Volatile trichloroethylene

The Occupational Exposure Standards imposed for trichloroethylene are Maximum Exposure Limits of 100 ppm (8 hr TWA) and 150 ppm (15 minute reference period). A skin notation Sk is applicable because of the potential for skin absorption. Because of its volatility, trichloroethylene is not recommended for cold cleaning it is normally used in partially enclosed vapour degreasing equipment provided with local exhaust ventilation. 

There has been an emphasis on recovery and recycling of trichloroethylene to reduce emissions of this photoreactive chemical to the atmosphere (CMR 1986 McNeill 1979). Photooxidative destruction has been successfully used in conjunction with air-stripping techniques to volatilize trichloroethylene from water and degrade it to nontoxic products (Bhowmick and Semmens 1994). If possible, recycling should be used instead of disposal. 

As a result of volatilization, significantly elevated indoor air levels of trichloroethylene can occur in homes that use water supplies contaminated with trichloroethylene (Andelman 1985a). The transfer of trichloroethylene from shower water to air in one study had a mean efficiency of 61% which was independent of water temperature (McKone and Knezovich 1991). The study authors concluded that showering for 10 minutes in water contaminated with trichloroethylene could result in a daily exposure by inhalation comparable to that expected by drinking contaminated tap water. Another study using a model shower system found that, in addition to shower spray, shower water collecting around the drain could be an important source of volatilized trichloroethylene, and the fraction volatilized could be affected by spray drop size and flow rate (Giardino et al. 1992). 

Derivatization is also useful to detect volatile metabolites. Liu et al. [282] described a specific, rapid, and sensitive in situ derivatization solid-phase microextraction (SPME) method for determination of volatile trichloroethylene (TCE) metabolites, trichloroacetic acid (TCA), dichloroacetic acid (DCA), and trichloroethanol (TCOH), in rat blood. The metabolites were derivatized to their ethyl esters with acidic ethanol, extracted by SPME and then analyzed by gas chromatography/negative chemical ionization mass spectrometry (GC-NCI-MS). After validation, the method was successfully applied to investigate the toxicokinetic behavior of TCE metabolites following an oral dose of TCE. Some of the common derivatization reagents include acetyl chloride and TV-methyl-iV- ft-b u (y Idi methyl si I y I) tro (1 uoroacctam i nc (MTBSTFA) for phenols and aliphatic alcohols and amines, dansyl chloride and diazomethane for phenols, dansyl chloride for amines, acidic ethanol and diazomethane for carboxylic acids, and hydrazine for aldehydes. 

PROBABLE FATE photolysis, tropospheric photooxidation of volatilized trichloroethylene by hydroxyl radicals to phosgene and dichloroacetyl chloride is very rapid, C-Cl bond can photolyze slowly oxidation not important except for photooxidation, photooxidation half-life in air 1.1-11.3 days hydrolysis not important under environmental conditions, first-order hydrolytic half-life 10.7 months volatilization rapid volatilization is the major transport process, evaporation from water 25°C of 1 ppm solution 50% after 19-24 min, 90% after 63-80 min ... 

AH volatile organic solvents are toxic to some degree. Excessive vapor inhalation of the volatile chloriaated solveats, and the central nervous system depression that results, is the greatest hazard for iadustrial use of these solvents. Proper protective equipment and operating procedures permit safe use of solvents such as methylene chloride, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene ia both cold and hot metal-cleaning operations. The toxicity of a solvent cannot be predicted from its chlorine content or chemical stmcture. For example, 1,1,1-trichloroethane is one of the least toxic metal-cleaning solvents and has a recommended threshold limit value (TLV) of 350 ppm. However, the 1,1,2-trichloroethane isomer is one of the more toxic chloriaated hydrocarboas, with a TLV of only 10 ppm. 

Trichloroethylene [79-01-6J, trichloroethene, CHCL=CCL2, commonly called "tri," is a colorless, sweet smelling (chloroformlike odor), volatile Hquid and a powerhil solvent for a large number of natural and synthetic substances. It is nonflammable under conditions of recommended use. In the absence of stabilizers, it is slowly decomposed (autoxidized) by air. The oxidation products are acidic and corrosive. Stabilizers are added to all commercial grades. Trichloroethylene is moderately toxic and has narcotic properties. 

In 1966, the Los Angeles Air Pollution Control Board designated trichloroethylene as a photochemically reactive solvent that decomposes in the lower atmosphere, contributing to air pollution. In 1970 all states were requited to submit pollution control plans to EPA to meet national air quaUty standards. These plans, known as State Implementation Plans (SIPS), controlled trichloroethylene as a volatile organic compound (VOC). They were designed to have each state achieve the National Ambient Air QuaUty Standard (NAAQS) for ozone. The regulations were estabUshed to control the emission of precursors for ozone, of which trichloroethylene is one. 

Typical precautions with trichloroethylene are summarized in Table 5.52. An important factor is that the vapours are much heavier than air they will therefore spread and may accumulate at low levels, particularly in undisturbed areas. Because of its volatility, releases to the environment usually reach the atmosphere. Here it reacts with hydroxyl or other radicals (estimated half-life for reaction with hydroxyl radicals is less than a week) and is not therefore expected to diffuse to the stratosphere to any significant extent. There is some evidence for both aerobic and anaerobic biodegradation of trichloroethylene. 

Remediation activities at American Thermostat included the excavation and thermal treatment of over 13,000 cubic yards of soil and sediments contaminated primarily with perchloroethylene, trichloroethylene, and solvents. The soil was excavated and treated using a thermal treatment unit called the low-temperature enhanced volatilization facility (LTEVF). The performance test for the site s thermal unit had just been completed at the time of the inspection, so there was limited activity. 

Efforts to identify the specific compounds responsible for the psychotropic effects of volatile solvents are complicated by the fact that many of these products contain more than one potentially psychoactive ingredient. Another factor obscuring the identity of the psychoactive ingredients of these agents is that patients addicted to these compounds frequendy seek the effects not of the product s primary ingredient but of a secondary ingredient such as the propellant gas (e.g., nitrous oxide). To date, the best-studied psychoactive compounds identified in volatile solvents include toluene, 1,1,1-trichloroethane, and trichloroethylene. However, other less well studied compounds, such as benzene, acetone, and methanol, also appear to have significant psychoactive effects. 

Similar to alcohol (Lovinger and White 1991) and volatile anesthetics (Machu and Harris 1994), trichoroethane, trichloroethylene, and toluene enhance 5-HT3 receptor function. All three inhalants significantly and reversibly potentiated, in a dose-dependent manner, 5-HT-activated currents, mediated by mouse 5-HT3 receptors expressed in Xenopus oocytes. Another feature common to these drugs is that the acute use of inhalants, as well as alcohol and volatile anesthetics, can produce nausea and vomiting (Meredith et al. 1989). It is believed that 5-HT3 receptors located in the area postrema mediate this action of alcohol and the volatile anesthetics (Aapro 1991). 

Common gases such as oxides of carbon and nitrogen, hydrogen sulphide, and inert gases. Liquids which pose a health hazard due to volatilization, e.g. mercury and degreasing with chlorinated solvent, i.e. dry cleaning with perchloroethylene or metal cleaning with trichloroethylene. 

PBPK models have also been used to explain the rate of excretion of inhaled trichloroethylene and its major metabolites (Bogen 1988 Fisher et al. 1989, 1990, 1991 Ikeda et al. 1972 Ramsey and Anderson 1984 Sato et al. 1977). One model was based on the results of trichloroethylene inhalation studies using volunteers who inhaled 100 ppm trichloroethylene for 4 horns (Sato et al. 1977). The model used first-order kinetics to describe the major metabolic pathways for trichloroethylene in vessel-rich tissues (brain, liver, kidney), low perfused muscle tissue, and poorly perfused fat tissue and assumed that the compartments were at equilibrium. A value of 104 L/hour for whole-body metabolic clearance of trichloroethylene was predicted. Another PBPK model was developed to fit human metabolism data to urinary metabolites measured in chronically exposed workers (Bogen 1988). This model assumed that pulmonary uptake is continuous, so that the alveolar concentration is in equilibrium with that in the blood and all tissue compartments, and was an expansion of a model developed to predict the behavior of styrene (another volatile organic compound) in four tissue groups (Ramsey and Andersen 1984). 

Most of the trichloroethylene used in the United States is released into the atmosphere by evaporation primarily from degreasing operations. Once in the atmosphere, the dominant trichloroethylene degradation process is reaction with hydroxyl radicals the estimated half-life for this process is approximately 7 days. This relatively short half-life indicates that trichloroethylene is not a persistent atmospheric compound. Most trichloroethylene deposited in surface waters or on soil surfaces volatilizes into the atmosphere, although its high mobility in soil may result in substantial percolation to subsurface regions before volatilization can occur. In these subsurface environments, trichloroethylene is only slowly degraded and may be relatively persistent. 

Release of trichloroethylene also occurs at treatment and disposal sites. Water treatment facilities may release trichloroethylene from contaminated water through volatilization and air-stripping procedures (EPA 1985e). Trichloroethylene is also released to the atmosphere through gaseous emissions from landfills. The compound may occur as either an original contaminant or as a result of the decomposition of tetrachloroethylene. Trichloroethylene has also been detected in stack emissions from the incineration of municipal and hazardous waste (James et al. 1985 Oppelt 1987). 

The Henry s law constant value of 2.Ox 10 atm-m /mol at 20°C suggests that trichloroethylene partitions rapidly to the atmosphere from surface water. The major route of removal of trichloroethylene from water is volatilization (EPA 1985c). Laboratory studies have demonstrated that trichloroethylene volatilizes rapidly from water (Chodola et al. 1989 Dilling 1977 Okouchi 1986 Roberts and Dandliker 1983). Dilling et al. (1975) reported the experimental half-life with respect to volatilization of 1 mg/L trichloroethylene from water to be an average of 21 minutes at approximately 25 °C in an open container. Although volatilization is rapid, actual volatilization rates are dependent upon temperature, water movement and depth, associated air movement, and other factors. A mathematical model based on Pick s diffusion law has been developed to describe trichloroethylene volatilization from quiescent water, and the rate constant was found to be inversely proportional to the square of the water depth (Peng et al. 1994). 

Mathematical modeling of trichloroethylene volatilization from a rapidly moving, shallow river (1 meter deep, flowing 1 meter per second, with a wind velocity of 3 meters per second) has estimated its half-life at 3.4 hours (Thomas 1982). Measured volatilization half-lives in a mesocosm, which simulated the Narragansett... 

Volatilization of trichloroethylene from soil is slower than it is from water but more rapid than that of many other volatile organic compounds (Park et al. 1988). This study found that an average of 37% of the applied trichloroethylene was volatilized 168 hours after treatment at 12°C, and 45% was volatilized at 21°C. This study also concluded that soil t> pe had no effect on rate of volatilization, although this may simply be a reflection of the fact that the differences between soils used in the study, particularly in organic carbon content, were not very great. 

The reaction of volatile chlorinated hydrocarbons with hydroxyl radicals is temperature dependent and thus varies with the seasons, although such variation in the atmospheric concentration of trichloroethylene may be minimal because of its brief residence time (EPA 1985c). The degradation products of this reaction include phosgene, dichloroacetyl chloride, and formyl chloride (Atkinson 1985 Gay et al. 1976 Kirchner et al. 1990). Reaction of trichloroethylene with ozone in the atmosphere is too slow to be an effective agent in trichloroethylene removal (Atkinson and Carter 1984). 

Since neither biodegradation nor hydrolysis occurs at a rapid rate, most trichloroethylene present in surface waters can be expected to volatilize into the atmosphere. However, because trichloroethylene is denser than and only moderately soluble in water, that which is not immediately volatilized may be expected to submerge and thus be removed from contact with the surface (Doust and Huang 1992). 

The majority of trichloroethylene present on soil surfaces will volatilize to the atmosphere or leach into the subsurface. Once trichloroethylene leaches into the soil, it appears not to become chemically transformed or undergo covalent bonding with soil components. When trichloroethylene was absorbed onto kaolinite and bentonite, the nuclear magnetic resonance (NMR) spectra showed no evidence of chemical reactions (Jurkiewicz and Maciel 1995). Because trichloroethylene is a dense nonaqueous phase liquid, it can move through the imsaturated zone into the saturated zone where it can displace soil pore water (Wershaw et al. 1994). 

Data gathered from several sites near Niigata, Japan, between April 1989 and March 1992 showed elevated levels of trichloroethylene and other volatile chlorinated hydrocarbons in the winter (Kawata and Fujieda 1993). A rural site in this study had armual mean concentrations between 0.17 and 0.32 ppb, while four industrial sites had mean concentrations between 0.029 and 4.8 ppb. The average trichloroethylene level detected in samples collected from ambient air in the Norwegian Arctic between 1982 and 1983 was 0.007 ppb (Hov et al. 1984). Average concentrations of trichloroethylene in Alaskan Arctic haze between 1980 and 1982 were 0.036 ppb in winter and 0.007 ppb in summer (Khalil and Rasmussen 1983). 

Some elevated outdoor air levels of triehloroethylene reported are associated with waste disposal sites. Average trichloroethylene levels of 0.08-2.43 ppb were detected in ambient air at six landfill sites in New Jersey the maximum concentration was 12.3 ppb (Harkov et al. 1985). Levels between 3.0 and 3.2 pg/m (0.56 ppb and 0.60 ppb) were found at a distance of 0.5-1.5 meters above the surface of a landfill known to contain halogenated volatile organic compounds in Germany (Koenig et al. 1987). 

A survey of 20 brands of typographical correction fluids found that several contained 10% or less trichloroethylene, although other volatile organic compounds present at higher levels probably posed a greater hazard to people using these products (Ong et al. 1993). Various other consumer products have been found to contain trichloroethylene, such as paint removers, strippers, adhesives, and lubricants (Frankenberry et al. 1987). 

As part of the Third National Health and Nutrition Evaluation Survey (NHANES 111), the Environmental Health Laboratory Sciences Division of the National Center for Environmental Health, Centers for Disease Control, will be analyzing human blood samples for trichloroethylene and other volatile organic compounds. These data will give an indication of the frequency of occurrence and background levels of these compounds in the general population. 

Purge-and-trap methods have also been used to analyze biological fluids for the presence of trichloroethylene. Breast milk and blood were analyzed for trichloroethylene by purging onto a Tenax gas chromatograph to concentrate the volatiles, followed by thermal desorption and analysis by GC/MS (Antoine et al. 1986 Pellizzari et al. 1982). However, the breast milk analysis was only qualitative, and recoveries appeared to be low for those chemicals analyzed (Pellizzari et al. 1982). Precision (Antoine et al. 1986) and sensitivity (Pellizzari et al. 1982) were comparable to headspace analysis. 

Headspace analysis has also been used to determine trichloroethylene in water samples. High accuracy and excellent precision were reported when GC/ECD was used to analyze headspace gases over water (Dietz and Singley 1979). Direct injection of water into a portable GC suitable for field use employed an ultraviolet detector (Motwani et al. 1986). While detection was comparable to the more common methods (low ppb), recovery was very low. Solid waste leachates from sanitary landfills have been analyzed for trichloroethylene and other volatile organic compounds (Schultz and Kjeldsen 1986). Detection limits for the procedure, which involves extraction with pentane followed by GC/MS analysis, are in the low-ppb and low-ppm ranges for concentrated and unconcentrated samples, respectively. Accuracy and precision data were not reported. 

Giardino NJ, Esmen NA, Andelman JB. 1992. Modeling volatilization of trichloroethylene from a domestic shower spray the role of drop-size distribution. Environmental Science and Technology 26 1602-1606. 

Okouchi S. 1986. Volatilization coefficient for stripping trichloroethylene, 1,1,1-trichloroethane and tetrachloroethylene from water. Water Sci Technol 18 137-138. 

Metal working, degreasing, and painting are the main phases in this production process. The degreasing of the metal sections has been carried out in the past by using the volatile organic compound trichloroethylene, which is a pollutant and an environmental hazard. 

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