1 RATIONALE FOR THE DEVELOPMENT OF ONTARIO AIR STANDARDS FOR ACRYLONITRILE 1 February 2000 Standards Development Branch Ontario Ministry of the Environment Ontario CE 1 Copyright Provisions and Restrictions on Copying: This Ontario Ministry of the Environment work is protected by Crown copyright (unless otherwise indicated), which is held by the Queen's Printer for Ontario. It may be reproduced for non-commercial purposes if credit is given and Crown copyright is acknowledged. It may not be reproduced, in all or in part, for any commercial purpose except under a licence from the Queen's Printer for Ontario. For information on reproducing Government of Ontario works, please contact ServiceOntario Publications at copyright aontario.ca 1 Executive Summary The Ontario Ministry of the Environment (MOE) 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 and revised in October, 1999, identified candidate substances for which current air standards will be reviewed over the next several years. Acrylonitrile was identified as a priority compound for review based on its pattern of use in Ontario and recent toxicological information that was published subsequent to the development of the existing guideline in 1985. A review of the scientific and technical information relevant to setting an ambient air quality standard for acrylonitrile has previously been provided to stakeholders for their comments. This document provides the rationale for recommending Ambient Air Quality Criteria (AAQC) and a half-hour point of impingement (POI) standard for acrylonitrile. Acrylonitrile is a colourless liquid with a faintly sweet and pungent odour. It is widely used as a chemical intermediate in a variety of industrial and commercial products and processes. Acrylonitrile does not occur naturally in the environment. It is produced industrially on a large scale and is emitted in large amounts in the form of vapours, and in aqueous effluents from facilities producing and using the chemical. Acrylonitrile is used as a raw material in the manufacturing of acrylic and modacrylic fibres, and in the production of plastics, and styrene-acrylonitrile, nitrile rubbers, nitrile barrier resins, adiponitrile, and acrylamide. Acrylonitrile is not currently produced in Canada and is only used in the manufacturing of other products. According to occupational exposure and emission data, there appears to be greater exposure to humans and the environment from the use of acrylonitrile in end-user plants (3,000 to 20,000 compared to production facilities (100 to 4,000 µg/m3). Similarly, acrylonitrile levels around user plants are greater than around producing plants. The majority of acrylonitrile emitted is released into the air. According to the data reported in the National Pollutant Release Inventory (NPRI) of Environment Canada, one facility is responsible for nearly all releases in Ontario. The total reported atmospheric releases in Ontario for the years of 1993, 1994, 1995, 1996 and 1997, were 16.6, 17.6, 14.2, 8.9 and 5.2 tonnes, respectively. Acrylonitrile is not routinely monitored in Canada, however, ambient air monitoring results from the MOE Air Quality Study in Windsor indicates that acrylonitriie levels were below the detection limits which ranged from 0.21 to 0.64 ggW. Humans can be exposed to acrylonitrile through air, water and food. It is absorbed by the body through inhalation, oral, and to some extent dermal routes. The reported odour detection thresholds range from 8,000 to 50,000 ggld. Exposure to acrylonitrile at concentrations of 7 to 45 pg/rrr for 20 to 45 minutes leads to irritation of the mucous membranes, nausea, headaches and nervous irritability. Individuals also experience low grade anaemia, leukocytosis, kidney irritation and mild jaundice, i however, these effects subside when the exposure to acrylonitrile is terminated. Results have shown that children are more sensitive than adults. Acrylonitrile is classified as a probable human carcinogen (class B 1) by the United States Environmental Protection Agency (US EPA). This is based upon the observation of a statistically significant increase of lung cancer in humans and astrocytomas (cancer of non-neuron supportive cells) in the brain of rats. The International Agency for Research in Cancer (IARC) has classified acrylonitrile as a probable human carcinogen (group 2A) on the basis of sufficient evidence of carcinogenicity for animals, and limited evidence for humans. Data from animal carcinogenicity studies indicated a significant dose-dependent increase in cancer incidence, and may provide support to the carcinogenicity in humans. Genetic toxicology studies showed acrylonitrile induced gene mutations in bacteria, yeast, and mammalian cells, sister chromatid exchange in mammalian cells, and cell transformation of three different cell types. On the basis of these results, acrylonitrile is considered a non-threshold carcinogen. The Toxicology Excellence for Risk Assessment (TERA) has recommended that the carcinogenicity of acrylonitrile in humans be reviewed based on more recent data. Under the CEPA (Canadian Environmental Protection Act), Environment Canada and Health Canada have recently completed a health and environmental assessment for acrylonitrile and consider that this compound is toxic and carcinogenic to humans. The US EPA has established an inhalation cancer unit risk for lifetime exposure to acrylonitrile of 6.8 x 10-5 per (pg/m'). That is, for a lifetime exposure to this chemical, at an ambient air concentration of 0.01 pg/m3, the probability of a cancer incidence is one in a million. Agencies, such as New Jersey, Massachusetts, Michigan and New York, have adopted the assessment and unit risk estimate from the US EPA to derive their long-term guidelines. California developed its own cancer unit risk estimate which resulted in a more conservative guideline. The WHO established its cancer unit risk estimate based on the same epidemiological study used by the US EPA but employed a different method of calculation which resulted in a unit risk of 2 x 10'5 per (pgln'). Environment Canada and Health Canada have derived a tumourigenic concentration at 5% increase in tumour incidence (TC05) of 6 mg/m', based on data in female rats. In addition, several states have adopted the US EPA Chronic (non-cancer) Reference Concentration (RfC) of 2 pg/m' as a benchmark for shorter averaging periods. The current AAQC for acry lonitrile in Ontario is 100 µg/m' for a 24-hour averaging time. The half-hour POI guideline is 300 pg/rnr'. Both criteria were established based on the protection of human health. In revising the air quality standards for Ontario, the Ministry of the Environment is reviewing and considering risk assessments, standards, and guidelines used by environmental agencies world-wide. This report reviews the scientific basis for air quality guidelines and standards developed by the US EPA, the States of California, New York, New Jersey and Michigan, the Commonwealth of Massachusetts, the World Health Organization, the Netherlands, the Swedish Institute of Environmental Medicine and the Canadian Federal Government. Of the criteria reviewed from other agencies, the Ministry has evaluated and accepts the scientific rationale and risk assessment employed by Environment Canada and Health Canada to develop their TC05 value of 6 mg/d. The application of margin of safety factors of 5,000 and 50,000 to the TC05 produces risk concentrations of 1.2 and 0.12 gg/m', representing excess cancer risk of 1 in 100,000 and I in 1,000,000, respectively. The Ministry proposes to derive an annual AAQC based on the risk specific concentration of 0.12 µg/rn'. In summary, based on the information reviewed from leading agencies and the assessment of toxicological information, the Ministry is proposing the following Ambient Air Quality Criteria for acrylonitrile: an annual average AAQC of 0.12 pg/m' (micrograms per cubic metre of air) for acrylonitrile based on the carcinogenic effect of this compound; and, a 24-hour average AAQC of 0.6 pg/m' (micrograms per cubic metre of air) for acrylonitrile based on the carcinogenic effect of this compound. Based on supporting science and dispersion modelling, a half-hour POI standard of 1.8 pg/m' can be derived. However, considering the magnitude of the reduction from the current guideline of 300 µgJm' to this revised level of 1.8 pg/m', meeting this proposed POI standard immediately may not be possible due to implementation issues related to economic/technical feasibility and the required timeframe to establish appropriate emission control technology. In light of these potential concerns, the Ministry is proposing to determine an interim POI standard from the following range of values: 1.8 gg/m' to 180 pg/m' (micrograms per cubic metre of air) for acrylonitrile; these concentrations are equivalent to risk levels of 1 excess cancer in a population of 1,000,000 (10-6) over a lifetime up to I excess cancer in a population of 10,000 (10') over a lifetime, respectively. The proposed final POI standard will be the lower number of the range from which the interim standard is selected. The establishment of an interim standard is considered an initial step in a scheduled reduction process over an achievable timeframe to the final standard. Details of the reduction process will be discussed with stakeholders as a part of a detailed risk management plan. The interim standard will constitute the POI standard in force until such time it is revised through the risk management process. 1 III UI Table of Contents ............................................................. Executive Summary i 1.0 Introduction ...............................................................1 2.0 Generallnformation ................................................................................................... 3 2.1 Physical and Chemical Properties 3 2.2 Uses ...............................................................4 2.3 Sources and Levels ....................................................4 2.4 Environmental Fate ....................................................5 ..................................................... 3.0 Toxicology of Acrylonitr.il.e. ..................................................... 5 3.1 Acute Toxicity 6 .......................................... 1 3.2 Subchronic and Chronic Toxicity 7 ................................... 3.3 Developmental and Reproductive Toxicity 7 .........................................................7 3.4 Genotoxicity ........................................................ 3.5 Carcinogenicit 8 ................................................. 3.6 Environmental Effects 12 I ................................................... 4.0 Existing Air Quality Criteria 13 ..........................................................13 4.1 Overview ........................................... 4.2 Evaluation of Existing Criteria 16 ................................. 5.0 Responses of Stakeholders to the Information Draft 21 ................. 6.0 Overview of the Next Phase of the Ministry's Standards Setting Process 21 .............. 7.0 Considerations in the Development of Air Quality Standards for Acrylonitrile 22 ..........................................................23 8.0 Recommendations ................................ 9.0 A Guide for Stakeholders Responding to this Posting 24 ..............................................................28 11 10.0 References ........................ 11.0 Appendix: Agency-Specific Reviews of Air Quality Guidelines 36 ............. 11.1 Agency-Specific Summary: Federal Govemmen.t .o.f. t.h.e .U.n.i.te.d. .S.ta.t.es. ............. 36 11.2 Agency-Specific Summary: State ofCalifomia 40 iv 1 .......................... 11.3 Agency-Specific Summary: State of Massachusetts 43 .............................. 11.4 Agency-Specific Summary: State of Michigan 46 ............................ 11.5 Agency-Specific Summary: State of New Jersey 48 ............................. 11.6 Agency-Specific Summary: State of New York 50 ................. 11.7 Agency-Specific Summary: World Health Organization (WHO) 52 ............................... 11.8 Agency-Specific Summary: The Netherlands 55 .......... 11.9 Agency-Specific Summary: Swedish Institute of Environmental Medicine 58 ............ 11.10 Agency-Specific Summary: Federal Government of Canada (CEPA) 59 ........................................ 12.0 Acronyms, Abbreviations and Definitions 62 1 v t 1.0 Introduction 1 Ontario regulates air emissions in order to achieve and maintain air quality which is protective of human health and the environment. The Env=ironmental Protection Act (Section 9) requires that all stationary sources that emit, or have the potential to emit, a contaminant obtain a Certificate of Approval which outlines the conditions under which the facility can operate. The Ministry of the Environment uses a combination of regulated point of impingement (POI) standards 1 and point of impingement guidelines in reviewing Certificates of Approval (MOEE, 1994a), each of which is derived by mathematical scaling, from an ambient air quality criterion (AAQC). Ambient Air Quality Criterion (AAQCs) represent human health or environmental effect-based values, and are normally set at a level not expected to cause adverse effects based on continuous exposure. As such, economic factors, such as technical feasibility and costs, are not explicitly considered when establishing AAQCs. Point of impingement standards are scheduled in Regulation 346 and can be used directly as enforcement tools. The regulation (Section 5(3)) specifies that a source cannot, "cause or permit the concentration of a contaminant at a point of impingement to exceed the standard prescribed in Schedule I". All sources are required to comply with the standards in Regulation 346 unless they are specifically exempt. The concentration of a contaminant at a POI may be calculated in accordance with the Appendix of Regulation 346 (Air Dispersion Models). Since POI standards specified under Regulation 346 apply to all sources, economic issues need to be taken into account in their development to ensure that the standards are technically feasible, and that both the benefits and costs of improved ambient air quality are assessed. In addition to POI standards established under Regulation 346, the Ministry also has a large number of POI guidelines. These are used by the Ministry to assess general air quality, and the potential for causing adverse effect (MOEE, 1994a). Like the POI standards specified in Regulation 346, POI guidelines are used in reviewing applications for Certificates of Approval, to approve new and modified emission sources. Once incorporated into a legal instrument such as a Certificate of Approval, POI guidelines are legally binding. However, unlike POI standards in Regulation 346, they do not automatically apply to existing sources at the time they are approved. In assessing the available information for a substance, when the Ministry believes that meeting the proposed standard immediately will not be possible due to implementation issues related to economics, technical feasibility and the time needed to establish appropriate control technology, the Ministry will propose a range of values within which an interim standard will be set. This range of values is based on the following considerations: I 1 For carcinogens, the interim standard will be set within a range of air concentrations which corresponds to a risk level of excess cancer in a population of 1,000,000 (10") over a 1 lifetime up to, but no higher than, excess cancer in a population of 10,000 (10') over a 1 lifetime and; 1 For non-carcinogens, the range under consideration for the interim standard is from the proposed POI standard up to 10 times this proposed standard. In cases where the reduction in the standard for a non-carcinogen is less than 10-fold overall, the upper end of the range for the interim standard is selected at a value which at least 90% of facilities in Ontario are anticipated to be able to presently meet based on MOE's records of emissions and modelled ground level t concentrations. The interim standard which is ultimately selected will be considered a first step in a ramping down process to a final standard. The final POI standard will be the lower number of the range from which the interim standard is selected. The ramping down characteristics, including an appropriate timeframe, will be discussed with stakeholders as part of the detailed risk management phase which will be undertaken by the Ministry subsequent to this posting. An interim standard will constitute the POI standard in force until such time it is revised through the risk management process. The Ontario Ministry of the Environment has identified the need to develop and/or update air guide ines/standards for priority toxic contaminants. The Ministry's Standards Plan, which was I released in October, 1996 and revised in October, 1999 (MOEE, 1996; MOE, 1999), identified 70 high priority substances for which current air standards will be reviewed, over the next several years. Factors used by the Ministry to determine which contaminants require priority include potential degree of exposure, volume of use, toxicity, Federal/Provincial commitments and sensitive sub-populations, including children. All high priority substances will be standards (as opposed to guidelines) and will be in Schedule I of Regulation 346. In March 1998, following the 1996 initiative, the Ministry proposed a multi-step process for developing air quality standards (MOE, 1998). As an initial step, risk assessment and risk management information, relevant to establishing a standard for a particular compound, was documented and made available for stakeholder review. This provided stakeholders with the opportunity to critically review the information and provide any additional information they felt should be considered by the Ministry in setting an air quality standard for a particular compound. Acrylonitrile was identified as a priority for review based on its pattern of use in Ontario, and recent J toxicological information that has been published subsequent to the development of the existing guideline in 1985. A review of scientific and technical information relevant to setting an ambient air quality standard for acrylonitrile had been provided in a previous document, and was distributed to stakeholders for their comments. This document therefore provides the rationale for recommending AAQC and a POI standard for acrylonitrile. 2 2.0 General Information 2.1 Physical and Chemical Properties Acrylonitrile is a volatile, flammable, colourless liquid with a faintly sweet, yet, pungent odour. The following list provides some of its properties: CAS # 39447 RTECS # AT5250000 UN # UN 1093 Conversion Factors ppm = 2.17 mg/m3 at 25 °C 1 Boiling Point 77.3 °C F1 Melting Point -82 °C Henry's Law Constant 8.8x 105 atm-m'/mol Flash Point 0 °C Density 0.806 at 20 °C Water Solubility 73,500 mg/L Log Kow -0.07 CAN Formula Molecular Weight 53.1 g/mol Vapour Density (air = 1) 1.9 Vapour Pressure 100 mmHg at 23 °C Common Synonyms acrylic acid nitrile, acrylon, carbacryl, cyanoethylene, 2-propenenitrile, vinyl cyanide The odour detection threshold, as reported by the American Industrial Hygiene Association (AIHA) is 1.6 ppm (3400 pg/m ; this is also the geometric mean of air odour threshold). Similarly, the American Conference of Government Industrial Hygienists (ACGIH) states an odour threshold of is 9,700 pg/rn. The Quebec Workplace Health and Safety Commission is in general agreement with the ACGIH, listing an odour detection limit at 8,000 vg/m' (CSST, 1997). The odour detection threshold for acrylonitrile in air has been reported to be as high as 47,000 pg/rrr' (Verschueren, 1983). The odour recognition thresholds have been reported to range from 3,700 to 50,000 pg/m' (Cheminfo, 1996). 3