EPA 560/6-77-030 MULTIMEDIA LEVELS METHYLCHLOROFORM SEPTEMBER 1977 (J.S.ENVRONMENTAL PROTECTION AGENCY OFFICE OF TOXIC SUBSTANCES WASHINGTON, D.C. 20460 ------- EPA 560/6-77-030 MULTIMEDIA LEVELS METHYLCHLOROFORM September 1977 BATTELLE Columbus Laboratories 505 King Avenue Columbus, Ohio 43201 Vincent J. DeCarlo Project Officer Contract No. 68-01-1983 ENVIRONMENTAL PROTECTION AGENCY OFFICE OF TOXIC SUBSTANCES WASHINGTON, D.C. 20460 ------- NOTICE This report has been reviewed by the Office of Toxic Substances, Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the Environmental Protection Agency. Mention of tradenames or commercial products is for purposes of clarity only and does not constitute endorsement or recommendation for use. ii ------- TABLE OF CONTENTS Page 1. INTRODUCTION 1-1 2. OCCURRENCE OF METHYLCHLOROFORM IN THE ENVIRONMENT 2-1 Methylchloroform in the Atmosphere 2-1 Methylchloroform in Soil and Sediment 2-6 Methylchloroform in Surface Waters 2-6 Methylchloroform in Drinking Water 2-9 Methylchloroform Near Industrial Sites— Multimedia Levels 2-9 3. TRANSFORMATIONS OF METHYLCHLOROFORM IN THE ENVIRONMENT 3-1 4. OCCURRENCE OF METHYLCHLOROFORM IN FOOD 4-1 5. EXPOSURE AND BIOLOGICAL ACCUMULATION OF METHYLCHLOROFORM IN MAN 5-1 Exposure 5-1 Biological Accumulation 5-2 6. BIBLIOGRAPHY 6-1 FIGURES Number Page 2.1 Industrialized areas where surface water was sampled. . . . 2-7 2.2 Sampling locations at Dow Chemical Plant A, Freeport, Texas—methylchloroform production site 2-11 2.3 Sampling locations at Vulcan Materials Company, Geismar, Louisiana—methylchloroform production site 2-13 2.4 Sampling locations at Ethyl Corporation, Baton Rouge, Louisiana—methylchloroform production site 2-15 iii ------- FIGURES (Continued) Number Page 2.5 Sampling locations at PPG Industries, Lake Charles, Louisiana—methylchloroform production site 2-17 2.6 Sampling locations at Boeing Company, Auburn, Washington— methylchloroform user site 2-19 2.7 Sampling locations at St. Francis National Forest, Helena, Arkansas—background site 2-21 3.1 Transformations of methylchloroform 3-3 3.2 Simulated sea level irradiation of methylchloroform .... 3-4 3.3 High altitude photoreaction of methylchloroform 3-5 TABLES 2.1 Maximum and Minimum Levels of Methylchloroform in the Atmosphere at Various Locations in the United States. . . 2-2 2.2 Typical Levels of Methylchloroform in the Atmosphere. . . . 2-3 2.3 Miscellaneous Monitoring Data for Methylchloroform in the Atmosphere 2-4 2.4 Methylchloroform Concentration in Surface Water Samples Taken by the Institute for Environmental Studies 2-8 2.5 Concentration of Methylchloroform in Air, Water, Soil, and Sediment at Dow Chemical Plant A (Methylchloroform Producer 2-10 2.6 Concentration of Methylchloroform in Air, Water, Soil, and Sediment at Vulcan Materials Company (Methylchloroform Producer) 2-12 2.7 Concentration of Methylchloroform in Air, Water, Soil, and Sediment at Ethyl Corporation (Methylchloroform Producer) 2-14 2.8 Concentration of Methylchloroform in Air, Water, Soil, and Sediment at PPG Industries (Methylchloroform Produder). . 2-16 2.9 Concentration of Methylchloroform in Air, Water, Soil, and Sediment at Boeing Company (Methylchloroform User).... 2-18 iv ------- TABLES (Continued) Number Page 2.10 Concentration of Methylchloroform in Air, Water, Soil, and Sediment at St. Francis National Forest (Background). . . 2-20 3.1 Transformations of Methylchloroform in the Environment. . . 3-2 3.2 Evaporation of Methylchloroform under Various Conditions. . 3-6 4.1 Methylchloroform in Foodstuffs 4-1 5.1 Chlorinated Hydrocarbons in Marine Organisms 5-3 v and vi ------- EXECUTIVE SUMMARY This report discusses environmental levels of methylchloroform, based on a review of the literature and other information sources. The concentrations of methylchloroform in the atmosphere of the U.S. range from about 0.1 yg/m3 (20 ppt) in remote areas to over 500 yg/m3 (100 ppb) in some areas near where the substance is manufactured or used. The concentration drops off rapidly as one moves away from a source facility. Surface water concentrations of methylchloroform range from somewhat less than 1 ppb to several hundred ppb in the vicinity of methylchloroform manufacturers. The highest measurement reported (3 ppm) was made"in a roadside ditch near a producer site. Methylchloroform has been detected but not quantified in U.S. drinking water except in one case when approximately 10 ppb was reported. Soil and sediment concentrations of methylchloroform appear to be no higher near manufacturers and users than in rural areas, though the data are very limited. The levels are on the order of fractions of a ppb. Methylchloroform is a saturated chlorinated hydrocarbon which is relatively stable in the atmosphere. However, the molecule is susceptible to hydrolysis or dehydrohalogenation and reacts with water relatively rapidly and is thus degraded in soil and water. There are very few data on the presence of methylchloroform in food raised and sold in the U.S. However, data from the United Kingdom suggest that methylchloroform is found on the order of parts per billion in some common foodstuffs. There is little evidence to judge whether methylchloroform accumulates in living organisms. Limited data on levels in marine organisms show levels on the order of a few parts per billion. vii ------- 1. INTRODUCTION Methylchloroform (MC) is one of the chemicals whose health and ecological effects, environmental behavior, and technologic and economic aspects are important to the U.S. Environmental Protection Agency. The literature has been searched in an effort to determine the environmental levels of methylchloroform, the behavior of methylchloroform in the environment, and the ways in which methylchloroform may come in contact with man. The literature has been examined using the following search strategy. An initial computer search of the following data bases was conducted: • National Technical Information Service (NTIS) • Smithsonian Science Information Exchange (SCD-SSIE) •, Engineering Index • Pollution Abstracts • TOXLINE • MEDLARS (National Library .of Medicine's National Interactive Retrieval Service) • Air Pollution Technical Information Center (APTIC) • USGS Water Quality Monitoring Data. All searches were carried out in June, 1976. Original journal articles with relevant titles or abstracts were then examined and data extracted. In addition, various journals were screened manually through December, 1976. These journals included: Analytical Chemistry, Atmospheric Environ- ment, Bulletin of Environmental Contamination and Toxicology, CRC Critical Reviews in Environmental Control, Environment, Environmental Pollution, Environmental Research, Environmental Science and Technology, International Journal of Environmental Analytical Chemistry, Journal of Environmental Science and Health, Journal Water Pollution Control Federation, and Water Research. Other journals were also screened but are not listed because they did not cover the indicated period, or were of more limited interest to those seeking information on environmental levels of methylchloroform. Several important reviews on the subject of methylchloroform were also consulted. Specifically, a preliminary study of selected potential 1-1 ------- environmental contaminants including methylchloroform (U.S. Environmental Protection Agency, 1975a), a preliminary economic impact assessment of possible regulatory action to control atmospheric emissions and selected halocarbons (Shamel, 1975), a criteria for a recommended standard for occupational exposure to 1,1,1-trichloroethane (methylchloroform) (U.S. National Institute for Occupational Safety and Health, 1976), and a toxicology study called "Methylchloroform and Trichloroethylene in the Environment" (Aviado et al., 1976) were consulted. 1-2 ------- 2. OCCURRENCE OF METHYLCHLOROFORM IN THE ENVIRONMENT METHYLCHLOROFORM IN THE ATMOSPHERE No extensive monitoring program designed specifically for methylchloro- form has been identified. However, methylchloroform has been detected along with other halocarbons at various locations throughout the U.S. and around the world. The most extensive data are reproduced in Tables 2.1 and 2.2. These data are taken from a study done at Cook College, Rutgers University (Lillian et al., 1975). Other data are summarized in Table 2.3. In addition, various industrial sites were monitored for methylchloroform in a study carried out by the Battelle Columbus Laboratories in late 1976 and early 1977 (see the last section of this chapter, "Methylchloroform Near Industrial Sites—Multimedia Levels"). The concentration of methylchloroform in the atmosphere ranges from about 0.1 yg/m3 (20 ppt) in remote areas to over 500 vig/m3 (100 ppb) in areas where the substance is manufactured or used. Pearson and McConnell (1975) point out that as one moves away from a manufacturing facility, the concentration of methylchloroform in air drops off rapidly (Table 2.3). Battelle data support this conclusion and Ohta et al. (1976) make a similar observation. They state that the distribution peak for methylchloroform coincides with locations of machine or metal products plants which use the solvent. It was found in the Battelle study that the highest concentrations of methylchloroform are generally observed downwind from a producer or user site and the concentration seems to be dependent on the distance from the discharge point. Most of the higher concentrations are observed at distances of less than 1 .km. Considerable variation, however, was observed in the maximum downwind levels of methylchloroform at various production sites. The variations in the observed maximum concentration among plants may be due to differences in (1) production processes, (2) emission control equipment, (3) meteorological conditions, and (4) distance from the plant. Higher production capacity apparently does not necessarily imply higher emissions since the maximum concentrations observed at the larger plants were no higher than those observed at the smaller operations, and were sometimes lower. Large temporal variations are observed when measuring these chlorinated hydrocarbons downwind from a production facility. 2-1 ------- TABLE 2.1. MAXIMUM AND MINIMUM LEVELS OF METHYLCHLOROFORM IN THE ATMOSPHERE AT VARIOUS LOCATIONS IN THE UNITED STATES Monitoring Period and Location Concentration, Levels ppb June 18-19, 1974 Maximum Seagrit, New Jersey Minimum (National Guard Base) Mean June 27-28, 1974 Maximum New York, New York Minimum (45th and Lexington) Mean July 2-5, 1974 Maximum Sandy Hook, New Jersey Minimum (Fort Hancock) Mean July 8-10, 1974 Maximum Delaware City, Delaware Minimum (Road 448 and Route 72 Mean intersection) July 11-12, 1974 Maximum Baltimore, Maryland Minimum (1701 Poncabird Pass, Mean Ford Holabird area) July 16-26, 1974 Maximum Wilmington, Ohio Minimum (Clinton County Air Mean Force Base) September 16-19, 1974 Maximum White Face Mountains Minimum (New York State) Mean March-December, 1973 Maximum Bayonne, New Jersey Minimum Mean 0.20 0.044 0.10 1.6 0.10 0.61 0.33 0.030 0.15 0.30 0.03 0.10 0.21 0.044 0.12 0.35 0.030 0.097 0.13 0.032 0.067 14.4 0.075 1.59 Source: Lillian et al., 1975. 2-2 ------- TABLE 2.2. TYPICAL LEVELS OF METHYLCHLOROFORM IN THE ATMOSPHERE Date and Time Location Methylchloroform Concentration, ppb June 27, 1974 2300 September 17, 1974 1200 July 2, 1974 1400 July 19, 1974 1300 July 17, 1974 July 17, 1974 1203 New York, New York 0.28 Urban White Face Mountains 0.083 New York State (nonurban) Over Ocean 0.18 Sandy Hook, New Jersey 4.8 km (3 mi) offshore) Seagirt, New Jersey 0.072 (National Guard Base) Above the Inversion 0.025 elevated 1500 m (5000 ft) Wilmington, Ohio Inversion Layer 0.065 elevation 450 m (1500 ft) Wilmington, Ohio Source: Lillian et al., 1975. 2-3 ------- TABLE 2.3. MISCELLANEOUS MONITORING DATA FOR METHYLCHLOROFORM IN THE ATMOSPHERE Location Los Angeles Basin San Bernadino Mts. New Brunswick NJ ii Kansas City-NASN Station Worldwide Houston TX and vicinity Los Angeles Basin Pullman WA Date of Data Collection Fall 1972 Fall 1972 1973 Unreported 1974 1974 Nov. 1974 April 1975 Dec. 1974 to Concentration 0.37 ppb (avg.) 0.05 ppb (avg.) 0.27 ppb 0.83 ppb Detected 5xlO-9 ml/ml of air Detected it 100115 ppt Method3 GC/EC n Coulometric GC n GC/MS Estimate GC/MS computer n GC/MS Reference Simmonds et al., 1974 it ii Lillian and Singh, 1974 n n Bunn et al. , 1975 Goldberg, 1975 Pellizzari et al., 1976 n n Grimsrud and Rasmussen, 197 Western Ireland North Atlantic Britain, perimeter of a manufacturing plant Heath, near the above plant Suburban area, re- moved from plant Tokyo Southern Hemisphere Northern Hemisphere Stanford Hills CA Point Reyes CA Feb. 1975 June/July 1974 Oct. 1973 1972-74 1972-74 1972-74 May 1974-April 1975 1974 1974 Nov. 1975 Dec. 1975 64.8 ppt 75.1 ppt 16 ppb (mass) 6.2 to 11 ppb (mass) <0.1 to 6 ppb (mass) 0.8 ppb (annual avg.) 24.4 ppt 64.8 ppt 77.6 ppt (avg. 75 measurements) 90.3 ppt (avg. 300 measurements) Coulometric GC ii GC/EC Lovelock, 1974 ii Pearson and McConnell, 1975 Ohta et al., 1976 Cox et al., 1976 n n Singh et al., 1977 GC/EC = Gas chromatography with electron capture detector; GC/MS = Gas chromatography, mass spectroscopy ------- Changes in meteorological conditions, particularly wind speed and direction, and/or variations in the emissions may account for this phenomenon. There is some question about the source of methylchloroform in the atmosphere. Lovelock (1974) suggested that some methylchloroform may occur naturally while discussing evidence for the natural origin of carbon tetrachloride. He suggests that carbon tetrachloride may result from a biological source such as algae or more probably from an atmospheric process. He cites the following reasons for postulating a natural origin of carbon tetrachloride: (1) the abundance of carbon tetrachloride does not differ appreciably between the northern and southern hemispheres, which is not consistent with a northern industrial source, (2) air arriving at Western Ireland shows a strong correlation between the concentration of fluorocarbons and continental European origin. No such correlation is observed for carbon tetrachloride, (3) reaction in air between methane and chlorine at a concentration of 10"^ results in the production of small but significant amounts of carbon tetrachloride in the laboratory. After this discussion, Lovelock concludes that "there is some indication from their spatial distribution that chloroform and methylchloroform may also in part at least have a similar natural origin to carbon tetrachloride". More recently, Cox et al. (1976), in considering oxidation of methyl- chloroform and other halocarbons by OH radicals, came to the conclusion that the industrial output of methylene chloride, chloroform, and methyl- chloroform is probably insufficient to balance the sink due to OH attack, pointing to a natural source. These workers point out, however, that the observed hemispheric concentration differences are consistent with an anthropogenic source (see Table 2.3). The natural source theory for carbon tetrachloride has recently come under attack. Galbalby (1976) concludes that a large fraction, perhaps all of the carbon tetrachloride observed in the atmosphere, could be man-made, and carbon tetrachloride is a global atmospheric pollutant. He attributes the ubiquitous nature of carbon tetrachloride and the similar concentra- tions found in background air in both hemispheres to the fact that carbon tetrachloride has a long lifetime in the atmosphere, and that a near equilibrium state of man-made emissions and destruction of the compound in the atmosphere exists. If this is true, it seems unlikely that a more complicated G£ molecule such as methylchloroform could be generated in the atmosphere in any quantity. From chemical kinetic computations, Graedel and Allara (1976) conclude that the possibility is remote that any of the observed atmospheric halo- carbons including methylchloroform and carbon tetrachloride are produced from natural or anthropogenic precursors by atmospheric chemical processes. Based on their measured background concentration for methylchloroform of 84 ppt in the northern hemisphere (Table 2.3)' and on a calculated cumulative worldwide emissions output of 3.3 million tons of methylchloro- form up to December, 1975, which they calculate would correspond to a background atmospheric concentration of 146 ppt, Singh et al. (1977) . 2-5 ------- conclude that no natural sources for methylchloroform can be inferred. However, they suggest that methylchloroform residence time in the tropo- sphere must be much longer than the 1.1 years suggested by others (Table 3.1) or else secondary anthropogenic or natural sources must exist. The resolution of this question depends on the gathering of more data and a better understanding of the atmospheric chemistry of halocarbons, METHYLCHLOROFORM IN SOIL AND SEDIMENT The only information available on methylchloroform levels in soil and sediment was obtained from the Battelle study (Battelle's Columbus Labora- tories, 1977). This information is presented in the section on Methyl- chloroform Near Industrial Sites. In general, the concentrations in soil range from less than 0.1 ppb to about 1 ppb. There does not seem to be any correlation with the distance from production or user sources, and a concentration of 0.42 ppb was found in a background sample taken many miles from any known source of methyl- chloroform. . Methylchloroform levels in sediment samples were somewhat higher on the average than the levels in soil. Levels in sediment ranged from less than 0.1 ppb to about 6 ppb. The background level was 0.45 ppb at a site far removed from known sources of methylchloroform. METHYLCHLOROFORM IN SURFACE WATERS Approximately 200 water samples have been collected and analyzed for various organic substances (Chian and Ewing, 1976). These samples were collected from 14 heavily industrialized river basins. These areas and the approximate number of samples taken at each location are indicated in Figure 2.1 (Chian and Ewing, 1976, Progress Report No. 4). The results are summarized in Table 2.4. Methylchloroform was detected in 63 of the approximately 200 samples analysed and the concentrations ranged from less than 1 ppb to 8 ppb in these surface waters. In the vicinity of production plants, the concentration of methylchloro- form in surface waters is much higher. Levels up to 200 ppb are common and at one site a level of 3.3 ppm was found. The data appear in the last section of this chapter. Pearson and McConnell (1975) report methylchloroform concentrations of 0.09 ppb in rainwater collected in Runcorn, England. The highest concen- trations that these researchers measured in upland river waters was 0.3 ppb. These same authors also reported that they have never detected organo- chlorines in well waters. With a normal detection limit of 0.2 ppb, Pearson and McConnell (1975), between April and August, 1973, determined that the maximum concentration of methylchloroform in Liverpool Bay 2-6 ------- ho I Encircled numbers Indicate quantity of samples to be collected In each area. Figure 2.1. Industrialized areas where surface water was sampled (Source: Chian and Ewing, 1976), ------- TABLE 2.4. METHYLCHLOROFORM CONCENTRATION IN SURFACE WATER SAMPLES TAKEN BY THE INSTITUTE FOR ENVIRONMENTAL STUDIES Area Type of Water Analyzed Concentration Number of Range (Average) , Samples ppb Chicago Lake Michigan, sewage 7 treatment plant effluent, filtration plant, chan- nels Illinois Illinois River 11 Pennsylvania Delaware, Schuylkill, 12 0.5 to 8(3) <1 to 3 (<1) <1 to 3 (<1) New York City area Hudson River area Upper and Middle Mississippi River Lower Mississippi River Houston area Ohio River Basin Great Lakes Tennessee River Basin and Lehigh Rivers Hudson River and bays 14 Hudson River 1 Mississippi River 3 Mississippi River 1 Galveston Bay and 3 channels Ohio River and tribu- 3 taries Lake Superior, Michigan, 6 Huron, Ontario, Erie, and vicinity Tennessee River and 2 tributaries to 2 (<1) 1 to 2 (1) and 4 (<2) 2-8 ------- seawater was 3.3 ppb. In Liverpool Bay sediments, a maximum combined concentration of methylchloroform and carbon tetrachloride was 9.9 ppb. METHYLCHLOROFORM IN DRINKING WATER The National Organics Reconnaissance Survey (NORS) was initiated by the U.S. Environmental Protection Agency in November, 1974. NORS had three major objectives: (1) Determine the extent of the presence of four trihalomethanes in finished water; (2) Determine what effects the source and treatment of water had on the formation of these compounds; (3) Characterize as completely as possible the organic content of 10 drinking waters from sites representing five major categories of raw water souces. During the survey of 10 cities, at least 129 compounds were identi- fied in drinking water. Some were quantified and others were detected without quantification. Methylchloroform was one of the latter. Its presence was detected in the drinking water in Ottumwa, Iowa; Philadelphia, Pennsylvania; and Cincinnati, Ohio (U.S. Environmental Protection Agency, 1975b). Methylchloroform was also detected in the drinking water from the Belmont water treatment plant in Philadelphia, Pennsylvania, on August 8, 1975, using continuous liquid-liquid extraction of the water followed by identification by gas chromatography/mas spectrometry (Keith, 1976). Methylchloroform was also detected in tap water at the National Institute of Environmental Health Sciences, Research Triangle Park, North Carolina, on May 7, 1975, using gas chromatography/mass spectrometry (Keith, 1976). Methylchloroform was identified as a component of New Orleans drinking water but it was not quantified (Dowty et al., 1975a). The only quantita- tive information available was that reported by Bellar et al. (1974). In an investigation of the chlorination of water for purification and the potential for the formation of potentially harmful chlorinated compounds by the process, scientists at the National Environmental Research Center at the Environmental .Protection Agency in Cincinnati, Ohio, reported the following concentrations of methylchloroform in water from a sewage- treatment plant: influent before treatment, 16.5 yg/S,; effluent before chlorination, 9.0 yg/£; and effluent after chlorination, 8.5 METHYLCHLOROFORM NEAR INDUSTRIAL SITES—MULTIMEDIA LEVELS A program to determine environmental levels of methylchloroform was initiated in 1976 at Battelle's Columbus Laboratories. During late 1976 and early 1977, samples were collected from various production sites, a user site, and a background site. The samples were analyzed and the results are summarized in Tables 2.5 through 2.10 and in the corresponding maps of the plant locations on which the sampling sites are indicated Figures 2.2 through 2.7). Details of the results and methodology are given in a com- panion report, EPA-560/6-77-025 (Battelle's Columbus Laboratories, 1977). 2-9 ------- TABLE 2.5. CONCENTRATION OF METHYLCHLOROFORM IN AIR, WATER, SOIL, AND SEDIMENT AT DOW CHEMICAL PLANT A (METHYLCHLOROFORM PRODUCER) Air Distance Upwind (U) , Concentration, From Plant, Downwind (D) , Site ppbva km or Variable (V) Site Al A2 A5 A6 A7 A8 A2,A4, A7,A12 A1S ASS A7S 1A <0. 3 to 2.3 2.6 2A <0.3 to 1.1 1.9 3A <0. 3 to 1.2 3.2 4A <0.3 2.1 5A <0.3 to 0.7 0.8 6A <0.3 /1.9 7A <0. 3 to 1.1 2.6 8A <0. 3 to 2.2 2.6 10A <0.3 3.2 12A <0.3 to 11.5 2.6 13A <0.3 to 0.5 5.1 14A <0.3 7.8 Water, Soil, and Sediment Description of Media Surface water, 10 m upstream of effluent canal Water, as above, except 2.5 m deep Surface water, 400 m downstream of plant outfall Water, as above except 4 m deep Surface water, 800 m upstream of plant outfall Surface water, bayou 2.6 km from plant Soil, quadrants around plant at 2 km Sediment, from effluent canal D V D D U U V D D D D D Concentration, ppb 117 119 0.8 1.0 0.1 12 0.06 to 0.68 6.1 Sediment, 400 m downstream of plant outfall 0.34 Sediment , 800 m upstream of plant outfall . 0.31 Limits of detection: 0.3 ppbv. To convert to yg/m3 at 25 C, multiply ppbv by 5.46. 2-10 ------- Residential O Emission Source -Highway Railroad Plant Proper Industrial Q Marsh • Air Site • Soil Site * Water Site ~ Sediment Site Figure 2.2. ------- TABLE 2.6. CONCENTRATION OF METHYLCHLOROFORM IN AIR, WATER, SOIL, AND SEDIMENT AT VULCAN MATERIALS COMPANY (METHYLCHLOROFORM PRODUCER) Air Distance Upwind (U), Concentration, From Plant, Downwind (D) , Site El E2 E3 E4 E6,E7 E1S E3S Site ppbva km or 1 <0.3 to 18 0.4 2 <0.3 to 140 0.3 3 <0.3 0.3 4 <0.3 to 75 0.4 5 5.5 to 155 0.6 6 1.2 to 14 0.6 7 1.4 to 4.0 0.4 8 <0.3 to 0.8 0.3 9 <0.3 to 0.5 3.0 Water, Soil, and Sediment Description of Media Surface water, 30 m upstream from plant outfall Surface water, at end of outfall pipe Surface water, 75 m upstream of plant outfall Surface water, roadside ditch 60 m from plant Variable (V) V . V V D D D - V D Concentration, ppb 2 344 169 3,314 Soil, within 200 m of plant on each side 0.45 and 0.94 Sediment, shoreline 30 m upstream of plant outfall Sediment, shoreline 75 m downstream of plant outfall 0.13 2.6 Limits of detection 0.3 ppbv. To convert to yg/m3 at 25 C, multiply ppbv by 5.46. 2-12 ------- Emission Source Highway Plant Proper Residential Air Site Soil Site Water Site Sediment Site Figure 2.3. site. 2-13 ------- TABLE 2.7. CONCENTRATION OF METHYLCHLOROFORM IN AIR, WATER, SOIL, AND SEDIMENT AT ETHYL CORPORATION (METHYLCHLOROFORM PRODUCER) Air Distance Concentration, From Plant, Upwind (U) , Downwind (D) , Site ppbva km or Variable (V) Site Cl C2 C3 C4,C7 C2S C3S 1 <0.3 0.4 2 <0.3 0.2 3 <0.3 to 3.9 2.4 4 <0.3 2.6 5 <0.3 2.2 6 <0.3 0.7 7 <0.3 2.2 8 <0.3 3.2 Water, Soil, and Sediment Description of Media Surface water, immediately above settling pond Surface water, 200 m upstream of plant outfall D D D D - U - D Concentration, ppb 74 9,4 Surface water, 300 m downstream of plant 20 outfall Soil, various locations in vicinity of plant Sediment, 200 m upstream of plant outfall Sediment, 300 m downstream of plant outfall 0.13 to 0.28 0.81 None detected Q O Limits of detection: 0.3 ppbv. To convert to yg/md at 25 C, multiply ppbv by 5.46. 2-14 ------- O Emission Source Highway Railroad Plant Proper Industrial Residential Air Site Soil Site Water Site Sediment Site Mile 1/2 I -• 0 •5 1 Kilometer Figure 2.4. Sampling locations at Ethyl Corporation, Baton Rouge, Louisiana—methylchloroform production site. ------- TABLE 2.8. CONCENTRATION OF METHYLCHLOROFORM IN AIR, WATER, SOIL, AND SEDIMENT AT PPG INDUSTRIES (METHYLCHLOROFORM PRODUCER) Air Distance Upwind (U) Concentration, From Plant, Downwind (D) , Site ppbva km or Variable (V) Site Fl F2 F3 F4 F5 F6-F9 F1S F3S 1 0.8 to 1.3 1.3 2 <0.3 4.2 3 <0.3 to 0.7 3.5 4 <0.3 2.7 5 <0.3 1.4 6 <0.3 to 8.5 4.0 7 <0.3 0.6 8 0.4 1.3 Water, Soil, and Sediment Description of Media Surface water, 50 m upstream of plant outfall Surface water, at plant outfall No. 1 Surface water, at plant outfall No. 2 Surface water, 50 m downstream of outfall No. 2 Surface water, lake downstream of plant outfall Soil, quadrants surrounding plant Sediment , 50 m upstream of plant outfall Sediment, at plant outfall No. 2 U U V U D D U U Concentration, ppb 132 181 58 161 5 0.14 to 1.0 2.2 1.1 Limits of detection: 0.3 ppbv. To convert to yg/m3 at 25 C, multiply ppbv by 5.46. 2-16 ------- M ~J Emission Source Highway Railroad Industrial Plant Proper Residential Marsh Tailings Pond Air Site Soil Site Water Site Sediment Site .5 1 Kilometer • 2 Figure 2.5. Sampling locations at PPG Industries, Lake Charles, Louisiana—methylchloroform production site. ------- TABLE 2.9. CONCENTRATION OF METHYLCHLOROFORM IN AIR, WATER, SOIL, AND SEDIMENT AT BOEING COMPANY (METHYLCHLOROFORM USER) Concentration , Site ppbva Site J2 J6 J3 J4 1 2 3 4 5 6 7 8 9 10 Surface pond Surface from Surface plant Surface 0.8 to 10.0 0.4 to 0.5 0.4 to 5.0 0.6 to 6.2 0.9 1.6 to 2.3 4.8 to 7.4 7.8 to 8.4 4.0 to 4.4 7.0 to 8.1 Water, Soil Description water, outfall water, outfall plant water, outfall Air Distance Upwind (U) From Plant , Downwind (D) , km or Variable (V) 0.7 D 0.6 U 0.9 U 1.1 0.9 0.4 1.2 D 2.0 2.9 U 1.1 , and Sediment Concentration , of Media ppb from settling 18 canal, 1.5 km 18 canal, 3 km from 12 water, 100 m downstream of plant 6 J5 Jl J7 J4S J5S outfall Surface water, 30 m upstream of plant outfall Soil, about 1 km from plant Soil, about 0.5 km from plant Sediment, 100 m downstream of plant outfall . , 0.40 0.65 0.039 Sediment, 30 m upstream of plant outfall None detected aLimits of detection: 0.3 ppbv. To convert to yg/m3 at 25 C, multiply ppbv by 5.46. 2-18 ------- Emission Source Highway Railroad Industrial Plant Proper Residential Air Site Soil Site Water Site Sediment Site 0 .5 1 Kilometer Figure 2.6. Sampling locations at Boeing Company, Auburn, Washington—methylchloroform user site. 2-19 ------- TABLE 2.10. CONCENTRATION OF METHYLCHLOROFORM IN AIR, WATER, SOIL, AND SEDIMENT AT ST. FRANCIS NATIONAL FOREST (BACKGROUND) Media Concentration Air <0.3 ppbv Surface water, from lake 0.4 ppb (average) Soil 0.42 ppb (average) Sediment 0.45 ppb (average 2-20 ------- Dam I| Parking Lot Air Site Soil Site Water Site Sediment Site Meters Figure 2.7. Sampling locations at St. Francis National Forest, Helena, Arkansas—background site. 2-21 ------- In general, concentrations of methylchloroform downwind from the various industrial sites were higher than in the upwind direction, but considerable variation was observed in the maximum downwind levels at various production plants. Concentrations of methylchloroform in ambient air ranged from less than 0.3 ppb (limit of detection) to 155 ppb. Concentrations of methylchloroform in surface water in the vicinity of the production and user plants was even more variable ranging from fractions of a ppb to over 16 ppm. Concentrations in soil and sediment ranged from the limits of detection to 6.1 ppb. 2-22 ------- 3. TRANSFORMATIONS OF METHYLCHLOROFORM IN THE ENVIRONMENT This section indicates the changes that methylchloroform can undergo in various real and simulated environmental media. The information on the subject is summarized in Table 3.1 and represented schematically in Figure 3.1. Methylchloroform is oxidized photochemically in the troposphere. The photochemical removal rate is estimated to be 0.9 million tons per year (Cox et al., 1976), which is in excess of world production resulting in release estimated by the same authors to be 0.28 millions tons per year. The implications of these results are discussed in Chapter 2. The residence of methylchloroform in the troposphere is longer than that for a compound containing unsaturation such as trichloroethylene, but much shorter than the residence time for completely halogenated compounds such as carbon tetrachloride or the freons with lifetimes of over 300 years. There is evidence that methylchloroform is relatively stable under simulated sea-level conditions as shown in Figure 3.2 Sunlight in these experiments was initiated using sunlamps with an intensity of one to two times that of noontime sea-level sunlight at wavelengths greater than 295 nm. Figure 3.3 shows the rapid oxidation of methylchloroform at simulated high-altitude conditions. These conditions, however, are some 10 to 100 times as intense as would be observed from 40 km upward, and so the rate is probably exaggerated. These results indicate that methyl- chloroform is fairly nonreactive in sea-level atmospheres but as it mixes upward its photochemical decomposition increases. Methylchloroform has a half-life of 30 weeks in sea water of pH 8 at 10 C. The primary degradation product is vinylidene chloride (Pearson and McConnell, 1975). However, at higher temperatures (approximately 70 C), methylchloroform hydrolyses to acetic acid. Evaporation from water into the atmosphere is probably the principal mode of removal. Billing et al. (1975) estimate that a half-life of 17 minutes for evaporation. In good agreement is the data from Dow Chemical, Table 3.2. Here evaporation from a variety of substances is reported. Pearson and McConnell (1975) were unable to identify any biological oxygen demand (BOD) for the chlorinated hydrocarbons. 3-1 ------- TABLE 3.1. TRANSFORMATIONS OF METHYLCHLOROFORM IN THE ENVIRONMENT Media Change or Products Observed Reference Simulated atmospheric conditions Simulated atmospheric conditions Simulated atmospheric conditions One ppm in water con- taining natural and added contaminants Water, 25C Sea Water (pH 8, 10 C) Atmosphere Troposphere Troposphere, 4.4 parts/thousand Smog chamber Atmosphere near welding <5% decomposed in 23.5 hr with (NO) <5% decomposed in 8 hr (50 ppm methylchloroform 10 ppm N0~) Est. half-life »1700 hr 17 min half-life for evaporation Billing, et al., 1976 Billing, et al., 1976 Billing, et al., 1976 Billing, et al., 1975 6.9 mo half-life for hydrolysis Dilling, et al., 1975 McConnell, etal,, 1975 McConnell, et al., 1975 1.1 years (lifetime) 26 weeks half life 9 mo half-life, vinylidene chloride and acetic acid 10-33 weeks half life Cox, et al., 1976 Ozone HC1, Cl£ (in low concentra- tions) Pearson and McConnell, 1975 Farber, 1973 Rinzema and Silverstein, 1972 3-2 ------- OJ U3 Air, Light t-1/2 » 1700 hr (Billing et al., 1976) CO, C02, H20, HC1, C12 (McConnell et al., 1975) C13CCH3 Lt-l/2a 39 Water, 70 C [CH'QCOC1] CH2 = CC12 Vinylidene Chloride (Pearson and McConnell, 1976) CH3C(TCOCH3 Acetic Anhydride t-1/2 = time required for one-half of the chlorinated hydrocarbon to disappear by the indicated process. Figure 3.1. Transformations of methylchloroform. ------- 80 70 60 50 40 30 ( — - • 1 • • 1 * t . I • o I * • • 9 i BOppmCHjCCIj — lOppmNO- 30% RH 27 °C 1 II 1 1 1 1 1 1 1 1 ) 2 4 6 8 10 12 14 16 18 20 22 24 26 28 TIME (days) 80 70 60 I 50 40 30 — - - l ? 1 9 I • • 1 • • ° • • 50ppmCH,CCI- __ « w 35% RH — ', 25-26 °C 1 1 1 I 1 1 1 1 1 3 2 4 6 8 10 12 14 16 18 TIME (days) Figure 3.2. Simulated sea level irradiation of methylchloroform (Source: Dow Chemical Company data as reported by Study Panel on Assessing Potential Ocean Pollutants, 1975). 3-4 ------- SOppmCHjCCIj OppmNO., 35% RH 25-3 3 °C 6 a 15 TIME (minutes) 20 30 Figure 3.3. High altitude photoreaction of methylchloroform (Source: Dow Chemical Company data as reported by Study Panel on Assessing Potential Ocean Pollutants, 1975). 3-5 ------- TABLE 3.2. EVAPORATION OF METHYLCHLOROFORM UNDER VARIOUS CONDITIONS3 Time (min) fo'r 50% Condition Disappearance Tap water @ 25° 22 Tap water @ 1-2° 33 3% Salt solution 25 ^500 ppm peat moss 20 ^500 ppm wet bentonite clay 20 2.2 mph wind 17 Conditions: 250 ml beaker with 20 ml water with 1 ppm solute initially at 25°. Stirred at 200 rpm.- Source: Dow Chemical Company data as reported by Study Panel on Assessing Potential Ocean Pollutants, 1975. 3-6 ------- 4. OCCURRENCE OF METHYLCHLOROFORM IN FOOD There are very few data on the presence of methylchloroform in food raised and sold in the United States, but there is some information on the presence of methylchloroform in foodstuffs found in the United Kingdom. This information is summarized in Table 4.1. Methylchloroform concentra- tions on the order of parts per billion are found in several common foodstuffs. TABLE 4.1. METHYLCHLOROFORM IN FOODSTUFFS Concentration, yg/kg Meat English beef, steak 3 English beef, fat 6 Pig's liver 4 Oils and fats Olive oil (Spanish) 10 Cod liver oil 5 Castor oil 6 Fruits and vegetables Potatoes (S. Wales) 4 Potatoes (N.W. England) 1 Apples 3 Pears 2 Tea (packet) 7 Fresh bread 2 Source: McConnell et al., 1975. 4-1 ------- 5. EXPOSURE AND BIOLOGICAL ACCUMULATION OF METHYLCHLOROFORM IN MAN EXPOSURE NIOSH estimates that 100,000 workers are exposed to methylchloroform (U.S. National Institute for Occupational Safety and Health, 1976). Methyl- chloroform is the principal solvent in wet cleaning applications and its use as a vapor degreaser is expected to increase by 10 percent per year as tri- chloroethylene undergoes further restrictions (U.S. Environmental Protection Agency, 1975a). A two-year series of studies involving cleaning operations throughout the United States was carried out by Dow Chemical (Skory et al., 1974). The purpose was to determine the extent of worker exposure during solvent vapor degreasing and to compare the three most commonly used chlorinated solvents: methylchloroform, trichloroethylene, and perchloroethylene. Dow estimates that there are over 25,000 chlorinated solvent vapor degreasers throughout the United States. The studies were conducted in the worker breathing zones which were adjacent to some 275 industrial vapor degreasing operations. The results of this study show that trichloroethylene and perchloroethylene vapor concentrations measured around vapor degreasers frequently exceeded the allowable standards for health and safety. Peak concentrations were high enough to present a definite health and safety hazard from anesthetic effects such as dizziness, lack of coordination, and impaired judgment. These authors further concluded that methyl- chloroform emissions during vapor degreasing can be controlled easily at levels below standards established by OSHA. Although the national primary and secondary photochemical oxidant standards for chlorinated solvents are less than 3 Ib/hour or 15 Ib/day maximum for each equipment, it is not uncommon for an idling open-top vapor degreaser measuring 24 x 58 inches to lose 47 Ib/day trichloroethylene or 33 Ib/day methylchloroform (Archer, 1973). Judging from production figures, this material is being lost to the atmosphere and is then replaced. It is estimated that 2 x 105 tons of chlorinated hydrocarbons are lost to the environment each year (Murray and Riley, 1973) and that 3 x 105 tons of methylchloroform are discharged annually (Shamel et al., 1975). In Los Angeles County alone, it is estimated that 500 tons/day of industrial effluents are released into the air, and of this amount, 25 tons are dry cleaning fluids and 95 tons are degreasing solvents, that is, chlorinated hydrocarbons (Simmonds et al., 1974). 5-1 ------- BIOLOGICAL ACCUMULATION Dowty et al, (1975b) in a paper on halogenated hydrocarbons in drinking water concludes that "in view of the lipophilic nature of halogenated hydro- carbons and their occurrence in drinking water, it is not surprising that they might be found accumulating in blood or other tissues". These authors, however, present no data or references to support their contentions. A Study Panel on Assessing Potential Ocean Pollutants (1975) reports that the bioaccumulation of low-molecular weight chlorinated hydrocarbons is quite low compared to accumulation of chlorinated pesticides in verte- brates. This same group reports on another study in which it was determined that the bioaccumulation factor is determined by the partition of the compound between the water and the tissues of the organism, and further that the log of bioaccumulation is linearly related to the log of the partition coefficient between octanol and water for some compounds. This relationship offers a method of estimating bioaccumulation. Bioaccumulation for methylchloroform was estimated to be 13. This compound would be expected to act similarly to carbon tetrachloride in organisms, exhibiting rapid uptake to steady state concentration, and rapid clearance. By far the most definitive study on bioaccumulation was carried out by Pearson and McConnell (1975. Some of the results that they report are complicated by the fact that methylchloroform and carbon tetrachloride were not distinguished in the early analytical work that was done. Nevertheless, these authors determined the amount of methylchloroform present in a large number of species and their results are tabulated in Table 5.1. They estimated that the maximum overall increase in concentration, between sea water and the tissues of animals at the top of the food chains such as fish liver, bird eggs, and seal blubber is less than 100-fold for solvents similar to methylchloroform; while a higher molecular weight chlorinated compound such as hexachlorobutadiene would have a maximum factor of 1000. They further concluded that the pattern of extensive bioaccumulation of marine food chains, which is postulated for chlorinated insecticides, does not appear. In laboratory tests where organisms are maintained for up to 3 months in apparatus similar to that used for toxicity determinations, Pearson and McConnell (1975) have shown that bioaccumulation can occur. Their results indicate the following: (1) the concentration of chlorinated hydrocarbons accumulated in a tissue tends to an asymptotic level, (2) con- centrations in fatty tissues such as liver are higher than in muscle— concentration is proportional to fat content, and (3) when the test organism is returned to clean sea water, the concentration of the chlorinated hydro- carbon in the tissue falls. These researchers conclude that there is no evidence for the bioaccumulation of C-±/C2 compounds in food chains and the maximum concentrations found in the higher trophic levels are still only parts per 108 by mass. Despite this strong statement, it is based on a limited set of data, and caution should be exercised. More information is needed before final judgment is made about the accumulation of volatile chlorinated hydrocarbons in the tissues of animals and man. 5-2 ------- TABLE 5.1. CHLORINATED HYDROCARBONS IN MARINE ORGANISMS (concentrations expressed as parts per 109 by mass on wet tissue) Ul I Species Plankton Plankton Nereis diversicolor (ragworm) Mvtilus edulis (mussel) Cerastoderma edule (cockle) Ostrea edulis (oyster) B_uccinum undatum (whelk) Crepidula fornicata (slipper limpot) Cancer pagurus (crab) Carcinus maenas (shore crab) Eupagurus bernhardus (hermit crab) Source Liverpool Bay Torbay Mersey Estuary Liverpool Bay Firth of Forth Thames Estuary Liverpool Bay Thames Estuary Thames Estuary Thames Estuary Tees Bay Liverpool Bay Firth of Forth Firth of Forth Firth of Forth Thames Estuary CC12CHC1 Invertebrates 0.05-0.4 0.0 ND 4-11.9 9 ft 6-11 2 ND 9 2.6 10-12 15 12 15 5 CC12CC!2 CHjCCl,^ 0.05-0.5 0.03-10.7 0.04-0.9 2.3 2.2 2.9 0.6 1.3-6.4 2.4-5.4 9 10 2 1 5 0.7 2-3 0-2 0.4-1 0.5 0.9 0.1 1.6 0.9 2 4 0.3 2.3 8.4 8-9 5-34 3-5 71 2 6 14 3 15 0.7 1 2 2 0.2 ------- TABLE 5.1. (Continued) Ui I Species Crangon crangon (shrimp) Asterias rubens (starfish) Sqlaster sp. (sunstar) Echinus esculentus (sea urchin) Enteromorpha compressa Ulva lactuca Fucus vesiculosus Fucus serratus Fucus spiralis Raja clavata (ray) flesh liver Pleurone c t e s p_latessa flesh (plaice) liver Source Firth of Forth Thames Estuary Thames Estuary Thames Estuary Mersey Estuary Mersey Estuary Mersey Estuary Mersey Estuary Mersey Estuary Liverpool Bay Liverpool Bay Liverpool Bay Liverpool Bay CC1 CHC1 16 5 2 1 Marine algae 19-20 23 17-18 22 16 Fish 0.8-5 5-56 0.8-8 16-20 CC12CC12 CH3CC13+CC14 3 26 1 5 0.8 2 3 0.2 1 3 0.1 14-14.5 24-27 22 12 13-20 9.4-10.5 15 35 13 17 0.3-8 2-13 14-41 1.5-18 4-8 0.7-7 11-28 2-47 ------- TABLE 5.1. (Continued) Species Platycthys flesus (flounder) Limanda limanda (dab) Scomber scombrus (mackerel) Limanda limanda Pleuronectes platessa §olea solea (sole) Aspitrigla cucuius flesh liver flesh liver flesh liver flesh flesh flesh flesh guts flesh guts Source Liverpool Bay Liverpool Bay Liverpool Bay Liverpool Bay Liverpool Bay Liverpool Bay Redear , Yorks Thames Estuary Thames Estuary Thames Estuary Thames Estuary Thames Estuary Thames Estuary CCL2CHC1 3 2 3-5 12-21 5 8 4.6 2 3 2 11 11 6 cci2cci2 2 1 1.5-11 15-30 1 ND 5.1 3 3 4 1 1 2 4 3 5 3 4 3 2 26 4 10 CH3CC13+CC1A 2 0.3 1.3-8 2-14 2 ND 9.9 0.3 0.9 6 1 0.6 0.3 (red gurnard) Trachurus trachurus (scad) flesh Thames Estuary Trisopterus luscus flesh (pout) ScLualus acanthias flesh (spurdog) Thames Estuary Thames Estuary ND 0.3 ------- TABLE 5.1. (Continued) Ul Species Scomber scombrus flesh (mackerel) CjLu£ea sprattus flesh Gadus morrhus flesh (cod) air bladder Sula bassana liver (gannot) eggs Phalacrocerax aristotelis eggs (shag) Alca torda (razorbill) eggs Rissa tridactyla (kittiwake) eggs Cyj»nus olor liver (swan) kidney Gallinula liver chloropus muscle (moorhen) eggs Ana_s platyrhyncos (mallard) eggs Source Torbay , Devon Torbay , Devon Torbay, Devon Torbay, Devon Irish Sea Irish Sea Irish Sea Irish Sea North Sea Frodsham Marsh (Merseyside) (Merseyside) (Merseyside) (Merseyside) (Merseyside) CC12CHC1 2.1 3.4 0.8 <0. 1 Sea and freshwater 4.5-6 9-17 2.4 23-26 33 2.1 14 6 2.5 6.2-7.8 9.8-16 cci2cci2 ND 1.0 <0.1 3.6 birds 1.5-3.2 4.5-26 1.4 19-29 25 1.9 6.4 3.1 0.7 1.3-2.5 1.9-4.5 CH3CC13+CC1 2.4 5.6 3.3 NA 1.2-1.9 17-20 39.4-41 35-43 40 4.7 2.4 1.6 1.1 14.5-21.8 4.2-24 ------- TABLE 5.1. (Continued) Species Source Halichoer_us grypus blubber Fame Is. (grey seal) liver Fame Is, Sorex araneus Frodsham Marsh (common shrew) (~*r* 1 fu/"1"! r*r* i /T*I fxj /"i/"ii 1001 OO J- « V./n.O J- VjVjX,-iVJ^iJL-i Ull n\J V> -L rtTV>*-^ J- » 2 22 334 Mammals 2.5-7.2 0.6-19 16-30 3-6.2 0-3.2 0.3-4.6 2.6-7.8 1 2.3-7 Source: Pearson and McConnell, 1975. Note: NA = no analysis; ND = not detectable. ------- 6. BIBLIOGRAPHY Archer, W. L. 1973. Selection of a Proper Vapor Degreasing Solvent. In: Cleaning Stainless Steels, Special Technical Publication No. 538. American Society of Testing Materials, pp 54-64. Aviado, D. M., S. Zakhari, J. A. Simaan, and A. G. Ulsamer. 1976. Methyl- chloroform and Trichloroethylene in the Environment. CRC Press, Inc., Cleveland, Ohio. 102 p. Battelle's Columbus Laboratories. 1977. Environmental Monitoring Near Industrial Sites—Methylchloroform. EPA-56-/6-77-025. U.S. Environmental Protection Agency, Office of Toxic Substances, Washington, D.C. Bellar, T. A., J. J. Lichtenberg, and R. C. Kroner. 1974. The Occurrence of Organohalides in Chlorinated Drinking Waters. Journal of the American Water Works Association. 66;703-706. Bunn, W. W., E. R. Deane, D. W. Kelin, and R. D. Kleopfer. 1975. Sampling and Characterization of Air for Organic Compounds. Water, Air and Soil Pollution. 4_: 367-380. Chian, E.S.K. and B. B. Ewing. 1976. Monitoring Data to Detect Previously Unrecognized Pollutants. Progress Reports 1 to 5. U.S. Environmental Protection Agency. Contract No. 68-01-3234. Institute for Environmental Studies, University of Illinois at Urbana-Champaign. Cox, R. A., R. G. Derwent, A.E.J". Eggleton, and J. E. Lovelock. 1976. Photochemical Oxidation of Halocarbons in the Troposphere. Atmospheric Environment. 10;305-308. Dilling, W. L., C. J. Bredeweg, and N. B. Tefertiller. 1976. Organic Photochemistry—Simulated Atmospheric Photodecomposition Rates of Methylene Chloride, 1,1,1-Trichloroethane, Trichloroethylene, Tetrachloroethylene, and Other Compounds. Environmental Science and Technology. 10(4);351-356. Dilling, W. L., N. B. Terfertiller, and G. J. Kallos. 1975. Evaporation Rates and Reactivities of Methylene Chloride, Chloroform, 1,1,1-Trichloro- ethane, Trichloroethylene, Tetrachloroethylene, and Other Chlorinated Compounds in Dilute Aqueous Solutions. Environmental Science and Technology. 9/9):833-838. Dowty, B., D. Carlisle, J. L. Laseter, and J. Storer. 1975a. New Orleans Drinking Water Sources Tested by Gas Chromatography-Mass Spectrometry. Environmental Science and Technology. j?:762-765. ------- Dowty, B., D. Carlisle, J. L. Laseter, and J. Storer. 1975b. Halogenated Hydrocarbons in New Orleans Drinking Water and Blood Plasma. Science. 187:75-77. Farber, H. A. 1973. Chlorinated Solvents and the Environment. In: Textile Solvent Technology-Update '73. Sponsored by the Solvent Processing Techno- logy Committee of the American Association of Textile Chemists and Colorists. January 10-11, 1973. pp 6-12. Galbally, I. E. 1976. Man-Made Carbon Tetrachloride in the Atmosphere. Science. 193:573-576. Goldberg, E. D. (chmn.) 1975. A:Entry, Distribution, and Fate of Heavy Metals and Organohalogens in the Physical Environment. In: Ecological Toxicology Research: Effects of Heavy Metal and Organohalogen Compounds. Proceedings of a NATO Science Committee Conference held at Mont Gabriel, Quebec, May 6-10, 1974. Plenum Press, New York, pp 233-256. Graedel, T. E. and D. L. Allara. 1976. Tropospheric Halocarbons: Estimates of Atmospheric Chemical Production. Atmospheric Environment. 10:385-388. Grimsrud, E. P. and R. A. Rasmussen. 1975. Survey and Analyses of Halo- carbons in the Atmosphere by Gas Chromatography-Mass Spectrometry. Atmospheric Environment. j)1014-1017. Keith, L. H. (ed.). 1976. Identification and Analysis of Organic Pollu- tants in Water. Ann Arbor Science Publishers, Inc. 766 p. Lillian, D. and H. B. Singh. 1974. Absolute Determination of Atmospheric Halocarbons by Gas Phase Coulometry. Analytical Chemistry. 46(8);1060-1063. Lillian, D., H. B. Singh, A. Appleby, L. Lobban, R. Arnts, R. Gumpert, R. Hague, J. Toomey, J. Kazazis, M. Antell, D. Hansen, and B. Scott. 1975- Atmospheric Fates of Halogenated Compounds. Environmental Science and Technology. 9^(12): 1042-1048. Lovelock, J. E. 1974. Atmospheric Halocarbons and Stratospheric Ozone. Nature. 252:272-274. McConnell, G., D. M. Ferguson, and C. R. Pearson. 1975. Chlorinated Hydrocarbons and the Environment. Endeavour. 34(121);13-18. Murray, A. J. and J. P. Riley. 1973. Occurrence of Some Chlorinated Aliphatic Hydrocarbons in the Environment. Nature. 242(5392):37-38. Ohta, T., M. Masatoshi, and I. Mizoguchi. 1976. Local Distribution of Chlorinated Hydrocarbons in the Ambient Air in Tokyo. Atmospheric Environment. 10:557-560. Pearson, C. R. and G. McConnell. 1975. Chlorinated GI and C2 Hydrocarbons in the Marine Environment. Proceedings of the Royal Society of London. B. 189:305-332. 6-2 ------- Pellizzari, E. C., J. E. Bunch, R. E. Berkley, and J. McRae. 1976. Determination of _race Hazardous Organic Vapor Pollutants in Ambient Atmospheres by Gas Chromatography/Mass Spectrometry/Computer. Analytical Chemistry. 48(6);803-807. Rinzema, L. C. and L. G. Silverstein. 1972. Hazards from Chlorinated Hydrocarbon Decomposition During Welding. American Industrial Hygiene Association Journal 33(1);35-40. Shamel, R. E., R. Williams, J. K. O'Neill, R. Eller, R. Green, K. D. Hallock, and R. P. Tschirch. 1975. Preliminary Economic Impact Assessment of Possi- ble Regulatory Action to Control Atmospheric Emissions of Selected Halo- carbons. EPA-450/3-75-073, PB 247 115. U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, Research Triangle Park, North Carolina. Simmonds, P. G., S. L. Kerrin, J. E. Lovelock, and F. H. Shair. 1974. Distribution of Atmospheric Halocarbons in the Air Over the Los Angeles Basin. Atmospheric Environment. 8>(3) :209-216. Singh, H. B., L. J. Salas, and L. A. Cavanagh. 1977. Distribution, Sources, and Sinks of Atmospheric Halogenated Compounds. Journal of the Air Pollution Control Association. 27(4) :332-336. Skory, L., J. Fulkerson, and D. Ritzema. 1974. Vapor Degreasing Solvents: When Safe? Products Finishing. 38_(5) :64-71. Study Panel on Assessing Potential Ocean Pollutants. 1975. Report to the Ocean Affairs Board, Commission on Natural Resources, National Research Council, Assessing Potential Ocean Pollutants. National Academy of Sciences, Washington, D.C. U.S. Environmental Protection Agency. 1975a. Preliminary Study of Selected Potential Environmental Contaminants-Optical Brighteners, Methylchloroform, Trichloroethylene, Tetrachloroethylene, Ion Exchange Resins. Final Report. July 1975. EPA-560/2-72-002. U.S. Environmental Protection Agency, Office of Toxic Substances. Washington, D.C. 286 p. U.S. Environemntal Protection Agency. 1975b. Preliminary Assessment of Suspected Carcinogens in Drinking Water. Report to Congress. U.S. Environ- mental Protection Agency, Office of Toxic Substances, Washington, D.C. 52 p. U.S. National Institute for Occupational Safety and Health. 1976. Criteria for a Recommended Standard-Occupational Exposure to 1,1,1-Trichloroctane (Methylchloroform). HEW Publication No. (NIOSH) 76-184. U.S. Department of Health, Education, and Welfare, National Institute for Occupational Safety and Health, Cincinnati, Ohio. 179 p. 6-3 ------- TECHNICAL REPORT DATA (Pirate rcad /nslnirtitinx on Ilic reverse before completing) 1. HLPQRT NO. EPA-560/6-77-030 2. 4. TITLE AND SUBTITLE MULTIMEDIA LEVELS—METHYLCHLOROFORM 5. REPORT DATE September 1977 6. PERFOFtMING ORGANIZATION CODE 3. RCCIPILNT'S ACCESSION NO. 7. AUTHOR(S) Battelle Columbus Laboratories 8. PERFORMING ORGANIZATION REPORT NO 9. PERFORMING ORGANIZATION NAME AND ADDRESS Battelle Columbus Laboratories 505 King Avenue Columbus, Oh'io 43201 10. PROGRAM ELEMENT NO. 11. CONTRACT/GRANT NO. 68-01-1983 12. SPONSORING AGENCY NAME AND ADDRESS Environmental Protection Agency Office of Toxic Substances Washington, D.C. 20460 13. TYPE OF REPORT AND PERIOD COVERED 14. SPONSORING AGENCY CODE 15. SUPPLEMENTARY NOTES 16. ABSTRACT This report discusses environmental levels of methylchloroform (MC) based on a review of the literature and other information sources. The concentrations of MC in the U.S. atmosphere ranges from about 0.1 ug/m3 (20 ppt) in remote areas to over 500 pg/m3 (100 ppb) in some areas near where the substance is manufactured or used. The concentration drops off rapidly as one moves away from a source facility. Surface water contamination of MC range from somewhat less than 1 ppb to several hundred ppb in the vicinity of MC manufacturers. The highest measurement reported (3 ppm) was made in a roadside ditch near a producer site. MC has been detected but not quantified in U.S. drinking water except in one case when approximately 10 ppb was reported. Soil and sediment concentra- tions of MC appear to be no higher near manufacturers and users than in rural areas, though the data are very limited. The levels are on the order of fractions of a ppb. MC is a saturated chlorinated hydrocarbon which is relatively stable in the atmosphere. However, the molecule is susceptible to hydrolysis or dehydrohalogenation and reacts with water relatively rapidly and is thus degraded in soil and water. There are very few data on presence of MC in food raised and sold in the U.S. However, data from the United Kingdom suggest that MC is found on the order of parts per billion in some common foodstuffs. There is little evidence to judge whether MC accumulates in living organisms. Limited data on levels in marine organisms show levels on the order of a few parts per billion. 7. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS Methylchloroform Water Sediment Soil Air Human Food Behavior b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI l-'iclil/Group 8. DISTRIBUTION STATEMENT Distribution unlimited 19. SECURITY CLASS (This Keport) Unclassified 21. NO. OF CAGES 20. SECURITY CLASS (This page) Unclassified 22. PRICE EPA form 2220-1 (Rov. 4-77) PREVIOUS COITION is OOSOLETIC ------- |