Furniture Applications DTSC Workshop January 31, 2017 Sacramento, - PowerPoint PPT Presentation

PFASs in Carpet and Furniture Applications DTSC Workshop January 31, 2017 Sacramento, CA

Overview  Introduction to FluoroCouncil and PFASs  Short-chain-based products – safe for their intended use  Regulatory oversight of short chains  Status of long chains  Summary and conclusions 2

Introduction to FluoroCouncil and PFASs 3

About the FluoroCouncil • Represents leading manufacturers of FluoroTechnology products • Member companies: – Archroma Management LLC - Arkema France – Asahi Glass Co., Ltd. - Daikin Industries, Ltd. – Solvay Specialty Polymers - The Chemours Company LLC – Dynax and W.L. Gore and Associates (provisional members) • Other manufacturers of fluorinated products also serve this market, including manufacturers in other countries and of other technology. 4

FluoroTechnology Used in Carpets/Furniture Surface Modifiers Plastics/Polymers Gases and Liquids • High molecular weight • Modify material properties : • Refrigerants polymers • Cleaning solvents surface modification & • PTFE, Melt • Blowing agents protection, water & oil Copolymers, • Etching agents repellency, soil resistance and Thermoset Elastomers release, wetting and spreading • CFC alternatives • Fluorinated (e.g., HFCs ) “backbone” • Applications : Textiles, • Material properties : Protective Medical/First chemical resistance, Responder Gear, Carpets, thermal stability, Paper, Stone & Tile, AFFF, resilience (elastomers) Surfactants • Applications : Breathable membranes, • Chemistry: Fluorinated chains Aerospace materials, attached to organic polymer Hydraulic tubing, backbones. Chemical processing, Semiconductor manufacture, Transportation 5

FluoroTechnology Used in Mill Treatments of Carpets/Furniture OECD(2013), OECD/UNEP Global PFC Group, Synthesis paper on per- and polyfluorinated chemicals (PFCs), 6 Environment, Health and Safety, Environment Directorate, OECD.

Structure of a side-chain fluorinated polymer Hydrocarbon non- Fluorinated side-chains - F(CF 2 ) n - fluorinated side-chains Polymer Backbone • The key functionality is provided by the fluorinated side-chain ‒ n = 8 – long chain; n = 6 – short chain • The polymer backbone is NOT fluorinated • PFOA is not used in carpets/furniture, but was a byproduct, impurity, and potential degradation product of C8 long-chain fluorinated polymer • Regulatory focus on long-chain fluorinated polymers (>= C8) or ECF-based sulfonated (>=C6) 7 substances

Defining long chains vs. short chains • Distinction based on science and policy – Began at EPA in 2006 in reviews of long chain replacements, recognizing hazard profiles of short chain alternatives were clearly more favorable than long chains • Recognized among global regulators and OECD (www.oecd.org/ehs/pfc/) Short Chains Long Chains • Example Product: Fluorinated polymer with C8 side- • Example Product: Fluorinated polymer with C6 side- chain chain • Example Degradation Products: PFOA, PFOS • Example Degradation Products: PFHxA, PFBS • Focus of regulatory action • Well studied • PFOA/PFOS classified as PBT substances • Reviewed and approved by regulators as alternatives to long chains • Phased out by Stewardship Program* companies • Products in use for over 30 years and pathway to • Production/use/trade continues by non- full conversion over past ~10 years Stewardship Program companies 8 * https://www.epa.gov/assessing-and-managing-chemicals-under-tsca/and-polyfluoroalkyl-substances-pfass-under-tsca#tab-3

Supply Chain Overview Side-chain Fluorinated Polymer Manufacturers Consumers Carpet/Textile Mills short chains (includes all FluoroCouncil members) After market treatments long chains 9

Key Benefits of Side-Chain Fluorinated Polymers in Carpet/Furniture Applications • Combination water repellency, oil repellency, stain resistance and soil release with abrasion resistant finishes • Durability – Treated products stay cleaner longer, reducing need for washing and use of cleaning products • Longer useful product life, reducing raw material, energy and water used to manufacture replacements 10

Short chain-based products – safe for their intended use 11

Degradation products are focus of risk assessment • Scientific consensus that fluorinated polymers do not present toxicity concerns – Not bioavailable – Considered low risk to humans/environment – Not a focus of regulators • Consistent with direction of EPA, studies have focused on degradation products to characterize toxicity profiles of short-chain-based products. • Studies show short-chain-based products do not present significant adverse impacts. 12

Short-chain-based products - well studied • Rich database on short-chain-based products, including data provided by FluoroCouncil member companies. • Toxicity and environmental data developed and submitted to regulators on: – Short-chain products – Raw materials used to produce those products – Degradation products • Studies conducted include: – testing for cancer – reproductive/developmental toxicity – systemic toxicity – bioaccumulation – ecological endpoints – environmental fate and transport • Relevant studies developed by FluoroCouncil and others available at www.fluorocouncil.org/resources/research 13

PFHxA*: Toxicity Summary • Does not represent a reproductive, developmental or neurobehavioral hazard • Not carcinogenic • Not mutagenic • Does not bioaccumulate in fish • Quickly eliminated from living organisms • Not an endocrine disruptor * PFHxA is an impurity/degradation product 14

PFHx Toxicity Profile Impurity/Degradation product - Perfluorohexanoate (PFHx) * Repeated-Dose Mammalian (Oral) • 2-year chronic (rat) Summary – NOAEL M 15 mg/kg/day; F 30 mg/kg/day – Not carcinogenic • Not damaging to DNA, not genotoxic or • 90-day sub chronic (rat) mutagenic – NOAEL 100 mg/kg/day • Not a selective developmental or reproductive – Target: liver , body weight toxicant • One-Generation Reproduction (rat) • Not carcinogenic^ – NOAEL 100 mg/kg/day – No effects on reproductive parameters • Rapid bioelimination, not bioaccumulative ¥ • Repro/Development (mouse) • Not expected to be harmful to human health or – NOAEL 100 mg/kg/day • Development (rat) the environment at environmentally relevant concentrations – NOAEL 100 mg/kg/day • Pharmacokinetics (rat, mouse, monkey) – Single and repeated dose studies completed: rapid *Loveless et al., Toxicology, 2009 , 264(1-2),32-44 elimination for both genders in all species Chengelis et al., Repro Tox, 2009, 24(3-4) , 342-351 Gannon et al., Toxicology, 2011 , 283(1): 55-62 ¥ Conder et al., Environ Sci Technol, 2008 , 42(4): 995-1003 ^ Klaunig JE et al., Toxicol Pathol ., 2015, 43(2):209-20 15

Very Different Toxicological Profiles for PFCAs Study Type PFOA PFHxA PFHxA Rat Rat Mouse 3 mg/kg/d M 100 mg/kg/d 100 mg/kg/d Repro-Developmental F1 10 mg/kg/d F M&F M&F NOAEL (Butenhoff, 2004; York 2002) (Loveless, 2009) (Iwai, 2014) 1.3 mg/kg/d M 15 mg/kg/d M 2 yr Chronic Toxicity - 30 mg/kg/d F 1.6 mg/kg/d F (Butenhoff, 2012) (WIL Research Labs, 2010 ) Leydig cell tumor, No carcinogenicity at Carcinogenicity - liver adenoma, maximum tolerated pancreatic tumor doses 300ppm diet 100 mg/kg/d M 200 mg/kg/d F 14.2 mg/kg M 16.1 mg/kg F (Klaunig, 2015) (Butenhoff, 2012) PFHxA NOEL is at least 10x higher and non-carcinogenic Iwai H et al. (2014) Int J Toxicol.;33(3):219-237 Butenhoff, J.L . et al. (2004) Toxicol. 196: 95-116. Butenhoff J. L . et al. (2012) Toxicology. Aug 16;298(1-3):1-13 York, R.G. 2002. Protocol Number: 418-020, Sponsor Study Number: T-6889.6, WIL Research Laboratories (2010) Study No. WIL-534009 March 26, 2002. U.S. Environmental Protection Agency 16 Klaunig JE et al. (2015) Toxicol Pathol.;43(2):209-20 Administrative Record 226-1092 (as cited in SIAR, 2006). Loveless, SE et al. (2009) Toxciol.264 (1-2): 32-44.

Elimination Half-life Studies in Plasma - Perfluoroalkyl acids (PFAAs) short-chain long-chain Elimination t 1/2 (Days) PFBA PFBS PFHxA PFHxS PFOS PFOA 0.2 – Rat 0.3 0.2 7 5 25 0.05 Monkey 2 4 1 100 21 45 3 4 5 6 7 8 # Fluorinated Carbons • BIG difference between “long” and “short” chain PFAAs • Short chain PFAAs eliminate rapidly and significantly less toxic Gannon et al., Toxicology 2011, 283 , (1), 55-62. 9 November 2012 17 17 R. C. Buck Chengelis et al., Repro Tox (27), 400-406.

Grouping and read-across for PFASs are inappropriate • Data demonstrate short chains have distinct hazard profiles from long chains. • Chemical risk management decisions should be based on chemical-specific data whenever available, not on unsubstantiated references to other chemicals. • Grouping and read-across, which are useful when data are unavailable, are inappropriate here and unnecessary because data on short chains are available. 18

Persistence of Short-chain-based Fluorinated Polymers • Common recognition that short chains products are persistent. • Persistent properties are linked to their technological strengths as durable materials, the very performance properties relied on by users. • No evidence of bioaccumulation or sufficient toxicity to warrant regulation – Not PBTs. • Persistence of a substance alone is not a sufficient basis for regulation. 19

Regulatory Oversight of Short Chains 20