there was an Individual risk of 71 x 10 " per ppm of llfellmr exposure In VC by the linear oxtrapolallon mellwd, and that the log-problt results were one*tenth to one-hundredth of that. Ihls effort Is subject to several serious criticisms, (he exposure data used for human experience was that fron a group with less than average exposure, while the ASI. rate was chosen from only those plants which did report cases, and Ignored the remainder of the population. Ihus, their Incidence rate of 7.5X cooparas to an actual figure of about 0.IX. they used at their primary mclliod a linear extrapolation of rat data, which often has been seen to overesLlnato Use actual ratal by at least two orders of magnitude, and they assumed the total CAbCrr rale to be twice that found for A$t. Ihls same estimate was used by the (PA (1979) to estimate the concentration of VC In drink lug water which would produce various levels of risk, Ihm eillmales are, of course, subject to the sane crlllcltmt. Hlsbet (1978) challenged the estimate of Kuinack and HcGaughy (1975) when It was used by Wilson In testimony before the OSIIA hearing on Its generic cancer policy. Hlsbet slated that his calculations showed the risk to be 10*30 tines greater, by the saoe calculation Method. Wilson (1978) suggested several flaws 82-9.2 4 CM* 01A71 n t > i| `vs In the Hlsbet procedure. Including the fact that he chose for his extrapolation one point at 25 ppn from Hallonl experlnrnt 81-15, and that this point Is not In good agreement with the whole body of data, further, he chose to use total cancer Incidence In the rats, Including those at cymbal glands, which have no counterpart in humans. Both Wilson and Kuinack and HcGaughy had used a factor of two times ASt to account for possible Cancer at other sites. Wilson did acknowledge a mathematical error which made his results half the proper number. Albert (1978) applied this same general procedure to other poten tially carcinogenic air pollutants In the United States and calculated the expected annual cancer deaths as follows: Arsenic Deniene Cadmium Coke ovens VC (after regulation) 15.6 77.8 25.2 149.5 1.0 Gehrtng, 1979 Gehrlng, et al., (1979) applied an experimentally derived biotransformation correction (Gehrlng, el al., 1978) to rat data and estimated the incidence In humans at two different exposures by means of four different extrapolation models, (heir estimates at 500 ami 200 ppm (WA bracket the observed experience for humans when derived from the problt and the unconstrained linear models, (he 1(near*through-lero and one-hit models consistently over estimated the Incidence. Although not considered by the authors, the linear and problt models match rather closaly the totat U.S. experience of occupational ASL al an assumed 1,000 ppn exposure. The linear model predicts no Incidence below 99 ppg.tn humans. The problt model predicts a human risk of 1.5 x 10 at I ppm. Titus, a mechanism for adjusting for the difference In metabolism between animals and humans appears to bo useful. A limitation of the Gehrlng procedure Is that It uses partial Heltonl data, and tesla the results against Ute CHA epidemiology study. That study was not the "end of the experiment"; It stopped at the end of 1973, and several deaths have occurred since then. Neither did It cover the entire population, but only the employees of those plants which met certain criteria for data retention and length of operation, (he Stafford (1901) data does cover the entire population and extends the history for seven years, (he site of the population Is not known, but a reasonable estimate, based on normal worker turnover rates and the number of plants not Included In the CHA study. Is certainly not lass than 25,000. This would give o gross Incidence of about 0,IX. Of these, (he number actually exposed to substantial exposures would be about 25*30 per plant at any one time. Multiplication by 25 plants, and a factor ot three for the turnover during this period, would give about 2,000 highly exposed persons, for on efftcllvo Inc I- drnce of Just over IX. Prrsonal experience would Indicate that, for the period prior to 1%4, when alt of the first exposures of the fatal 2G cases had occurred, the average exposures of this highly exposed group certainly was In excess of 1,000 ppn for the working day., Mallonl (1970) found a IX Incidence at about 1-10 ppn In rats. Calculation of the dose equivalent to a IX Incidence In rats gives 0 ppo by the linear Method and 7.5 ppn Iron the log-problt equation for the combined Hattoni inhalation experinents. Ilils crude and subjective estimate would then say that nan Is about 100 tines as resistant as the rat to VC Inhala tion, a figure generally in agreenent with other eslinates (NCAO, 1979). Food Safety Council 1970, 1900 Ihe Food Safely Council has recommended (FSC, 1970) the use of Ihe gamma nulll-hlt node) because of its flexibility In handling dose response data of varying curvI linearity at low doses. It has calculated (FSC, 1980) the naxlnun likely and lower 97.5X llntt doses for substances at vafious risk levels and with diffeient node Is. for VC, at 10 * risk, these results are as Follows (based on early Mallonl data): One-hit Amitage-Doll WelbulI Multi-hit 2.0 x 10 PP* 2.0 x 10-9 PP* 2.1 3.9 x x 10 10 -10PpP"pn For this substance, the qoodness of fit of the Welhull nodel (0.56) was superior to that of the nultl-hll (0.32). Neither of the other two node Is gave acceptable fits. This was In part became of the concave shape of the curve, which Included oil of the hlyh doses In the dose response data. Onw, 1979 A pnv Heath Fean perfumed relative risk ejtlnatlon for several compounds (longer, rl *1., IVI) wh|i It Icoin dr It| probable expo sure , the consequence of exposure, llie physical sidle ill lilt substance during processing, and the current exposure standards. Ilils resuHrd In a value of toil for VC In a "closed systen but with employees In the vicinity." Ihe sane procedure assigned haiard rating values to sunt other substances as follows; benitne, 10; phosgene. <10; hydrogen sulfide, 5; arsine, 9,700; ami bls-chloronethyl ether, 59,700. In a batch operation with occasional manual handling, tha haiard rating for VC Increased to 9,700 by this netliod. Ilthh, 1900 Haiti r, el al., (1900) conducted a series of tests for tha Consuner Product Safely Commission, a part of which consisted of exposing rals and mice to a dries of short, high exposures, rather than 010672 the usual extended low dosage. Ihey Included one-hour exposures to rats and nice at SO, S00, S,000, and SO,000 ppn, 10 and 40 hour exposures at S00 ppm, and 49 and 100 one-hour exposures at SO ppm. After lifetime observation they found no effects on rats, or their offspring, nor on mice exposed to less thao S00 ppn. those exposed to over S00 ppm developed .pulmonary adenomas, hut they also had suffered from pneumonitis. i They considered the published data on animal exposures and concluded that there was a lifetime dose below which no oncogenic response Is seen. This was estimated to be 5,000 ppm-hrs for mice and greater than SO,000 ppm for rats, regardless of whether the dose was administered over a short or long period. This concept of equality of effectiveness for all modes of exposure does not have general acceptance and would not appear to be correct, based on our present understanding of carcinogenesis. Dose-rate effects are, of course, well known. However, the degree to which this can-fae extended to all types of effects Is not known. These authors also used the Crump-Guess model (Crump, Guess and Deal, 1977) to evaluate their data on nouse pulmonary cancer, and estimated that exposure to 5,000 ppn VC doubles the probability of cancer, while 50,000 ppn increased the risk nine-fold. In view of the fact that pneumonitis was present In all animals exposed above 500 ppn, It Is questionable If this was a direct oncogenic response, or the result of an nongenelic event because of severe lung damage. Haltonl (1979) also reports an increase in lung tumors In nice, but not in rats or hamsters. Thus, the significance of this finding to risk In humans Is questionable. 7. Anderson, 1900 IF* -n Anderson, rt a)., (1900) extended the work of Gehrlng, ct a)., (1970 and 1979) lo Incorporate the amount of metabolic products from VC which actually was bound to the UNA of exposed rals, (Gehrlng and Olati, 1977) rather than Uie total amount metabolised, |liny at*|nurd various values In l|ip |tA|\imnWs In a Hldurl!)' HiTtUH GljUJlItm dt'llitliiig Uie kinetics of the metabolic process, ami compared the results from extrapolation lo low doses by log-|irotill and multi-hit models. they found that the two extrap olation models responded quite differently to these variations at very low dnses, and that It was not possible to select one made) as the more appropriate from the high-dose data. Use of the values of Gehrlng for the primary parameter},gave estimates of the dose equivalent lo lifeline risks of 10 ' of less than I ppm for the prohit model and less than 2 ppm for the multistage model, a correspondence which the authors pointed out was better than the precision of Interspecies comparisons. I [PA, I960 The final version of the water quality criteria dociMent for VC (IPA, 1980) used a different approach for risk estimation. The slope of lh|e Incidence of all tumors at the lowest doses of Hal tool experiment 61*I was adjusted for the fraction of exposure, the equivalent feeding level to give the tame blood concentration of VC as by Inhalation (see Wlthey and Collins, 1171), and the ratio of the surface area of humans.ys. rats, to produce an estimate that a lifetime risk of 10 9 would be caused by drinking I l/day of water containing 20 g/1. There Is some confusion In the mathematics given In the report, and the assumptions on which the adjustments are made are far from having general acceptance, although generally following HAS recommendations. It appears that this procedure overstates the risk by several orders of magnitude. HAS, 1900 the National Academy of Science (1922) calculated the upper 9S% confidence limit for risk from drinking water containing vinyl chloride from the probabilistic multistage model and earjy HaltonI rat data. They report (NAJ. 1980) a lifetime risk of 10 9 as being equivalent to 3.0810 9 mg/kg/day. for a 20 kg person consuming 2 l/day, this would calculate to an acceptable level of I g/l. the difference between the [PA and HAS numbers comes from the different curve-filling methods for the animal data. Caylor and Kodelt (1900) applied linear "Interpolation" to the sane early Haltonl data used by the Food Safely Council (1928) to arrive at a predicted maximum risk of 10 . Ihe upper 92.SX confidence limit of the animal data was taken as one point on the Inlerpolallve line, and tero Incidence at tero exposure as the oilier. jb(s produced a lower 91.ST confidence limit dosage of 2.1 a 10 * ppm for a lifetime risk of 10 " in rats. Their appli cation of the Arnitj|e*0olI multistage model gave S.2 j-10 4 ppm as the dosage at 10 * lifetime risk compared to 2 x 10 * by the food Safrty Council, llie difference Is due to alternative assump tions on the value of llie exponential dose term, , Crump and fiuess (1900) reviewed some of Uw earlier risk estimates for vinyl chloride In drinking water, and recalculated the risks, using the one-hit and multistage models. Ihey arrived at an upper 9SX confidence limit of ItfeJJme risk for drinking water containing 1 g/l of VC of 4 a 10 , based on early Haltonl Inhalation data. Using the assumption that a 0.2X Inc Idenee of Ail In workers had resulted from a lifetime exposure of 20 g/kg, they obtained a maximum likelihood risk of 10 from 0,31 g/l by both the multistage and linear node Is, with 9SX lower confidence limits of the same risk at 0.24 g/l. These two models reduce to a linear form when used at very low doses end with the assumption of no threshold value. 82-9.1 4 CMA O 73 'i tb . These authors cite EPA data on the occurrrnce of VC In public water supplies which by their methods yield a lifetime risk of 3.2 x 10 , or 12 deaths per year from this cause in the United States. Hone of these has been observed, despite the accumula tion of IS years' data on ASL deaths (Popper, 1928). 0 12. Scott (1981) ascribed the decreased Incidence of tumors In rats at the higher doses to a cell killing process, and adopted the Welbull model to account for this. Application of the model to some early Haltonl data produced a curve which fit the data from SO-10,000 ppm. He did not attempt to extrapolate to doses beyond the experimental range. 13. Carlhorg, 1981, also applied the Welbull model to 31 bloassay reports on a variety of animal carcinogens. Me concluded that the one-hit model was not appropriate and that carcinogens could be divided into categories according to the shape of lire curve, e.g-, concave or convex., lie found that the early Haltonl data on VC fell Into the former category. Application of Ills parameter estimates to those data, assuming no spontaneous Incidence of ASL, gives 2.S x 10 ppm for a llfetlmp risk of 10 9 for rats. Later calculations Including all of the published Haltonl data did not change the results significantly (personal communi cation). He found tho Welbull shape parameter to be approximately 0.S, which Is assumed to be the number of stages for tumor Initiation. This Is consistent with the finding by Gchrlng (1922) of a satur able metabolic path which produces the proximate carcinogen. It also suggests that the number of "stages" Is the number of finiterate steps before thn rale-limiting step. There may be other stages following, but they are not rate controlling. Actually, there appears to be at least two saturable mechanisms Involved In tho pharmacokinetics of VC, the metabolism to the ultimate carcin ogen and the detoxification by sutfhydryl groups. 11. One further evaluation of human risk can be made from the experi ence of persons residing near VC-PVC plants. The EPA estimated (Kuimack and HcGaughy, 192b) that five million persons lived within flvt Hites of these plants, and were exposed to an annual average concentration of 12 ppb. The present distribution of plants was generally wot1-eilabtlshed by 19b9, thus we have 22 years ef history, or about 110 million person-years. About five or six of these plants, with 1*2 million neighbors, go back another 20 years, but Lhasa data arc not firm enough for Inclusion. The fact that no case of ASL has been confirmed as arising from these ambient.exposures places the upper bound of risk at lets than 2.7 m 19 per pp**yr. It Is believed that tha exposure data were overestimated by EPA, and thus this result may be too low, but it Is In the same general range as that arrived at by fiehrlng (1929) and Anderson (1980) after making corrections for . pharmacokinetics. *k " .1 * ' v a fxtrnding this crude calculation, these five million persons ere now supposed by EPA to be exposed to 0.2 ppb (probably a high figure), which would predict no more than 0.0001 deaths per year, or one per 1,700 years in that whole population due to VC exposure. But It also oust be recognised that with approximately 20 cases per year of, ASL in the general population, there can be expected Iron a purely statistical basis tt|at there should be one case every two years or so among this group of S Million plant neigh bors. the results of these estimates djscussed above are coopared In fable I, ifter conversion to a uni for* 10 0 lifetime risk. siinales 5, (Oow 1979) and 12 (Scott, 1901) were not In a font to perntl this comparison. See OSIIA, (1900), for references to a few other estimates that were iot considered here. It can be seen that the results fall Into two Major categories, those -hlch project that the risk of 10 occurs at exposures of greater than I ppm, and those which find that risk In the ppb range. The estimates which yield the higher allowable exposures are based on imnan data (Nos. 1, 7 and 14) or use a log-problt extrapolation Model (No. 2, second eslinate), or predict a threshold (No. 6). The remainder generally are based on the linear, non-threshold model, and nake no biological correction. The result Is a difference of 3 or 4 orders of magnitude, the estimates which yield the higher allowable exposures are In better agreement with human experience than are those of the other group. Additional Data All of the extrapolations reported here have used for the original -la It on I data from his experiment Bl-l. Me hat now reported (Haltonl, 1979) three other comparable Inhalation experiments on the same strain if rats, and one on another strain. In addition to two ingestion Uudfes. Hit results of these experiments are shown in Figure 1, on a log-problt scale. It can be seen that they ail follow a similar lattern, but that there are large variations In slope between the various data groups. Table III contains the log-problt equations alcnlalrd from some of tho Individual experiments, and various groups 'I experiments. Excellent fits are obtained fnr a single experiment, it would be expected from the small number of data points, but adequate 'Its are obtained for the group as a whole. Inclusion of the historic onlrot data on AH (0.09X spontaneous Incidence) did not affect tho 'It substantially, except for the very low dose data. Inclusion of itie 0,0 (origin) as a data point did give significantly poorer fits, ihe combined experiments Indicate that a lifetime risk of 10 * for all Is obtained from a dose In the 1-2 ppb range, ,lmller variation Is seen with the oilier mathematical expressions, uch as linear or exponential equations, 1-9.I ' 4 O10674 to ^3 Regulatory Status The current regulatory status of vinyl chloride Is sunwarlicd In Table 11. The first regulatory action on VC was taken in 197) when the Bureau of lax. Alcohol and Firearms prohibited the use of rigid PVC as liquor containers. This was based on It being present as an adulterant, and not on any consideration of risk. The Consumer Product Safely Commission (CPSC), Uic Food and Drug Administration, (FDA), and the (PA all acted to ban the use of VC as an aerosol propellant thus establishing a rero risk position. The FDA proposed (FDA, 1975) to withdraw the prior sanction status of rigid PVC as a food package component because of the concern for residual VC that might migrate. The FDA lias taken no further action on this proposal, and now is considering a "constituent" policy which would permit a lifetime exposure at some jcccplnble risk level. This risk has been proposed recently to be 10 " lifetime for the gluttonous consumer. As was discussed above, the EPA required a best available technology approach which reduces the average exposure to those within 5 miles of a plant to about 0.2 ppb, by EPA estimates. OSIIA established a rule in 1974 which set 1 pi* tor 0 hours as the maximum permissible exposure, and also set 0.5 ppm as an action level below which most features of the regulation did not apply. These were chosen as feasible levels, and not necessarily "safe" doses (OSIIA, 1974; EPA, I97G). The EPA has established an exposure to the general population only 0.IX of that allowed in the workplace. The CPSC has required tero exposure, and the FDA has considered that approach. Depending on which method of estimation the FDA may choose. Its allowable exposure could be either greater or less than those currently set by EPA and OSIIA. It has been estimated that the maximum amount of VC Ingested by the average European, who uses much more plastic packaging than we, is lejs than J, g/day, (CEFIC, 1976) which would be In the order of a 10 3 or 10 * lifetime risk by even the most conservative models. lhere have been various estimates made of the cost-effectiveness of the Federal regulation for vinyl chloride. Graham and Vaupel (1901) estimated that the OSIIA rule cost $7.5 million per life saved, and 1490 thousand per life-year saved over the option of leaving the exposure limit at 50 ppm. I.ukcn ami Hiller (19111) stale that the Imputed value of l life from the OSIIA standard Is 14 million. Horrell (1902) uses an annual cost of $20 million and an annual benefit of 0.1 life saved to derive a cosi/benefit of $200 million per life for the OSIIA rule. The LPA has reported (EPA, 1979) that the coil of compt , ancc with Its VC simulat'd was $796 million through July 7, 1981, and will be an additional $470 million during the next rive years, all In 1977 dollars. If the EPA estimate of up to 20 dealths par year were correct, this would be a cost of 14,7 million per life. However, as discussed here, there is no evidence that any lives hava been saved by this rule. There are many difficulties In obtaining accurate estimates of this type, and serious problems In determining the proper value to be assigned to a life, nevertheless, the doubtful nature of the claims 1-4.1 <>r any significant benefit fro* Mine rules suggests that at best, i.rie regulations are excessively cosily lo society. Iherefore, we si attempt to improve both our date base and our methods for inter* icling and applying the data. iscussion , tal can be learned from this exercise ocher than IN already cognited fact that various extrapolation Models can yield very iffrrent results! In this case, at least, there are several points ilch are worth considering. I. Vinyl chloride Is no exception lo the rule that hunan data always must be Incorporated whenever possible. Ihe epidemic of occupa* tionaiiy induced ASL which was feared in 1974 has not materialijed, probably due lo the steps that were taken in the early 1960's to reduce exposure because of the discovery of Mi. Ho instances of Ait trim exposure to VC in the general population have been substantiated. Ihe overprediction of occupational cases was due lo the uodereslination of worker exposure and overreliance on raw aninal data without proper pharnacoklnetlc adjustment. We are not now able to extrapolate reliably between similar species and certainly not from rodents to humans, without much additional data. 7. The regulations for vinyl chloride were not based primarily on scientific data, hut on socioeconomic and political decisions. This is no surprise (Crandall and lave, I9B1), but is a fact which should be acknowledged openly, along with the understanding that this position will continue to pcnalite good science. ]. Mathematical extrapolation models are not adequate in themselves for predictions of risks much beyond Use experimental range, no matter how good the fit is to the data in the observed range. The variability of relatively small experimental groups adds to the error range, thus, bioassays Intended for quantitative risk assessment applications should be at as low doses as possible, and as large as possible, and should be Interpreted very cau* tiously. 4. Ihe current stale of the art Is such that quantitative risk assessments may be useful for determining relative risks from similarly acting carcinogens, but are not suitable for across* tlie-board application Lo all mechanisms of carcinogenesis. This Is not to say that we should abandon efforts at developing tore effective risk assessment methods. Wo must, however, recognlie the problem* Inherent In blind application of mathematical models without proper assessment of the available biochemical data, or on understanding of how applicable the experimental data art to humans. CMA 010675 .4 11 > We have available to us at least as much data regarding vinyl chloride . as we have for any other substance, and we still have difficulty in deriving a suitable expression lor risk from a purely mathematical or statistical basis. Only when human relevance Is considered can we arrive at a prediction that approximates actual experience. 02 Ihe regulators are faced with a tremendously difficult' task when they are presented with a few pieces of animal data which suggest the need for concern and potential regulation. We must develop a suitable program to obtain and use as much relevant data as possible to assure that rational regulations are possible. The vinyl chloride experience can help us understand the kind of data which are heeded. 378S-AI 2/19/62 Ibh o *-r i References Uirrl, R. t. , letter to R. S. H.ivren, IPA, "Comparison of vinyl ,)di life carcinogenic risks wlUi risk fro* oilier pollutants", thlnglon, DC, 16 June 1926. iderson, H. M., et el., lor. Atipl. Phara. 55,. 154 (I960). inter, P. J., end A. J. fox, Lancet. 1976 245. irlborg, f. V., Fdj_ Cosmet. Ton. 19 255 (1981). 91C Cornitltee for the loxlclty of Vinyl Chloride, "Vinyl Chloride irIcily end the use of PVC for Packaging foodsluffs," Brussels, ftb. >76. ilane, t., Octup. Med. 22 (10) 677 (I960). nlane, L., Jr., W. E. Nichols, end 0. Wong, 1977). Occup. Hed.. 19 623 rendell, R. W., and l. lave, "The Scientific Oasis of Health and ifety Regulations," Brookings Institution, Washington, 1961. ruup. k. 5., end II. A. Guess, "Drinking Veter end Cancer", UBI-12B167, December, I960. rump, K. S.. II. A. Guess, and K. L. Deal, Biometrics. 33 4370451 1977). uck, D. W,, J. T. Carter, and I. J. Coombos, lancet 1975 II, 1197. dmonds, l.. "Birth Defects and Vinyl Chloride", Proc. Conference on amen and the Workplace. Washington, DC, 1976, also Teratology. 17 137 19)6). dmonds, l. 0,, H. Falk end J. E. Nlssla, The lancet 1975 1096. nvlroimrnta) Protection Agency, Standard for Vinyl Chloride, 41 Fed^ eg. 46,560 (1976). nvironmental Protection Agency "Vinyl Chloride, Ambient Veter quality rtlorla", PB-292446, Washington, OC, 1979. nvlronoentil Protection Agency "Ambient Veter QuAllty Crlltrli for Inyl Chloride," CPA 440/5-60-076, October, I960. nvlrnomentel Protection Agency "The Cost of Cleen Air and Clean aier", Annuel Report to Lite Congress, December, 1979b. Senate ocumenl Ho. 96-36. U.S. Government Printing Office, WathtngUm, 0C. *1-9.2 CMA 010676 14 it Equitable Environmental Health, Inc., "Epidemiological Study of Vinyl Chloride Workers, final Report". Prepared for Manufacturing Chemists Assoc., Was III nylon, OC, January, 1970. food and Drug Administration, Hotlce of proposed rulemaking, 40 Fed Reg. . 40.529 (1375). -----' food Safety Council Final Report "Proposed System for Food Safety Assessment", Washington, 0C, June, 1900. Food Safety Council, Scientific Committee "Proposed System for Food Safety Assessment." Food and Cosmct. lo. 16 Suppl. 2 Oecember 1976. fok, A. J., and P. f. Collier, Br^ J^ Ind. Had. 34 1 (1977). frentiel-Beyme, R., T. Schmlla, and A. H. lhtess. Arb. Soclalmed. Prevent., 13 216 (1976). ------------------------ Gaylor, D. V., and R. 1. Kodell, R. L.. J. Environ. Pathol. Ton. 4 305 (I960). ----------------------------------------- Goewhrnln.g, P. J., end G. E. Bleu, -J-. --E-n-v-i-ro-n-.--P--et:-h-o-l.--T--o-x-i-c-o-l.--1 163 Gehrlng, P. J., P. G. Wetenebe, end C. H. Park. Tox. and Aool. Pharm. 49 15 (1979). --------------- ------------------ Gehrlng, P. J., et el,, Tox, Appl. Pharmacol. 44 581 (1976). Graham, J. 0., and J. W. Vaupel, Risk Analysis | 69 (1981). Granlger, R. G., A. . Walker, and A. H. Ward "Vinyl Chloride Honomer-Induced Disease; Clinical, Radiological and Immunological Aspects," Chapter II in "Induced Disease; Drug, Irradiation, Occupation", l. Preger, ed., Grime and Stratton, London, 1900. liensleene, l.-l., et ml.. Hut. Res. 70 211 (1978). llehlr, 6. H., et el., "Toxicology, CarcfnogenlclLy ar.d Reproductive Cffpcl* of Single and HuHIple Exposure* id Vinyl Chloride In Bad ind HUl"t PrcpiibllciHon drift, feb. i, 1900, U.S. Consumer Product lately Commits Ion, Washington, DC. Hopkins, J., Fil Co use t, Toxicol.. 17 542 (1979). John, J. A., et ||., Tox^ am} Appt, Pharmacol. 39 497 (1977). Kuinack, A. M., end R, E, KcGaughy, "Quantitative Risk'Assessment for Community Exposure to Vinyl Chloride", U.S. EPA, Washington, 0C, December 5, 1975. Unger, R, R., S. K, Norwood, G. E. Sochi, end II. R. Hoyte, Am. Ind. jtyg. Assn, jk, (12) 1039 (1979). ------------- H.II. , and S. G. Hiller, J. Air Pol. Control Assoc. II (254 I, C., G. lefcmine, A. Cflihertf, G. Cottl, and 0. Carrettl, Chloride Carcinogenicity flio.issays, (0 I Project) as an nenlal Hodel for Risk Identification and Assessment In menial and Occupational Carcinogenesis? Presented At "te Club erogenete Chimtque", Institute Curie, Paris, Hoe. 10, 1029. il Academy of Science, "Drinking Water and Health", National / Press, 1911. iI Acadeoy of Science, "Drinking Water and Health", Vol. 3, p. ltonal Acadeoy Press, 1900. I Cancer Advisory Hoard, "The Relation of Dtoassay Dose to the ent ol the Risk o( Carcinogens (or lluoans under Conditions of .nsure", Subcomaltlee on Environmental Carcinogenesis, Draft of King data Iron HrseIson and Russell, 1919. , I.C.T., Post-hearing statement to OSIIA docket 090, September '8. tonal Safely and Health Administration, Standard for Exposure A Chloride, 19 fed^ Rcc^ 35.090 (1924). , H. et al.. la. J, Pathol. 92 349 (1970). Leman, H. A., H. Hanlcl, and C. C. Brown, Aon. HV Acad. Set.. ' (1925). 0. R., Bull, Mathematical Biology, In press, 1981. d, J. , private communication (1901). J., J. Drtjman, and H. Valaskal, Hed. Intern. 15 967 ()963). )l, G., and P. Allard, Ocruj^ Hed.. 21 (10) 671 (1901), tlngcn, W. f., public Health Service Publication No. 414, U.S. rnt of Health, tdueaIIon and Welfare, Washington, DC, 1955. tr, I., cl al., "An (pldfhlologlcal Investl pi |G!l 3f in Excess ncer Risk In a Synthetic Chemical* Plant", Presented at Che nth International Congress lor Occupational Health, Dubrovnik, Sept., 1978. r. "Response to cooments or 1. C. KUbel," Post'hearing record cket 090, 1928. J. S., and i. 1. Collins, Ion, tnvlr. Health, 2 311 (1976), CMA 010677 #1*9.1 too DOSE. G/KO/Vn. 10 1.0 I 0.1 not 1 .4 * FIGURE 1 GRAPHICAL REPRESENTATION OF TABLE III LOG-PROBIT PLOT 82-5.2 ItGCNO IKilALAli or i c OT 2 A BIO C oris -C IHGtSTIO BTIi B an; - rnoaiTs in "'T'l i--1 I TABLE I ccl SUMMARY OF o.`QUANTITATIVE RISK ASSESSMENTS FOR VC nu,! ESTIMATE MO. AUTtlon BASE SPECIES EXPOSURE FOR 10 ( LIFETIME RISK COMMENTS 1 SCHNEIOERMAN, 1976 BAT 73 nob 119 i>|iU 3 ppt> LOOPROQIT LOGIT SLOPE - 3.48 LOGIT SLOPE 1.3, l-IIIT 7 KUSMACK A McCAUGHY, RAT, HUMAN M ppb 1975 140 1400 ppb LINEAR THROUGH ZEnO LOGPROOIT 3 GEHRING. 1975 RAT, HUMAN > 1 ppm BIOTRANSFORMAL data and LINEAR OR LOG PnOOIT 4 FOOD SAFETY COUNCIL, 1980 nAT 7 X 10 6 ppb WEI0ULL , 6 HEHIR, 1900 nAT, MOUSE THRESHOLDS SEEN IN DOTH SPECIES 7 ANDERSON, 1980 RAT, HUMAN > 1 ppm ONA BINDING 9 EPA. 1980 RAT 4 *i G/DAY FOOD OR WATER 9 NAS. 1990 RAT 3 X 10 s MG/KG/DAY WATER 10 GAYLOR A KODELl. 1990 RAT 0.7 ppb 0.5 ppb UPPER 97,6% CONFIDENCE LIMIT OF LINEAR MODEL ARMITAGE DOLL MODEL 11 CRU7AP A GUESS. 1980 HUMAN RAT 0.7*1 G/DAY 0.6*1 G/DAY APPLYING WORKER DATA TO WATER, UPPER 09% CONFIDENCE LIMITS 13 CARLOORO, 1001 RAT 3.8 X 10'6 ppb WIEOULL H THIS PAPER HUMAN > 1 ppm NEGATIVE EPIDEMIOLOGY a t uj Q or O .j x u >- z > u. 111 O -J CO OQ < 3 I-- H< CO > cc g 5 CD HI CC CrvsOO o >- o UJ -1 CD < hn. UJ o _J o xa *- ui X> o UI UJ o f- UJ o Ul _J < _J m h >* 2 o 2 0Q < _J t<o xX a. O to O < DC UJ H _l 3 O SC to DC o cc UJ DC UJ O 2^ o"? < > < h* to UI to IU O a. < N U DC at to H t_> o E Q a 2 UJ _i a o O in o >UJ UJ O IU 1r~ O 03 DC O n g n to < DC a. OC UJ 5 D to 2 o O Z < V o < Q. Q O O u. aO UJ gZ 5 XI D a a s n >: o' < >- _J IU h* < o > ci Z -J UJ s OC U_JI o a: h a IU Z a UJ Z cc O Z 1w x o tc X to z GO 2 2 2 IU UJ a. u. t- O < < to u a. ao O 03 00 O , < r-- >- o Z UJ ID < u. h< m O to Ou o < a UL < <I CL to IU O TABLE III i) EQUATIONS FOR CURVES FITTED TO VARIOUS SI AND COMBINED MALTONI EXPERIMENTS EXPERIMENT LINEAR y-i * b t br LOG PROBIT P- IN POSE* fa br CONCENTRATION AT 10'6 RlSK> ILOG-PRQ3IT), ppm BT-1 PLUS CONTROLS BT-2 PLUS CONTROLS BT.J5 PLUS CONTROLS ALL INHALATION STUDIES (4) PLUS CONTROLS ALL INGESTION STUDIES (2) PLUS CONTROLS ALL STUDIES (6) PLUS CONTROLS ALL STUDIES; LOW DOSES ONLY PLUS CONTROLS 0.26 0.27 3.05 1.52 6.5 5.28 0.2S 0.27 1.75 1.74 0.29 0.29 3.36 2.47 -8.S9 1.13 1.06 0.30 3.07 2.B0 0.15 0.20 3.60 3.41 1.03 0.97 0.97 0.97 1.0 0.88 1.0 0.95 0.91 0.91 0.95 0.95 0.73 0.72 0.79 0.35 1.60 0.69 0.27 0.30 0.27 0.51 0.17 176 0.88 3.46 196 122 3.05 153 171 0.99 1.0 1.0 0.82 0.88 0.82 0.75 0.49 0.03 23 Q.3 0.002 0.002 0-001 0.42 0.0002 J rt-t* 0*0679 APPENDIX V HEALTH EFFECTS REQUEST-TO DHS AND LETTER OF RESPONSE Memorandum Kenneth Kizer, Director Department of Health Services 714 P Street SacrajD^nto, CA r> a ^j Dc** June 17/ 1985 Subject:: Evaluation of Vinyl chloride From : I am writing to request formally that the Department evaluate the health effects of vinyl chloride as a candidate toxic air contaminant in accordance with Assembly Bill 1807 (Tanner). According to Health and safety Code Sections 39660-62, your Department has ninety days to submit a written evaluation and recommendations on the health effects of vinyl chloride to the Air Resources 3oard and may request a thirty day extension. Attached for your staff's consideration in evaluating vinyl chloride are: Attachment I - a suggested list of topics that we believe should be included in your vinyl chloride evaluation'and recommendations; Attachment II - a list of references on vinyl chloride health effects which were presented in an ARB letter of public inquiry; Attachment III - additional references and comments received from the public in response to the inquiry letter; and Attachment IV - ambient vinyl chloride concentration data and emission data which should be used to estimate the range of risk to California residents as required in Health and safety code Section 39660(c). Ky staff is available for consultation in conducting this health effects evaluation. We look forward to continuing to work closely with you and your staff in carrying out this legislative mandate. If you have any further questions regarding this matter, please contact me at 445-4383. Attachments cc: Jananne Sharpless Alex Kelter, w/attachments Raymond Neutra, w/attachments Peter D. Venturini Assemblywoman Sally Tanner Claire Berryhill Emil Mrak, chairman and Members of the Scientific Review panel Senator Ralph Dills Senator Art Torres John Holmes AR3 CMA 010681 actack::i::: :v a SUMMARY OF AMBIIKT VIICYI OHIO?.ZDS CONCENTRATIONS Vinyl chloride has be en procuced m one industrial facility and used by four facil it ies in California, all of them in the South Coast Air Basin (SCA3 ). Zn y.ay 1978, the Air Resources Board (ARB) adopted an ambient ai - duality standard for vinyl chloride of 10 ppb, 24-hour ave ra ce. Subsequent ambient monitoring in the SCAB found the 10 p?b st a: ca c to be exceeded frequently in the vicinity of these facilitie s - r ~ 1979-1981. However, since 1982 the recent monitoring data :c r VC near these vinyl chloride facilities has shown all values :c o e below 10 ppb, without a determination of the actual val These reductions in ambient concentrations are likely cue t o t.ne closure of the production facility in 1982 and implements :icn of regulations by the South Coast Air Quality Management Oi t ;SCAQKD) designed to red'uce vinyl chloride emissions. Vinyl chloride has been detected in the community n ar SK BKK Class X landfill in West. Ccvir.a. in 1983, the Department of Health services (DKS), ARB, and the South Coast Air Quality Management District issued a report detailing ambient concentrations (report attached). As the report indicates, the average vinyl chloride concentrations varied with location. The worst case residential location, station A, had mean 24-hour VC concentrations of 7.1-7.3 ppb, with a maximum reading of about 39 ppb. Data for this report were collected over three months (July 19--October 15, 1982), with 24-hour samples taken five days per week. A newly discovered potential source of vinyl chlorid emissions into the air is that of sewage treatment facilities. An ERA contractor recently made some estimates of vinyl chloride emissions, as well as other volatile aromatic compounds, from the Top 20" sewage treatment plants, nationwide. (Please see Appendix D of Versar Memorandum, Attachment ZVC.) In this document, the Hyperion facility, which is located in the SCA3, was calculated to release 171 metric tons/year of vinyl chloride. ARB staff modeled this emission estimate (assumptions on Attachment IVB) and predicted 8 ppb above any background as an annual average vinyl chloride concentration. The 24-nour maximum VC concentration prediction is 23 ppb above background. ARB and SCAQHD = iar. tc confirm these estimates with source and ambient vir.yl crlcride testing at the Hyperion facility in the summer c 1985. CMA 010682 Summary of the Health Effects qt Vinyl Chloride HEALTH EFFECTS The health effects of vinyl chloride have ceen reviewed by several sources. Two good reviews are by the International Agency for Research on Cancer (IARC, 1979) ana the U.S. Department of health. Education and Welfare (U.S. HEW, 1978). A. Carcinogenicity 1. Humans - Epidemiological studies have shown that vinyl chloride causes angiosarcoma-of the liver in humans. Strong evidence also exists that vinyl chlorioe may cause cancer of the central nervous system, especially glioblastoma multi forme. Evidence also exists that vinyl chloride induces cancers of the lung anc lymphatic system but this evidence is ,weaker. (IARC, 1979; J.S. HEW, 1978) 2. Animals - Vinyl chloride has been shown to be carcinogenic in several animal species after oral and inhalation administration. Liver angiosarcomas were observed in mice, rats and hamsters exposed to vinyl chloride. Other tumors seen were mammary adenocarcinomas, lung adenomas, Zymbal gland tumors and angiosarcomas at sites other than the liver. Doses in the inhalation experiments ranged from SO to 10,000 ppm. A significant increase in some tumors (angiosarcomas) was seen at the low dose (50 ppm) level. (IARC, 1979; U.S. HEW, 1978) CMA 010683 B. Hutagenesis Vinyl chloride is mutagenic in several test systems. Vinyl chloride has been found to be mutagenic in several strains of bacteria, insects and naircnalian cells. Chromosomal aberrations have been induced in workers exposed to vinyl chloride. (IARC, 1SS2) C. Teratogenicity Evidence that vinyl cnloride causes teratogenic effects in humans or animals is equivocal. Vinyl chloride has been implicated in causing increased fetal deaths in the wives of vinyl chloride exposed worker's and birth defects in children of workers. Evidence is inconclusive. (IARC, 1979) D. Pharmacokinetics The metabolism of vinyl chloride has been reviewed by several authors (IARC, 1979). Absorbed vinyl chloride is eliminated predominantly via metabolism and exretion of metabolites into the urine- A small amount is excreted via the expired air as unchanged vinyl chloride. As the concentration of vinyl chloride to which an animal Is exposed is raised, a larger percentage of the absorbed dose is eliminated as unchanged vinyl chloride in the expired air. The initial product of metabolism is believed to be chloroethylene oxide. Vinyl chloride, in the presence of a microsomal enzyme fraction, binds to R.\A in vitro and to RIVA and DNA 1 n vivo, Cnloroethylene oxide is believed to be involved in the covalent CMA 010684 binding to kIJA and DNA. Since an abundance of animal data exists, it may be possible to incorporate it into aose-response assessment. (IARC, 1979) E. Acute and Chronic Effects (non-carcinogenic} Acute exposure to vinyl chloride causes narcosis* cardiac irregularites and liver and kidney toxicity. These effects are seen at relatively high doses. Liver toxicity is evident as centrilcbular degeneration, hepatic fibrosis and necrosis. Degeneration of bone, nerves and connective tissue is seen after chronic exposure. Acroosteolysis, a degeneration of the bones in the fingers, occurs in workers. Disturbances in liver, kidney and pulmonary function also occur after chronic exposure. II. THRESHOLD The U.S. EPA proposed a National Emission Standard for vinyl chloride in 1975, which was promulgated in 1976. The proposal for the emission standard states that there is no known threshold for vinyl chloride's toxic effects. (Federal Register, 1975) 4 III. DOSE-RESPOUSE ASSESSMENT The U.S. EPA's Carcinogen Assessment Group has performed a risk assessment of vinyl chloride's carcinogenic effects (U.S. EPA, 1975). The potency slope for vinyl chloride, derived from an animal inhalation study, is 1.75 x 10~^(mg/kg/day . CMA 010685