SAN JOAQUIN VALLEY UNIFIED AIR POLLUTION CONTROL DISTRICT

DRAFT STAFF REPORT

Draft Amendments to Rule 1020 (Definitions)

November 18, 2010

Prepared by: Sandra Lowe-Leseth, Air Quality Engineer Jaime Horio, Air Quality Specialist, Air Toxics

Reviewed by: Joe Nazareno, Senior Air Quality Engineer, Rule Development Ester Davila, Supervising Air Quality Specialist, Air Toxics George Heinen, P.E., Supervising Air Quality Engineer, Rule Development Errol Villegas, Program Manager, Strategies and Incentives

I. SUMMARY

The United States Environmental Protection Agency (EPA) and the California Air Resources Board (ARB) have classified the San Joaquin Valley Air Basin as extreme and severe non-attainment area for federal and state ozone standards, respectively. In accordance with federal Clean Air Act requirements for non-attainment areas, the District adopted the 2007 Ozone Plan to establish the strategy for attaining the federal eight-hour ozone standard. The strategy included reductions in oxides of nitrogen (NOx) and volatile organic compounds (VOCs) in order for the District to achieve attainment.

The purpose of this rule project is to add dimethyl and to the District’s list of exempt compounds within the definition of VOC as a response to EPA’s findings, effective February 2009, that and propylene carbonate have a low potential to form ozone in the atmosphere. The basis for the finding was that these compounds are less photo-chemically reactive than ethane and, thus, have negligible contribution to ozone formation. In making the change to Rule 1020, the VOC-limiting rules for operations like coating operations and cleaning would limit the emission of carbon-containing compounds to those compounds most likely for form ozone in the atmosphere.

SAN JOAQUIN VALLEY UNIFIED AIR POLLUTION CONTROL DISTRICT

Draft Staff Report: Rule 1020 (Definitions) November 18, 2010

II. CLIMATE CHANGE

The California Global Warming Solutions Act of 2006 (AB 32) created a comprehensive, multi-year program to reduce green house gas (GHG) emissions in California, with the goal of restoring emissions to 1990 levels by 2020. In the coming years, the ARB and the Legislature will be developing policies and programs to implement Assembly Bill 32 (AB 32). There are many win-win strategies that can reduce both GHG and criteria/toxic pollutant emissions. However, the District’s primary mission remains to achieve attainment with air quality standards to protect public health. Therefore, when situations that involve tradeoffs between GHG and criteria or toxic pollutants arise, the District will give precedence to reducing criteria or toxic pollutant emissions due to the more immediate public health concerns associated with such pollutants.

III. RULE DEVELOPMENT PROCESS

The draft amendments to Rule 1020 and the Draft Staff Report will be published and made available to affected sources and interested parties for their review and comments. Comments received from affected source operators, interested parties, ARB and EPA staff will be evaluated and, if appropriate, incorporated into the draft amendments to the rule. District staff intends to submit proposed rule amendments to the District Governing Board for consideration of adoption by the first quarter of 2011.

IV. BACKGROUND

Not all VOCs have equal potential to form ozone in the atmosphere. EPA has revised the definition of VOC several times to exclude organic compounds from the definition of VOC based on their negligible contribution to ozone formation. In adding a compound to the list of exempt compounds, EPA is encouraging its use as a replacement for other chemicals that are significantly more likely to contribute to ozone formation. Effective February 2009, EPA added dimethyl carbonate and propylene carbonate to the exempt compounds list on the basis that these compounds are less photo-chemically reactive than ethane and, thus, have negligible contribution to ozone formation. The EPA announced the delisting of these chemicals in the Federal Register, which is attached as Appendix A.

If a chemical can be replaced by one with a lower potential to form ozone, the amount of ozone formed in the atmosphere will be reduced. Because both dimethyl carbonate and propylene carbonate appear to be likely candidates to replace VOCs in a number of high-use products, District staff proposes amendments to Rule 1020 (Definitions) to add these dimethyl carbonate and propylene carbonate to the District’s list of exempt compounds.

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V. DRAFT AMENDMENTS TO RULE 1020

Section 3.53 of the rule defines VOC as well as listing compounds that are both organic and volatile but are considered by the District to have low ability to form ozone. The draft amendment would change the definition of VOC in Section 3.53 to add dimethyl carbonate and propylene carbonate to the list of exempt compounds. In exempting dimethyl carbonate and propylene carbonate, manufacturers of coatings or solvent cleaning materials have additional compounds with which to formulate low-VOC coatings and cleaning materials.

A. Dimethyl Carbonate (DMC)

1. General Information

Dimethyl carbonate is a colorless, fast-evaporating solvent with a substantial polar nature. It is expected to be effective in replacing esters, glycol ethers and ketones in formulations.

For some cleaning applications, dimethyl carbonate may be used to replace isopropyl although dimethyl carbonate is less polar than and therefore may not work as efficiently as isopropyl alcohol. In addition, dimethyl carbonate has solubility and other properties that might make it a replacement for trichloroethylene in solvent cleaning operations.

The flash point of dimethyl carbonate is higher than some already in wide- spread use like , , and methyl ethyl ketone (MEK), thus making dimethyl carbonate an attractive replacement in applications that use these solvents. By contrast, the flammability of dimethyl carbonate may limit its use in consumer coatings, indoor application coatings, and as a hand-wipe cleaning solvent.

2. Human Exposure to Dimethyl Carbonate

Dimethyl carbonate may replace some compounds such as xylene, , MEK and hexane which have been identified as toxic air contaminants by the ARB. Other possible compounds for substitutions are ethyl acetate and isopropyl alcohol. Base on the following information and the Risk Management Review detailed below, the exemption of dimethyl carbonate as a VOC is not expected to pose a significant health risk to Valley residents if substituted for a non-exempt VOC.

Given that strongest potential application of dimethyl carbonate is as a replacement in coatings or as a cleaning solvent, inhalation is expected to be the primary pathway of human exposure due to evaporation of the solvent. This exposure would be similar to any other paint, sealant and adhesive solvent that dimethyl carbonate would be intended to replace. There may also be some minor skin exposure from coatings

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splattering or careless mixing operations. Oral exposure would be rare and is limited to accidental ingestion.

Data from Kowa American, the manufacturer of this chemical, indicates that once dimethyl carbonate enters the body, it can be converted into and carbon dioxide. The Office of Environmental Health Hazard Assessment (OEHHA) has conducted an assessment of the health effects of exposure to dimethyl carbonate. No data were available in the peer-reviewed literature for chronic exposure of humans to dimethyl carbonate. However, one teratology study conducted by Exxon in 1992 indicates maternal and developmental toxicity on mice at high (3,000 ppmv) inhalation exposure level. No observed effects were reported at 1,000 ppmv exposure level. These results are consistent with the studies of the inhalation of methanol.

There are no data available on the chronic effects or carcinogenicity of dimethyl carbonate. Since so little toxicity information on dimethyl carbonate itself is available, the toxicity of methanol was used to develop a Reference Exposure Level (REL) for dimethyl carbonate. The OEHHA-proposed interim acute REL of 18, 000 mg/m3 and chronic REL of 5,500 mg/m3 are expected to be protective of anticipated adverse health effects, including the developmental toxicity observed in the Exxon study noted above. The OEHHA evaluation is attached as Appendix B.

No exposure guidelines have been established for dimethyl carbonate by the Occupational Safety and Health Agency (OSHA), the American Conference of Industrial Hygienists (ACGIH), or the National Institute for Occupational Safety and Health (NIOSH). However, Kowa American recommends an occupational exposure level of 200 ppmv over an 8-hour period based on the exposure limit established by OSHA and ACGIH for methanol, one of the chemicals to which the body converts dimethyl carbonate. This exposure level limit is in line with other solvents that dimethyl carbonate would replace.

2. Risk Management Review (RMR) of Dimethyl Carbonate

The District’s Technical Services performed a refined Health Risk Assessment for dimethyl carbonate. After reviewing the Health Risk Assessment conducted by South Coast Air Quality Management District (SCAQMD) for a similar rule amendment, a Health Risk Assessment was conducted using a typical coating operation release stack with an unobstructed flow, and a second run was performed with the same stack having a fixed-type rain cap added. Coating usage was based on four facility usage amounts, as found in the SCQAMD “Proposed Amended Rule 102 Final Staff Report.” Emissions of methanol from the SCAQMD Final Staff Report were input into the Health Risk Assessment, Emission Inventory, Air Quality Analysis, Risk Management Review and Toxics System (HEARTS) database. The Aermic model (AERMOD) was used, with the parameters outlined in Table 1 and meteorological data for 2005 through 2009 from each county within the District to determine the worst-case dispersion factors for a receptor grid. These dispersion factors served as input to the Hot Spots Analysis and

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Reporting Program (HARP) risk assessment module to calculate the chronic and acute hazard indices.

Table 1 - Analysis Parameters* Source Type Point Location Type Urban Stack Height (m) 7.16 Closest Receptor (m) 5 Stack Diameter. (m) 0.48 Type of Receptor Residential Stack Exit Velocity (m/s) 38.71/0.001 Max Hours per Year 8760 Without rain cap/With rain cap Stack Exit Temp. (°K) 293

The maximum risk score calculated was 0.03, which is well below the District’s significance threshold of 1.0. Therefore, the exemption of dimethyl carbonate as a VOC is not expected to pose a significant health risk to Valley residents if substituted for a non-exempt VOC. Results of the analysis are summarized in Table 2.

Table 2 - RMR Summary for Dimethyl Carbonate Point Source With Significance Point Source Categories Cap Threshold Maximum Acute Hazard Index 0.0161 0.0316 1.0 Maximum Chronic Hazard Index 0.00182 0.0102 1.0

B. Propylene Carbonate

1. General Information

Propylene carbonate is an odorless, non-viscous clear liquid with a low vapor pressure, and very slow evaporation rate. It is combustible, with flash point of 132 °C. The compound has been used in adhesives, paint strippers, and as a solvent for aerial pesticide application. Propylene carbonate is also used in more than 1,300 individual cosmetic products such as mascara, lip gloss, foundation, sunscreen, lip liner, deodorant, anti-aging and concealers. Other known applications of propylene carbonate include special purpose lubricant, general purpose degreasers for industrial use, rubberized coatings, and non-flat aerosol paint products. Propylene carbonate may also be used as tail solvent because of its slow evaporation rate, and in certain solvent cleaning applications.

2. Human Exposure to Propylene Carbonate

Propylene carbonate is not listed as a hazardous air pollutant under the Clean Air Act. It contains no chlorine or bromine and, therefore, it does not deplete the stratospheric ozone. Based on available data, propylene carbonate has low acute toxicity. However, prolonged contact with the skin as well as eye contact may cause irritation. No data is

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available on health effects caused by chronic exposure to the chemical. In addition, there is no established airborne occupational exposure limit for propylene carbonate.

3. Risk Management Review (RMR) of Propylene Carbonate

There is no health risk OEHHA-established Reference Exposure Level (REL) associated with propylene carbonate; therefore, no health risk assessment could be performed for this compound. However, because this compound has been approved for use in cosmetics like lip gloss, sun screen and deodorant, which are applied to the skin, it is anticipated that using this chemical in other applications will not pose a significant added risk to Valley residents.

C. Comparison of Currently Used Compounds and Draft Exempt Compounds

Table 3 summarizes the physical and chemical properties of the compounds dimethyl carbonate and propylene carbonate might replace.

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Table 3 – Comparison of Currently-Used Solvents, Dimethyl Carbonate and Propylene Carbonate Ethylene Isopropyl Methyl Methyl Ethyl Dimethyl Propylene Property Acetone Glycol Alcohol Acetate Ketone Carbonate Carbonate Colorless Clear Colorless Colorless Colorless clear Clear colorless Colorless clear Appearance clear colorless clear liquid clear liquid liquid liquid liquid liquid liquid Rubbing Sharp mint-like Odor Ethereal Odorless Fragrance like Pleasant odor Odorless alcohol odor Molecular HOCH2 C3H6O (CH3)2CHOH CH3COOCH3 CH3COCH2 CH3 (CH3)2CO3 C4H6O3 Formula CH2OH Molecular 58.08 62.07 60.09 74.08 g/mole 72.11 g/mole 90.08 g/mole 102.09 g/mol Weight g/mole g/mole g/mole Density 2 g/mL 2.14 g/mL 2.1 g/mL 2.8 g/mL 2.5 g/mL 1.07 g/mL 1.25 g/mL Boiling Point 56.2 °C 197.6 °C 82 °C 57 °C 80 °C 90 °C 242 °C Melting Point -95.35 °C -13 °C -89 °C -98.05 °C -86 °C 2 °C -49.2 °C 180 0.06 mmHg 44 mmHg 173 mmHg 78 mmHg 55 mmHg 0.02 mmHg Vapor Pressure mmHg @ @ 20 °C @ 25 °C @ 20 °C @ 20 °C @ 25 °C @ 20 °C 20 °C Solubility in Soluble Soluble Miscible Soluble Soluble Soluble 1-10% Water Easily soluble Miscible with Miscible with Not Slightly Not Solvent Solubility in methanol, most organic most organic Not available available soluble available diethyl ether solvents solvents NFPAA Flammability 3 1 3 3 3 3 1 Rating Lower Explosive 2.5% 3.2% 2.0% 3.1% 1.4% 4.2% 1.21% Limit Upper Explosive 12.8% 36% 12.7% 16% 11.4% 12.9% 5.35% Limit Flash Point -20 °C 111 °C 12 °C -10 °C -9 °C 18 °C 132 °C A National Fire Protection Agency B Based on methanol as surrogate C OEHHA/ARB Approved Risk Assessment Health Values

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Table 3 (continued) – Comparison of Currently-Used Solvents to Dimethyl Carbonate and Propylene Carbonate Ethylene Isopropyl Methyl Methyl Ethyl Dimethyl Propylene Property Acetone Glycol Alcohol Acetate Ketone Carbonate Carbonate 1,000 OSHA PEL D None 400 ppmv 200 ppmv 200 ppmv 200 ppmv B,C None ppmv Acute Inhalation None None 3,200 ug/m3 None 18,000 ug/m3 18,000 ug/m3B,C None REL Chronic None 400 ug/m3 7,000 ug/m3 None None 5,000 ug/m3B,C None Inhalation REL Carcinogenic No No No No No No No A National Fire Protection Agency B Based on methanol as surrogate C OEHHA/ARB Approved Risk Assessment Health Values D Permissible Exposure Level

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IV. BASELINE EMISSION INVENTORY AND EMISSION REDUCTION ESTIMATE

The current baseline emissions and emission reductions impact of exempting dimethyl carbonate and propylene carbonate is difficult to quantify at this time. While there is some interest by coatings manufacturers to replace current coatings solvents with either compound, it would be difficult to assess the amount of VOC-containing solvent ultimately replaced by dimethyl carbonate and propylene carbonate; therefore, estimates of the current baseline emissions and potential VOC emission reductions are not included in this rule project.

V. COSTS AND COST EFFECTIVENESS ANALYSIS

The California Health and Safety Code Section 40920.6(a) requires District staff to conduct a cost effectiveness analysis of available emission control options prior to adopting each Best Available Retrofit Control Technology (BARCT) rule. The analysis serves as a guideline for developing the control requirements of the rule.

At this time, District staff believes that there is no additional cost to users for using coatings or solvent cleaning blends that contain dimethyl carbonate or propylene carbonate, since use of these compounds is strictly voluntary. However, having more exempt compounds from which to choose allows the end-user flexibility by providing with additional options in meeting the District’s strict VOC requirements in other rules, particularly rules limiting the VOC content of coatings or cleaning solvent operations.

VI. SOCIOECONOMIC IMPACT ANALYSIS

Pursuant to California Health and Safety Code Section 40728.5, “whenever a district intends to propose the adoption, amendment, or repeal of a rule or regulation that will significantly affect air quality or emissions limitations, that agency shall, to the extent data is available, perform an assessment of the socioeconomic impacts of the adoption, amendment, or repeal of the rule or regulation.” Staff has determined that a socioeconomic impact analysis is not needed because these amendments do not establish emission limitations and because these compounds have negligible reactivity and their exemption will not significantly affect air quality.

VII. ENVIRONMENTAL IMPACTS

Pursuant to the California Environmental Quality Act (CEQA), District staff has reviewed the possible environmental impacts of adding dimethyl carbonate and propylene carbonate to the exempt compounds list, contained in District Rule 1020 (Definitions). As presented in this Staff Report, the United States Environmental Protection Agency considers these chemicals to be non-volatile organic compounds; these chemicals are

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already in use in California in cosmetics and other products; and, while manufacturers and other businesses may choose to reformulate existing products, the amendments establish no requirement to do so. Although quantification of potential use of these compounds is too speculative, it is reasonable to conclude that substitution of non- volatile compounds for certain volatile organic compounds would have positive impacts on air quality within the San Joaquin Valley and would not have a cumulatively significant impact on global climate change.

District staff concludes that there is no substantial evidence in the whole record before the District that the proposed amendments to Rule 1020 would cause any adverse effects on the environment. The District finds that the project is exempt per the general rule that CEQA applies only to projects which have the potential for causing a significant effect on the environment (CEQA Guidelines §15061(b)(3)). For these reasons, staff is proposing to file a Notice of Exemption upon Board adoption of the proposed amendments to Rule 1020.

VIII. RULE CONSISTENCY ANALYSIS

Under California Health and Safety Code Section 40727.2, before adopting, amending, or repealing a rule or regulation, an air district must identify and evaluate any existing federal rules or rules within that air district that apply to the same equipment or source type. Elements of review include work practice, reporting, and recordkeeping requirements. Because the draft amendments to Rule 1020 do not target a specific emission source, it has been determined that requirement for rule consistency analysis does not apply to this rule project.

IX. REFERENCES

1. Environmental Protection Agency, Federal Register, Volume 74 pages 3437 – 3441; Air Quality: Revision to Definition of Volatile Organic Compounds-- Exclusion of Propylene Carbonate and Dimethyl Carbonate January 21, 2009.

2. South Coast Air Quality Management District, Final Staff Report for Proposed Amended Rule 102 - Definition of Terms September 2009.

3. Sacramento Metropolitan Air Quality Management District, Staff Report - Rule 101 – General Provisions and Definitions August 17, 2010.

4. Office of Environmental Health Hazard Assessment, Revised Health Risk Assessment for Dimethyl Carbonate December 8, 2009.

5. San Joaquin Valley Air Pollution Control District Risk Management Review for Dimethyl Carbonate August 5, 2010.

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