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 – Coatings Products – Adhesive Products – Personal Care Products – Misc. Specialty Products (Home, Auto, I&I, etc.) • Tabulated Thermodynamic Properties Data for Each Species • Identified Potential Alternative Fates by Product Uses • Assessed Potential Inventory Tonnages with Non‐Air Fates • Identified Potential Further Research to Assess Fate and Availability Current CARB VOC Emissions Inventory

Current (2012) Estimate Projected (2020) Estimate Major Sector (tons/day) (tons/day)

Coatings 105.6 98.5

Adhesives 8.1 12.4

Personal Care Products 58.8 71.6

Misc. Specialty Products 110.1 106.8

Totals 282.6 289.3 Largest Personal Product Categories in CARB VOC Emissions Inventory

• Hair Sprays • Personal Fragrance Products • Rubbing Alcohol • Deodorant Body Sprays • Other Personal Care Products • Hand Sanitizer Likelihood of Alternative Fates

Down‐the‐ Solid‐ Polymer‐film‐ Waste Sector Combustion drain waste coating Solvent

Coatings VU U VL VL L

Adhesives VU VU L VL VU

Personal Care VU VL L VU VU Products

Misc. Specialty LVLLLL Products

VU: Very unlikely; U: unlikely; P: possible; L: likely; and VL: very likely”. Assignments are based on our understanding of the consumer product use and application method. Key Thermodynamic Properties

• Vapor Pressure (Pvap)

• Octanol‐Water Partitioning Parameter (KOW)

• Henry’s Law Coefficient (KH) • Saturation Concentration (C*)

– C*= 1/Gas‐Particle Partitioning Constant (Kp) Mass Fraction of Compounds (Pvap)

Category 2020 tpd Pvap < 0.01 Pvap < 0.1 Pvap > 0.1 Unspeciated Coatings 98.5 0.114 0.236 0.418 0.344

Adhesives 12.4 0.001 0.012 0.774 0.214

Personal Care 71.6 0.046 0.065 0.601 0.334 Products

Misc. Specialty 106.8 0.083 0.089 0.672 0.239 Products Examples of Compounds (Pvap)

Category Pvap < 0.01 Pvap < 0.1 Pvap > 0.1 Texanol ethylene glycol propane propylene glycol xylenes Coatings diethylene glycol monobutyl ether toluene volatile methyl siloxanes

methyl ethyl ketone n‐butyl acetate Adhesives dimethyl ether hexane n‐heptadecane n‐hexadecane ethyl alcohol isopropyl alcohol Personal n‐icosane propylene glycol n‐pentacosane isobutane Care dimethyl ether n‐triacontane Products volatile methyl siloxanes glycerol

n‐heptadecane n‐hexadecane ethyl alcohol Misc. isobutane Specialty ethylene glycol monobutyl ether Products isopropyl alcohol Mass Fraction of Compounds (Kow)

Category 2020 tpd Log(Kow) < ‐1Log(Kow) < 1Log(Kow) > 1 Unspeciated

Coatings 98.5 0.102 0.233 0.367 0.394

Adhesives 12.4 0.004 0.242 0.514 0.244

Personal Care 71.6 0.003 0.529 0.145 0.326 Products

Misc. Specialty 106.8 0.015 0.254 0.394 0.352 Products Examples of Compounds (Kow)

Category Log(Kow) < ‐1Log(Kow) < 1Log(Kow) > 1 ethylene glycol propylene glycol Texanol diethylene glycol monobutyl ether propane Coatings xylenes volatile methyl siloxanes

methyl ethyl ketone n‐butyl acetate Adhesives dimethyl ether hexane tetrahydrofuran 2‐methylpentane

Personal ethyl alcohol Isobutane n‐heptadecane Care glycerol isopropyl alcohol n‐hexadecane Products dimethyl ether volatile methyl siloxanes

ethyl alcohol isobutane Misc. ethylene glycol monobutyl ether propane Specialty isopropyl alcohol n‐butane Products n‐dodecane Mass Fraction of Compounds (C*)

Category 2020 tpd C* < 10 C* < 5382 C* < 538200 C* > 538200 Unspeciated

Coatings 98.5 0.000 0.000 0.282 0.369 0.349

Adhesives 12.4 0.000 0.000 0.003 0.774 0.222

Personal Care 71.6 0.000 0.018 0.024 0.596 0.362 Products

MISC 106.8 0.000 0.009 0.019 0.667 0.305 Examples of Compounds (C*)

Category C* < 10 C* < 5382 C* < 538200 C* > 538200

propane Texanol xylenes ethylene glycol toluene Coatings propylene glycol n‐butane diethylene glycol monobutyl ether n‐undecane propylene carbonate volatile methyl siloxanes

methyl ethyl ketone n‐butyl acetate Adhesives dimethyl ether hexane

n‐heptadecane ethyl alcohol Personal n‐hexadecane isopropyl alcohol n‐pentacosane isobutane Care n‐triacontane propylene glycol n‐icosane dimethyl ether Products n‐pentadecane propane alpha‐terpineol volatile methyl siloxanes

n‐heptadecane ethyl alcohol n‐hexadecane isobutane n‐pentacosane n‐pentadecane ethylene glycol monobutyl MISC n‐triacontane n‐icosane ethylene glycol ether propylene glycol isopropyl alcohol diethylene glycol butyl ether propane Mass Fraction of Compounds (KH)

‐8 ‐4 ‐4 Category 2020 tpd KH < 10 KH < 10 KH>10 Unspeciated

0.031 0.384 0.274 0.342 Coatings 98.5

Adhesives 12.4 0.021 0.261 0.525 0.214

Personal Care 71.6 0.001 0.514 0.161 0.324 Products

MISC 106.8 0.004 0.279 0.453 0.268 Examples of Compounds (KH) ‐8 ‐4 ‐4 Category KH < 10 KH < 10 KH>10 Diethylene glycol monobutyl ether Texanol Propane ethylene glycol toluene propylene glycol n‐butane xylenes n‐decane Coatings ethylene glycol monobutyl ether n‐undecane n‐octane xylenes volatile methyl siloxanes n‐butyl acetate dimethyl ether methyl ethyl ketone hexane Adhesives cyclohexanone tetrahydrofuran 2‐methylpentane propane cyclohexane diethylene glycol monobutyl Isobutane ether ethyl alcohol n‐heptadecane Personal Care diethylene glycol monomethyl isopropyl alcohol n‐hexadecane Products ether propylene glycol propane n‐butyl alcohol glycerol n‐butane volatile methyl siloxanes Isobutane diethylene glycol monobutyl ether ethyl alcohol propane amino methyl propanol ethylene glycol monobutyl ether n‐butane propylene glycol methyl ether isopropyl alcohol MISC n‐dodecane diethylene glycol monomethyl propylene glycol n‐octane ether ethanolamine n‐decane triethanolamine methanol n‐undecane Top VOCs/LVPs for Personal Care

vap P (torr, KH (atm‐ Aqueous Molecula C* CAS Species Types tpd logKow MP °C BP °C 25 °C)** m3/mole) solubility (mg/l) r Weight (ug/m3)MIR 64‐17‐5 ethyl alcohol 28.225 ‐0.31 ‐114.1 78.2 59.3 5.00E‐06 295905 46.1 1.47E+08 1.53 67‐63‐0 isopropyl alcohol 7.993 0.05 ‐89.5 82.3 45.4 7.90E‐06 1000000 60.1 1.47E+08 0.61 75‐28‐5 Isobutane 2.950 2.76 ‐138.3 ‐11.7 2611 1.19E+00 Insoluble 58.1 8.17E+09 1.23 Fragrances 2.078 MMMM M M M M M 629‐78‐7 n‐heptadecane 1.599 8.69 22.0 302.0 0.00324 3.49 Insoluble 240.47 4.19E+04 8.69 35% @21.1ºC, dimethyl ether 1.063 0.1 ‐141.5 ‐25 4450 7.63E‐03 46.1 1.10E+10 0.81 115‐10‐6 7% @17.8ºC 544‐76‐3 n‐hexadecane 1.044 8.20 18.00 287 1.43e‐3 4.73E‐01 Insoluble 226.44 1.74E+04 0.45 volatile methyl siloxanes 0.816 (vms) (assume 1/3 D4 0.272 6.49 17.7 175 0.99 12.0 0.056 296.62 1.04E+08 ‐0.056 1/3 D5 0.272 7.26 ‐38 211 0.25 33.0 0.017 370.77 1.60E+08 ‐0.068 1/3 D6) 0.272 8.03 ‐3 245 0.035 24.7 0.00513 444.92 1.74 E+08 ‐0.06*** other, lumped vocs, individually < 2% of 0.780 MMMM M M M M M category 74‐98‐6 propane 0.621 2.36 ‐187.7 ‐42.1 7152 7.07E‐01 Insoluble 44.1 1.70E+10 0.49 106‐97‐8 n‐butane 0.565 2.745 −138 −0.5 1820 9.50E‐01 61 58.1 5.70E+09 1.15 112‐95‐8 n‐icosane 0.556 10.16 36.00 220 4.62E‐06 1.23E+01 0.00 282.55 7.03E+01 N/A 629‐99‐2 n‐pentacosane 0.556 12.62 53.50 259 1.51E‐06 1.54E+02 2.90 352.68 2.87E+01 N/A 638‐68‐6 n‐triacontane 0.556 15.07 66 455 2.73E‐11 3.65E+03 Insoluble 422.81 6.21E‐04 N/A 57‐55‐6 propylene glycol 0.330 ‐0.921 ‐60 187.6 0.129 1.70E‐07 1000000 76.1 5.29E+05 2.58 78‐78‐4 isopentane 0.251 2.72 ‐160 30 6.89E+02 1.40E+00 48 72.2 2.68E+09 1.45 56‐81‐5 glycerol 0.137 ‐1.76 18 290 1.68 E‐04 1.73E‐08 1000000 92.1 1.15E+08 3.15 ARR LVP/VOC Research Plan Additional Studies in Planning

• Chamber Studies or Modeling of Indoor Fates – Down the Drain or Solid Waste Fates • South Coast Ambient Air Speciation Studies to Evaluate Accuracy of Modeling • Air Quality Modeling of Ozone or PM2.5 Impacts for Consumer Product LVPs/VOCs • Other Studies on Outdoor Non‐Air Fates 2016 CARB SIP/ SCAQMD AQMP

• Attainment for Ozone (75, 84, 120 ppb) and PM2.5 (Annual/24‐hour) • Ozone Attainment Modeling Completed – Further Reductions: 50‐65% NOx and ~10% VOCs – Maybe Most VOC Reductions from NOx/GHG Rules? • May or May Not Target Consumer Products for Significant Further Reductions • May or May Not Reference the Need for Additional LVP

Research (Ozone and PM2.5) 2015 South Coast VOC Emissions

56 SCAQMD Ozone Attainment Modeling SCAQMD Ozone Attainment Modeling SCAQMD Ozone Attainment Modeling Schedule for 2016 AQMP/SIP Public Process

– White Paper Workgroups and AQMP Workgroup – 2014‐2015 – Final White Papers (VOC Controls, etc.) –October 2015 – Draft Air Quality Management Plan for Review – December 2015 – AQMD Workshops and Hearings – January‐March 2016 – Approval by SCAQMD Governing Board –April 2016 – CARB Ozone SIP Process –May 2016 – Approval of SIP by CARB Board – June 2016 – Submission of California SIP Revision to EPA –July 2016 CARB Planning for Next 35 Years

2030 Greenhouse Gas Emission Target

2031 2037 Attainment year for revised 8‐hour Ozone Standard

61 Prediction: Likely Future for Consumer Products in California 2015 • CARB 2013 Survey Data Shows Revised VOC/LVP Emissions • Draft South Coast AQMP Proposes More VOC Reductions 2016 • CARB Ozone SIP Commits to Further VOC/LVP Regulations • CARB PM2.5 SIP Commits to VOC/LVP Reductions? 2017 • CARB Begins New Rulemaking for Consumer Product VOCs/LVPs/Toxics/GHGs Thank You! Questions?

D. DOUGLAS FRATZ Senior Science Fellow & Aerosol Products Division Staff Executive Consumer Specialty Products Association [email protected]

Washington, DC ‐ USA