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The Science Behind CARB Consumer Product VOC Regulations

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The Science Behind CARB Consumer Product VOC Regulations The Science Behind CARB Consumer Product VOC Regulations D. Douglas Fratz Senior Science Fellow & Aerosol Products Division Staff Executive October 20, 2015 PCPC Science Symposium and Expo 2015 Newark Liberty International Airport Marriott Newark, New Jersey Washington, DC ‐ USA Today’s Presentation • CARB Consumer Product VOC Regulations • Ozone Science Background • Scientific Defense of LVP Exemption • CARB‐Funded Research • Industry‐Funded Research • California Ozone SIP Revision • Future CARB Consumer Product Regulations Total Number of VOC Limits for Currently Regulated Consumer Product Category Groups Product Category CARB OTC EPA Group Regulation Model Rule National Regulation Automotive 20 16 3 Household 55 50 23 Personal Care 27 11 7 Institutional 16 13 0 Pest Management 11 9 4 Adhesives 18 14 4 Aerosol Coatings 39 36 36 TOTAL 186 149 77 * Consumer Product Regulation Statutory Requirements . California Clean Air Act requires ARB to regulate consumer products . Maximum feasible VOC reduction . Establish technologically and commercially feasible limits . Cannot eliminate a product form . Necessary to meet air standards . Must have adequate data 4 Consumer Product Surveys . Numerous past Consumer and Commercial Products Surveys . Survey Updates or Technical Assessments: For specific product categories Latest: 2010 Survey Update for Aerosol Coating and Aerosol Adhesive Products . 2013 – 2015 Consumer and Commercial Products Survey . Most Comprehensive Ever Conducted! 5 CARB Consumer Product Regulations Categories Statewide Emissions Control Measure Regulated Reductions Achieved VOC limits ~130 ~220 tons per day Toxic Air 55 Over 13 tons per day Contaminants* ~0.23 million metric Greenhouse gases 10 tons of carbon dioxide equivalents per year *Methylene Chloride, Perchloroethylene, Trichloroethylene, Para-dichlorobenzene 6 Federal & States Consumer Product VOC Regulations Current Non-Attainment States for 75 ppb Ozone Standard Chemistry of Tropospheric Ozone Formation EPA Ozone Standard History Original EPA Ozone Standard 0.12 ppm –1 Hour Average (124 ppb) Revised EPA Ozone Standard (1997) 0.08 ppm –8 Hour Average (84 ppb) Revised EPA Ozone Standard (2008) 0.075 ppm –8 Hour Average (75 ppb) Revised EPA Ozone Standard (2015) 0.070 ppm – 8 Hour Average (70 ppb) Note: Natural background levels can cause 60 ppb or higher ozone Ozone Precursor Sources • Major NOx Sources – Automobiles / Mobile – Power Plants – Other Combustion – Natural • Major VOC Sources – Natural – Automobiles / Mobile – Industrial and Commercial – Residential VOC Reactivity Factors Affecting Reactivity of a VOC . Kinetic Reactivity –KOH Value (how fast) . Mechanistic Reactivity (how much) . Radical Promotion or Inhibition (change other VOCs’ reactivity) . NOx Depletion (make the engine smaller) . Atmospheric Availability and Fate Maximum Incremental Reactivity of Major VOC Sources (2004) Emissions Source Categories MIR Aircraft, Trains, Boats 5.3 - 6.8 Off-Road and Farm Equipment 4.4 - 5.4 Trucks (Gasoline, Diesel) 3.8 – 5.5 Buses (Gasoline, Diesel) 3.7 – 5.5 Passenger Vehicles 3.7 Architectural & Industrial Coatings 1.9 Consumer Products 1.5 Consumer Products Industry 2007 SIP Remodeling Study Results • Minimal Ozone Impact from Consumer Product VOCs in 2023 • No Further CP VOC Reductions Needed – In South Coast Air Basin – Beyond 12% Proposed by CARB by 2014 – IF All Proposed NOx Reductions Are Made • Key Science Policy Implications: – Ozone Attainment in South Coast Can Only Occur Under NOx‐limited Conditions – Low‐Reactivity VOC Reductions Not Needed NOx vs. VOC Limited If NOx >> VOCs – VOC Limited – VOC Controls Lower Ozone – Many Urban Cores If NOx << VOCs – NOx Limited – NOx Controls Lower Ozone – Undeveloped Areas, Most of U.S. California VOC Emissions California NOx Emissions Defense of the LVP Exemption • Low Vapor Pressure Exemption (0.1 mm Hg at 20oC) Adopted in 1989 • Key Basis for All VOC Limits in Consumer Product Regulations in California and Elsewhere • South Coast Began Objecting to CARB LVP Exemption for Consumer Products in 2011 • Industry Formed Alliance for Responsible Regulation (ARR) ‐ a Broad Coalition to Defend LVP Exemption in 2012 • CARB Funding $600,000 in LVP Studies Started in 2013 • ARR Began Funding Parallel LVP/VOC Research in 2013 CARB‐Funded LVP Research • UC Davis Environmental Fate Modeling ($400K) – Fate for LVPs Emitted in Air or Water – Modeling Completed/ Draft Report in April 2015 – Comprehensive CSPA Critique of Draft Report in May 2015 – Significantly Revised Study Report in June 2015 – CARB Research Screening Committee Approved July 8, 2015 • UC Riverside Chamber Studies ($200K) – LVP Evaporation Studies/ Product Formulations – Chamber Photochemistry: Ozone and PM – CSPA Members Providing Formulations/Materials – Contract Ends September 2016 CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study CARB UC Davis Modeling Study Why Did Modeling Show LVPs Staying in Air? • LVPs Emitted in Vapor Phase Throughout 3D Airshed – Concentrations Below Saturation Levels – Minimal Interactions with Ground or Particles • No Rain, Ultra‐Low Moisture Content in Air/Surfaces • Wind Direction Constant from West to East – Unreacted LVPs Move to Desert to React Next Day • Assumed All Indoor Emissions Go to Ambient Outdoor Air • Therefore Tropospheric Photo‐Oxidation Was Primary Fate CARB UC Riverside Chamber Studies • LVP Evaporation Rates – Pure LVP Compounds – Formulated Products with LVPs • LVP Impacts on Ozone Formation • LVP Impacts on Secondary Organic Aerosol (SOA) (=PM2.5) Formation Pure LVP‐VOC Chamber Study Results Chemical name Volatility Ozone PM Stability Propylene Glycol Volatile ↑ ↑ L Diethylene Glycol Ethyl Ether (DEGEE) Volatile ↑ ↑ Y Diethylene Glycol Monobutyl Ether Y (butoxyethoxyethanol) Volatile ↓ ↑↑ n-Tridecane (C13) Volatile ↓ ↑ L Dimethyl Glutarate (DB-5) Volatile → ↑ Y Dipropylene glycol methyl ether acetate Volatile ↑ ↑ Y Benzyl alcohol Volatile ↓ ↑↑↑ Y Texanol Volatile → ↓ Y Diethylene Glycol Semivolatile ↑ ↑ Y n-Heptadecane (C17) Semivolatile → ↑↑↑↑ TBD Glyceryl triacetate Semivolatile → ↓ Y Methyl Palmitate Nonvolatile N/A N/A N/A Triethanolamine Nonvolatile →↑N/A Glycerol Nonvolatile N/A N/A N/A LVP‐VOC Pure Compound Evaporation (Dry) Weight Loss in Evaporation Chamber 0.4 Methyl Palmitate Glycerol Triethanolamine 0.3 Nonvolatile diethylene_glycol propylene_glycol Semivolatile DEGEE DEGBE Glyceryl triacetate n_tridecane 0.2 n_heptadecane Dimethyl_Glutarate Weight/g n‐Heptadecane Triethanolamine Glycerol methyl_palmitate Diethylene glycol texanol 0.1 Volatile glyceryl triacetate DPGMEA Benzyl alcohol 0.0 DEGEE 100 200 300 400 Day Ozone Formation from LVPs with Surrogate Target: 1.1ppmC surrogate + 16.7 ppb NO+ 8.3 ppb NO2 250 DEGEE Propylene Glycol DPGMEA Diethylene Glycol 200 Surrogate n‐Heptadecane 150 DEGBE Tridecane Benzyl alcohol DBE‐5 Texanol EPA1886(A)_DEGEE EPA1887(A)_Diethylene Glycol 100 EPA1888(A)_Proplyene Glycol EPA1891(A)_DEGBE EPA1892(A)_n-Tridecane Ozone concentration (ppb) Ozone concentration Glyceryl Triacetate EPA1893(A)_Triethanolamine EPA1894(A)_Surrogate EPA1910(A)_n-Heptadecane 50 EPA1911(A)_DBE-5 EPA1987(A)_Benzylalcohol EPA2023(A)_DPGMEA EPA2024(A)_Texanol EPA2025(A)_Glyceryl Triacetate 0 100 200 300 400 500 600 700 Irradiation time (min) SOA Formation from LVPs with Surrogate Target: 1.1ppmC surrogate + 16.7 ppb NO+ 8.3 ppb NO2 20 EPA1877(A) Proplyene glycol EPA1886(A) DEGEE EPA1887(A) Diethylene glycol EPA1891(A) DEGBE ) EPA1892(A) n-Tridecane 3 EPA1893(A) Triethanolamine /cm EPA1894(A) Surrogate 3 15 EPA1910(A) n-Heptadecane DEGEE EPA1911(A) DBE-5 EPA1987(A) benzyl alcohol EPA2023(A)_DPGMEA EPA2024(A)_Texanol EPA2025(A)_Glyceryl triacetate Tridecane 10 n‐Heptadecane Benzyl alcohol DEGBE DBE‐5 5 DPGMEA PM volume corredted concentration (µm concentration corredted volume PM Proplyene glycol SurrogateTriethanolamine Diethylene Glycol 0 Texanol 0 100 200 300 400 500 600 Irradiation time (min) Glyceryl triacetate Alliance for Responsible Regulation Formed to articulate the legal, technical and scientific reasons why regulatory proposals related to LVPs are flawed and could have devastating impacts on the consumer products industry. Facilitating the sharing of information, developing coordinated strategic advocacy efforts, coordinating legal and scientific review and analysis of the proposals and supporting documents by participating organizations as well as fundraising to support outside legal and scientific review. Completed ARR‐Funded LVP/VOC Research • SENES LVP/VOC Environmental Fate Modeling (2014) – 43 VOCs, 9 Exempted VOCs, 23 LVPs – Standard Model with Default Settings – LVPs and VOCs Partitioned Out: Air to Water, Soil or Sediment – Results Very Different from UC Davis Modeling • UC Riverside VOC Emissions Inventory Study (2015) – Current CARB VOC Emissions Inventory for CP&AC – 280 TPD – Current VOC Inventory: LVP‐VOCs are 35% of Coatings, 10% of Personal Care, and 17% of CSPA Products! – Chemical Properties Predict Alternative (Non‐Air) Fate Potential for Most VOCs/LVPs UCR Inventory Study Protocol • Obtained CARB VOC Emissions Inventory – Consumer Products and Architectural & Industrial Maintenance Coatings – Tonnage and Speciation Profiles; 2012 and 2020 • Divided Inventory into Four Industry Sectors
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