RATIONALE FOR THE DEVELOPMENT OF ONTARIO AIR STANDARDS FOR METHYLENE CHLORIDE CONSULTATION DRAFT February 1998 Standards Development Branch Ontario Ministry of the Environment ®Ontario Executive Summary The Ontario Ministry of the Environment has identified the need to develop and/or update air quality standards for priority contaminants. The Ministry's Standards Plan which was released in October 1996, identified candidate substances for the development of air standards for the next several years (MOEE, 1996). Methylene chloride was identified as priority for review based both on its pattern of use in Ontario and recent toxicological information published since the existing standard was developed in 1988. Methylene chloride is a volatile, colourless liquid with a mildly sweet odour. It is widely used in paint removers, as a solvent for plastics, as a de greasing agent, in propellant mixtures for aerosol containers and as pharmaceutical intermediates. In a survey between 1989 and 1991, 24-hour average concentrations measured at Ontario air quality monitoring sites ranged from 0.7 to 5.6 11g/m3 (micrograms of methylene chloride per cubic metre of air). The maximum level measured in 1991 was 22.9 11g/m3 at a site in Hamilton. Average methylene chloride concentrations at sites across Canada range from 0.5 to 9.9 ~/m3. There is sufficient evidence to consider methylene chloride as an animal carcinogen with the liver and lungs as the main target organs. Other organs affected include the mammary and salivary glands. Human health data from epidemiological studies do not provide consistent evidence of carcinogenicity in humans. However, increases of melanoma (a type of tumour) and cancers in the buccal (mouth) cavity and pharynx, liver and biliary passages, and the breast have been observed in some workers exposed to methylene chloride and other solvents. Information obtained from studies of animals subjected to short-term exposure to methylene chloride, suggest that detrimental effects other than cancer may be induced. These include adverse effects on the central nervous system, liver, heart, lungs and the kidneys. In longer term exposure studies, adverse effects in the liver, kidney and brain tissues have been reported. The current Ontario standards for methylene chloride are as follows: the interim half-hour Point of-Impingement standard is 5300 ~/m3, while the 24-hour average Ambient Air Quality Criterion is 1765 ~/m3 Both of these are based on non-cancer human health effects. More recent toxicological information suggests that methylene chloride should be treated as a probable human carcinogen. Based on this information, the current Ontario standards developed in 1988 are now considered to be in need of review. In developing air quality standards for Ontario, the Ministry of the Environment is reviewing and considering air quality guidelines and standards used by environmental agencies world-wide. A number of agencies including the United States Environmental Protection Agency, the California Department of Health Services, the Department of Environmental Protection ofthe Commonwealth of Massachusetts as well as Health and Environment Canada, under the Canadian Environmental Protection Act, have developed cancer risk estimates for methylene chloride. Among these agencies, the assessment conducted by Health Canada was judged to have the most appropriate rationale and was used as the basis for recommending revised air quality standards for methylene chloride for Ontario. Methylene chloride has been assessed as toxic under the Canadian Environmental Protection Act. To minimize environmental releases of methylene chloride, Environment Canada is developing a management strategy under its Strategic Options Process to reduce the use and emission of methylene chloride in a variety of industrial processes and commercial products. Sectors participating in the Strategic Options Process have agreed in principle to reduce the use and release of methylene chloride by 50-90% by the year 2002 with further reductions being considered beyond that date. Based on the evaluation of recent toxicological information; the ambient air quality guidelines used in other jurisdictions; modelled ground level concentrations from recent applications for Certificates of Approval; the on-going federal Strategic Option Process and the levels of methylene chloride measured in Ontario, the Ministry is proposing: • an annual average Ambient Air Quality Criterion for methylene chloride of 44 ~J.g/m 3 (micrograms of methylene chloride per cubic metre of air). This value is based on the health assessment conducted by Health Canada and corresponds to an excess lifetime cancer risk of approximately 1 in 1,000,000; • a revision of the existing 24-hour Ambient Air Quality Criterion for methylene chloride from its current level of 1765 IJ.g/m 3 to 220 11g/m 3 • In light of the reduction strategies for methylene chloride being developed under the Canadian Environmental Protection Act, the Ministry is seeking additional information from stakeholders prior to recommending a revised point-of-impingement standard for this compound. The Ministry is asking Ontario sources of methylene chloride to assess the emission reductions being anticipated as a result of strategies being developed under the Canadian Environmental Protection Act. This information will be considered in setting a point-of-impingement standard for methylene chloride to be implemented on a timetable consistent with the recommendations under the Strategic Options Process. ii Table of Contents Executive Summary ......................................................... . 1. 0 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2. 0 Review and Evaluation .................................................... 2 2.1 General Information ................................................ 2 2.2 Sources and Levels ................................................. 3 2.3 Review of Existing Air Quality Regulations ............................... 4 2.4 Development of Strategic Options for the Management of Methylene Chloride under the Canadian Environmental Protection Act (CEP A) ..................... 4 3.0 Development of an Ambient Air Quality Criterion for Ontario ....................... 6 3.1 Discussion of Regulatory Approaches for Methylene Chloride ................. 6 3.1.1 Regulatory Approaches Based on Carcinogenicity Endpoint ........... 6 3.1.2 Regulatory Approaches Based on a Non-carcinogenic Endpoint ........ 7 3.2 Recommendation for an Ambient Air Quality Criterion for Methylene Chloride .... 8 4.0 Status of Stakeholder Consultations .......................................... 10 5.0 Recommendations ....................................................... 11 6. 0 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 7.0 Appendix: Agency-Specific Reviews of Air Quality Guidelines ...................... 15 7.1 Agency-Specific Summary: Federal Government ofthe United States ........... 15 7.2 Agency-Specific Summary: State ofCalifomia ............................ 18 7.3 Agency-Specific Summary: World Health Organization ..................... 22 7.4 Agency-Specific Summary: The Netherlands ............................. 24 7.5 Agency-Specific Summary: Swedish Institute of Environmental Medicine ........ 26 7.6 Agency-Specific Summary: New York State ............................. 28 7. 7 Agency-Specific Summary: State of Massachusetts ........................ 30 iii 1.0 Introduction Ontario's primary approach to regulating air emissions is based on achieving and maintaining air quality which is protective of human health and the environment. The Environmental Protection Act requires all stationary sources which emit or have the potential to emit a contaminant to obtain a Certificate of Approval which outlines the conditions under which the facility can operate. Compliance with air quality standards and guidelines is one of the criteria used to issue Certificates of Approval. Sources or potential sources of a contaminant are required to control emissions to ensure that the concentration of a contaminant specified by the standard is not exceeded at any point off their property. Dispersion modelling which incorporates detailed engineering calculations is used to relate emission rates from a source to resulting ambient concentrations of a particular contaminant. The Ministry of the Environment uses a combination of regulatory standards, ambient air quality criteria (AAQCs) and point-of-impingement (POI) guidelines in reviewing Certificates of Approval (MOEE, 1994a). Point of impingement standards are established under Regulation 346 and can be used directly as enforcement tools as the regulation specifies that a source cannot emit a contaminant at a level which would result in a standard being exceeded at its maximal point of impingement off its property (Section 5(3)). All sources are required to comply with Regulation 346 POI standards unless they are specifically exempted in regulation. As POI standards specified under Regulation 346 apply to all sources, socio-economic issues need to be taken into consideration in their development to ensure that the standards are technically feasible and there is a balance between the benefits and costs of improved ambient air quality. In addition to POI standards established under Regulation 346, the Ministry also has a larger number of ambient air quality criteria and point of impingement guidelines which are derived from AAQCs. These are used by the Ministry to assess general air quality and the potential for causing an adverse effect (MOEE 1994). Like POI standards specified in Regulation 346, point of impingement guidelines are also used in Certificates of Approval to approve new and modified emission sources. Once incorporated into a legal instrument like a Certificate of Approval, point of impingement guidelines are legally binding, however unlike Regulation 346 POI standards, they do not automatically apply to existing sources at the time they are promulgated. AAQCs are normally set at a level not expected to cause adverse human health or environmental effects based on continuous exposure. As such, socio-economic factors such as technical feasibility and costs are not explicitly considered when establishing such limits. Generally, point-of-impingement standards and guidelines which employ half-hour averaging times are set such that compliance with the standard or guideline will ensure that the Ambient Air Quality Criterion which is based on longer term averaging periods (e. g. 24-hours) will be met. In certain cases where the effect can occur over short-term exposures, like odours, the 24-hour 1 Ambient Air Quality Criterion and the half-hour point-of-impingement standard may have the same value. The Ontario Ministry of the Environment has identified the need to develop and/or update air guidelines/standards for priority toxic contaminants. The Ministry's Standards Plan which was released in October 1996, identified candidate substances for the development of air standards for the next several years. Methylene chloride was identified as a priority for review based both on its pattern of use in Ontario and recent toxicological information published since the existing standards were developed in 1988. This document provides the rationale for recommending revised AAQCs for methylene chloride. 2.0 Review and Evaluation 2.1 General Information Methylene chloride (CH Cl also known as dichloromethane, is a volatile, colourless liquid with 2 2), a mildly sweet odour. The odour threshold of methylene chloride ranges from 25 ppm to 150 ppm; at above 350 ppm, most people can detect the odour. This chemical readily vaporizes at ambient temperature. The Chemical Abstracts Service (CAS) identification number is 75-09-2, the Registry of Toxic Effects ofChemical Substances (RTECS) number is 805000 and the United Nations Hazardous Material number is 1593. At high concentrations in the workplace, methylene chloride has been observed to result in adverse effects on the nervous system, including dizziness, headache, irritability, numbness and tingling in the limbs; fatigue, stupor and rare reports of death due to anaesthesia. Eye and respiratory irritation and upset stomach have also been reported. At lower and chronic exposure, liver disease is the primary adverse effect reported. In addition, it has been reported that metabolism of methylene chloride within the human body results in the production of carbon monoxide, with a resulting increase in carboxyhemoglobin (COHb ), which can have an adverse effect associated with oxygen deficiency. Subchronic and chronic laboratory studies on rats have confirmed the observations in humans of liver effects and the increase in carboxyhemoglobin from exposure to methylene chloride. No adverse effects on development or reproduction were observed in studies on rats and mice (Environment Canada and Health Canada, 1993; ACGIH, 1991; CARB, 1989). According to the International Agency for Research on Cancer (!ARC; 1987) and the United States Environmental Protection Agency (U.S. EPA, 1997), the evidence from studies available in the workplace is inadequate to characterize methylene chloride as carcinogenic to humans. Exposure to rats and mice by inhalation increased the incidence of benign and malignant lung and liver tumours in mice and benign mammary tumours in rats. The evidence for carcinogenicity in laboratory animal studies was therefore considered sufficient for classifying methylene chloride as 2 a probable human carcinogen by both the International Agency for Research on Cancer (IARC Group 2B) and U.S. EPA (Group B2). 2.2 Sources and Levels Methylene chloride is widely used as an active chemical in paint removers, as a solvent for plastics, as a degreasing agent, in propellant mixtures for aerosol containers and as a blowing agent in foams. It is also used in photoresistant stripping operations, in film processing and as an extraction solvent for spice oleoresins and hops, for the removal of caffeine from coffee, and as pharmaceutical intermediates (ACGIH, 1991; Environment Canada and Health Canada, 1993). Methylene chloride is not manufactured in Canada. In 1995, of the 8500 tonnes imported (7,500 tonnes as a neat chemical, 600 tonnes in formulated products and 400 tonnes as recycled solvents) about 7 400 tonnes were used in Canada whereas about 1200 tonnes were exported. Environmental releases to the atmosphere were about 6300 tonnes or 85% of the total quantities used (Environment Canada and Health Canada, 1997). Based on the summary reports ofthe Canadian National Pollutants Release Inventory (NPRI), the total releases of methylene chloride in Canada had almost doubled from 1322 tonnes in 1993 to 2222 and 2207 tonnes in 1994 and 1995, respectively (NPRI 1993, 1994 & 1995). The total releases in Ontario showed a similar pattern. In 1993, 924 tonnes of methylene chloride were released, whereas this amount had increased to 1613 and 1610 tonnes in 1994 and 1995, respectively. The 1995 NPRI report listed 28 sources of atmospheric release of methylene chloride in Ontario. The vast majority of these releases were from foam and expanded plastics operations and pharmaceutical uses, a few covered such activities as adhesives and paint stripping uses, office furniture manufacturing and as industrial and household chemicals. An analysis of recent applications for Certificates of Approval in Ontario identified 56 facilities with emissions of methylene chloride covered by a Certificate. The majority ofthese approvals were for emissions from paint stripping and spray paint uses, foam and expanded plastics operations and pharmaceutical manufacturing. A few covered such uses as cleaning solvents, adhesives and in office furniture manufacturing. The median Ground Level Concentration predicted by Regulation 346 dispersion modelling for all 56 sources was approximately 61 )lglm 3 . The maximum and minimum were 72127 and 0.00049 11g/m3 respectively. Eleven sources had , predicted ground level concentrations above 500 11g/m 3 . Average 24-hour concentrations at Ontario sites ranged between 0. 7 11g/m 3 and 5.6 )lglm 3 over the period of 1989 to 1991. Maximum levels of methylene chloride measured in Ontario in 1991 ranged from 1.6 11g/m 3 at Walpole Island to 22.9 11g/m 3 at Hamilton. The three highest 24-hour average concentrations in Sarnia in 1996, as reported by the Lambton Industrial Society, ranged from 6.3 to 12.111g/m3 The highest annual average levels were observed in North York in 1989 . (3.41lg/m3 and in Hamilton in 1990 and 1991 (5.6 and 5.3 11g/m3 respectively) (MOEE, 1993). ) , 3 Across Canada, average methylene chloride levels range from 0.5 to 9.9 IJ.g/m3 The national . mean was 1. 7 and 2. 6 IJ.g/m 3 in two separate studies (Environment Canada and Health Canada, 1993). According to the Hazardous Substances Database (HSDB) (1996), in 1979, background concentrations in the Northern Hemisphere were reported to be 44 parts per trillion (0.16 IJ.g/m3 ) and in the Southern Hemisphere, 20 parts per trillion (0.07 IJ.g/m3 In the United States, in 1982, ). rural/remote areas were reported to be in the range of 45 parts per trillion (0.16 IJ.g/m3 ). Urban/suburban areas ranged from 414 to 12,000 parts per trillion (1.46- 42 11g/m3 with an ), average across 718 samples of 630 parts per trillion (2.2 1J.8Im 3 In source-dominated areas in the ). United States, concentrations ranged from 10 to 74000 parts per trillion (0.04- 261 IJ.g/m3 ). 2.3 Review of Existing Air Quality Regulations Agency-specific summaries of information concerning air quality guidelines for methylene chloride are presented in the Appendix of this report. A brief summary is presented in Table 1. 2.4 Development of Strategic Options for the Management of Methylene Chloride under the Canadian Environmental Protection Act (CEPA) Methylene chloride has been assessed as toxic under the Canadian Environmental Protection Act (CEP A). As such, Environment Canada is obliged to develop options to minimize the environmental release of this compound from all points in its life cycle in order to minimize exposure and the potential environmental and health risk. To develop management options for methylene chloride, Environment Canada has initiated a Strategic Options Process (SOP) to examine the options available for reducing the uses of this substance in the manufacturing of flexible foam, pharmaceuticals and adhesives as well as in paint stripping and some minor applications (CEP A, 1997). The SOP Issue Table is made up of representatives from government, industry and environmental non-governmental organizations. Issues being considered include the technical feasibility and cost of reducing methylene chloride usage in each sector and the benefits of such measures. Also considered are initiatives on-going in other jurisdictions such as the development ofNational Emission Standards for Hazardous Air Pollutants by the U.S. EPA. In a recent draft report members of the Issue Table agreed in principle to the following emission reduction targets for methylene chloride: • in aircraft paint stripping applications, a 50% reduction in annual emission by the year 2002 and 80% by 2006; the use of methylene chloride in consumer and commercial paint stripping applications and aerosols applications to be reduced by 20% ofthe 1995 levels; 4 Table 1. Summary of Existing Air Quality Guidelines1 for Methylene Chloride Agency, DateZ Guideline( s)3 Comments U.S. EPA (IRIS) no ambient air exposure limits are available 1997 20 flg/m3 (lifetime exposure) 1 * 1o ·5 additional cancer risk 2 flglm3 (lifetime exposure) 1 * 1o ·' additional cancer risk Both are based on a unit risk of 0.00000047 tumours/(flg/m 3) California 3500 flg/m3 (acute exposure) non-cancer acute exposure; inhalation 1993 reference exposure for non-cancer risks; 3000 flg/m3 (inhalation reference exposure level) (proposed REL based on effects on 300 flg/m3 (proposed chronic REL; OEHHA, 1997) cardiovascular and nervous systems) 10 flg/m3 (lifetime exposure) 1 * 10·5 additional cancer risk 1 flg/m3 (lifetime exposure) 1 * 1o ·' additional cancer risk Both are based on a unit risk ofO.OOOOOl tumours/(flg/m3) and risk levels of WHO 3000 flg/m3 (24-hour average) based on extrapolation from occupational 1987 exposure limits Netherlands 350000 flglm3 (maximum acceptable concentration) MAC is an occupational guideline; target 1987 20 flg/m3 (target value) based on risk assessment in Dutch 7.5 flglm3 (maximum emission concentration) Sweden4 350 flg/m3 (long-term average) safety factor of 5000 applied to LOEC 1993 from animal carcinogenicity tests New York 41000 flg/m3 (1-hour average) 1-hour average based on occupational 1990 exposure limits· 27 flg/m3 (annual average) 1 * 1o ~o additional cancer risk based on a unit risk of0.000000037 tumours/(flg/m 3) Massachusetts 9.45 flg/m3 (24-hour ceiling limit) 24-hour limit based on occupational 1990 exposure limit; 0.24 flg/m3 (allowable ambient limit) 1 * 1o ~o additional cancer risk based on a unit risk of0.0000041 tumours/(flg/m 3) Health Canada 2200 mg/m3 (Tumorigenic Concentration 05) 5% increase in incidence or mortality due to tum ours Ontario 5300 flg/m3 (half-hour point of impingement limit) point of impingement limiting effect and (current) 1765 flg/m3 (24-hour limit) AAQC limiting effect both based on 1988 health 1. Guidelines in this table can refer to: guidelines, risk-specific concentrations based on cancer potencies, and non-cancer-based reference concentrations. 2. Date here refers to when the health-based guideline background report or original legislative initiative was issued. The sources were the respective agency documents. 3. Using conditions of 1 atmosphere and l0°C, 1.0 flg/m3 = 0. 274 ppb. Various agencies use conversion factors based on a range ·c ·c. of temperatures, varying between 0 to 25 Depending on the selected temperature, conversion of units may vary slightly. 4. Proposed by the Swedish Institute of Environmental Medicine. 5 • a 50% reduction in the application in polyurethane foam blowing by the year 2002; a complete phase-out in use of methylene chloride as an auxiliary blowing agent is anticipated by 2007; • a 90% reduction in emissions from the pharmaceutical coating and chemical intermediates applications by the year 2002; • in adhesives application, a reduction of 70% in use in the formulated products by 2002; • in cleaning applications, if more than 10 tonnes are used annually, a 50% reduction by 2002; These reduction targets will be achieved through improved emission control, source substance substitution, consumer product labelling, improved work practice, restriction on import or development of regulations. If voluntary measures fail to achieve the reduction targets, Environment Canada has indicated that it will consider regulatory measures to mandate the reduction targets. 3.0 Development of an Ambient Air Quality Criterion for Ontario 3.1 Discussion of Regulatory Approaches for Methylene Chloride The development of ambient air standards and acceptable exposure limits for long-term exposure to methylene chloride in air is based on the avoidance of the non-carcinogenic injury to the liver and other organs as well as on the avoidance of cancer in the liver and the lung. The two approaches are examined separately. 3.1.1 Regulatory Approaches Based on Carcinogenicity Endpoint There is sufficient evidence to consider methylene chloride as an animal carcinogen. Liver and lung appear to be the main target organs for its carcinogenicity either by inhalation or ingestion route of exposure. Other organs affected include the mammary and salivary glands. Data from epidemiological studies do not provide consistent evidence of carcinogenicity in humans. However, increases of melanoma and cancers in buccal cavity and pharynx, liver and biliary passages, and breast have been observed in some cohort workers exposed to methylene chloride and other solvents (CEP A, 1993 ). All jurisdictions consider that methylene chloride is an animal carcinogen. In the U.S.A., carcinogenicity-based guidelines have been developed by jurisdictions where the federal and state governments mandate actions on the issue ofhuman carcinogenicity. Discussions on how most appropriately to employ some of the carcinogenicity-based approaches are ongoing. This is illustrated by the variety of reported unit risks. The CARB (1989) used the data on alveolar and/or bronchiolar adenomas or carcinomas of the lung in mice, observed in a NTP (1986) 6