Per'(and(poly'fluorinated(chemicals(in(branded(waterproof(clothing,( footwear,(hiking(and(camping(equipment((

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1 Per'andpoly'fluorinatedchemicalsinbrandedwaterproofclothing, footwear,hikingandcampingequipment KevinBrigden,ManfredSanten,DavidSantillo GreenpeaceResearchLaboratoriesTechnicalReport01'2016,January2016 Contents 1.Introduction Materialsandmethods ResultsandDiscussion Jackets Trousers Footwear Backpacks Sleepingbags Tents Rope Glove Conclusions References...19 Appendix1.ConcentrationsofPFCsinallarticlestested...21 Jackets...21 Trousers...25 Footwear...29 Backpacks...33 Sleepingbags,tents,ropeandglove...37 Appendix2.Analysisof2separatesectionsofthesamematerialfromanumberofarticles...41 Appendix3.Analysisofmaterialfrom3articlesinduplicate...51 GreenpeaceResearchLaboratories SchoolofBiosciences InnovationCentrePhase2 RennesDrive UniversityofExeter ExeterEX44RN,UK GreenpeaceResearchLaboratoriesTechnicalReport Page1of54

2 1.#Introduction# Finishedtextileproductscancontaincertainhazardouschemicalsusedduringtheirmanufacture, eitherbecauseoftheiruseascomponentsofmaterialsincorporatedwithintheproductordueto residuesremainingfromtheusewithinprocessesemployedduringmanufacture. Thisstudyfollowsonfrom,andextends,researchrecentlypublishedbyGreenpeacethatidentifieda range of hazardous chemicals in textile products sold by major brands, including per5 and poly5 fluorinatedchemicalsincertainitemsbrigdenetal.2012,2013;greenpeace2011,2012a,2012b, 2012c, 2013a, 2013b, 2013c, 2014a, 2014b).This study extends this work to include a set of 40 items intended for outdoor use, including clothing, footwear, hiking and camping products purchasedinoctober5november2015,whichincludedarticlessoldby11differentmajorbrandsand purchased in 19 countries/regions around the world. Details of the analyses carried out and informationonthevariouschemicalsquantifiedinthisstudyareprovidedwithinthisreport. 2.#Materials#and#methods# The40productswerepurchasedinOctoberandNovember2015eitherattheflagshipstoresofthe brands,orotherstoresauthorisedtosellthebrandedproducts,ororderedonline.theproducts includedclothingitemsjacketsandtrousers),footweararticles,aswellashikingandcamping equipmentincludingbackpacks,sleepingbags,tents,aropeandaglove.whilestillinthestore, purchasedproductswereimmediatelysealedinindividualidenticalcleanpolyethylenebags.sealed bagscontainingtheproductsweresenttoanindependentaccreditedlaboratoryforanalysis.a summaryofthenumberofproductsofeachtype,andthecountryofsale,isgivenintable1,with detailsoftheindividualarticlesprovidedinappendix1. Producttype Countryofsale jacket trouser footwear backpack sleeping bag tent rope glove Austria J5Wolfskin J5Wolfskin Chile Columbia NorthFace ChinaMainland Arc teryx, Vaude HongKong Patagonia NorthFace Taiwan Patagonia Arc teryx Denmark Haglöfs Haglöfs Finland Haglöfs Germany J5Wolfskin, Vaude Columbia Mammut Hungary NorthFace Italy Salewa Salewa Patagonia Korea Blackyak Patagonia Norway Norrona Haglöfs Russia Columbia, J5Wolfskin Slovakia Mammut Mammut Slovenia Mammut Salewa Sweden Arc teryx, NorthFace Switzerland Mammut NorthFace Mammut Turkey Columbia, J5Wolfskin UK North NorthFace Face TOTAL Table1.Summaryofthedifferenttypesofproductsandthecountryofsale.J5Wolfskin=JackWolfskin GreenpeaceResearchLaboratoriesTechnicalReport Page2of54

3 Foreachofthe40articles,asectionwasanalysedforarangeofper5andpoly5fluorinated compoundspfcs).forsomearticles,oneormoreadditionalsectionsofdifferentmaterialfromthe articlewereseparatelyanalysed.detailsofthepart,orparts,ofeacharticlethatwereanalysed, alongwiththeindividualpfcsquantifiedineachsampleandtheirdetectionlimitsinindividual samplesaregiveninappendix1.asamplewascutfromeacharticlewheretherewasnoprintingor labelling.twoseparateanalyseswerecarriedoutoneachsample.oneportionwasextractedwith methanolusingsoxhletextraction,theextractpurifiedusingsolidphaseextractionspe),anda rangeofionicpfcswerequantifiedusinghighperformanceliquidchromatographyhplc)combined withtandemmassspectrometryhplc5ms/ms).asecondportionwasextractedwithmethyl tertiarybutylethermtbe)usingultrasonicextractionandarangeofvolatileneutralpfcswere quantifiedusinggaschromatography5massspectrometrygc5ms). Thetwoseparateanalysescarriedoutwere: 1) analysisforarangeoflongchainandshortchainionicpfccompounds,predominantly perfluorosulfonatespfsas,includingperfluorooctanesulfonateorpfos),and perfluorinatedcarboxylicacidspfcas,includingperfluorooctanoicacidorpfoa). 2) analysisforarangeoflongchainandshortchainvolatilepfcswhichareusedasprecursors duringmanufacturingprocesses,consistingofcertainfluorotelomeralcoholsftohs), fluorotelomeracrylatesftas,alsoknownaspolyfluorinatedacrylates),andn5alkyl perfluorosulfonamides. ForbothsetsofPFCsionicandvolatile),bothlongchainversionsandshortchainversionswere quantified.theterm longchainpfcs referstocarbonchainlengthsc8andhigherinthecaseof PFCAsandtocarbonchainlengthsC6andhigherinthecaseofPFSAs,aswellastosubstancessuch aslongchainfluorotelomercompoundsthathavethepotentialtodegradetoformlong5chainpfcas orpfsas.shortchainpfcsreferstopfcasorpfsaswithshorterchainlengthsthanthese,or substancesthathavethepotentialtodegradetoshortchainpfcasorpfsas,includingcertainother longchainfluorotelomercompoundsoecd5unep2013). FluorotelomeralcoholsFTOHs)andfluorotelomeracrylatesFTAs)canactassourcesofPFCAs. FluorotelomeralcoholFTOHs)canbetransformedintoPFCAseitherthroughbiotransformation Frömel&Knepper2010,Buttet#al.2013),orabioticallyintheatmosphereYoung&Mabury2010). 6:2FTOHcangiverisetoC6compoundsincludingPFHxA,while8:2FTOHcangiverisetoC8 compoundsincludingpfoa,andsimilarly,10:2ftohcanyieldc10compounds,includingpfda.in addition,ftohsarevolatileandcanbereleasedfromproductsunderambientconditions Greenpeace2013c,Langeretal.2010,Schlummeretal.2013).Humansoccupationallyexposedto highlevelsof8:2ftohhavebeenfoundtohaverelativelyhighconcentrationsofpfoaintheir bloodnilssonet#al.2013).inaddition,thereareindicationsthatbiotransformationcanform intermediateproductsinthebodythatcanbemoreharmfulthanthepfcaendproductrand& Mabury2012). Foranumberofarticles,aseparatesectionofthesamematerialfromthearticlewassubsequently analysedtogainanunderstandingofthevariabilityinpfcconcentrationsfordifferentpartsofa fabric.thisrepeatanalysiswascarriedoutforionicpfcs4jacket,3trouser,5footwear,1backpack GreenpeaceResearchLaboratoriesTechnicalReport Page3of54

4 and1tentsamples)andforvolatilepfcs5jacket,3trouser,6footwear,2backpack,2sleepingbag and1tentsamples).detailsofthesesamplesaregiveninappendix2. Arangeofadditionalqualitycontrolcheckswerecarriedoutincludingtheanalysisofblanksandthe determinationoftherecoveryofarangeofdeuteratedand 13 ClabelledionicandvolatilePFC standards.tocheckreproducibilityoftheextractionprocess,foreachof3articlesthatwerefound tocontainawiderangeofionicandvolatilepfcsatrelativelymoderatetohighconcentrations1 trouser,1backpackand1sleepingbag),asectionofmaterialwascutintomultiplesmallpieces whichweremixedandthenseparatedintotwoapproximatelyequalportions,whichwereanalysed as2separatesamples.detailsofthethreesamplesanalysedinduplicatearegiveninappendix3. 3.#Results#and#Discussion# Theresultsforthevariousproductcategoriesarepresentedinthefollowingsections.Allresults fromtheanalysesoftheindividualarticlesareprovidedinappendix1. OneormorePFCwasdetectedinmaterialfrom36ofthe40articles,thoughthePFCconcentrations andthecompositionofthepfcspresentvariedgreatlybetweenindividualarticles.volatilepfcs werenotdetectedascommonlyasionicpfcs,mostnotablyforbackpacks,thoughwherevolatile PFCsweredetectedtheyweregenerallyfoundinconsiderablyhigherconcentrationsthanionicPFCs inthesamearticle.asummaryofthenumberofarticlesinwhichionicand/orvolatilepfcswere detectedisgivenintable2,togetherwiththerangeandmedianofthetotalconcentrationsbyarea ofionicpfcsinthevariousarticles,andthesameforvolatilepfcs.detailsoftheconcentrationsof individualpfcsinallarticles,bothbymassng/kg)andbyareaµg/m²),aregiveninappendix1,and arediscussedbyproducttypeintherelevantsectionsbelow.representationsofthetotalionicpfc andtotalvolatilepfcconcentrationsaregiveninfigure1a/b,togetherwithabreakdownof individualionicpfcsfigure2a/b)andindividualvolatilepfcsfigure3a/b). IonicPFCs volatilepfcs Articletype No.of articles No.in which PFCswere detected No.of articles inwhich detected totalconc. range μg/m 2 ) total conc. median μg/m 2 ) No.of articles inwhich detected totalconc. range μg/m 2 ) total conc. median μg/m 2 ) jacket ND ND trousers ND footwear ND ND backpack ND ND597 0 sleepingbag tent ND ND557 0 glove ND 5 0 ND 5 Table2.SummaryofarticlesinwhichPFCsweredetected,togetherwiththerangesandmediansofthetotal concentrationsbyareaforionicpfcsandvolatilepfcsμg/m 2 ).Theropesampleisnotincludedasdataare availableonlybymassng/kg).nd notdetected.rangeandmedianvalueswerecalculatedusingbothsets ofdataforthosesamplesfromwhichtwosectionsofequivalentfabricwereanalysed. Thedatafortheduplicateanalysisonthreesamplesdemonstratesacceptablereproducibilityforthe extractionandanalysismethod.fortwosamplesbackpackbp05andsleepingbagsb02),the differencebetweenconcentrationsinthetwoduplicateswasbelow140%.forthethirdsample GreenpeaceResearchLaboratoriesTechnicalReport Page4of54

5 GreenpeaceResearchLaboratoriesTechnicalReport Page5of54 TrouserTR04),thedifferencebetweenconcentrationsinthetwoduplicateswasbelow175%forall butoneanalyteseeappendix3fordetails). Thedatafortherepeatanalysisoftwoequivalentsectionsfromanumberofarticlesdemonstrated that,inmostcases,theconcentrationsofpfcsinthetwosectionswereingoodagreement.where theconcentrationofallpfcsdifferedbetweenthetwosectionsbyuptoafactorof2,theaverage concentrationisgiven.forthosematerialswheretheconcentrationofoneormorepfcsdiffered betweenthetwosectionsbyafactorof3ormore,thedataforbothsectionsarepresentedand discussedseparatelyseeappendix1fordetails).forthesampleswheredatafordifferentsection ofthesamefabricdifferedbyafactorof3ormore,thedifferencesclearlyreflectrealvariationsin concentrationsbetweendifferentpartsofthesamefabricanddonotresultfromthetesting method,asconfirmedbyqualitycontrolchecksseeappendix3). Figure1a.ComparisonoftotalionicPFCconcentrationsandtotalvolatilePFCconcentrationsby areaμg/m 2 )forallsamplesexceptrope Figure1b.ComparisonoftotalionicPFCconcentrationsandtotalvolatilePFCconcentrationsby areaμg/m 2 )forallsamplesexceptrope,withanexpandedaxis05500μg/m 2 ) J01 J03 J05 J07 J09 J10b J12 TR02 TR04a TR05 TR07 F01 F03 F05a F07 F08b F09b F11a BP01 BP03 BP04b BP06 BP08 BP10 BP12 BP14 SB02 TE01 TE03 TE05 TE07 G01 TotalionicPFCµg/m²) TotalvolaolePFCsµg/m²) concμg/m 2 ) J01 J03 J05 J07 J09 J10b J12 TR02 TR04a TR05 TR07 F01 F03 F05a F07 F08b F09b F11a BP01 BP03 BP04b BP06 BP08 BP10 BP12 BP14 SB02 TE01 TE03 TE05 TE07 G01 TotalionicPFCµg/m²) TotalvolaolePFCsµg/m²) concμg/m 2 )

6 concμg/m 2 ) :2FTS H2PFDA HPFHpA PF53,75 DMOA PFOSA PFTeA PFTrA PFDoA PFUnA PFDA PFNA 0 J01 J04 J07 J10a J12 TR03 TR05 TR08 F03 F06 F08b F10 BP02 BP04b BP07 BP10 BP13 SB02 TE02 TE05 G01 PFOA Figure2a.DetailsofionicPFCconcentrationsbyareaμg/m 2 )forallsamplesexceptrope concμg/m 2 ) :2FTS H2PFDA HPFHpA PF53,75 DMOA PFOSA PFTeA PFTrA PFDoA PFUnA 20 PFDA 0 J01 J04 J07 J10a J12 TR03 TR05 TR08 F03 F06 F08b F10 BP02 BP04b BP07 BP10 BP13 SB02 TE02 TE05 G01 PFNA PFOA Figure2b.DetailsofionicPFCconcentrationsbyareaμg/m 2 )forallsamplesexceptrope,withan expandedaxis05100μg/m 2 ) GreenpeaceResearchLaboratoriesTechnicalReport Page6of54

7 concμg/m 2 ) EtFOSA MeFOSA EtFOSE MeFOSE 10:2FTOH 8:2FTOH 6:2FTOH 4:2FTOH 10:2FTA 0 Figure3a.DetailsofvolatilePFCconcentrationsbyareaμg/m 2 )forallsamplesexceptrope 8:2FTA 6:2FTA concμg/m 2 ) EtFOSA MeFOSA EtFOSE MeFOSE 10:2FTOH 8:2FTOH 6:2FTOH 200 4:2FTOH 0 Figure3b.DetailsofvolatilePFCconcentrationsbyareaμg/m 2 )forallsamplesexceptrope,withan expandedaxis05800μg/m 2 ) 10:2FTA 8:2FTA 6:2FTA 3.1#Jackets# Overall,forthesamplesfromthe11jackets,thevolatilePFCswerethedominantPFCsby concentration.oneormorevolatilepfcwasdetectedinasampleoffabricfromajacketsoldbyall butthreebrandsvaude,j01;salewa,j11;jackwolfskin,j12).thejackwolfskinjacketwaslabelled as 100%fluorocarbonfree.Similarly,noionicPFCsweredetectedintheVaudejacketJ01)orthe GreenpeaceResearchLaboratoriesTechnicalReport Page7of54

8 JackWolfskinjacketJ12),thoughtheSalewajacketJ11)hadoneofthehighestconcentrationsof totalionicpfcsinjacketsamples,asdiscussedbelow. Oftheotherjackets,byfarthemostcommonlydetectedvolatilePFCwastheshortchain6:2FTOH, beingtheonlyvolatilepfcin6jacketsmammut,norrona,columbia,haglöfs,arc'teryxandthe NorthFace),withthePatagoniajacketJ10)containing6:2FTOHandarelativelylowconcentration of10:2ftoh6.7μg/m 2,3.9%ofthetotalvolatilePFCconcentration). Amongstallthejacketsamples,theNorronajacketJ03)hadbyfarthehighestconcentrationof6:2 FTOH,andoftotalvolatilePFCs,630μg/m 2 ),almostfourtimeshigherthanthe6:2ftoh concentrationinthetwosampleswiththenexthighestconcentrationsmammut,j02,170μg/m 2 ; Patagonia,J10,180μg/m 2 ). Incontrast,6:2FTOHwasnotdetectedintheinnerfabricoftheBlackyakjacketJ04),thoughthis didcontainthelongchain8:10ftoh56μg/m 2 )and10:2ftoh15μg/m 2 ). NovolatilePFCsweredetectedintheouterliningoftheBlackyakjacketJ05).Forallotherjackets, onlysamplesoftheouterfabricwereanalysed. InadditiontothevolatilePFCs,ionicPFCsweredetectedinallbut2jacketsVaude,J01;Jack Wolfskin,J12).Asnotedabove,novolatilePFCsweredetectedinthese2jackets.Inaddition,only relativelylowconcentrationsoftwoionicpfcsweredetectedinathenorthfacejacketj09), namelypfhxa0.18μg/m 2 )andpfoa0.11μg/m 2 ). ThoughtheionicPFCconcentrationswerenotablylowerthanthoseofthevolatilePFCs,theseare stillsignificantresults.thehighesttotalionicpfcconcentrationsbothshortandlongchain)were foundinsamplesfromthenoronajacketj03,99.9μg/m 2 )andthepatagoniajacketj10a,97.4 μg/m 2 andj10b,684μg/m 2 ),followedbythesalewajacketj11,62.4μg/m 2 ),consistingof14% J03),35%J10a),79%J10b),and100%J11)ofthetotalPFCconcentrationsforthesesamples, respectively. ThecompositionsofionicPFCsinthesethreejacketswerequitedifferenttoeachother.Forthe NoronajacketJ03),byfarthepredominantionicPFCswereshortchainPFCAs;theC6compound 76.4μg/m 2 PFHxA),whichwaspresenttogetherwiththeC41.72μg/m 2 PFBA),C510.6μg/m 2 PFPA)andC79.97μg/m 2 PFHpA)PFCAs,aswellaslowerconcentrationsoftheshortchainC4 sulfonate0.22μg/m 2 PFBS)andlongchainPFCAsincluding0.67μg/m 2 PFOA). Incontrast,forthePatagoniajacketJ10),theshortchainC4sulfonatePFBS)wasthepredominant ionicpfc,at28.9μg/m 2 inonesectionj10a)andat673μg/m 2 intheotherj10b).asseenforthe NoronajacketJ03),thePatagoniajacketJ10)alsocontainedrelativelyhighconcentrationsofshort chainpfcas,includingthec4pfba18.2μg/m 2 J10a,4.95μg/m 2 J10b),C6PFHxA25.1μg/m 2 J10a, 4.27μg/m 2 J10b)andC7PFHpA21.2μg/m 2 J10a,0.91μg/m 2 J10b),andtoalesserextenttheC5 PFPA3.79μg/m 2 J10a,1.04μg/m 2 J10b). ThecompositionwasverydifferentagainfortheSalewajacketJ11).AsforthePatagoniajacket J10),theshortchainC4sulfonatePFBS)wasthepredominantionicPFC,at31.6μg/m 2. GreenpeaceResearchLaboratoriesTechnicalReport Page8of54

9 Overall,therangeofconcentrationsofionicPFCsinthejacketsampleswasgenerallysimilarto thoseoftrousersandfootwear,andgenerallyhigherthanthoseinbackpacks,sleepingbagsand tents.asimilarpatternwasseenforvolatilepfcs,otherthanthattherangeofconcentrationsin thefootwearsampleswasgenerallyhigherthanforjacketssamples TworeportspreviouslypublishedbyGreenpeacein2012and2013includedresultsfromtheanalysis ofpfcsinanumberofwaterproofcoatsthatwerepurchasedintheyearofpublicationinbothcases Greenpeace2012c,2013c).Asinthecurrentstudy,bothionicandvolatilePFCswerecommonly detectedinwaterproofjacketsfrombothpreviousstudies.similarly,wherevolatilepfcswere detectedtheywerepresentatconsiderablyhigherconcentrationsthanionicpfcs,aswasthecasein thecurrentstudy. ConcentrationsofvolatilePFCsinthecurrentstudywereinasimilarrangeND 630μg/m 2 )tothose inthe2012reportupto464μg/m 2 ),butgenerallylowerthanthosefromthe2013report μg/m 2 ).Forthe2012study,bothlongandshortchainvolatilePFCcompoundsweredetected acrossalltheproducts.whilethepatternwassimilarforthe2013report,shortchainvolatilespfcs weremoreprevalentthanlongchainversions. Anotherstudypublishedin2015,forproductspurchasedin2010,alsodetectedbothshortandlong chainvolatileftohs,thoughinthiscaselongchainversions8:2ftohand10:2ftoh)dominated overshortchain6:2ftoh),withconcentrationsabove100μg/m 2 forboth8:2ftohand10:2ftoh Kotthoffet#al.2015). Thistrendfrom2010to2013continueswiththecurrentstudy,inwhichbothshortandlongchain volatilepfcsweredetected,butshortchainversionswereconsiderablymoreprevalentthanlong chainones,whichweredetectedinonly2ofthe12jacketsanalysed. Overall,totalionicPFCconcentrationsweresomewhathigherinthecurrentstudyND 684μg/m 2 ) thaninthestudyfrom μg/m 2 )andthatfrom2013. Inaddition,forthejacketsfromthe2012and2013reports,bothlongandshortchainionicPFCs werecommonlydetected,beingdominatedbypfcas,withthelongchainpfoabeinga predominantcompoundinmanycases.incontrast,ionicpfcsdetectedinthecurrentstudywere predominantlyshortchainpfcs.furthermore,shortchainsulfonatespfsas)weredetectedin manysamplesespeciallythec4pfbs),andthesewerethepredominantionicpfcsforsome samples,withveryhighconcentrationsintwocases μg/m 2 ).Thelongchainacid,PFOA, wasdetectedinmostsamples,thoughatlowerconcentrations μg/m 2 )thanthose generallyfoundinthe μg/m 2 )and μg/m 2 )reports. 3.1#Trousers# Asforthejacketsamples,thevolatilePFCswerethedominantPFCsbyconcentration.Oneormore volatilepfcwasdetectedinallsamplesoftrouserfabric.thehighesttotalvolatilepfc concentrationwasfoundinthejackwolfskintrouserstr04,530μg/m 2 ),thoughsomeother samplesalsohadhightotalvolatilepfcconcentrations,especiallythearc'teryxtrouserstr06,270 μg/m 2 ). GreenpeaceResearchLaboratoriesTechnicalReport Page9of54

10 ThemostcommonlydetectedvolatilePFCwastheshortchain6:2FTOH,identifiedinallbut1 sampletr05,patagonia),andwasgenerallythepfcwiththehighestconcentrationineachsample, withthearc'teryxtrouserstr006)containingthehighest6:2ftohconcentration270μg/m 2 ).6:2 FTOHwastheonlyvolatilePFCdetectedin4samplesTR02,Mammut;TR06,Arc'teryx;TR07, Haglöfs;TR08,Salewa),with2othersamplescontainingaround90%FTOHandwiththelongchain acrylate8:2ftaasaminorcomponenttr01,thenorthface;tr03,columbia). ThecompositionfortheJackWolfskintrousersTR04)wassomewhatdifferent.Threetelomer alcoholsweredetected,theshortchain6:2ftoh,andthelongchain8:2ftohand10:2ftoh,with 8:2FTOHconcentrationbeingslightlyhigherthantheothertwo240μg/m 2 ). TheotherexceptionfortrouserfabricwasthePatagoniatrousersTR05),forwhichthelongerchain telomeralcohols8:2ftohand10:2ftohweredetected,atnotablylowerconcentrationsthan6:2 FTOHintheothersamples.Inaddition,thecorrespondinglongchainfluorotelomeracrylates8:2 FTAand10:2FTAwerealsofound,atsimilarconcentrationstothealcohols. InadditiontothevolatilePFCs,ionicPFCsweredetectedinallbut1sampleTR07,Haglöfs).Though theionicpfcconcentrationswerenotablylowerthanthoseofthevolatilepfcs,thesearestill significantresults. Forthreesamples,theionicPFCsweredominatedbythepresenceoftheshortchainC4)sulfonate, PFBS.TheseweretheArc'teryxtrousersTR06,51μg/m 2 ),themammuttrouserstr02,36μg/m 2 ), andthejackwolfskintrouserstr0421μg/m 2 ).TheMammuttrousersTR02)alsocontaineda relativelylowconcentrationsofthelongchainc8sulfonate,pfos0.17μg/m 2 ). ThesethreesamplesalsocontainedappreciableamountsoftheC4andC6shortchainPFCAs,PFBA andpfhxa.inaddition,thejackwolfskintrouserstr04)alsocontainedhigherconcentrationsof thelongchaincompoundspfoac8,12.2μg/m 2 ),PFDAC10,8.78μg/m 2 )andpfdoac12,4.47 μg/m 2 ),aswellasrelativelylowerconcentrationsofarangeofotherlongchainpfcas. PFBSwasnotdetectedinthePatagoniatrousersTR05),thoughawiderangeofshortandlongchain PFCAswere,fromtheshortchainC4compoundPFBAtothelongchainC14compoundPFTeA,with thepredominantcompoundbeingthelongchainc8compoundpfoa2.47μg/m 2 ). ShortchainionicPFCswerealsodetectedintheSalewatrousersTR08),thoughatgenerallylower concentrations,withthemaincompoundbeingthec4pfba1.63μg/m 2 ). Asmentionedabove,noionicPFCsweredetectedintheHaglöfstrousersTR07),andtheColumbia trouserstr03)containedonlyrelativelylowconcentrationsoftheshortchainpfhxa0.41μg/m 2 ) andthelongchainpfoa0.20μg/m 2 ).Similarly,TheNorthFacetrousersTR01)containedtheshort chainpfhxa0.44μg/m 2 )andtwolongchaincompoundspfoa0.58μg/m 2 )andpfda0.13μg/m 2 ). Overall,therangeofconcentrationsofionicPFCsinthetrousersampleswasgenerallysimilarto thoseofjacketsandfootwear,andgenerallyhigherthanthoseinbackpacks,sleepingbagsand tents.asimilarpatternwasseenforvolatilepfcs,otherthanthattherangeofconcentrationsin thefootwearsampleswasgenerallyhigherthanfortrousersamples. GreenpeaceResearchLaboratoriesTechnicalReport Page10of54

11 TwopreviousGreenpeacestudieseachanalysedonewaterprooftrouserproduct,onepurchasedin 2012Greenpeace2012c)andtheotherin2013Greenpeace2014a).ThecompositionofPFCsfor thesetwoarticleswassomewhatdifferenttothatfoundinthecurrentstudy.novolatilepfcswere detectedinonestudygreenpeace2014a),andonlythelongchainfluorotelomeracrylate8:2fta 25.6μg/m 2 )detectedintheothergreenpeace2012c). Furthermore,oneiteminapreviousstudyhadahighconcentrationofthelongchainC6)sulfonate PFHxS542µg/m²and64.2µg/m²intwoseparateportionsfromthesamearticle),acompoundthat wasnotdetectedinthecurrentstudy.oneoftheportionsalsocontainedtheshortchainc4) sulfonatepfbs2.10µg/m²),thoughthiswasatanotablylowerconcentrationcomparedtothose samplescontainingpfbsinthecurrentstudy21to51µg/m²)greenpeace2014a).thisitemalso containedtheshortchainc6andc4pfcas,atconcentrationswithintherangefoundinthecurrent study. Similarly,fortheothertrouserarticlepreviouslyreported,anumberofPFCAsweredetectedwithin therangesfoundinthecurrentstudy,includingpfoaat2.31µg/m²greenpeace2012c). A2015paperreportingresultsforproductspurchasedin2010diddetectlongchainFTOHs,though atlowerconcentrationsthangenerallyfoundinthecurrentstudy,aswellasbothshortandlong chainionicpfcasatsimilarconcentrationstothecurrentstudy.noionicsulfonatesweredetected Kotthoffetal.2015). 3.2#Footwear# Asforjacketandtrousersamples,volatilePFCsweregenerallythedominantPFCsbyconcentration forfootwearsamples.thepatagoniabootf10)wastheonlyfootweararticleinwhichnovolatile PFCsweredetectedinanysample. Wheredetected,thetotalconcentrationsofvolatilePFCswerenotablyhigherinmostsamplesthan forothertypesofproduct.8sampleshadatotalvolatilepfcconcentrationofover1000μg/m 2, representingarticlesfromhaglöfs,salewa,mammut,thenorthface,jackwolfskinandcolumbia. OnesamplefromtheHaglöfsbootF02)hadthehighesttotalvolatilePFCconcentrationamongstall samplestestedfromallproducttypes3100μg/m 2 ),almostexclusivelycomposedoflongchain volatilepfcs. Foreachof2samplesF08,TheNorthFace;F11,Columbia),volatilePFCswerepresentatover1000 μg/m 2 inonesectionoffabricf08a,f11a)butnotdetectedinthesecondequivalentsectionof fabricineachcasef08b,f11b).qualitycontrolchecksconfirmthatsuchdifferencesreflectreal variationsinconcentrationsbetweendifferentpartsofthesamefabric. ForthosesamplesinwhichvolatilePFCsweredetected,theshortchain6:2FTOHwaseitherthe predominantoronlyvolatilepfcdetected,withtheexceptionof2ofthe3samplesfromthehaglöfs bootf02,outerpart;f03,innerpart).6:2ftohwasdetectedinoneormoresamplefromall brandswiththeexceptionofpatagonia,andwasdetectedatover1000μg/m 2 inonesamplefrom eachofthesalewa,thenorthface,jackwolfskinandcolumbiafootwear. GreenpeaceResearchLaboratoriesTechnicalReport Page11of54

12 ExamplesoflongchainvolatilePFCs,includingtelomeralcohols8:2FTOHand10:2FTOH)and fluorotelomeracrylates8:2ftaand10:2fta)weredetectedinallsamplesfromthehaglöfsf015 F03)andMammutF05)footwear,witharelativelylowamountinonesamplefromtheTheNorth FacebootF07). IonicPFCsweredetectedinallfootwearsamplesexceptonefromHaglöfsF03),though concentrationsweregenerallyconsiderablylowerthanvolatilepfcsinthesamesample.thetotal volatilepfcconcentrationwasover400timesthatofthetotalionicpfcconcentrationfor2samples F01,Haglöfs;F04,Salewa),thoughthetotalconcentrationsofionic&volatilePFCsintheSalewa samplewereamongstthelowerexamplesfromfootwear. ForaJackWolfskinsampleF09),theequivalentratiobetweenvolatileandionicPFCswas approximately100.lower,butstillsignificant,differenceswereseenbetweenthetotalvolatilepfc andtotalionicpfcconcentrationsforsamplesfrommammutf05),thenorthfacef07,f08a)and ColumbiaF11a). Acrossfootwearsamples,theconcentrationsandcompositionofionicPFCsvariedgreatlybetween individualsamples.examplesofbothshortandlongchainionicpfcswerefound,including examplesofeachwithrelativelyhighconcentrations. ThehighestconcentrationofionicPFCswasfortheshortchainC4)sulfonate,PFBS,inonesection fromasampleofthethenorthfacebootf08b,195μg/m 2 ),withtheconcentrationinthesecond sectionofthisfabricf08a)being22.5μg/m 2 ).AhighconcentrationofPFBSwasalsofoundina samplefromthecolumbiashoef11,52.7μg/m 2 )andfromthejackwolfskinbootf09b, 19.8μg/m 2 ;F09a3.62μg/m 2 ),andtoalesserextentinthemammutbootf05,1.50μg/m 2 ). AtleastonesamplesfromeachofTheNorthface,ColumbiaandMammutfootwearthoughnotthe JackWolfskinboot)alsocontainedtheequivalentC4PFCAPFBA)inappreciableconcentrations between5.99and10.9μg/m 2 ). ThoughPFBSwasnotdetectedintheHaglöfbootsamples,oneoftheseF02)didcontainPFBAinan appreciableconcentration4.39μg/m 2 ),togetherwitharangeofothershortchainandlongchain ionicpfcas,includingthehighestconcentrationofthelongchainpfoafoundinanyfootwear sample18.3μg/m 2 ). Similarly,theMammutsampleF05)alsocontainedawiderangeofshortchainandlongchainionic PFCAs,fromC4PFBA)toC14PFTeA),includingthesecondhighestPFOAconcentrationamongst footwearsamples12.7μg/m 2 ). TheconcentrationbyareaofPFOAintheHaglöfsampleF02)wasthehighestamongstallsamples ofallproducttypes,withthatforthemammutsamplef05)beingthethirdhighest. PFOAwasalsodetectedabove1μg/m 2 inanumberofothersamples,includingfromhaglöfsf01, 1.83μg/m 2 ),JackWolfskinF09a,3.53μg/m 2 ;F09b,4.99μg/m 2 ),PatagoniaF10,2.88μg/m 2 ) andcolumbiaf11,1.23μg/m 2 ).Similarly,theSalewasampleF04)containedPFOA1.80μg/m 2 )as wellastheequivalentlongchainsulfonate,pfosat1.07μg/m 2 ).LowerlevelsofPFOAwerealso detectedintwothenorthfacesamplesf07,f08a)at0.223and0.813μg/m 2 respectively. GreenpeaceResearchLaboratoriesTechnicalReport Page12of54

13 OtherexamplesofshortchainPFHxA)andlongchainPFDA)ionicPFCswerealsodetectedina numberofsamplesatbetween152μg/m 2. TwoadditionalionicPFCsweredetectedinsamplesfromtheNorthFaceshoe,HPFHpA1.13μg/m 2 ) and6:2fts0.251μg/m 2 and2.03μg/m 2 ).ThesePFCsweredetectedinonlyasmallnumberof samplesacrossallproducttypesinthisstudyandinlowerconcentrations,withtheexceptionof6:2 FTSinonejacketJ11,23.6μg/m 2 ). InapreviousGreenpeacestudyGreenpeace2014a),ionicPFCsweredetectedinthreefootwear sampleswithintherangeofconcentrationfoundinthecurrentstudy,thoughinthelowerpartof therange μg/m 2 ).Inthatstudy,shortchainC4)PFCsdominated,aswasthecasefora numberofsamplesinthisstudy,thoughonesamplefromthepreviousstudycontainedthelong chainpfosat0.855μg/m 2. Incontrasttothisstudy,volatilePFCsweredetectedinonly1ofthe3samples,andatlower concentrationsthanvolatilepfcsinthecurrentstudy390μg/m 2 totalvolatilepfcs).onlylong chainvolatilepfcsweredetected. Itshouldbenoted,however,thatthefootweartestedinthepreviousstudywasintendedfornormal everydayuseratherthanbeingintendedforhiking. 3.3#Backpacks# Atotalof14sampleswereanalysed,from8individualbackpacks.VolatilePFCsweredetectedin threesamples,theouterfabricfromthejackwolfskinbackpackbp01),andboththebottomfabric BP05)andblueouterfabricblueBP06)fromtheMammutbackpack.NovolatilePFCswere detectedinsamplesfromtheother6backpacks Thelongchain8:2FTOHwastheonlyvolatilePFCdetectedintheouterfabricoftheJackWolfskin backpackbp01),at37μg/m 2.Forthe2samplesfromtheMammutbackpack,8:2FTOHwasalso detectedinboth,at72μg/m 2 inthebottomfabricbp05)and54μg/m 2 intheouterfabricbp06). ThetwosamplesfromtheMammutbackpackalsocontainedthelongchain10:2FTOHat23μg/m 2 and15μg/m 2 inthebottomfabricbp05)andouterfabricbp06),respectively. ThetotalconcentrationofvolatilePFCsinthebottomfabricBP05)oftheMammutbackpackwas12 timesthetotalionicpfcconcentration,and60timesgreatintheouterfabricbp06).noionicpfcs weredetectedintheouterfabricofthejackwolfskinbackpackbp01)whichcontainedavolatile PFC. OneormoreionicPFCwasdetectedin11ofthe14samples,withexamplesfromallbutone backpack.noionic,andnovolatilepfcs,weredetectedinthehaglöfsbackpackbp14).also,onlya relativelylowamountofasinglecompound,thelongchainpfoa,wasdetectedintheouterfabricof thearc'teryxbackpackbp09,0.14μg/m 2 ),andsimilarlyonlypfoawasdetectedinthebeltfabricof thejackwolfskinbackpack,thoughatamoderatelyhigherconcentrationbp02,0.79μg/m 2 ). Similarly,arelativelylowamountofPFOAwasdetectedintheTheNorthFacebackpackBP11,0.09 μg/m 2 ),togetherwithaslightlyhigherleveloftheshortchainpfhxa0.18μg/m 2 ). GreenpeaceResearchLaboratoriesTechnicalReport Page13of54

14 AnumberofshortandlongchainionicPFCsweredetectedintheColumbiabackpackBP12&BP13), allatrelativelylowtomoderateconcentrations,withindividualpfcsintherange μg/m 2 including0.44μg/m 2 ofthelongchainpfoainthelightblueouterfabricbp12). ForbothsamplesfromtheVaudebackpackBP07&BP08),asingleionicPFCwasdetected,thelong chainpfoa,at μg/m 2. ThecompositionfortheMammutbackpacksamplesBP05&BP06)wassomewhatdifferent.Both samplescontainedthelongchainpfoa,at4.24μg/m2bottomfabric,bp05)and1.16μg/m 2 blue outerfabric,bp06)respectively.inaddition,otherlongchainpfcsweredetectedinthebottom fabricbp05),namelythec10pfda)andc12pfdoa)compounds,at2.40μg/m 2 and1.43μg/m 2, respectively. Incontrast,onefabricfromthePatagoniabackpackBP04a,BP04b)containedtheshortchain sulfonatepfbsbp04a9.42μg/m 2,BP04b3.18μg/m 2 ).ThisPFCwasnotedetectedinanyofthe otherbackpacksamples,andtheconcentrationinoneofthepatagoniabackpacksamplesbp04a) wasthehighestofanyionicpfcinallbackpacksamples.thissamplebp04a)alsocontainedother shortchainpfcas,includingthec4pfba3.98μg/m 2 ),aswellasalowtomoderateconcentrations ofthelongchainc8pfcapfoa,0.29μg/m 2 )andc8pfsapfos0.09μg/m 2 ). ThetotalionicPFCconcentrationsforonefabricfromthePatagoniabackpackBP04a,BP04b)and onefromthemammutbackpackbp05)weremorethan5timesthetotalionicpfcconcentrations inallsamplesfromallotherbackpacks. VolatileandionicPFCswerelesscommonlydetectedinbackpacksamplesand,wheredetected, werepresentatgenerallylowerconcentrationscomparedtojackets,trousers,footwear.where detected,volatilepfcconcentrationsweresimilartothoseforsleepingbagandtentsamples, thoughvolatilepfcswerelessfrequentlydetectedinbackpacksamples.wheredetected,totalionic PFCconcentrationsweregenerallysimilartothoseforsleepingbagsandhigherthanthosefortent samples. NopreviousdataforPFCsinbackpackfabriccouldbefoundforcomparison. 3.4#Sleeping#bags# ForoneofthetwosleepingbagsSB02&SB03,TheNorthFace),arangeoflongandshortchain ionicpfcs,predominantlylongchainpfcas,aswellaslongchainvolatilepfcs,weredetectedin boththeoutersb02)andinnersb03)fabric,withhigherconcentrationsintheouterfabric.forthe outerfabricsb02),thetotalvolatilepfcsconcentrationwas92%ofthetotalpfcconcentration, withanequivalentfigureof98%fortheinnerfabricsb03). OfthePFCAs,thepredominantcompoundswerethelongchainC8PFOAandC10PFDAcompounds forboththeoutersb02)andinnersb03)fabric: TheouterfabricSB02)containedPFOA7.10μg/m 2,59%oftotalionicPFCs)andPFDA2.84 μg/m 2,24%oftotalionicPFCs); GreenpeaceResearchLaboratoriesTechnicalReport Page14of54

15 TheinnerfabricSB03)containedPFOA0.36μg/m 2,43%oftotalionicPFCs)andPFDA0.20 μg/m 2,24%oftotalionicPFCs). OtherlongchainPFCAswerealsodetectedinbothfabrics,includingtheC12PFDoA. OtherionicPFCswerealsodetectedintheinnerfabricofthissleepingbagSB03),thoughat relativelylowconcentrations,namelyhpfhpa0.07μg/m 2 )and6:2fts0.02μg/m 2 ).Overallinthis study,neitherofthesetwopfcsweredetectedinthemajorityofsamples,with6:2ftsbeingfound inonlytwojacketsj07&j11)andtwofootwearsamplesf07&f08),atsimilarorsomewhathigher concentrations,andwithanotablyhigherconcentrationof6:2ftsforonejacketj11,23.6μg/m 2 ). ThepredominantvolatilePFCswerethelongchaintelomeralcohols,8:2FTOH52μg/m 2 and35 μg/m 2 intheouterandinnerfabricrespectively)and10:2ftoh15μg/m 2 and12μg/m 2 intheouter andinnerfabricrespectively).forboththeouterandinnerfabric,theconcentrationsof8:2ftoh and10:2ftohwereinaratioofapproximately3:1,withtheseftohscomposing100%and90%of thetotalvolatilesconcentrationfortheouterandinnerfabric,respectively.twolongchainftas werealsodetectedintheinnerfabric;8:2fta3.3μg/m 2 )and10:2fta1.5μg/m 2 ),atbetween8to 10timeslessconcentrationscomparedtotheequivalentalcohols8:2FTOHand10:2FTOH). ThecompositionofindividualvolatilePFCsforbothsamplesreflectsthatofionicPFCs,withtheC8 compounddominating,followedbythec10,andwiththerelativeproportionsofc8andc10 compoundsbeinginasimilarratioforbothvolatileandionicpfcs.thissuggestsalinkbetweenthe originoftheionicandthevolatilec8andc10compounds. FortheothersleepingbagSB01,Mammut),onlyasinglevolatilePFCandasingleionicPFCwere detectedintheouterfabric.byfarthepredominantcompoundwastheshortchainvolatilepfc,6:2 FTOH41μg/m 2 ),atasimilarconcentrationtothatofthemainftohthelongchain8:2ftoh, 52μg/m 2 )inthethenorthfacesleepingbagouterfabricsb02).theionicpfcinthemammut sleepingbag,theshortchainpfhpa,waspresentatarelativelylowconcentration0.17μg/m 2 ). TheouterfabricfromtheTheNorthFacesleepingbagSB02)containedthehighestconcentrationof PFOAbymass157000ng/kg)ofallsamplesfromall40products.Inaddition,thetotalionic concentrationbymasswasoneofthehighest.furthermore,thetotalvolatileconcentrationsby massforthethreesleepingbagsamplesweresomeofthehighestofallsamples,especiallyforthe outerfabricofthethenorthfacesleepingbagsb02,1500µg/kg).inaddition,theindividual concentrationsofthelongchaintelomeralcohols,8:2ftohand10:2ftoh,inthethenorthface samplessb02,sb03)weresomeofthehighestconcentrationsbymassofallsamples. Thoughconcentrationsbetweenindividualsamplesvariedgreatlywithindifferentproducttypes, somecomparisoncanbemadewithothertypesofproduct.therangeandmedianconcentrations forbothionicandvolatilepfcsinthethreesleepingbagsamplesweresimilartothoseforbackpack samples.incontrast,concentrationsofionicandvolatilepfcsinsleepingbagsweregenerallylower thanthoseinjackets,trousersandfootwear,butgenerallyhigherthanthoseintentsamples. NopreviousdataforPFCsinsleepingbagfabriccouldbefoundforcomparison. GreenpeaceResearchLaboratoriesTechnicalReport Page15of54

16 3.5#Tents# ForoneofthetwotentsTE055TE07,JackWolfskin),volatilePFCsweredetectedintwoofthethree fabricssamplesanalysed.twolongchainftohsweredetectedintheinnerfabricte06),8:2ftoh 34μg/m 2 )and10:2ftoh8.8μg/m 2 ),aswellastwolongchainftas,8:2fta10μg/m 2 )and10:2 FTA3.7μg/m 2 ).TheFTAconcentrationswerebetween2to3timeslowerthantheconcentrations oftheequivalentalcohols8:2ftohand10:2ftoh).fortheouterfabricte05),theonlyvolatile PFCdetectedwas8:2FTOH12μg/m 2 ). IonicPFCswerealsodetectedinthetwosamplesinwhichFTOHswerefound,withtotal concentrationsofionicpfcsintheinnerfabricte06,0.58μg/m 2 )andouterfabricte05,2.10 μg/m 2 )constituting1%and15%ofthetotalpfcconcentrationinthesetwofabrics,respectively. FortheinnerfabricTE06)andouterfabricTE05),thetotalvolatilePFCconcentrationwas98times and5.7timesthetotalionicpfcconcentrationineachsample,respectively. OftheionicPFCs,thelongchaincompound,PFOA,wasthemaincompoundinboththeinnerfabric TE06)andouterfabricTE05),at0.35μg/m 2 and0.68μg/m 2,respectively,withtheouterfabric TE05)alsocontaininganotherlongchaincompound,PFDA,ataslightlylowerconcentration0.56 μg/m 2 ). TheionicPFCsintheJackWolfskintentsamplesweredominatedbyshortandlongchainPFCAs, thoughalongchainsulphonamide,pfosa,wasalsodetectedintheouterfabricte05,0.13μg/m 2 ). ThiswastheonlysamplefromthiswholestudyinwhichthisPFCwasdetected. FortheothertentTE015TE04,TheNorthFace),theinnerfabricTE02)containedonevolatilePFC, theshortchain6:2ftoh37μg/m 2 ),constitutingover99.7%ofthetotalpfcconcentration.this compoundistheshorterchainversionoftheftohsdetectedinthesamplesfromthejackwolfskin tentte05,te06).novolatilepfcsweredetectedintheotherthreesamplesfromthethenorth FacetentTE01,TE03,TE04).ArelativelylowconcentrationofasingleshortchainionicPFCwas alsodetectedintheinnerfabricte02,0.09μg/m 2 PFHxA).PFOA,thelongchainequivalentof PFHxA,wasdetectedatasimilarlevelintheoutercompositefabricTE03,0.04μg/m 2 PFOA),with noionicpfcsbeingdetectedineithertheouterfabricte01)ortheinnerfabricbottom)te04). Thoughconcentrationsbetweenindividualsamplesvariedconsiderably,especiallyforionicPFCs, somecomparisoncanbemadewithothertypesofproduct.volatilepfcsweregenerallyless prevalentinthetentsamplescomparedtothosefromothertypesofproduct,withtheexceptionof backpacks.similarly,concentrationsofionicpfcsweregenerallyfarlowerinthetentsamplesthan thosefoundinothertypesofproduct,withthepossibleexceptionofsleepingbags,thoughonly3 sleepingbagsampleswereanalysed. NopreviousdataforPFCsintentfabriccouldbefoundforcomparison. 3.6#Rope# ThreeshortchainPFCAsweredetectedinthesampleofclimbingropeR01,Mammut),including PFBA2570ng/kg),PFPA2350ng/kg)andPFHxA6510ng/kg),aswellasoneshortchaintelomer alcohol,6:2ftoh646μg/kg).astheropedidnotcontainflatfabric,dataarenotgivenbyarea GreenpeaceResearchLaboratoriesTechnicalReport Page16of54

17 μg/m 2 ).AsforotheritemsinwhichbothvolatileandionicPFCsweredetected,theconcentration of6:2ftohwasconsiderablyhigherthanthetotalconcentrationofionicpfcs57timeshigher). Comparingwithothertypesofproducts,theconcentrationbymassof6:2FTOHtheonlyvolatile PFCdetected)wasintherangeofFTOHconcentrationsbymassforjackets,trousers,footwearand sleepingbags,andsomewhathigherthanconcentrationsofftohsinsamplesfrombackpacksand tents.longchaintelomeralcohols,identifiedinmanyexamplesoftheotherproducttypes,were notdetectedintheropesample.thetotalionicpfcconcentrationbymassintherope11400 ng/kg=11.4μg/kg)wasintherangeofequivalentconcentrationsofotherproducttypes. Itshouldbenoted,however,thatonlyasinglesampleofropewasanalysed,andthePFC compositionofotherequivalentropeproductscouldvarysignificantly,aswasseenforothertypes ofproduct.foreachoftheothertypesofproduct,therewereindividualexampleswitheithera notablylowerorhigherconcentrationoftotalionicpfcs.forvolatilepfcs,thetotalconcentration inmanyexamplesfromothertypesofproductsweresimilartothatfoundintherope,thoughagain therewereexampleswitheitheralowerorhighertotalvolatilepfcconcentrationformanytypesof product.itis,therefore,notpossibletomakeanygeneralcomparisonbetweenclimbingropeand othertheothertypesofproductsintermsofthepfccontent. NopreviousdataforPFCsinclimbingropecouldbefoundforcomparison 3.7#Glove# NoPFCsweredetectedintheGloveGL01).Thoughnotdirectlycomparable,PFCswerepreviously reportedinwaterproofglovespurchasedin2013inapreviousgreenpeaceinvestigation,including PFOS9.5μg/m 2 )inonegloveandhighconcentrationsofftohsinanother1900μg/m 2 ) Greenpeace2013b). Similarly,a2015reportforproductspurchasedin2010foundthelongchainsulfonate,PFOS,atover 100μg/m 2 aswellasftohs,predominantlythelongchain8:2ftohand10:2ftohatover10μg/m 2 Kotthoffetal.2015) 4.#Conclusions# ThisstudyhasdemonstratedthepresenceofPFCswithinabroadrangeofoutdoorproducts.Ionic and/orvolatilepfcsofsometypeweredetectedinalloftheproductsanalysed,withtheexception of2ofthe11jacketsvaude,j01andjackwolfskinjacket,j12),1ofthe8backpackshaglöfs,bp14) andtheoneglovesample.forbothionicandvolatilepfcs,concentrationsvariedconsiderably betweenindividualarticleswithineachproductgroup,andalsoacrossallsamplesasawhole.in general,forarticlesinwhichbothionicandvolatilepfcsweredetected,volatilepfcswerepresent inconsiderablehigherconcentrationsthanionicpfcs.forotherarticles,concentrationsofvolatile PFCswerehigherthanconcentrationsofionicPFCsfoundthearticle,orthanthosetypicallyfoundin otherarticlesofthesametypeofproduct. GreenpeaceResearchLaboratoriesTechnicalReport Page17of54

18 Therewere,however,examplesforwhichneitherionicnorvolatilePFCsweredetected,including2 jacketsvaude,j01;jackwolfskin,j12),abackpackhaglöfs,bp14),andtheglovethenorthface, G01). SpecificvolatilePFCscandegradeintospecificionicPFCs,includingPFCAs.Forexample,8:2FTOH cangiverisetothec8pfca,pfoa.forallsamples,whereatelomeralcoholftoh)andthe correspondingpfcawerebothdetectedforexample8:2ftohandpfoa),theftohconcentration wasalwayshigherthanthatofthecorrespondingpfca,andoftenconsiderablyhigher.therewas, however,nootherconsistentrelationshipbetweentheftohconcentrationandthatofthe correspondingpfca. For9ofthe11brandsincludedinthisstudy,oneormorearticlefromeachbrandhadanotablyhigh concentrationofatleastoneionicpfc.inaddition,oneormorearticlefromeachbrandhada notablyhighconcentrationofatleastonevolatilepfc.forblackyak,thiswasalsothecasefor volatilepfcs,butnotforionicpfcs.althoughsomeionicpfcsweredetectedintheblackyakjacket, equivalentarticlesfromotherbrandshadconsiderablyhigherconcentrationsofionicpfcs. ForVaude,novolatilePFCsweredetectedinanyofthe3samplesfrom2articles.Similarly,onlya singleionicpfc,thelongchainpfoa,wasdetectedinthe2samplesfromthevaudebackpack.the PFOAconcentrationsweresignificant,beingjustover1μg/m 2,andintherangeforotherbackpack samples,thoughsomeotherbackpacksampleshadnotablyhighertotalionicpfcconcentrations. Itshouldbenoted,however,thatsomebrandswererepresentedbymoresamplesthanothersin thisstudy,eitherduetoagreaternumberofarticlesoragreaternumberofseparatematerials analysedcomparedtoothersbrands.itisnotpossible,therefore,todirectlycomparethebrands productsasawholeonthebasisofthisstudy. Aswellasthetwosubgroupsofionicandvolatilecompounds,PFCscanalsobedistinguishedas eithershortchainorlongchaincompounds.ionicpfcscanbeeithershortchainorlongchain,and volatilepfcscanbeeithershortchainorlongchainseesection2fordetails). Forjackets,bothionicandvolatilePFCswerepredominantlyshortchaincompounds.Onesample hadbyfarthehighestconcentrationoftheionicc4compoundpfbsofallproductsinthestudy. ThoughonejackethadhighconcentrationoflongchainvolatilePFCs8:2FTOHand10:2FTOH; Blackyak),forallotherjacketsonlytheshortchaincompound,6:2FTOH,waspresentwhenvolatile PFCweredetected ThispatternfurthersupportsashiftinthetypeofPFCsinjacketsovertimecomparedtowhatwas discoveredinpreviousgreenpeacereportsfrom2012and2013greenpeace2012c,2013c)anda paperfromanotherresearchgroupfrom2015basedonproductspurchasedin2010kotthoffetal. 2015)..Bothshortandlongchaincompoundswererepresentedinjacketsfromthesestudies,with longchaincompoundsbeingthepredominantionicpfcs.similarly,longchainvolatileftohswere predominantintheproductspurchasedin2010kotthoffetal.2015),whileshortchainversions weremorerepresentedinthe2013greenpeacestudy.thecurrentstudysuggeststhatashift towardsgreateruseofshortchainpfcscontinues,forbothvolatileandioniccompounds. GreenpeaceResearchLaboratoriesTechnicalReport Page18of54

19 Fortrousers,backpacksandfootwear,thecurrentstudyfoundthatbothshortandlongchainionic PFCsweresimilarlyrepresented,thoughtherewasonenotablyhighconcentrationofshortchain C4)ionicPFCsinonebackpackPatagonia). Thepattern,however,wassomewhatdifferentforvolatilePFCs.Greater,thoughnotexclusive, prevalenceofshortchainvolatilepfcswasseenfortrouserandfootwearsamples,thoughonlylong chainvolatilepfcsweredetectedinbackpacksamples,withnovolatilepfcsbeingdetectedinmost backpacksamples. Asforjackets,thecurrentstudydoesfurthersupportashifttowardsshortchainPFCsintrousers. BothshortandlongchainPFCsweresimilarlyrepresentedinasinglearticleina2012Greenpeace reportgreenpeace2012c)andanotherreportforproductspurchasedin2010,withonlylongchain volatileftohsdetectedinthe2010itemkotthoffetal.2015).incontrast,theionicpfcsidentified wereexclusivelyshortchaincompoundsinasinglearticlepurchasedin2013,inwhichnovolatile PFCsweredetectedGreenpeace2014a). Incontrast,shortchainC4)ionicPFCsdominatedinfootwearsamplesfromonepreviousstudy, whilebothlongandshortchainionicpfcswerefoundinthecurrentstudy,whichdoesnotreflecta shifttowardsshortchainpfcsforfootwear,thoughthisisbasedononlythreesamplesinthe previousstudywhichmaynothavebeenrepresentativeoffootwearingeneralsoldatthetime Greenpeace2014a).Inthispreviousstudy,however,only3footweararticlesweretested,and thesewereintendedfornormaleverydayuseratherthanbeingintendedforhiking,andsonot directlycomparabletothecurrentstudy. BothshortandlongchainionicPFCsweresimilarlyrepresentedforsleepingbagandtentsamples, thoughwithonly2articlesforeachproducttypeitisdifficulttodrawanyconclusionsfromthese dataregardingapatternintheuseofshortorlongchaincompounds.fortheropesample,only shortchainversionsofbothionicandvolatilepfcsweredetected,thoughonlyasinglearticlewas tested. 5.#References# Brigden K, Santillo D & Johnston P 2012). Nonylphenol ethoxylates NPEs) in textile products, and their release through laundering. Greenpeace Research Laboratories Technical Report 01/2012, 14pp. Brigden, K., Wang, M., Hetherington, S., Santillo, D. & Johnston, P. 2013) Hazardous chemicals in a selection of textile products manufactured in Shishi City & Huzhou City during Greenpeace Research Laboratories Technical Report , December Butt, C.M., Muir, D.C., Mabury, S.A. 2013) Biotransformation pathways of fluorotelomer-based polyfluoroalkyl substances: A review. Environmental Toxicology & Chemistry 332): Frömel, T., & Knepper, T.P. 2010) Biodegradation of fluorinated alkyl substances. Reviews of Environmental Contamination and Toxicology 208: Greenpeace 2011). Dirty Laundry 2: Hung Out to Dry - Unravelling the toxic trail from pipes to products, GreenpeaceResearchLaboratoriesTechnicalReport Page19of54

20 pp32. nufacture_china.pdf Greenpeace 2012a). Toxic Threads: The Big Fashion Stitch-Up. Stitch-Up/ Greenpeace 2012b) Dirty Laundry: Reloaded - How big brands are making consumers unwitting accomplices in the toxic water cycle, pp48. Greenpeace 2012c) Chemistry for any weather: Greenpeace tests outdoor clothes for perfluorinated toxins; Greenpeace 2013a) Greenpeace: Bademoden mit gefährlichen Chemikalien belastet German). Greenpeace 2013b) Schadstoffe in G-Star Produkten German) Greenpeace 2013c). Chemistry for any weather II. December eport%202013_1.pdf Greenpeace 2014a). A little story about the monsters in your closet. Greenpeace 2014b). A Red Card for sportswear brands: Hazardous chemicals found in World Cup merchandise. Langer, V., Dreyer, A., Ebinghaus, R. 2010) Polyfluorinated compounds in residential and nonresidential indoor air. Environmental Science & Technology 4421): Nilsson, H., Kärrman, A., Rotander, A., van Bavel, B., Lindström, G., Westberg, H. 2013) Biotransformation of fluorotelomer compound to perfluorocarboxylates in humans. Environment International 51: 8-12 OECD-UNEP 2013) Synthesis paper on per- and polyfluorinated chemicals PFCs). OECD/UNEP Global PFC Group, Organisation for Economic Cooperation and Development OECD) & United Nations Environment Program UNEP). Rand, A.A., Mabury, S.A. 2012) In vitro interactions of biological nucleophiles with fluorotelomer unsaturated acids and aldehydes: fate and consequences. Environmental Science & Technology 4613): Schlummer, M., Gruber, L., Fiedler, D., Kizlauskas, M., Müller, J. 2013) Detection of fluorotelomer alcohols in indoor environments and their relevance for human exposure. Environment International 57-58: 42-9 Young, C.J. & Mabury, S.A. 2010) Atmospheric perfluorinated acid precursors: chemistry, occurrence, and impacts. Reviews of Environmental Contamination and Toxicology 208): GreenpeaceResearchLaboratoriesTechnicalReport Page20of54

21 Appendix1.ConcentrationsofPFCsinallarticlestested Jackets, Sample,code, J01 J02 J03i) J04 J05i) J06 J07i) J08 J09 J10a J10b J11 J12 Brand, Product,name, Vaude Mammut Norrona Blackyak Columbia Haglöfs Arc'teryx TheNorth Face Fjordan men Nordwand ProHS Hooded Lofoten Gore5tex pro U5Jade#1 Alpine action L.I.MIII AlphaSL Women Stratos Patagonia Salewa Jack Wolfskin PATAGONIAMEN'S SUPERALPINE UltarGTX ACTM Amply3in1 Part,analysed, backpart backpart backpart inner outer backpart backpart backpart backpart mixedmaterials backpart backpart China, Turkey, China, Vietnam, Vietnam, China China Bangladesh, Vietnam, Vietnam, unknown, Country,of,production, Mainland), Mainland), Place,of,sale, Germany, Switzerland, Norway, Korea, Chile, Finland, Sweden, Sweden, Taiwan, Italy, Austria, Ionic,PFCs,ng/kg),,,,,,,,,,,,,, PFBS < < < < <1050 PFHxS <3970 <1010 <769 <528 < <847 <938 <658 <714 <3410 <725 <1050 PFHpS <3970 <1010 <769 <528 <746 <796 <847 <938 <658 <714 <3410 <725 <1050 PFOS <2650 <671 <513 <352 < <565 <625 <439 <476 < <697 PFDS <3970 <1010 <769 <528 <746 <796 <847 <938 <658 <714 <3410 <725 <1050 PFBA < < < <697 PFPA < < < < <697 PFHxA < < <697 PFHpA < <352 <498 < < <697 PFOA <2650 < < <697 PFNA <2650 < <352 <498 <531 <565 <625 <439 <476 <2270 <483 <697 PFDA <2650 < < <625 < <2270 <483 <697 PFUnA <2650 <671 <513 <352 <498 <531 <565 <625 <439 <476 < <697 PFDoA <2650 <671 < <498 <531 <565 <625 <439 <476 <2270 <483 <697 PFTrA <2650 <671 <513 <352 <498 <531 <565 <625 <439 <476 <2270 <483 <697 PFTeA <2650 <671 <513 <352 <498 <531 <565 <625 <439 <476 <2270 <483 <697 PFOSA <529 <336 <513 <352 <498 <531 <565 <625 <439 <476 <2270 <483 <697 PF53,75DMOA <5290 <1340 <1030 <704 <995 <1060 <1130 <1250 <877 <952 <4550 <966 <1390 HPFHpA <5290 <1340 <1030 <704 <995 <1060 <1130 <1250 <877 <952 <4550 <966 <1390 H2PFDA <5290 <1450 <1030 <704 <995 <1440 <1640 <5780 <4810 <3860 <4550 <966 <1590 H4PFOS;6:2FTS <3970 <1010 <769 <528 <746 < <2450 <658 <714 < <1050 Total,ionic,PFCs, GreenpeaceResearchLaboratoriesTechnicalReport Page21of54