Per'andpoly'fluorinatedchemicalsinbrandedwaterproofclothing, footwear,hikingandcampingequipment KevinBrigden,ManfredSanten,DavidSantillo GreenpeaceResearchLaboratoriesTechnicalReport01'2016,January2016 Contents 1.Introduction...2 2.Materialsandmethods...2 3.ResultsandDiscussion...4 3.1Jackets...7 3.1Trousers...9 3.2Footwear...11 3.3Backpacks...13 3.4Sleepingbags...14 3.5Tents...16 3.6Rope...16 3.7Glove...17 4.Conclusions...17 5.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 GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page1of54
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 11 8 7 8 2 2 1 1 40 Table1.Summaryofthedifferenttypesofproductsandthecountryofsale.J5Wolfskin=JackWolfskin GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page2of54
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 GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page3of54
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 11 9 9 ND5684 5.16 8 ND5640 72 trousers 8 8 7 ND 75.5 42.1 8 46 700 150 footwear 7 7 7 ND 195 19.4 6 ND53100 1200 backpack 8 7 7 ND 14.4 0.79 2 ND597 0 sleepingbag 2 2 2 0.17512.0 0.83 2 31 67 51 tent 2 2 2 ND 2.24 0.07 2 ND557 0 glove 1 0 0 ND 5 0 ND 5 Table2.SummaryofarticlesinwhichPFCsweredetected,togetherwiththerangesandmediansofthetotal concentrationsbyareaforionicpfcsandvolatilepfcsμg/m 2 ).Theropesampleisnotincludedasdataare availableonlybymassng/kg).nd notdetected.rangeandmedianvalueswerecalculatedusingbothsets ofdataforthosesamplesfromwhichtwosectionsofequivalentfabricwereanalysed. Thedatafortheduplicateanalysisonthreesamplesdemonstratesacceptablereproducibilityforthe extractionandanalysismethod.fortwosamplesbackpackbp05andsleepingbagsb02),the differencebetweenconcentrationsinthetwoduplicateswasbelow140%.forthethirdsample GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page4of54
GreenpeaceResearchLaboratoriesTechnicalReport0152016 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 ) 0 500 1000 1500 2000 2500 3000 3500 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 ) 0 100 200 300 400 500 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 )
concμg/m 2 ) 700 600 500 400 300 200 100 6:2FTS 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 ) 100 80 60 40 6:2FTS 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 ) GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page6of54
concμg/m 2 ) 3500 3000 2500 2000 1500 1000 500 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 ) 800 600 400 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 GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page7of54
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. GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page8of54
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 ),butgenerallylowerthanthosefromthe2013report48.95 2090μg/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 ) thaninthestudyfrom20120.58 10.96μg/m 2 )andthatfrom2013. Inaddition,forthejacketsfromthe2012and2013reports,bothlongandshortchainionicPFCs werecommonlydetected,beingdominatedbypfcas,withthelongchainpfoabeinga predominantcompoundinmanycases.incontrast,ionicpfcsdetectedinthecurrentstudywere predominantlyshortchainpfcs.furthermore,shortchainsulfonatespfsas)weredetectedin manysamplesespeciallythec4pfbs),andthesewerethepredominantionicpfcsforsome samples,withveryhighconcentrationsintwocases28.95672μg/m 2 ).Thelongchainacid,PFOA, wasdetectedinmostsamples,thoughatlowerconcentrations0.07 0.67μg/m 2 )thanthose generallyfoundinthe20120.255.0μg/m 2 )and20130.156.3μg/m 2 )reports. 3.1#Trousers# Asforthejacketsamples,thevolatilePFCswerethedominantPFCsbyconcentration.Oneormore volatilepfcwasdetectedinallsamplesoftrouserfabric.thehighesttotalvolatilepfc concentrationwasfoundinthejackwolfskintrouserstr04,530μg/m 2 ),thoughsomeother samplesalsohadhightotalvolatilepfcconcentrations,especiallythearc'teryxtrouserstr06,270 μg/m 2 ). GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page9of54
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. GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page10of54
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. GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page11of54
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. GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page12of54
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 therange2.23519.7μg/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 ). GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page13of54
AnumberofshortandlongchainionicPFCsweredetectedintheColumbiabackpackBP12&BP13), allatrelativelylowtomoderateconcentrations,withindividualpfcsintherange0.0950.44μg/m 2 including0.44μg/m 2 ofthelongchainpfoainthelightblueouterfabricbp12). ForbothsamplesfromtheVaudebackpackBP07&BP08),asingleionicPFCwasdetected,thelong chainpfoa,at1.151.2μg/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); GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page14of54
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. GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page15of54
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 GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page16of54
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. GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page17of54
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. GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page18of54
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. http://www.greenpeace.to/greenpeace/wpcontent/uploads/2012/03/dirty_laundry_product_testing_technical_report_01-2012.pdf 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 2013. Greenpeace Research Laboratories Technical Report 05-2013, December 2013. http://www.greenpeace.to/greenpeace/?p=1684 Butt, C.M., Muir, D.C., Mabury, S.A. 2013) Biotransformation pathways of fluorotelomer-based polyfluoroalkyl substances: A review. Environmental Toxicology & Chemistry 332): 243-267 Frömel, T., & Knepper, T.P. 2010) Biodegradation of fluorinated alkyl substances. Reviews of Environmental Contamination and Toxicology 208: 161 177 Greenpeace 2011). Dirty Laundry 2: Hung Out to Dry - Unravelling the toxic trail from pipes to products, GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page19of54
pp32. http://www.greenpeace.org/international/global/international/publications/toxics/water%202011/textilema nufacture_china.pdf Greenpeace 2012a). Toxic Threads: The Big Fashion Stitch-Up. http://www.greenpeace.org/international/en/publications/campaign-reports/toxics-reports/big-fashion- Stitch-Up/ Greenpeace 2012b) Dirty Laundry: Reloaded - How big brands are making consumers unwitting accomplices in the toxic water cycle, pp48. http://www.greenpeace.org/international/en/publications/campaignreports/toxics-reports/dirty-laundry-reloaded/ Greenpeace 2012c) Chemistry for any weather: Greenpeace tests outdoor clothes for perfluorinated toxins; http://www.greenpeace.org/romania/global/romania/detox/chemistry%20for%20any%20weather.pdf Greenpeace 2013a) Greenpeace: Bademoden mit gefährlichen Chemikalien belastet German). https://www.greenpeace.de/presse/presseerklaerungen/greenpeace-bademoden-mit-gefaehrlichenchemikalien-belastet Greenpeace 2013b) Schadstoffe in G-Star Produkten German) https://www.greenpeace.de/themen/endlagerumwelt/schadstoffe-g-star-produkten Greenpeace 2013c). Chemistry for any weather II. December 2013. http://m.greenpeace.org/italy/global/italy/report/2013/toxics/execsummary_greenpeace%20outdoor%20r eport%202013_1.pdf Greenpeace 2014a). A little story about the monsters in your closet. http://www.greenpeace.org/eastasia/publications/reports/toxics/2014/little-story-monsters-closet/ Greenpeace 2014b). A Red Card for sportswear brands: Hazardous chemicals found in World Cup merchandise. http://www.greenpeace.org/international/en/publications/campaign-reports/toxicsreports/detox-football/ Langer, V., Dreyer, A., Ebinghaus, R. 2010) Polyfluorinated compounds in residential and nonresidential indoor air. Environmental Science & Technology 4421): 8075-81 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). http://www.oecd.org/env/ehs/risk-management/synthesis-paper-on-per-andpolyfluorinated-chemicals.htm 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): 7398-406 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): 1 109 GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page20of54
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 <3970 6000 1540 <528 11300 <796 1300 4620 <658 235000 5470000 244000 <1050 PFHxS <3970 <1010 <769 <528 <746 897 <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 <498 2620 <565 <625 <439 <476 <2270 525 <697 PFDS <3970 <1010 <769 <528 <746 <796 <847 <938 <658 <714 <3410 <725 <1050 PFBA <2650 3940 12300 3060 17300 <531 7790 5700 <439 148000 40200 44900 <697 PFPA <2650 1740 75500 <352 601 <531 9770 3480 <439 30800 8430 1440 <697 PFHxA <2650 16600 546000 1310 3410 <531 106000 25100 1260 204000 34700 4730 <697 PFHpA <2650 2020 71300 <352 <498 <531 17400 12300 <439 172000 7400 632 <697 PFOA <2650 <671 4820 2320 1090 531 2280 625 744 1580 <2270 1270 <697 PFNA <2650 <671 762 <352 <498 <531 <565 <625 <439 <476 <2270 <483 <697 PFDA <2650 <671 2200 1900 681 <531 1130 <625 <439 581 <2270 <483 <697 PFUnA <2650 <671 <513 <352 <498 <531 <565 <625 <439 <476 <2270 557 <697 PFDoA <2650 <671 <513 1240 <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 <796 1730 <2450 <658 <714 <3410 182000 <1050 Total,ionic,PFCs, 5 30300 714000 9830 34400 4050 147000 51800 2000 792000 5560000 480000 5 GreenpeaceResearchLaboratoriesTechnicalReport0152016 Page21of54