1、W.L.Gore&Associates,Inc.INTRODUCTION TO PFAS AND FLUOROPOLYMERSBarbara J.Henry,Ph.D.W.L.Gore&AssociatesSlide 1/13W.L.Gore&Associates,Inc.PFAS are Related But Different!Slide 2/13W.L.Gore&Associates,Inc.OverviewPer-and Polyfluoroalkyl Substances(PFAS)Thousands of PFASwith a wide variety of properties

2、Differences1 fully fluorinated carbonSimilaritiesStabilitysecondsthousands of yearsToxicitylowhighMobilityinsoluble/non-volatileHighly mobileSizeMW less than 1,000 DaltonsMW multi-million DaltonsFFCPTFE on the spectrumGasesLiquidsSolidsSlide 3/13W.L.Gore&Associates,Inc.5 Classes1 GroupPFAS Per-and P

3、olyfluoroalkyl substancesOverviewPer-and Polyfluoroalkyl Substances(PFAS)FFFFCFFCPerfluoroalkyl SubstancesFFHFCFFCPolyfluoroalkyl SubstancesFFCFFCFFCOPolymeric Perfluoropolyethers Carbon and oxygen polymer backbone with fluorines directly attached to carbonFFCFFCFFCFFCFluoropolymersCarbon-only polym

4、er backbone with fluorines directly attachedNon-FspacerCCCSide-chain Fluorinated PolymersVariable composition non-fluorinated polymer backbone with fluorinated side chains2 CategoriesNon-PolymersPolymersCompounds for which all hydrogens on all carbons (except for carbons associated with functional g

5、roups)have been replaced by fluorinesCompounds for which all hydrogens on at least one(but not all)carbon have been replaced by fluorinesPerfluoroalkyl Acids(PFAAs)such as PFOA,PFOS,PFHxS,etc.4Slide 4/13W.L.Gore&Associates,Inc.W.L.Gore&Associates,Inc.Per-and Polyfluoroalkyl Substances(PFAS)5Slide 5/

6、13W.L.Gore&Associates,Inc.OECD(2018):4,730 PFAS US EPA(2019)7,000 PFAS using CompTox Chemicals Dashboard PFAS#depends on the PFAS definition Buck et al.,2011:highly fluorinated aliphatic(organic)substances with 1 C with all H replaced by F,so CnF2n+1,when n=1,F=3 OECD 2018:highly fluorinated substan

7、ces with 1 C with all H replaced by F,so they have 1 aliphatic PFC moiety,such as:CnF2n”.CA Environmental Contaminant Biomonitoring Program:chemicals containing 1 fully fluorinated C atom(CF2or CF3)#of PFAS notified to EPA(TSCA PMN)#of PFAS in commerce 256 PFAS are commercially relevant globally(Buc

8、k et al.,Integr Environ Assess Manag2021;17:1045-1055.)TSCA Inventory lists 1,000 PFAS,of which half are known to be commercially active within the last decade.(PFAS Action Plan)How many(commercialized)PFAS are there?Slide 6/13W.L.Gore&Associates,Inc.ABSTRACTPer-and polyfluoroalkyl substances(PFAS)a

9、re a group of fluorinated substances that are in the focus of researchers and regulators due to widespread presence in the environment and biota,including humans,of perfluorooctane sulfonate(PFOS)and perfluorooctanoic acid(PFOA).Fluoropolymers,high molecular weight polymers,have unique properties th

10、at constitute a distinct class within the PFAS groupThis paper brings together fluoropolymer toxicity data,human clinical data,and physical,chemical,thermal,and biological data for review and assessment to show that fluoropolymers satisfy widely accepted assessment criteria to be considered as“polym

11、ers of low concern”(PLC).This review concludes that fluoropolymers are distinctly different from other polymeric and nonpolymeric PFAS and should be separated from them for hazard assessment or regulatory purposes.Grouping fluoropolymers with all classes of PFAS for“read across”or structureactivity

12、relationship assessment is not scientifically appropriate.7W.L.Gore&Associates,Inc.Slide 7/13W.L.Gore&Associates,Inc.OECD Polymer of Low Concern CriteriaPolymer compositionMW,Mn,MWDwt%oligomerElectrical chargeReactive Functional Groups(RFG)Functional Group Equivalent Weight(FGEW)Low MW leachablesPar

13、ticle sizePolymer stabilityThermal stabilityAbiotic stabilityBiotic stabilityWater/lipid solubility,octanol water partition13 CriteriaSlide 8/13W.L.Gore&Associates,Inc.Fluoropolymers,generally,have low Health and Environmental Hazards These OECD PLC properties are predictive of low health and enviro

14、nmental hazard Not bioavailable-Very high molecular weight(and“rule of 5”)prevents crossing cell membrane Not toxic(Supplement to Henry et al.,2018)Not bioaccumulative(not bioavailable)Stable at environmentally relevant conditionsPTFE,for ex.is thermally stable for years at 260CDoesnt oxidize,hydrol

15、yze,photolyze,not degraded by microorganisms Inert;not chemically reactive;doesnt transform to PFAAs Not mobile;not water soluble,doesnt adsorb to soil;not volatileSlide 9/13W.L.Gore&Associates,Inc.PTFE,FEP,and a TFE/PAVE copolymer passed these GLP testsCytotoxicity(MEM)(ISO 10993-5)Not CytotoxicSki

16、n Sensitization(ISO 10993-10;OECD 406)Non-SensitizingIrritation(ISO 10993-10;OECD 406)Not IrritatingAcute Systemic Toxicity(ISO 10993-11;OECD 408)Not Toxic90-Day Subchronic Systemic Toxicity(ISO 10993-11;OECD 408)Not ToxicTwo In Vitro+One In Vivo Genotoxicity(ISO 10993-3;OECD 471,OECD 474,OECD 476)N

17、ot Mutagenic2-or 4-Week Implantation(ISO 10993-6)No Significant ResponseHemocompatibility(ISO 10993-4;ASTM F756.ASTMF2382)HemocompatibleNote:90-Day Subchronic Toxicity Studies included hematology,urinalysis,clinical chemistry,gross pathology,microscopic histopathology,organ weights,clinical observat

18、ions.Histopathology performed on:ovaries,testes,brain,heart,liver,kidneys,spleen,thymus,adrenal glands,lymph nodes45 years of patients receiving permanently implanted PTFE,FEP or TFE/PAVE copolymer cardiovascular medical devices demonstrate no chronic toxicity,carcinogenicity,reproductive,developmen

19、tal or endocrine toxicity.Fluoropolymers Toxicity and Clinical DataW.L.Gore&Associates,Inc.Slide 10/13W.L.Gore&Associates,Inc.Dont Group All PFAS TogetherPFAS:No structural similarities beyond-CF3Presence of CF3 alone is not predictive of health or environmental hazard5 Classes of PFAS do not share

20、a mode of action.(Those with very high MW,like PLC fluoropolymers,are not even bioavailable to have a mode of action.)5 classes do not share chemical or physical properties(e.g.,MW,solubility,vapor pressure,mobility,stability,etc.)5 Classes do not share toxicity endpointsFluoropolymers,especially PL

21、Cs,should be separated from other PFASW.L.Gore&Associates,Inc.Slide 11/13W.L.Gore&Associates,Inc.All PFAS are Hazardous All Birds are HazardousSlide 12/13W.L.Gore&Associates,Inc.Thank YouQuestions?Contact:Barbara Henry,Ph.D.W.L.Gore&Associates,IContact Barb HenrySlide 13/13U.S.and EU PFAS UpdateJuly

22、 11,2023Owen P.Jappen10th BPSA International Single-Use SummitAgenda010203STATESFEDERALEUROPENot All PFAS Are The SamePolymersNon-PolymersFluoropolymersincluding fluoroelastomersCarbon-only polymer backbone with fluorines directly attachedPerfluoropolyethersCarbon and oxygen polymer backbone with fl

23、uorines directly attached to carbonSide-chain Fluorinated PolymersVariable composition non-fluorinated polymer backbone with fluorinated side chains Fluorinated acrylate and methacrylate polymers Fluorinated urethane polymers Fluorinated oxetane polymersPerfluoroalkyl SubstancesCompounds for which a

24、ll hydrogens on all carbons(except for carbons associated with functional groups)have been replaced by fluorines (Aliphatic)perfluorocarbons(PFCs)Perfluoroalkyl acids Perfluoroalkane sulfonyl fluorides Perfluoroalkane sulfonamides Perfluoroalkyl iodides Perfluoroalkyl aldehydesPolyfluoroalkyl Substa

25、ncesCompounds for which all hydrogens on at least one(but not all)carbon have been replaced by fluorines Perfluoroalkane sulfonamido derivatives Fluorotelomer-based compounds Semifluorinated n-alkanes and alkenesGROUPCLASSCATEGORYPer-and Poly-fluoroalkyl substances(PFAS)Buck et al.,2011.http:/dx.doi

26、.org/10.1002/ieam.258 States2023 State Activity at a Glance235+PFAS-related bills introduced in 2023Issue areas-Bills restricting uses,some specific and some constructed broadly-Bills requiring notification of PFAS intentionally used in products-Maximum contaminant levels and clean up standards-Bios

27、olids and relief for land(incl.groundwater)contaminated by PFASConsistent use of a broad definition of PFAS-Fluorinated organic chemicals containing one fully fluorinated carbon atom(if it has but one CF3 or CF2 group,its in)Maine Public Law 447 enacted July 15,2021 Beginning January 1,2023:-Manufac

28、turers of a product for sale in ME that contains intentionally added PFAS to submit written notification of product description,PFAS purpose,amount,etc.to Dept.of Env.Protection(DEP);-Prohibits sale of carpet/rug or fabric treatment that contains intentionally added PFAS.Over 2,000 companies were be

29、en granted notification deadline extensions to July 1,2023.Multiple bills introduced to amend P.L.477.-Proposed changes in those bills include modifying the definition of“PFAS”,extending the reporting deadline to 2025,eliminating the 2030 ban,adequately protecting confidential business information,s

30、mall business exemption for reporting,and others.MaineAs of January 1,2030,sale or distribution permitted only if DEP determines by rule that the use is“currently unavoidable”.Proposed rule defines“currently unavoidable use”as“essential for health,safety,or the functioning of society”-Includes,but i

31、s not limited to,technologies to address climate mitigation,critical infrastructure,delivery of medicine,lifesaving equipment,public transport,and construction.-Required by federal or state laws and regulations-And for which alternatives are not reasonably available.MinnesotaMulti-Use Ban BillCarpet

32、s and rugsCleaning productsCookwareCosmeticsFabric treatmentsJuvenile productsSki waxTextile furnishingsUpholstered furnitureNotificationBy January 1,2025Fees to be established by ruleCertificate of complianceCurrently Unavoidable UseJanuary 1,2030Determination by ruleCan be specific products or cat

33、egories of productsFederalThree pillars:Research,Restrict,Remediate600 PFAS substances in commerce Strong focus on contaminated drinking waterEPA working to identify groups(not one class)Risk-based approachEnvironmental justice considerations throughoutPermanent disposal and/or destructionValidated

34、methodsSeveral future rulemakings(TSCA,air,water,etc.)U.S EPAs PFAS Strategic RoadmapProposed March 14,2023(link to EPA website)Proposal includes PFOA,PFOS,PFNA,HPFO-DA,PFHxS,PFBSWould require public water systems to monitor,notify the public of levels,reduce levels if in exceedance of the proposed

35、standardProposed levels:-4.0 ppt(ng/L)PFOA and PFOS-1.0(unitless)Hazard Index for others,assuming additive effectsEPA hopes to finalize by the end of 2023Proposed NationalPrimary Drinking Water RegulationProposed CERCLA Designation Designation of PFOA and PFOS as hazardous substances proposed Sept 2

36、022 First time EPA has proposed to use CERCLA 102(a)listing authority Issues raised by the proposal-Potential for significant unintended consequences for local governments and others-Uncertainty about appropriate disposal/destruction approaches-Cleanup target levels defined by MCL,once establishedMa

37、ndated by National Defense Authorization Act(NDAA)of fiscal year 2020Requires electronic reporting of information regarding PFAS uses,production volumes,disposal,exposures,and hazardsManufacturers that manufacture or have manufactured covered chemical substances in any year since January 1,2011.Arti

38、cles containing PFAS,including imported articles,are in scope.Structural definition of PFAS:-Per and polyfluorinated substances that structurally contain the unit R-(CF2)-C(F)(R)R.Both the CF2 and CF moieties are saturated carbons and none of the R groups(R,R or R)can be hydrogenProposed TSCA 8(a)(7

39、)Reporting RuleWould apply to 330 PFAS that are“Inactive”on the Toxics Substances Control Act Inventory and are not already subject to a SNUR.“Inactive”means that a substance has not been manufactured,imported,or processed in the United States since June 21,2006.Proposed Significant New Use Rule(SNU

40、R)EuropeREACH Restriction ProposalDenmark,Germany,The Netherlands,Norway,and SwedenEnvisions restricting the manufacture,placing on the market,or use of PFAS-Inclusive of PFAS-containing mixtures and articles-“Any substance that contains at least one fully fluorinated methyl(CF3-)or methylene(-CF2-)

41、carbon atom(without any H/Cl/Br/I attached to it)”-Some exemptions for plant protection and biocidal products,others-Covers PFAS broadly,including future“theoretical”PFAS,to avoid one PFAS being replaced with another-Proposes ban on the manufacture and use of all fluoropolymers in all applicationsRE

42、ACH Restriction ProposalConstruction productsLubricantsPetroleum and miningTextile,upholstery,leather,apparel and carpetsFood contact materials and packagingMetal plating and manufacture of medical productsPFAS manufacturingFluorinated gassesMedical devicesTransportElectronics and semiconductorsEner

43、gy sectorConsumer mixturesCosmeticsSki waxQ1 2023 Q2 2023Q3 2023Q4 2023Q1 2024Q2 2024Q3 2024Q4 2024202320242025Dossier scrutiny by European Parliament and Member StatesQ1 2024Adoption of RAC opinion Adoption of SEAC opinion Q2 2024Completion of ECHA phase:RAC and SEAC opinions are submitted to ECFol

44、lowing consultation with Member States,EC Proposal to amend REACH Art.XVIIQ3 2024Q4 2024Entry into force will depend on the outcomes of the restriction discussionQ3 2025(TBC)Publication of the restriction dossier6-month stakeholder consultation22 MARCH 25 SEPTEMBER 2023ECHA online information sessio

45、n on the restriction process 5 April 2023Q1 2023Tentative timeline of EU PFAS REACH Restriction:2023-2025Q4 2023SEAC draft opinion&consultationREACH Restriction Proposal18-month transition period after finalization(“entry into force”)Time-limited derogations(or lack thereof)are based on specific use

46、s and the proposers understanding of the availability of suitable alternatives 1.5 years(transition period)for uses with no derogations-Chemical industry,pharmaceutical manufacturing,aerospace,military and defense,semiconductor manufacturing,water and wastewater treatment-Any use that does not have

47、a proposed derogation mentioned in the textThank You!Owen_JCOLLABORATION,TECHNOLOGY&INNOVATION:SHAPING THE FUTURE OF SINGLE-USE JULY 10-JULY 12,FOUR SEASON HOTEL,WASHINGTON,DCMonica Cardona Senior Program Manager,Single Use&Integrated SystemsPFAS Customer InquiriesGeneral Time-LineCustomer Inquiries

48、-GeneralWhich Filtration&Single Use products are impacted?Have you identified replacements?If so,provide alternate SKUsHave you performed an impact assessment?If not yet identified,What is your timeline for replacement,qualification&availabilityCustomer Inquiries Specific Which PFAS is contained in

49、products supplied to us,CAS#,function and quantity used?Do you use PFAS chemicals in the production process for any of the products you supply to us,or even for products not supplied to us?This is primarily to aide us in cross contamination probability assessment.Do you suspect that the products we use could unintentionally contain PFAS?If yes,could you let us know the rationale?Customer InquiriesFor liquid(hydrophilic)applications,there are functional replacement options.For air/vent(hydrophobic)applications,functional replacement options currently limited/challenging.Challenges