February 1994
White Paper on Methyl Chloroform
(1,1,1-Trichloroethane)
Executive Summary
The widespread use of methyl chloroform as an industrial solvent and early interest in the chemical as an anesthetic have resulted in extensive study of its health effects. Research on the carcinogenic effects of the chemical on rats and mice has produced no significant adverse findings, nor have studies of possible teratogenic or reproductive effects in animals. Similarly, a study of the non-carcinogenic health effects of methyl chloroform on an exposed human population found no differences between the study and control groups.
After reviewing the available data, the Environmental Protection Agency (EPA) Health Assessment Document for methyl chloroform concluded that "[t]he weight of available evidence obtained from both human and animal data suggest that long-term exposure to environmental levels of methyl chloroform poses no serious health concern to the general population." While no definitive assessment of the compound's carcinogenic potential for humans is possible, EPA concluded that "[t]he likelihood of adverse health effects resulting from chronic exposure to the ambient air levels commonly encountered appears to be extremely low based on presently available data." Nevertheless, methyl chloroform is included, along with 188 other substances, in a list of hazardous air pollutants in Section 112 of the Clean Air Act, as amended in 1990. EPA will be regulating certain major and area sources of these substances, such as degreasing operations, in the coming years.
More significantly, the production of methyl chloroform is being phased out under the Montreal Protocol on Substances That Deplete the Ozone Layer, as amended in June 1990 and November 1992 and under Title VI of the federal Clean Air Act. Title VI of the Clean Air Act also establishes controls on certain uses of methyl chloroform and imposes labeling requirements for certain products containing or made with the substance. In addition, methyl chloroform produced or imported after January 1, 1991 is subject to a federal excise tax under the Omnibus Budget Reconciliation Act of 1990, as amended in 1992.
Accordingly, it will be necessary to eliminate the use of methyl chloroform, except as a chemical intermediate-feedstock.
IntroductionMethyl chloroform is a versatile, all purpose solvent, popular with industry because of its powerful cleaning properties, low flammability, and low relative toxicity. It was introduced in the mid-1950's as a cold cleaning solvent substitute for carbon tetrachloride. Today, methyl chloroform is used primarily for vapor degreasing and cold cleaning of fabricated metal parts and other materials. The chemical also is used in fluoropolymer synthesis, as a solvent in adhesive and aerosol formulations, for the production of certain coatings and inks, for a variety of textile applications, and for dry cleaning leather and suede garments.
Methyl chloroform is a member of a family of saturated aliphatic halogenated hydrocarbons. The colorless, volatile liquid is produced in the United States by Dow Chemical U.S.A., PPG Industries, Inc., and Vulcan Materials Company. Total U.S. demand for the solvent in 1989 was 308,000 metric tons (680 million pounds) of which a small percentage was imported.
Permissible levels of methyl chloroform in the workplace have been established in several countries. In the United States, the Occupational Safety and Health Administration (OSHA) limits worker exposure to the chemical to a time-weighted average concentration of 350 parts per million (ppm) in the workplace air in any 8-hour work shift of a 40-hour week. This 350-ppm standard is well above the concentration at which presence of the chemical is noticeable (odor threshold = 100 ppm), and at or below EPA's estimated no-observed-effect level for short-term exposure of humans (350 to 500 ppm). OSHA also has established a short-term exposure limit, or STEL, of 450 ppm for any 15-minute period. No adverse health effects are likely to arise from the industrial use of methyl chloroform when it is handled in accordance with the manufacturer's instructions.
UsesAmong the properties that have contributed to the widespread use of methyl chloroform as an industrial solvent are the following:
- low toxicity
- high solvency
- low flammability
- relatively high stability
- low boiling point
- non-photochemical reactivity (does not form ozone in the lower atmosphere)
- low solubility in water
- ability to be recycled
In addition, all commercial formulations of methyl chloroform are stabilized to retard or prevent solvent breakdown caused by contaminants such as acids, alkalies, metal chips and fines, and overexposure to oxygen, light, and heat. The stabilizers also help to protect the surface being cleaned.
In 1989 industrial use of methyl chloroform could be summarized as follows:
metal degreasing 32% cold cleaning 19% aerosols 11% adhesives 9% chemical intermediate 9% electronics 7% coatings and inks 6% textiles 3% miscellaneous 4%
METAL DEGREASING
Metal vapor degreasing is an important process in industrial manufacture, used to remove oils and oil-borne soils (i.e., chips, metal fines, and fluxes) from objects that have been stamped, machined, welded, soldered, molded, or diecast. Vapor degreased parts vary from tiny transistors to aircraft and spacecraft assemblies.
COLD CLEANING
Methyl chloroform is an excellent solvent for the cold (room temperature) cleaning of a wide variety of manufacturing equipment and products including yarns, threads, finished cloth, reinforced fiberglass, plastics, and common and exotic metals. The solvent removes most greases, oils, lubricants, waxes, adhesives, inks, fluxes, paints, stamping and drawing compounds, tars, and other soils.
AEROSOLS
As an aerosol solvent, methyl chloroform can be used in conjunction with either carbon dioxide or hydrocarbon propellants to reduce the flammability of the aerosol package. The solvent can solubilize many of the active ingredients in aerosol formulations, improving the spray characteristics and reducing valve clogging.
ADHESIVES
The main reasons for the use of methyl chloroform in formulations for urethane and neoprene/phenolic contact adhesives, mastics, sealants, and natural rubber tire repair cements are its ability to substantially reduce flammability, its non-photochemical reactivity, and the favorable characteristics of the resulting adhesive formulation.
ELECTRONICS
The main applications of methyl chloroform in the electronics industry are in circuit board fabrication, where it is used to develop dry film photoresist, and in the semiconductor industry where it is used for secondary cleaning.
CHEMICAL INTERMEDIATES
Methyl chloroform serves as a raw material for the manufacture of polyvinylidene fluoride fluoropolymer. It also can be used as a raw material for the production of certain hydrochlorofluorocarbons having relatively short atmospheric residence times.
COATINGS AND INKS
In the coatings manufacturing industry, methyl chloroform is used as a solvent in the formulation of protective and decorative coatings and as a thinner to reduce the viscosity of high-solid content coatings for spray application. The chemical also can be used in the production of rotogravure and flexographic inks.
MISCELLANEOUS
In addition to the above uses, methyl chloroform is used to dry clean leather and suede products and to clean motion picture film.Health Effects
GENERAL
The health effects of methyl chloroform are well characterized after many years of industrial use. The primary effects of acute overexposure to the chemical are to the central nervous system (e.g., light-headedness, drowsiness, headache). Lethal effects of excessive concentrations (at 1 0,000 ppm) of the chemical have been reported after accidental exposure or abuse. In these cases, death resulted from respiratory and cardiac failure caused by depression of the central nervous system. Cardiac sensitization also may have contributed. Prolonged exposure (15 minutes or more) to high concentrations (1000 to 2000 ppm) of the solvent in the air results in mild irritation of the eyes and respiratory tract. In its liquid form, methyl chloroform causes irritation to the skin and eyes upon contact.
Studies of workers occupationally exposed to methyl chloroform for up to 6 years have demonstrated no adverse health effects. Animal studies of chronic exposure to the chemical at levels ranging up to 1750 ppm similarly have found no adverse health effects.
MUTAGENICITY
Several in vivo (living animal) and in vitro (glass or test tube) tests of the mutagenic effects of methyl chloroform have been conducted. The majority of these experiments have failed to produce positive mutagenic effects. Based on the weight of available evidence, it is believed that commercially available samples of methyl chloroform may be weakly mutagenic in bacteria. These results, however, may be due to small amounts of stabilizers present in the commercial formulations tested. The preponderance of tests conducted in higher level organisms indicates that metho chloroform is not likely to be mutagenic.
CARCINOGENICITY
Animal Studies
Several bioassays have been conducted in laboratory animals to test the carcinogenic potential of commercial formulations of methyl chloroform administered by inhalation or by oral intubation (gavage). None of these studies has produced positive results for carcinogenicity.
In 1977 the National Cancer Institute performed a gavage study of Osborne-Mendel rats and B6C3Fl mice. In this study, treatments of 750 and 1500 milligrams/kilogram (mg/kg) body weight five times a week for 78 weeks did not induce tumors. However, the relatively high mortality of the treated animals limited the study's sensitivity. A second gavage study, conducted by the National Toxicology Program (NTP), was judged inadequate by NTP to evaluate the carcinogenicity of methyl chloroform.
A more conclusive study was performed by The Dow Chemical Company, exposing Sprague-Dawley rats by inhalation to 875 and 1750 ppm of methyl chloroform under conditions similar to those of exposed workers (6 hours/day, 5 days/week, for 12 months). After observing the animals until the age of 31 months, no significant difference in tumor incidence was found between the treatment and control animals.
A second study by Dow Chemical exposed B6C3Fl mice and Fischer 344 rats by inhalation to levels between 150 and 1500 ppm for 6 hours/day, 5 days/week over the animals' lifetime (24 months). Again, no observable difference in the incidence of benign or malignant tumors between the test animals and their respective controls was found.
Based on the laboratory research, it does not appear that exposure to methyl chloroform at current occupational levels presents a risk of cancer in humans. Two of the stabilizing additives sometimes used in commercial formulations of the chemical, 1,2-epoxybutane (butyiene oxide) and 1,4-dioxane (diethylene dioxide), have been identified as potential carcinogens based on animal studies. The commercial formulations of methyl chloroform employed in the previously described bioassays contained small amounts of butylene oxide and/or diethylene dioxide, however, and no carcinogenic effects were observed in the exposed animals.
EPIDEMIOLOGY
No epidemiology studies investigating the carcinogenicity of methyl chloroform have been conducted. In one study examining the prevalence of adverse health effects in methyl chloroform-exposed workers, however, no differences in general health were observed in textile workers exposed for up to six years as compared to a non-exposed group.
REPRODUCTIVE AND DEVELOPMENTAL TOXICITY
Methyl chloroform has been evaluated in several studies for its potential to adversely affect reproductive outcome in laboratory animals. Inhalation studies in rats and mice at levels of 875 and 2100 ppm did not produce abnormal birth ef f ects.
In a multigenerational study of ICR Swiss mice exposed to concentrations of between 100 and 1000 mg/kg body weight per day in their drinking water, no adverse effects on fertility, gestation, or pup survival were observed.
Pursuant to an EPA test rule, HSIA sponsored developmental toxicity studies of inhaled methyl chloroform in Sprague Dawley rats and New Zealand white rabbits at exposure concentrations of 0, 1000, 3000, and 6000 ppm. The chemical did not produce developmental effects in the offspring of either species following exposure of pregnant females to doses that were high enough to elicit toxicity in the females. Some reduction in maternal weight gain was noted in the rats at concentrations above 1000 ppm and in the rabbits above 3000 ppm.
On the basis of these animal studies, it does not appear that exposure to methyl chloroform results in teratogenic effects in rats or mice. Delays in fetal development have been observed in both species, but these were found to be reversible effects. As a result, it is unlikely that methyl chloroform will have an adverse effect on human reproduction when good industrial hygiene practices are employed.
NEUROTOXICITY
Pursuant to an EPA consent order, HSIA sponsored extensive testing for both adult and developmental neurotoxicity effects in rats. All testing has been completed, with results indicating no significant neurotoxic effects in either adults or offspring.
Environmental FateContamination of surface and ground water by methyl chloroform has been reported at some sites, generally at levels of 1 part per billion (ppb) or less. Because of its volatility and the low concentration levels expected in natural aquatic environments, the chemical is believed to be nonpersistent. Based on the limited data available, moreover, methyl chloroform appears to be relatively low in toxicity to aquatic organisms, and does not appear to be biomagnified or bioconcentrated to any significant degree.
TROPOSPHERIC AND STRATOSPHERIC OZONE EFFECTS
Industrial usage of methyl chloroform does not contribute significantly to an increased ambient ozone (smog) concentration in the troposphere (lower atmosphere) or to the resulting public health risk. Rather than reacting in the lower atmosphere to form smog, methyl chloroform is removed through a reaction with readily available hydroxyl radicals (*OH). As a result, methyl chloroform is not regulated by EPA or by most states as a volatile organic compound.
The solvent's relatively short atmospheric lifetime of 6 to 7 years means that most of it is removed before reaching the stratosphere (upper atmosphere). Its stratospheric ozone depletion potential is about one-tenth that of chlorofluorocarbon (CFC) 1 1, which has a considerably longer atmospheric lifetime.
GLOBAL WARMING
As a result of its relatively short atmospheric residence time and low concentration in the atmosphere, methyl chloroform is not thought to contribute significantly to global warming.
Production and Use Regulations
In response to concern about its stratospheric ozone depletion potential, methyl chloroform is subject to a phase-out schedule under national law and international treaty.
PRODUCTION PHASE-OUT SCHEDULE
Under EPA's accelerated phase-out schedule adopted pursuant to the Clean Air Act, production (and import) of methyl chloroform for other than feedstock uses will be phased out in accordance with the following schedule (allowable production expressed as a percentage of 1989 production)
1994 - 50 %
1995 - 30 %
1996 - essential uses only
The accelerated phase-out schedule contains somewhat more stringent production limits than the amended Montreal Protocol, allowing only 30 percent of 1989 production (instead of 50 percent) in 1995. Both the accelerated phase-out schedule and the amended Protocol, however, require a 50 percent reduction in 1994, and phase out production of methyl chloroform in 1996.
Beginning in fall 1994, the Parties to the Montreal Protocol will decide whether any essential use exemptions will be provided for methyl chloroform. Under the Montreal Protocol as amended in November 1992, a use will be "essential" only if "it is necessary for the health, safety or is critical for the functioning of society" and "no available technically and economically feasible alternatives or substitutes ... are acceptable from the standpoint of environment and health." After 2002 the Clean Air Act restrictions may limit essential use exemptions for methyl chloroform.
USE RESTRICTIONS AND LABELING REQUIREMENTS
Replacement of methyl chloroform in various uses, including metal cleaning, adhesives and coatings, and aerosols, will be directly affected by the significant new alternatives policy (SNAP) program, which EPA is in the process of implementing. A number of acceptable and unacceptable alternatives to methyl chloroform have been identified in these use sectors. EPA has provisionally designated perchloroethylene, trichloroethylene, and methylene chloride as acceptable alternatives for most methyl chloroform applications.
Effective May 15, 1993, containers of and products containing methyl chloroform introduced into commerce must bear a "clearly legible and conspicious" label stating that they contain a substance which harms public health and environment by destroying ozone in the upper atmosphere. Products made using methyl chloroform must bear a label so stating unless: (i) they were manufactured solely for export and are clearly identified as such, (ii) their manufacturer has achieved a total reduction of solvent use of methyl chloroform and/or CFC-113 of 95 percent or more, or (iii) EPA determines that no acceptable substitute product or processes exists.
Methyl chloroform is generally unaffected by the bans on non-essential products adopted by EPA in 1993 and 1994.
Additional state or local restrictions may apply.
EXCISE TAX
As part of the 1990 budget reconciliation, Congress extended the excise tax on substances with ozone depletion potential to methyl chloroform. The change conformed the list of taxable substances to the list of substances controlled under the amended Montreal Protocol. The tax applies to methyl chloroform sold or used by a producer or importer after December 31, 1990.
In 1992, the excise tax was amended to increase the tax for all substances, including methyl chloroform. Effective January 1, 1993, the increased tax applies to methyl chloroform according to the following schedule:
Year Excise Tax (cents/lb.)
1993 21.1
1994 43.5
1995 53.5
After 1995, the excise tax on methyl chloroform will increase by 4.5 cents/lb each year.
Individual methyl chloroform users and distributors are not directly responsible for paying the tax to the Internal Revenue Service (IRS) on quantities of the virgin chemical purchased after 1990. They are responsible, however, for paying tax on quantities of the chemical in stock on January 1 of 1991, 1993, and the first of the year for each year thereafter (tax-increase dates). This "floor-stocks" tax generally applies to users and distributors who, on a tax-increase date, hold more than 400 pounds of methyl chloroform and other taxable chemicals for use or sale. Proposed regulations would modify this rule beginning January 1, 1995. The floor stocks tax must be paid on or before June 30. In addition, a tax is applied to imported products made with more than a de minimis amount of methyl chloroform.
Neither the producers tax nor the floor-stocks tax applies to recycled or used methyl chloroform. Discussions with IRS suggest that solvent contained in a degreaser will be considered "used" and, therefore, not subject to the floor-stocks tax. Neither tax applies to methyl chloroform used, held, or sold to be used as feedstock in the production of other substances.
Regulatory and Other Information for Methylene Chloride
| Chemical Formula | CH,CCI, |
| Molecular Weight | 133.4 |
| CAS Number | 71-55-6 |
| OSHA PEL | |
| 8-hour TWA | 350 ppm |
| 15-minute STEL | 450 ppm |
| ACGIH TLV | |
| 8-hour TWA | 350 ppm |
| 15-minute STEL | 450 ppm |
| CERCLA Reportable Quantity (RQ) | 1000 pounds |
| Maximum Contaminant Level (Drinking Water) | 200 ug/l |
| RCRA Hazardous Waste Number | U 226 |
| DOT Hazard Classification | 6.1 (packing group III) |
| DOT ID Number | U N 2831 |
Information in this paper is believed to be accurate as of the date of publication, but HSIA can not guarantee its completeness or accuracy. In publishing this paper, HSIA does not assume or undertake any duty imposed on any party by law or regulation. It is the user's responsibility to determine the suitability of the solvent described in this paper, and HSIA assumes no responsibility arising out if such use.