Chemistry for any weather

Chemistry for any weatherGreenpeace tests outdoor clothesfor perfluorinated toxinswww . greenpeace . de

041Summary

1. Summary05Greenpeace finds environmentally damaging toxins in outdoor clothing.Tests were conducted on 14 rain jackets and rain pants.Each sample contained perfluorinated compounds (PFC).Images of pristine nature are oftenused for advertising outdoor clothing.But nature does not remain untouchedby the chemicals in weather-resistantfabrics. All over the world, from secludedmountain lakes and Arctic polar iceto deep in the oceans, traces can befound of perfluorinated and polyfluorinatedcompounds (PFCs), pollutantswith properties that are harmful to theenvironment and health.Outdoor clothing is in close contact with awhole range of chemicals before it is usedfor hiking or skiing. Yarns, fabrics and evenready-made garments are treated with chemicalsubstances to enhance functionalityand make items easy to care for. Most brandname manufacturers use PFCs so that westay dry in our outdoor wear, inside andoutside. These man-made compounds ofcarbon and fluorine are so stable that theycan hardly be removed from the environment,if at all.For the consumer, it is not clear whichchemicals have been used during the productionof outdoor clothing and whichharmful substances clothing may stillcontain. PFCs and other chemicals reachdrinking water, food and ultimately humanblood and breast milk from such varioussources as manufacturing and householdwastewater, dust, and the disposal of textiles.It is even possible to inhale them.The Detox campaign worksto improve the environmentalbalance of textile productionIn the context of the international Detoxcampaign, Greenpeace is calling on textilemanufacturers to replace hazardous productionchemicals with harmless alternatives.Greenpeace is also calling on governmentsto regulate more chemicals that are hazardous.PFCs are among the groups of substances1) on the Detox campaign’s prioritylist. Some PFCs are known to be endocrinedisruptors and are harmful to the reproductivesystem.As early as 2011, Greenpeace proved thatPFCs from the production of brand nametextiles in China were discharged to rivers. 2)This study proves that residues of PFCs andother chemicals are in the outdoor wearmade by well-known manufacturers.Commissioned by Greenpeace, two independentlaboratories tested weatherproofjackets and pants between June and September2012. PFCs 3) were found in all 14samples; among them was the well-knownhazardous compound perfluorooctanoicacid (PFOA). In five samples, PFOA wasfound in significant concentrations.In addition, six samples had fluorotelomeralcohols (FTOHs) in high concentrations.Hazardous chemicals must beremoved from outdoor clothingproductionThe findings from this product investigationunderline the urgent need to ban PFCs fromoutdoor wear production. PFC-free materialsare already available today. The outdoorclothing industry must continue to developsafer alternatives and use them in processingtheir products.The hazardous properties of well-researchedPFCs such as PFOS and PFOA and insufficientdata on other PFCs call for much morestringent regulation to protect health andthe environment. Greenpeace supports theinitiative of Germany’s Federal EnvironmentAgency to place PFOA on the CandidateList of Substances of Very High Concern(SVHC) so that they are subject to furtherrestriction through REACH 4) .In view of the hazardous properties ofC8 PFCs (PFOA and PFOS), and in view ofresearch findings indicating that otherPFCs (C6) might possess similar hazardousproperties, it is not enough to regulate onlysingle substances such as PFOA. Greenpeacedemands that the entire group of PFCsis put under scrutiny for a possible regulativeban.1) See Section 7.1 in the Appendix.2) http://www.greenpeace.de/fileadmin/gpd/user_upload/themen/chemie/GP_2011_Dirty_Laundry_Brochure_D_02.pdf3) PFCs are differentiated into perfluorinated and polyfluorinated compounds. The subgroup of perfluorinated compounds includes perfluorinated carboxylic acids (PFCAs) and perfluorocarbon sulfonic acids (PFSAs);the subgroup of polyfluorinated compounds includes fluorotelomer alcohols (FTOHs). Each of these subgroups includes a number of individual substances, so that, for example, perfluorooctanoic acid (PFOA) is a PFCA,and perfluorooctane sulfonate (PFOS) is a PFSA. The fluorotelomer alcohols include polyfluorinated substances such as 8:2 FTOH (to be exact: 1H,1H,2H,2H-perfluoro-1-decanol).4) REACH (Registration, Evaluation, and Authorisation of CHemicals), the main general European Union chemicals regulation.

062Sampling and methodology

2. Sampling andmethodology072.1 What was tested?In the spring of 2012, Greenpeace pur cha s-ed 13 items of outdoor clothing bearingwell-known outdoor brand names. Theseincluded four jackets and one pair of pantsfor children, and eight jackets for women. 5)Nine jackets were purchased in Germany,two in Switzerland, and two in Austria. Theproducts were bought either in flagship orspecialized stores, or ordered online. In additionto these purchased items, a rain jacketmade especially for Greenpeace activists(manufactured by Zimtstern) was also tested.These jackets are not available for sale.Two jackets, one from Zimtstern (made forGreenpeace) and one from Fjällräven, werelabeled as PFC-free. According to the labels,eleven of the 14 products were made inChina, and one each was made in Indonesia,Vietnam and Ukraine.The products were either purchased in theiroriginal packaging or put into an uncontaminatedplastic bag immediately afterpurchase. The samples were registered atGreenpeace and documented in photos.A sample of fabric measuring 20 x 20 cmwas cut out of the back of each garmentwhere there was no printing or labeling.Samples were individually wrapped tightlyin aluminum foil and tested in two independentlabs.Table 1: The outdoor clothing items that were testedBrandNameCountry ofProductionProduct Name orDescriptionTechnology for Coating/FinishEnvironmentalLabel or ClaimStorePurchased inGermanyZimtstern /GreenpeaceJack WolfskinVaudeVaudeNorth FaceMountainEquipmentMarmotFjällrävenPatagoniaAdidasPurchased inAustriaNorthlandSevenSummitsPurchased inSwitzerlansMammutKaikkiallaChinaIndonesiaChinaVietnamChinaUkraineChinaChinaChinaChinaChinaChinaChinaChinaLight rain jacketfor womenCloud Stream Jacket(for children/boys)Kids Escape JacketEscape Bike Jacket III(for women)Sutherland Jacket(for women)WMNS Firefox-JacketBoy’s Torrey Pant #64310Eco-Trail Jacket Women(Trekking)Piolet Jacket Lady Black(Modell 2012)Terrex Feather Jacket(for women)Basic Child Rain PonchoTamina Kinder-Regenjacke(child’s rain jacket)Fujiyama Jacket WomenAnnuka Jacket Womens XSMembrane: polyester (SympaTex),Dendrimer finish (Bionic finish ECO)Membrane: Texapore AIR,Outer shell: 100% polyamideMembrane: Ceplex advanced, 100% PUOuter shell: polyamide, PU-coatingMembrane: Ceplex advanced, 100% PUOuter shell: polyamide, PU-coatingMembrane: PTFE(Gore-Tex), 100%100% polyester laminatedMembrane: PTFE(Gore-Tex)UPF / UV40:96% Nylon, 4% ElastanMembrane: Eco-Shell100% recycled polyesterMembrane: PTFE(Gore-Tex)Outer shell: 100% nylonMembrane: PTFE(Gore-Tex),100% polyamideMembrane: 100% polyesterMembrane: Ice Tech 5000 MM5000 MVP / polyamideMembrane: PTFE(Gore-Tex)Membrane: Toray DermizaxEVBluesignGreenShapeBluesignFluorcarbon-freeCommon ThreatsInitiativeOwn productGlobetrotterVaude.deglobetrotter.deglobetrotter.deGlobetrotterGlobetrotterAmazon.deSportausstatterMeinungerBackpacking ForEverAdidas.deNorthland store inin train station, ViennaIntersport EyblMegastore, ViennaMammut Store, ZurichTransa, Zurich5) Only women’s jackets were purchased because they can be worn in small sizes by young teenagers.

0822.2 How was testing done?The samples were sent to two laboratoriesand tested for perfluorinated and polyfluorinatedcompounds and for other hazar douschemicals such as plasticizers (phthalates),surfactants (nonylphenol ethoxylates),organotin compounds, and carcinogenicamines that can be released from azo dyes.The first lab tested for a comprehensivelist of perfluorinated and polyfluorinatedcompounds, among them perfluorinatedcarboxylic acids such as PFOA and perfluorinatedsulfonic acids such as PFOS. Thelist also included, among other compounds,fluorotelomer alcohols (FTOHs) 6) ; FTOHsare the main starting product today inthe synthesis of fluorinated polymers. 7)Polymers ensure the waterproofing and/ordirt-repellent properties of the PFC finishon outdoor textiles. 8) To the best of ourknowledge, very few studies so far havetested for such a comprehensive list ofPFCs in outdoor clothing. 9)The Bremer Umweltinstitut [environmental institute]analyzed outdoor textiles for Greenpeace.The testing covered the PFCs that could beextracted using solvents. The analysis ofPFCAs extracted with methanol was doneusing high-performance liquid chromatographycombined with tandem mass spectrometry(HPLC-MS/MS), and the FTOHsextracted with methyl tertiary butyl ether(MTBE) were analyzed using gas chromatographycoupled with mass spectrometry(GC-MS).The second lab tested the clothing for othertoxins. The selection of substances for testingwas determined by the nature of thefabrics. Among others, alkylphenol ethoxylates,plasticizers (phthalates), aromaticamines released from azo dyes, isocyanates,and organotin compounds were measuredusing GC-MS. Among the alkylphenolethoxylates were nonylphenol ethoxylates(NPEs), which have been discussed extensivelyin earlier Greenpeace reports. 10)Some samples were tested for antimony.A scanning electron microscope (SEM)was used in qualitative testing to detect thepresence of fluorine. This testing indicateswhether a membrane or fabric containsfluorine. Fluorine is not subject to officialdeclaration. It is already a known fact thatGore-Tex and Teflon membranes containfluorine in the form of polytetrafluoroethylene(PTFE). For other membranes, SEManalysis provides valuable information onthe mode of production.PFCsPer- and Polyfluorinated chemicals(PFC) 11) are chemical compounds inwhich the hydrogen atoms on a carbonskeleton are replaced completely (perfluorinated)or partially (polyfluorinated)by fluorine atoms. PFCs do not occurin nature. They have been made formore than 50 years by fluorochemicalmanufacturers. The OECD (Organizationfor Economic Cooperation and Development)lists a total of 853 differentfluorine compounds.In the apparel industry, perfluorinatedcarboxylic acids (PFCAs) such as perfluorooctanoicacid (PFOA), for ins tance,and the fluorotelomer alcohols (FTOHs)play a role. Because the carbon-fluorinebond is the most stable in organicchemistry, PFCs are very persistent.Once they have been released to theenvironment, they barely degrade andremain there for long periods of time.It is therefore not surprising that thesechemicals have been found around theglobe. Scientists have found them inthe snow of the Alps and the waters ofthe deep sea. Even the blood of Arcticpolar bears and the dung of penguinson Tierra del Fuego are contaminatedwith PFCs.PFCs accumulate mainly in blood. Thesechemicals enter the human body in food,air and drinking water. According topresent knowledge, absorption throughthe skin is rather low. The fact is thatPFCs are detectable in human bloodaround the world (Bonefeld-Jorgensen2011), and have even been found in the6) X:Y-FTOH: Telomers are derived from alcohols (-OH). Figure X stands for the number of fluorinated carbon atoms, figure Y for the number of non-fluorinated carbon atoms. Because some carbons atoms in telomers are never fluorinated,these are called polyfluorinated and not perfluorinated. FTOHs are more volatile than ionic perfluorinated carboxylic acids (PFCAs).7) Walters A, Santillo D.: Uses of Perfluorinated Substances, Greenpeace Research Laboratories Technical Note 06/2006 (http://www.greenpeace.to/greenpeace/wp-content/uploads/2011/05/uses-of-perfluorinated-chemicals.pdf) andWalters A, Santillo D, Johnston P: An Overview of Textiles Processing and Related Environmental Concerns (http://www.greenpeace.org/seasia/th/Global/seasia/report/2008/5/textile-processing.pdf)8) Fluorotelomer alcohols are usually not taken into account in other investigations testing for hazardous residues in textiles. This is a serious deficit because these very volatile compounds are often the main contaminant in textiles.Moreover, within the body and in the atmosphere they degrade into PFOAs and other carboxylates.9) Friends of the Earth Norway (2006): Fluorinated pollutants in all-weather clothing: http://www.snf.se/pdf/rap-hmv-allvadersklader-eng.pdfBerger U, Herzke D (2006). Per- and polyfluorinated alkyl substances (PFAS) extracted from textile samples. Poster presentation10) http://www.greenpeace.org/international/en/publications/reports/Dirty-Laundry-2/11) References for text see Section 7.2 in the Appendix.

09blood of umbilical cords and newborns(Fromme 2010). This is particularly worrisomebecause PFCs circulate throughthe human body for a relatively long time.The retention time for perfluorooctanoicacid (PFOA) is more than three years onaverage. PFCs have been found in breastmilk (Fromme 2010). Although concentrationsare lower than in blood, they arenevertheless problematic because infantsare still developing and therefore areparticularly sensitive. A study carried outin Germany showed that infants actuallyhad higher PFC contaminations than theirmothers (Fromme 2010).Animal testing has shown that some PFCsare harmful to reproduction. They can alsopromote the growth of tumors (UBA 2009).There is growing evidence that PFOA inparticular does other harm, and it is suspectedof being an endocrine disruptor.Recent epidemiological studies havesuggested an association between PFOAExamples of PFCs and their chemical structureGroup 12)Perfluorinated sulfonicacidsPerfluorinatedcarboxylic acidsFluorotelomer alcoholsFluorocarbon polymersFluorinated polymersExample for a compoundPFOSPFOA8:2 FTOHPolytetrafluoroethylene (PTFE)(Breathable membranes such asGore-Tex)Perfluoroalkyl monomer(Waterproofing and dirt-repellenttreatment of textiles)Chemical Structureexposure and adiposity (Thorhallur 2012),diminished fertility (Fei 2009), immunedisorders (Grandjean 2012) and thyroiddiseases (Melzer 2010). PFOA is currentlynot subject to legal regulation. Germany’sFederal Environment Agency is workingto put PFOA on the REACH CandidateList of Substances of Very High Concern(SVHC) (Vierke 2012).PFCs end up in the environment eitherdirectly – during production – or indirectlywhen products containing PFCs are usedand disposed of. The apparel industryuses PFCs in particular for coating andfinishing outdoor garments or sportinggoods (1) or for the production of breathablemembranes (2).F F F F F F F F OF C C C C C C C C SF F F F F F F F OFFCFFCFFCFFCFFCFFCFFCFFCFOCOF F F F F F F H HF C C C C C C C C CF F F F F F F H HFCFCOHOHF F nH R O H H F F F F F F F F F FC C C O C C C C C C C C C C C CHH H F F F F F F F F F FF1. Coatings and finishesFluorotelomer alcohols (FTOHs) areprocessed on a large scale into fluorinatedpolymers which are used tomake textiles waterproof, dirt-repellentor grease-resistant. Many impregnatingfabric care products also contain fluorinatedpolymers. Finished products suchas outdoor jackets or impregnatingsprays can contain residues of FTOH.Annual FTOH production is estimatedat 11,000 to 14,000 tons around theworld. Since fluorotelomer alcohols arevolatile compounds, they are thought toplay an important role in global spreading.Air currents can transport themeven to remote areas (Weinberg 2011),and they can be inhaled and retainedin the body. These substances are problematicbecause they can be convertedinto perfluorinated carboxylic acids(such as PFOA) in the environment andin organisms. There are indications thatduring this conversion process, intermediateproducts form in the body thatcan actually be much more harmfulthan the end product of perfluorinatedcarboxylic acid (Rand und Mabury 2012).Even the production of FTOHs is itselfa problem because PFOA can form asan impurity.2. MembranesCompounds containing fluorine are alsoused to produce outdoor membranes(Gore-Tex, Teflon). Many of these membranesare made of polytetrafluoroethylene(PTFE), for which PFOA is usedas a process additive during manufacturing.This can be found again as animpurity in the finished product. Somemanufacturers have therefore alreadyswitched to using other fluorine-containingadditives. But these are also persistentand therefore not environmentallycompatible.12) http://www.umweltdaten.de/publikationen/fpdf-l/3818.pdf

102In the production and processing of texti lescontaining PFCs, chemicals are releasedinto wastewater. Even private householdscan be a source (UBA 2009) when, forexample, coated textiles are washed. Howmuch PFC is released during washinghas not been investigated. Most PFCs donot degrade in sewage treatment plants.Some of these chemicals are collected insewage sludge. The rest reaches rivers andlakes in “clean” sewage water (UBA 2009)and disperses through waterways allaround the globe. Due to its high nutrientcontent, sewage sludge is often used asagricultural fertilizer. In this way, PFCs leachinto the soil and into groundwater, or accumulatein plants which are processed intofood. A few years ago, the use of PFCcontaminatedsewage sludge around thetown of Arnsberg (in western Germany’sHochsauerland district) meant that drinkingwater had become highly contaminated.Tests in Arnsberg revealed that people whohad consumed contaminated drinkingwater had concentrations of up to eighttimes more PFOA in their blood than thosewho had not been exposed (UBA 2009).Scientists have found PFCs in fish, meat,milk products and plants, including ingrains grown on contaminated soils. PFCsare in dust and indoor air. In fact, the indoorair of houses, apartments and officesis 30 to 570 times more contaminated thanoutdoor air (UBA 2009). Air measurementstaken inside two outdoor equipment storesin Germany showed particularly highconcentrations of FTOHs (Langer 2010).Scientists suspect that PFCs evaporatingfrom products such as impregnatedclothing are the source of this contamination.Testing for PFCs in rainwear fromNorway and Sweden also found residuesof FTOHs and perfluorinated carboxylicacids (PFCAs) (Berger 2006).It is not clear what happens to an outdoorjacket when it is no longer worn and endsup in the rubbish. Occasional air measurementsat waste dumps have shown increasedPFC contamination in these locations(Weinberg 2010). However, there are nodata on the chemical behavior of materialscontaining PFCs when they are incineratedas waste. If combustion is incomplete, itis conceivable that dioxin-like substan cesform. Here there is an urgent need forresearch.Since the public debate on PFOA (eightcarbon atoms) is ongoing, the industryhas also recently begun to use short-chainPFCs (with four to six carbon atoms).In 2006, eight major fluorochemical manufacturers pledged to reduce their PFOAemissions and residues in products by95 percent by 2010. Samples taken in theenvironment since then show an increasingcontami nation with short-chain PFCsin water (Möller 2010) and air (Weinberg2011). These short-chain alternativeshave also been found in Antarctica (Llorca2012), in snow (Cai 2012), in drinkingwater (Dauchy 2012) and in rainwater(Eschauzier 2010).The accumulation potential of thesesubstances in the body is lower than forPFOA. A study carried out in Norwayshows however that the contaminationof blood with these substances has increasedsignificantly in the Norwegianpopulation in recent years (Berger 2012,presentation). Samples of breast milkfrom China and Sweden were also contaminated(Jensen 2008). Short-chainPFCs are as persistent as PFOA. It isalso worrisome that short-chain PFCscan reach groundwater more easily becausethey bond less well to particles.Compared to PFOA, short-chain PFCshave been poorly investigated, a situationwhich must be addressed urgentlydue to the increasing use and pervasivenessof these compounds. Germany’sFederal Environment Agency does notrate these chemicals as environmentallyfriendlyalternatives due to their highstability and potential to contaminatedrinking water (UBA 2009).

312Results for perfluorinated and polyfluorinated compounds (PFCs)

3. Results for perfluorinatedand polyfluorinatedcompounds (PFCs)13All 14 samples of outdoor clothing Significant levels of PFOA (> 1 μg/m 2 ) 15)contained extractable PFCs. This was were found in five of 14 samples, in theregardless of whether the label indicatedthat the product was made with a Face, Patagonia and Kaikkialla, and thejackets made by Jack Wolfskin, The Northfluorine membrane such as Gore-Tex child’s pants from Marmot (see Figure 1).or Teflon, or finished with a coatingcontaining fluorine compounds.The lowest concentrations of PFOAwere found in jackets made by MountainEven the items of clothing for which productionintentionally abstained from using (manufactured for Greenpeace). In sixEquipment, Vaude Women and Zimtsternfluorochemicals, such as the jackets from of 14 samples, concentrations of PFOAFjällräven and Zimtstern, contained a small were above the detection level but belowamount of fluorine chemicals (see Table 3 0.3 μg/m 2 . Samples were from the brandsin the Appendix). 13) The sources of these just named as well as from Adidas,low concentrations are unclear. PFCs are Fjällräven and Seven Summits.persistent and – as a consequence of theirindustrial use – they are so widespread that The highest sums of all perfluorinatedit may be a real challenge to engage in clean carboxylic acids (PFCAs) were found inproduction in which chemicals and/or jackets made by Kaikkialla (11 μg/m 2 ) andproduction facilities are not contaminated Patagonia (8.5 μg/m 2 ), and in the child’sby PFCs. 14) pants from Marmot (6.3 μg/m 2 ). Sums werelowest in the samples from MountainEquipment, Seven Summits and Zimtstern(Greenpeace).Perfluorooctane sulfonate (PFOS) was notdetected in any sample. The 2008 ban onthis substance is apparently effective.The findings of the PFC study are describedbelow according to the class of substance.The test results are listed in detail in Tables1 to 4 of the Appendix.Fluorotelomer alcohols were found ineight of 14 samples. Where FTOHs werefound, their concentrations were significantlyhigher than concentrations of perfluorinatedcarboxylic acids. The highestFTOH concentrations (> 400 μg/m 2 ) were inthe jackets made by Mammut and VaudeKids. Likewise, high FTOH concentrations(> 100 μg/m 2 ) were found in the samplesfrom Kaikkialla and Patagonia (see Figure 2).13) The Greenpeace jacket from Zimtstern, made with SympaTex and finished with BIONIC-FINISH ECO had the lowest residues of PFOA in the test series. That PFCs were detected at all may have various reasons (see section 3.1).14) Greenpeace is taking on this challenge and will work together with manufacturers to investigate sources of contamination and produce jackets for its activists that are free of fluorocarbon compounds.(Kindly note that these jackets are not for sale.) Contamination must cease.15) Significant concentration: the EU permissible limit for perfluorooctane sulfonate (PFOS) of 1µg/m² (micrograms of PFOS per square meter of fabric) is used as the comparison value.PFOA’s hazardous properties are similar to those of PFOS – it is harmful to fertility (toxic to reproduction) and is suspected of being an endocrine (hormonal) disruptor.

1433.1 Perfluorinated carboxylic acids (PFCAs) withperfluorooctanoic acid (PFOA)Among the PFCs found in every sample wasperfluorooctanoic acid (PFOA), a subs tancewith hazardous properties. Since thereare no regulations for PFOA, the EU limitvalue for perfluorooctane sulfonate (PFOS)of 1 μg/m 2 (micrograms of PFOS per squaremeter of fabric) was used as the comparisonvalue. PFOA’s hazardous properties aresimilar to those of PFOS – it is harmful forfertility (toxic to reproduction) and is suspectedof being an endocrine (hormonal)disruptor.PFOA concentration of 1 μg/m 2 was exceededin five samples: the Jack Wolfskin child’sjacket, the North Face woman’s jacket,the Marmot child’s pants, the Patagoniawoman’s jacket and the Kaikkiallawoman’s jacket (see Figure 1).In six of 14 samples, the PFOA concentrationwas above the detection level but below0.3 μg/m 2 . The lowest concentrationsof PFOA were measured in the jackets madeby Mountain Equipment, Vaude Women,Zimtstern (manufactured for Greenpeace),Adidas, Fjällräven and Seven Summits. Itremains unclear where the contaminationcame from. It may be that factories producingtextiles containing fluorine compoundsare not able to manufacture fabrics thatare completely free of PFCs. This wouldnecessitate textiles being manufacturedin plants that completely exclude usingperfluorinated chemicals. But it is alsoconceivable that contamination occurs intransit, during storage or in the store.Even the process of sampling and testingcan lead to contamination.Greenpeace believes that even minorcontamination during production shouldcease. To reach this objective, outdoorclothing producers and their material suppliers,but also the chemicals industry,must work together and strictly controlwhich substances are used in production.Greenpeace will work together with themanufacturers of its activists’ jackets(not for sale) to investigate sources of PFCcontamination and take corrective action.Figure 1: Concentrations of perfluorinated carboxylic acids (PFCAs) in 14 samples of outdoor clothingPFOASum PFCAconcentration in μg/m 2– 1211,0– 11– 108,5– 9– 85,16,35,45,0– 7– 6– 50,30,7Zimtstern /GreenpeaceLightJacket2,0JackWolfskinChild’sJacket0,6VaudeChild’sJacket2,80,21,2VaudeWoman’sJacket1,63,4North FaceWoman’sJacket0,20,6MountainEquipementWoman’sJacket2,3MarmotChild’sPants0,31,2FjällrävenWoman’sJacketn2,2PatagoniaWoman’sJacket0,31,0adidasWoman’sJacket0,41,2NorthlandChild’sPoncho0,3SevenSummitsChild’sJacket0,7 0,6MammutWoman’sJacketKaikkiallaWoman’sJacket– 4– 3– 2– 1– 0

153.2 Fluorotelomer alcohols (FTOHs)FTOHs were found in eight of the 14 samples.The highest concentration of fluorote lomeralcohols was found in the jacket fromMammut (464 μg/m 2 ). The child’s jacketmade by Vaude also had a high concentrationof FTOHs at 419 μg/m 2 (see Figure 2).Test results showed that some manufacturersare already using C6 telomer alcohols,which were dominant in the jackets fromAdidas und Fjällräven. The item fromAdidas contained 99 μg/m 2 of 6:2 FTOH.Although the Fjällräven jacket was explici t lylabeled as PFC-free, it contained 52 μg/m 2of this substance.C6 telomer alcohols were also found inthe Northland child’s poncho purchased inAustria (17.6 μg/m 2 of 6:2 FTOH) and inthe two jackets purchased in Switzerland,with the Kaikkialla article containing27.0 μg/m 2 of 6:2 FTOH, and the Mammutitem containing (considerably higher)352 μg/m 2 of 6:2 FTOH. Long-chain C10telomers were used in the products fromVaude, Patagonia, Mammut and Kaikkialla.Next to the fluorotelomer alcohols, fluorotelomeracrylates (FTAs), also known aspolyfluorinated acrylates, were also detectedin some samples. These acrylates areintermediates in the production of fluorinatedpolymers. Like the C8 telomers, theycan be converted into PFOA through oxidation.Significant C8 FTA concentrationswere found in the items from Vaude, TheNorth Face, Marmot and Patagonia, as wellas in the Mammut and Kaikkialla itemspurchased in Switzerland. Lower concentrationsof C8 FTA were found in theJack Wolfskin, Mountain Equipment andAdidas items, and the lowest concentrationof C8-FTA was found in the Greenpeace(Zimtstern) jacket.Fluorotelomer alcohols, when used forwaterproof and dirt-repellent finishes, aresupposed to ensure that fewer PFC intermediatessuch as PFOS are formed. Theyare divided into long-chain and short-chaincompounds. Basically, the longer theirchains, the more these toxic substances canaccumulate in an organism. The compound8:2 FTOH must be evaluated critically becauseit is converted into PFOA throughoxidation in the atmosphere and in thebody. Some manufacturers therefore wantto switch from C8 to short-chain substancessuch as 6:2 FTOH. But C6 and C4 PFCs,used as alternatives, are also persistent andfound in the environment and in humansaround the world. They can also oxidizeinto their respective carboxylic acids, whichare potentially hazardous to health.So far, no regulation or value limits havebeen established for fluorotelomer alcohols.Figure 2: Concentrations of fluorotelomer alcohols (FTOHs) in 14 samples of outdoor clothing8:2 FTOHSum FTOH6:2 FTOHSum FTAconcentration in μg/m 2– 500– 450– 400– 350– 300– 250– 200– 150– 100– 50Zimtstern /GreenpeaceLightJacketJackWolfskinChild’sJacketVaudeChild’sJacketVaudeWoman’sJacketNorth FaceWoman’sJacketMountainEquipementWoman’sJacketMarmotChild’sPantsFjällrävenWoman’sJacketPatagoniaWoman’sJacketadidasWoman’sJacketNorthlandChild’sPonchoSevenSummitsChild’sJacketMammutWoman’sJacketKaikkiallaWoman’sJacket– 0

1633.3 Perfluorinated sulfonate (PFOS)No perfluorooctane sulfonate (PFOS) wasfound in the investigation. PFOS is rated asa PBT substance (Persistent, Bioaccumulative,Toxic). The use and marketing of PFOShas been banned in the EU since 2008,with a few exceptions. Evidently the banon PFOS has been effective.PFOS has been covered by the StockholmConvention since 2009. A permissible limitwas set for PFOS of 1 µg/m2 (one microgramof PFOS per 1 square meter of fabric)for textiles and coatings. This value alsoapplies to imported products such astextiles.

418Results for other toxins

4. Results for other toxins19All samples of outdoor clothing were tes tedfor alkylphenol ethoxylates, which are usedas tensides or surfactants in wet processesin textile production. All samples were alsotested for the phthalate group of subs tanceswhich are used as plasticizers.Depending on the nature of the textiles inquestion, some samples were additionallyscreened for other toxins. Testing wasdone for aromatic compounds releasedfrom azo dyes, organotin compoundsand antimony. The specialist laboratoryitself selected which products to test forthese harmful substances.Other chemicals used in textile production,itemized on Greenpeace’s Detox List, 16)were not inves ti gated if there was no immediatesuspicion of their presence.The findings of the test series and the methodologyapplied are explained in detailin Tables 5 and 6 of the Appendix. Here isan overview of the most important results.Table 2: Results for other harmful substancesBrandNamePurchased ingekauftZimtstern /GreenpeaceJack WolfskinVaudeVaudeNorth FaceMountainEquipmentMarmotFjällrävenPatagoniaAdidasPurchased inAustriaNorthlandSeven SummitsPurchased inSwitzerlandMammutKaikkiallaCountry ofProductionChinaIndonesiaChinaVietnamChinaUkraineChinaChinaChinaChinaChinaChinaChinaChinaProduct Name orDescriptionLight rain jacket for womenCloud Stream Jacket (for children/boys)Kids Escape JacketEscape Bike Jacket III (for women)Sutherland Jacket (for women)WMNS Firefox-JacketBoy’s Torrey Pant #64310Eco-Trail Jacket Women (Trekking)Piolet Jacket Lady Black (Modell 2012)Terrex Feather Jacket (for women)Basic Child Rain PonchoTamina Kinder-Regenjacke(child’s rain jacket)Fujiyama Jacket WomenAnnuka Jacket Womens XSNonylphenolEthoxylate 17)mg/kg1319 (NP; 8)20 (NP; 8)3209Phthalate(Sum) 18)mg/kg159310511516416*570027088*22*Organotins Antimonymg/kg mg/kg33013 (MOT 19) ) 104,8 (DOT 20) )40120351012,3 / 0,55 / 5,8 / 25,6 / 0,18 21)Isocyanatesmg/kg23 (TDI 22) )1616) See Section 7.1 in the Appendix.17) The detection limit for nonylphenol ethoxylate (NPE) was 5 mg/kg in the method used; for nonylphenol (NP) it was 3 mg/kg.18) In the samples marked with an asterisk*, testing was done on the fabric’s plastisol print.19) Monooctyltin20) Dioctyltin21) Monobutytin MBT, Monooctyltin MOT, Dibutyltin DBT, Dioctyltin DOT, Tetraethyltin TeEtT22) Toluylene diisocyanate

2044.1 Alkylphenol ethoxylatesNonylphenol ethoxylates (NPEs) were foundin five of the 14 samples. NPEs belong tothe substance group of alkylphenol ethoxylates,are very harmful to the environmentand should not be detectable becausethey degrade to nonylphenol (NP). NP ispersistent, bioaccumulative and toxic,and can disrupt the endocrine (hormonal)systems of animals and humans.The highest concentration of NPEs wasfound in the Seven Summits child’s rainjacket purchased in Austria. This samplecontained 320 mg/kg of NPE. Other significantconcentrations were found in thejackets from Vaude (NPE 13 mg/kg),Fjällräven (NPE 19 mg/kg, plus NP 8 mg/kg)and Adidas (NPE 20 mg/kg). The Kaikkiallajacket purchased in Switzerland containedan NPE concentration of 9 mg/kg. 23)Lower levels of NPEs do not necessarilyindicate that NPEs were used in loweramounts during manufacturing. Greenpeacereported in 2012 that NPE residues canbe washed out in just a few washes.All of these items were manufactured inChina. In 2011, Greenpeace proved thatnonylphenol from the textile industrycon stitutes a serious problem of waterpollution in China. 24) NPEs are used in thedyeing process. Their effect is similarto that of estrogen and they can disruptthe development of reproductive organsin fish and other aquatic animals. SinceJanuary 2005, textiles containing morethan 0.1 percent of NPs or NPEs are notmarketable.25) GOTS: Global Organic Textile Standard: http://tilth.org/files/certification/GOTSStandard.pdf4.2 Phthalate plasticizersPlasticizers in the phthalate group ofsubstances were detected in every sample.The highest concentration, 5,700 mg/kg,was in the Northland child’s rain poncho.The di-2-ethylhexyl phthalate (DEHP) foundis considered to be particularly harmful.In comparison, the currently valid EUguideline for toys or objects that childrencan put into their mouths prescribes apermissible limit of 1,000 mg/kg (equivalentto 0.1 percent by mass). Because the producttested is a rain poncho for children,the concentration found is unacceptable.Northland is an Austrian outdoor brandwith high market shares, especially inChina and South America.The Seven Summits child’s jacket pur chasedin Austria also contained significantconcentrations of phthalates (270 mg/kg,dominated by 260 ppm of DiNP). In comparison,the sum of phthalates in textilesmanufactured in compliance with theGOTS standard 25) is not allowed to be morethan 100mg/kg.In the other twelve samples, phthalate concentrationswere lower than 100mg/kg, andin six samples they were below 10mg/kg.These concentrations indicate that phthalateswere probably not used intentionallyas plasticizers, but are contaminants. 26)Phthalates are used as plasticizers, forinstance to soften the rigid plastic PVC.In the textile industry they are used forartificial leather, rubber and for printing(plastisol or dyes). Phthalates can severelydisrupt the endocrine system and leadto infertility and adiposity. Accordingto the EU chemicals regulation REACH(Registration, Evaluation, and Authorisationof CHemicals), some compounds in thisgroup will be banned from 2015.23) The non-detection of NPEs does not rule out NPEs being used in the production of a garment, as the finished clothing may have undergone thorough washing prior to retailing. This may have washed out all residues of NPEsfrom the fabric prior to sale. Such washing would only have further contributed to inputs of NPEs/NP into the environment during the manufacturing stage.24) http://www.greenpeace.de/fileadmin/gpd/user_upload/themen/chemie/Dirty_LaundryHung_Out_to_Dry_WEB_FINAL2.pdf und http://www.greenpeace.de/fileadmin/gpd/user_upload/themen/chemie/20110826_FS_Nonylphenol_FINAL2.pdf25) GOTS: Global Organic Textile Standard: http://tilth.org/files/certification/GOTSStandard.pdf26) Either phthalates were used elsewhere in the production facilities or contamination was a result of samples being in contact with other items that contained phthalates.

214.3 Azo dyes4.4 Organotin compoundsTesting was also done for carcinogenicaromatic amines that can be released fromazo dyes. They were not detected in anyof the samples tested, which were from theproducts made by Vaude, The North Face,Adidas, Seven Summits, Mammut andKaikkialla. Some azo dyes used in thetextile industry can cause cancer whenthey release cancerogenic amines.The use of organotin compounds is alreadyheavily restricted due to the toxicity of thesechemicals. The GOTS standard allows nomore than 0.05 mg/kg of tributyltin (TBT),and the OEKO-TEX standard for textiles setsa limit of 0.5 mg/kg for TBT and 1.0 mg/kgfor dioctyltin (DOT). The samples fromVaude, Mammut and Kaikkialla were tested.Both standards’ limits were significantlyexceeded in the Vaude jacket for women;the value for DOT was 4.8 kg/mg and formonooctyltin (MOT) 13 mg/kg. The Kaikkiallajacket contained 5.6 mg/kg of DOT,18 mg/kg of tetraethyltin (TeET), 2.3 mg/kgof monobutyltin (MBT), 0.55 mg/kg of MOT,and 5.8 mg/kg of dibutyltin (DBT).Organic tin compounds are used as biocidesand anti-fungal agents. They havean antibacterial effect on socks, shoes andsportswear and are supposed to preventodors. They are also used in PU as an accelerator.If tributyltin (TBT) is released intothe environment, it can accumulate in thebody where it disrupts the immune systemand diminishes fertility.4.5 AntimonyAntimony is used in the production ofpolyester; its toxicity is often compared tothat of arsenic. Antimony should not be inchildren’s clothing. Because antimony isused to manufacture polyester, all jacketswith a polyester membrane were tested.These were from Vaude, The North Face,Fjällräven, Northland, Patagonia, Mammutand Kaikkialla.The highest concentration was found in theFjällräven jacket (120 mg/kg). The NorthFace jacket contained 40 mg/kg, and thejacket from Patagonia contained 35 mg/kgof antimony. Much lower concentrationswere detected in the jackets from Northland(10 mg/kg), Mammut (1 mg/kg), Kaikkialla(2 mg/kg) and Zimtstern (manufacturedfor Greenpeace, 3 mg/kg).4.6 IsocyanatesIllustration 1: Soxhlet solvent extractionIllustration 2: Textile sample in a separatingIsocyanates are used in polyurethane (PU)production. They can trigger allergies andcause severe irritation to the respiratorytract; they can also damage the lungs andcause asthma. Some of them are suspectedof being carcinogenic; one such compoundis toluene diisocyanate.Polyurethane thermal insulation and PUmembranes come into question as sourcesof isocyanates. The membranes of bothVaude jackets were made either of PU orof polyester laminated with PU, and isocyanateswere detected in both. The KidsEscape Jacket contained 23 mg/kg of toluenediisocyanate, and the Escape Bike Jacketfor women contained 16 mg/kg of thissubstance. Testing was done in a VOCscreening process.funnel (GC-MS)Illustration 3: Analysis in the gas chromatographIllustration 4: Inserting samples into the scanningelectron microscope (SEM)Illustration 5: Analysis of clothing samplesin the SEMIllustration 6: Analysis of polyester membraneat a magnification of 70

224The outdoor industry –still not trailblazers in protecting the environmentThe outdoor industry stands for cuttingloose and being close to nature. This positiveimage has brought strong doubledigitgrowth in recent years to the suppliersof weather clothing. The Europeanmarket in 2010 was worth about 4.5 billioneuros. Germany, with a turnover of 1.02billion euros, is the leader in Europe, followedby Great Britain, Ireland and France.Jackets and pants are the most popularitems (50 percent), followed by shoes(25 percent), and backpacks (6 percent).Consumers often pay several hundredeuros for an extra warm deluxe anorakand – unlike in the fast fashion industry –do not haggle over every cent. Profits ofthe VF Corporation, to which the world’slargest outdoor wear supplier The NorthFace belongs as a brand, rose between2007 and 2011 from 24 to 36 milliondollars.Brands like The North Face, Patagonia,Vaude or Jack Wolfskin have long sincebecome household names, not only formountain climbers and hikers. The industryhas gone from being a specialistsupplier to a producer of trendy everydayclothes. Every city’s downtown areaboasts brand name stores. Jack Wolfskin(from Idstein in Germany) alone has200 of its own stores between the NorthSea and the Alps, and in China it sellsits products in more than 300 stores.Advertising uses pictures of daring skiersplunging through deep snow and fearlessclimbers scaling dizzying heights –although most customers are not exceptionalathletes but city dwellers lookingto stay warm and dry during a bike rideor a walk in the rain. Nevertheless, theindustry has started a veritable arms raceso that outdoor clothing can withstandever more extreme weather conditions –and this has been accompanied by asteady increase in chemical pollution,especially from controversial PFCs.The latest novelties can be admired at theOutDoor show in Friedrichshafen, wherein July 2012 more than 900 businessesand manufacturers exhibited their products.But the hazards of the substancesused for production are kept secret fromnature-conscious clientele. Instead, thetalk is about natural fibers made of corn,coconut, hemp and merino wool. Theindustry has made real progress in environmentalprotection elsewhere, buthere it has been criminally careless,neglecting to replace the problematicchemical compounds used in membranes,coatings and finishings. Greenpeace’sDetox campaign is now stirring this up.ChinaChina is Germany’s largest importtrade partner for textiles. Some30 percent of total annual imports oftextiles and apparel come from thePeople’s Republic. Textile productionsteps for 95 percent of the textilesavailable on the German market arepartially or wholly outsourced abroad.This makes it particularly difficultto control the use of substancesthat are harmful to the environmentand health.

524Alternatives to fluorocarbon coatings and finishes

265Figure 3: Fluorine-free alternatives under the electron microscopeSample 1:SympaTex ® : membrane at a magnification of 220Illustration 1 – membraneSample 1:SympaTex ® finish at a magnification of 130Illustration 2 – fabric with finishSample 2:Schoeller Ecorepel ® at a magnification of 130Illustration 1 – fabric with finishSample 4:Freudenberg at a magnification of 130Illustration 1 – fabric with finish

628Conclusions and recommendations

6. Conclusionsand recommendations29The outdoor clothing industry presentsa very flattering image of itself and expressescommitment to environmentalprotection in numerous publicationsand promotional activities. However,the Greenpeace investigation describedhere points out a mismatch betweenassertion and action. The industry is stillfar from reducing its use of hazardouschemicals to zero and thereby ending itspollution of waters and drinking water.Water is a scarce and threatened resourcein many regions of the world.Since 2011, Greenpeace activists havebeen working around the world in theDetox campaign for the production oftextiles free from harmful substances. Bytesting samples of wastewater and textiles,Greenpeace has revealed that the textileindustry releases chemical compoundsthat are harmful to the environment andhealth. Eleven groups of substances arenamed which must be phased out of textileproduction due to their hazardous properties.Among these groups are the perfluorinatedchemical compounds (PFCs).Some PFCs are known to be endocrine(hormone system) disruptors and harmfulto the reproductive system.This study identified per- and polyfluorinatedchemicals in outdoor articles manufacturedfor major brands and drew conclusionsabout environmental risks andthe safety of consumers. Although someoutdoor clothing manufacturers haveswitched to using short-chain alternativesin their production, Greenpeace’s test serieshas shown that the use of C8 fluorotelomeralcohols is still common practice. Textilesare free of PFOS, but still contain PFOAas an impurity or degraded product.Our investigation also tested for othersubstances hazardous to health such asplasticizers and alkylphenol ethoxylates.Our findings emphasize the urgentneed to ban dangerous chemicals fromoutdoor clothing production.Outdoor clothing brands make the consumersof their products unwitting assistantsin releasing perfluorinated compoundsto the environment. Even if the amountof PFC is low in single items of clothingtested, the total amount released from themassive volume of clothing sold todaycan be substantial. Greenpeace is workingon instituting a register of hazardoussubstance emissions in China. Only inthis way can local residents find out whichchemicals have contaminated the wastewaterfrom “their” textile factory.Next to this analytical investigation ofhazardous substances, Greenpeace alsohelped to see through a research project on“Alternatives to Fluorocarbon Finishesfor Textiles” carried out at the Berlin Universityof Applied Sciences in 2012. In thiscontext, fluorine-free alternative fabricswere physically tested for their capabilitiesand chemically tested for hazardous substances.The project proved that fluorinefreematerials are already on the marketthat largely meet expectations for outdoorclothing and that can be used in theirproduction.What must happen nextThe outdoor clothing industry is calledon to ban hazardous substances suchas PFCs from its production processesand immediately switch to safe functionalalternatives wherever possible. The industrymust immediately take steps tofurther develop safer alternatives and usethem in production. Greenpeace callson all manufacturers of outdoor clothingto immediately address this issue andbegin phasing out the entire group ofPFC compounds from production.The key elements for a toxin-freefuture are:The phaseout of PFC chemistryand authentic commitment tothis endeavor.All dangerous chemicals must be bannedfrom manufacturing processes and theirproducts. The findings from this productinvestigation underline the urgent need toban PFCs from outdoor wear pro duc tion.PFC-free materials are already availabletoday. The outdoor clothing industry mustcontinue to develop safer alternatives anduse them in processing their products. 28)Precaution.The hazardous properties of well-researched PFCs such as PFOS and PFOAand insufficient data on other PFCs callfor much more stringent regulation toprotect health and the environment. Inview of the hazardous properties ofC8 PFCs (PFOA and PFOS) and in viewof research findings indicating that otherPFCs (C6) possess similar hazardousproperties, it is not enough to regulateonly single substances such as PFOA.The entire group of PFCs has to be underscrutiny for a possible regulative ban.It’s time to act. Now.www.greenpeace.de/detox28) http://www.ipe.org.cn/En/pollution/

730AppendixKey steps to Detox our clothesTo effectively stop the pollution of ourwaters with hazardous chemicals, brandsshould:credibly commit to phasing out theuse of all toxic chemicals in their globalsupply chains and in all products by1 January 2020.Credible commitment means that threefundamental principles are unambiguouslyadopted – precaution 29) , comprehensiveand complete elimination (including zerodischarges) 30) , and the right to know 31) .walk the talk by committing to rapidand full public disclosure of the use andrelease of toxic chemicals in and fromsuppliers’ facilities. This information mustbe precise and comprehensive, and itmust be updated at regular and relevantintervals (at least once a year), especiallywith regard to local/national inhabitants.Credible public information platforms 32) )should be used for this purpose. Clear andambitious deadlines must be set for theelimination of priority substances suchas APEs, and a new sectoral blacklist ofhazardous chemicals to be eliminatedmust be drawn up which is based on andtakes into account the intrinsic propertiesalready identified in other hazardouschemicals.The need for government actionGovernments need to do their share aswell and adopt political commitment to thezero discharge of all hazardous chemicalswithin one generation, based on theprecautionary principle and includinga preventative approach by avoidingthe production and use, and therefore,exposure to hazardous chemicals.This commitment must be matched withan implementation plan containing intermediateshort-term targets, a dynamic listof priority hazardous substances requiringimmediate action based on the substitutionprinciple, and a publicly availableregister of data on discharge emissionsand losses of hazardous substances,such as a Pollutant Release and TransferRegister (PRTR).Governments must adopt comprehensivechemicals management policies andregulations in order to:level the playing field and make leadingbrands’ actions a reality throughout theentire sector and beyond, as many of thehazardous chemicals used in textiles arealso in use in other sectors;give industry a clear direction by showingthat hazardous chemicals have no placein a sustainable society, which will inturn drive innovation towards safer alternatives;andprevent ongoing releases into the environmentthat may require future clean-upand have serious impact on the environmentand on people’s health and livelihoods,especially in the Global South.29) This means "caution practiced in the context of uncertainty." An action (such as the use of a chemical substance and/or process) should not be taken if the consequences are uncertain and potentially dangerous.30) "Zero" means zero use of all hazardous substances, via all pathways of release (i.e., discharges, emissions and losses), in global supply chains and in all products. “Elimination” means “not detectable,” to the limits of current technology,and where only naturally occurring (where relevant) background levels are acceptable.31) All local communities sharing their water systems with the production of apparel/footwear and/or the products produced, all workers within this global supplier chain, and all customers have the right to know, on an ongoing basis,precisely which substances are being released from precisely which facilities during production and from the products themselves.32) For example, IPE in China; see http://www.ipe.org.cn/en/pollution/

7. Appendix31Results for perfluorinated and polyfluorinated compoundsTable 1: PFCs (perfluorinated compounds) in outdoor clothing purchased in GermanyMaterialCountry ofProductionPFOAPFCA(Sum)PFS(Sum)FTA(Sum)8:2 FTOHFTOH(Sum)Greenpeace in Germany, jacketJack Wolfskin, child’s jacketVaude, child’s outdoor jacketVaude, woman’s jacketThe North Face, woman’s jacketMountain Equipment, woman’s jacketMarmot, boys rain pantsFjällräven, woman’s jacketPatagonia, outdoor-jacketAdidas, outdoor-jacketChinaIndonesiaChinaVietnamChinaUkraineChinaChinaChinaChinaμg/m 20,272,010,580,241,580,202,310,292,160,29μg/m 20,705,112,781,213,370,586,291,178,481,04μg/m 2n.d.n.d.n.d.n.d.n.d.n.d.n.d.n.d.n.d.n.d.μg/m 21,410,1n.d.19,523,86,125,620,865,05,6μg/m 2n.d.n.d.230n.d.n.d.n.d.n.d.n.d.30n.d.μg/m 2n.d.n.d.418,5n.d.n.d.n.d.n.d.52,0123,099,0Table 2: PFCs (perfluorinated compounds) in outdoor clothing purchasedin Austria (AT) and Switzerland (CH)MaterialCountry ofProductionPFOAPFCA(Sum)PFS(Sum)FTA(Sum)8:2 FTOHFTOH(Sum)Northland, child’s ponchoSeven Summits, child’s jacketMammut, woman’s jacketKaikkialla, woman’s jacketChinaChinaChinaChinaμg/m 20,450,300,654,98μg/m 21,200,665,3910,96μg/m 2n.d.n.d.n.d.n.d.μg/m 2n.d.n.d.57,278,3μg/m 2n.d.40,678,187,8μg/m 217,640,6464,2175,5

327Table 3: PFC concentrations of PFCAs (perfluorinated carboxylic acids) and PFSAs (perfluorinated sulfonic acids)in outdoor clothingZimtstern /GreenpeaceJackWolfskinVaudeVaudeNorthFaceMountainEquipmentMarmotFjällrävenPatagoniaadidasNorthlandSevenSummitsMammutFujiyamaKaikkiallaactivist’sjacketchild’sjacketchild’sjacketwoman’sjacketwoman’sJacketwoman’sJacketchild'spantswoman’sJacketwoman’sJacketwoman’sJacketchild’sponchochild’sJacketwoman’sJacketwoman’sJacketPolyesterSympaTex,Bionic-FinishEcoTexaporeAir,100%polyamideCeplex ad,100% PU,polyamide+ PU coatingCeplex ad,100% PU,polyamide+ PU coatingPTFE-(GoreTex)polyesterlaminateGoreTex,outer shell:100%polyamide96%nylon,4%elastaneEco-Shell,PFC-free,100% rec.polyesterGoreTex,outer shell:100%nylonGoreTex,Pro Shell,100%polyamide100%polyesterIce Tech5000100%polyamidePTFE(Gore Tex)Membrane:TorayDermizaxEVconc. μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2PerfluorobutanesulfonatePFBS

33Table 4: PFC concentrations of PFCAs (perfluorinated carboxylic acids), PFSAs (perfluorinated sulfonic acids) andfluorotelomer alcohols (FTOHs) in outdoor clothingZimtstern /GreenpeaceJackWolfskinVaudeVaudeNorthFaceMountainEquipmentMarmotFjällrävenPatagoniaadidasNorthlandSevenSummitsMammutFujiyamaKaikkiallaactivist’sjacketchild’sjacketchild’sjacketwoman’sjacketwoman’sjacketwoman’sjacketchild’spantswoman’sjacketwoman’sjacketwoman’sjacketshild’sponchochild’sjacketwoman’sjacketwoman’sjacketPolyesterSympaTex,Bionic-FinishEcoTexaporeAir,100%polyamideCeplex ad,100% PU,polyamide+ PU coatingCeplex ad,100% PU,polyamide+ PU coatingPTFE-(GoreTex)polyesterlaminateGoreTex,outer shell:100%polyamide96%nylon,4%elastanEco-Shell,PFC-free,100% rec.polyesterGoreTex,outer shell:100%nylonGoreTex,Pro Shell,100%polyamide100%polyesterIce Tech5000100%polyamidePTFE(Gore Tex)Membrane:TorayDermizaxEVconc. μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2Perfluoro-3,7-dimethyloctanecarboxylatePF-3,7-DMOA

347Children’s clothing (sum PFCA in μg/m 2 )PFOASum PFCA and PFSconcentration in μg/m 2– 6–– 5–– 4––3–– 2–– 1–Seven Summitschild’s jacketNorthlandchild’s ponchoVaudechild’s jacketJack Wolfskinchild’s jacketMarmotchild’s pants– 0Perfluorinated compounds in children’s clothesWoman’s jacket (sum PFCA in μg/m 2 )PFOASum PFCA and PFSconcentration in μg/m 2– 12– 11– 10– 9– 8– 7– 6– 5– 4– 3– 2– 1Zimtstern /Greenpeacelight jacketMountainEquipementwoman’s jacketadidaswoman’s jacketFjällrävenwoman’s jacketVaudewoman’s jacketNorth Facewoman’s jacketMammutwoman’s jacketPatagoniawoman’s jacketKaikkiallawoman’s jacket– 0Perfluorinated compounds in woman’s jackets

35Results: Perfluorinated andpolyfluorinated compounds of separate brandsGreenpeace Jack Wolfskin VaudePFBAPFOA8:2 FTASumextractable PFC:2 μg/m 2PFOA8:2 FTASumextractable PFC:15 μg/m 2PFDASum10:2 FTOH extractable PFC: 8:2 FTOH421 μg/m 2PFCconcentration/amountPFBAPFHxAPFHpAPFOA8:2 FTAconcentration in μg/m 2amount PFC in %μg/m 20,30,10,10,31,4%13441366PFCconcentration/amountPFBAPFPAPFHxAPFHpAPFOAPFNAPFDAPFUnAPFDoAH4PFUnA8:2 FTAμg/m 20,20,20,50,22,00,31,00,10,50,210,1%1132132713166PFCconcentration/amountPFBAPFPAPFHxAPFHpAPFOAPFDAPFUnA8:2 FTOH10:2 FTOHconcentration in μg/m 2amount PFC in %μg/m 20,90,40,40,20,60,20,1229,5189,0%00000005445concentration in μg/m 2amount PFC in %Zimtstern / Greenpeace | activist’s jacket Jack Wolfskin | child's jacket Vaude | child’s Jacket

367Vaude North Face Mountain Equipment8:2 FTASumextractable PFC:21 μg/m 28:2 FTASumextractable PFC:27 μg/m 2 PFOA8:2 FTAPFBASumextractable PFC:7 μg/m 2PFCconcentration/amountPFBAμg/m 20,2%1PFCconcentration/amountPFBAμg/m 20,3%1PFCconcentration/amountPFBAμg/m 20,4%6PFOAPFDAH4PFUnA8:2 FTAconcentration in μg/m 2amount PFC in %0,20,10,719,510394PFHxAPFHpAPFOAPFNAPFDAPFDoAH4PFUnA8:2 FTA0,60,11,60,10,40,10,123,8206020188PFOA8:2 FTAconcentration in μg/m 2amount PFC in %0,26,1391concentration in μg/m 2amount PFC in %Vaude | woman’s jacket North Face | woman’s jacket Mountain Equipment | woman’s jacket

39Mammut FujiyamaKaikkialla10:2 FTOH8:2 FTA8:2 FTOH10:2 FTOH8:2 FTASumextractable PFC:527 μg/m 26:2 FTOHSumextractable PFC:265 μg/m 2 6:2 FTOH10:2 FTA8:2 FTOHPFCconcentration/amountPFBAPFPAPFHxAPFHpAPFOAPFNAPFDAPFUnAPFDoA8:2 FTA10:2 FTA6:2 FTOH8:2 FTOH10:2 FTOHμg/m 20,51,30,60,90,60,60,40,20,239,617,6352,078,134,1%0000000008367156PFCconcentration/amountPFBAPFPAPFHxAPFHpAPFOAPFNAPFDAPFUnAPFDoA8:2 FTA10:2 FTA6:2 FTOH8:2 FTOH10:2 FTOHμg/m 20,60,21,50,55,00,42,00,20,658,120,327,087,860,8%001020100228103323concentration in μg/m 2amount PFC in %concentration in μg/m 2amount PFC in %Mammut Fujiyama | woman’s jacketKaikkialla | woman’s jacket

41Table 6: Compilation of the results of further testing of outdoor clothing for organotin compounds, antimony,aromatic amines, and volatile organic compounds (VOC)Zimtstern /GreenpeaceJackWolfskinVaudeVaudeNorthFaceMountainEquipmentMarmotFjällrävenPatagoniaadidasNorthlandSevenSummitsMammutFujiyamaKaikkiallaactivist’sjacketchild’sjacketchild’sjacketwomen’sjacketwomen’sjacketwomen’sjacketchild'spantswomen’sjacketwomen’sjacketwomen’sjacketchild’sponchochild’sjacketwomen’sjacketwomen’sjacketPolyesterSympaTex,Bionic-FinishEcoTexaporeAir,100%PolyamidCeplex ad,100% PU,polyamide+ PU coatingCeplex ad,100% PU,polyamide+ PU coatingPTFE-(GoreTex)polyesterlaminateGoreTex,outer shell:100%polyamide96%nylon,4%elastanEco Shell,PFC-free,100%Rec.PESGoreTex,outer shell:100%nylonGoreTex,Pro Shell,100%polyamide100%polyesterIce Tech5000100%polyamidePTFE(Gore Tex)Membrane:TorayDermizaxEVconc. μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2 μg/m 2Organotin compoundsMonobutyltinMBT

4277.1 GlossarHazardous substances in the textile industry – 11 groups of chemicalsThese eleven groups of chemicals areused extensively in the textile industry.Once released, many of them accumulatein the environment – in rivers,the oceans, in the soil and in plants.These substances are transported toa certain extent around the world andcontaminate ecosystems far fromwhere they were initially introducedto the environment. They are definedas persistent. Some substances arebioaccumulative, meaning they canaccumulate in the blood, organsand tissues of living organisms anddamage health.Alkylphenols:The alkylphenols include nonylphenol andoctylphenol. They are released from theirethoxylates. In this way, nonylphenols(NPs) are a product of nonylphenol ethoxylates(NPEs). NPEs are frequently usedin the textile industry to wash materialsduring the dyeing process. The NPs generatedin wastewater from NPEs behavesimilarly to estrogen and can disrupt thedevelopment of the reproductive organsof fish and other aquatic animals. Thesale of products containing more than0.1 percent of nonylphenols or nonylphenolethoxylates has been severely restrictedin the European Union since 2005.Phthalates:Phthalates are used as plasticizers, forinstance to soften the rigid plastic PVC.In the textile industry they are used forartificial leather, rubber and in dyes.Specifically, di-2-ethylhexyl phthalate(DEHP) and dibutyl phthalate (DBP) areconsidered hazardous because theyinhibit the development of reproductiveorgans in mammals. Since 2005, fourphthalates (DBP, BBP, DEHP and DIBP)have been on the REACH Candidate Listof Substances of Very High Concernfor Authorisation. [REACH (Registration,Evaluation, and Authorisation of CHemicals)is the main general European Unionchemicals regulation]. This means theyare subject to severe restriction criteria.Brominated and chlorinatedflame retardants:Many brominated flame retardants (BFRs)accumulate in the environment and cannow be found everywhere. These chemicalsare used for fire control, in textilestoo. Specifically, polybrominated diphenylethers (PBDEs) are considered “particularlyhazardous” according to EU waterlegislation. They are hormonally active andcan damage the growth and developmentof reproductive organs. Their use in theEuropean Union is subject to tight restrictionsin order to protect surface waters.Azo dyes:Azo dyes are widely used in the textileindustry. Some azo dyes release aromaticamines, of which some such as3.3'-dimethoxybenzidine (also knownas o-dianisidine dihydrochloride), cancause skin cancer. According to EUregulations, 22 azo dyes may no longerbe used for textiles worn directly on theskin. A similar regulation exists in China.Organotin compounds:Organic tin compounds are used asbiocides and anti-fungal agents in manyproducts. They have an antibacterialeffect on socks, shoes and sportswearand are supposed to prevent odors.If tributyltin (TBT) is released into the environment,it can accumulate in the bodiesof humans and animals and disrupt theimmune system and reduce fertility.Perfluorinated compounds (PFCs):PFCs are used to make textiles andleather products water-repellent anddirt-repellent. They are persistent andsome PFCs accumulate in human tissueand blood. They can damage the liver anddisrupt the body’s endocrine (hormonal)system. Perfluorooctane sulfonate (PFOS)is restricted around the world by theStockholm Convention and is on theCandidate List of Substances of Very HighConcern for Authorisation (SVHC). It isbanned in Europe for certain applications.Germany’s Federal Environment Agencyhas proposed putting perfluorooctanoicacid (PFOA) on the SVHC list as well.Chlorobenzenes:Chlorobenzenes are used as biocidesand solvents in textile production. Someof them damage the liver, the thyroidand the central nervous system. Hexachlorobenzene(HCB) is persistent andhormonally active. Like the polychlorinatedbiphenyls (PCBs), their use is severelyrestricted by the Stockholm Convention.

437.2 ReferencesChlorinated solvents:Chlorinated solvents such as trichloroethylene(TCE) are used to removechemical residues from textiles and toclean them. TCE is damaging to theozone layer. Moreover, it can damagethe central nervous system, the liverand kidneys in humans and animals.Since 2008, TCE has been allowed onlylimited use in the EU.Chlorophenols:Chlorophenols are used as biocides inthe textile industry. Pentachlorophenol(PCP) in particular is highly toxic toaquatic organisms and can damagehuman organs and the central nervoussystem. The production and use ofPCP has been banned in the EuropeanUnion since 1991.Short-chain chlorinated paraffins(SCCPs):Short-chain chlorinated paraffins areused in the textile industry as flameretardants and to finish textiles andleather. They are considered toxic toaquatic organisms and accumulate inliving organisms. Their use has beenrestricted in the EU since 2004.Heavy metals:Heavy metals like cadmium, lead andcopper are in dyes and pigments. Theycan accumulate in the body and damageorgans as well as the central nervoussystem. Chromium is used for tanningleather. As chromium VI, it is a potentenvironmental toxin even at low concentrations.Chromium VI, mercury andcadmium can cause cancer. The use ofthese heavy metals in the EU is subjectto strict conditions.Berger U, Herzke D (2006).Per- and polyfluorinated alkyl substan ces (PFAS) extracted fromtextile samples. 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Environ Sci Technol.44(19):7450-5.Fei C, McLaughlin JK, Lipworth L, Olsen J (2009).Maternal levels of perfluorinated chemicals and subfecundity.Hum Reprod. 24(5):1200-5.Friends of the Earth Norway (2006).Fluorinated pollutants in all-weather clothing:http://www.snf.se/pdf/rap-hmv-allvadersklader-eng.pdfFromme H, Mosch C, Morovitz M, Alba-Alejandre I, Boehmer S,Kiranoglu M, Faber F, Hannibal I, Genzel-Boroviczény O,Koletzko B, Völkel W (2010).Pre- and postnatal exposure to perfluorinated compounds (PFCs).Environ Sci Technol. 44(18):7123-9.GOTS – Global Organic Textile Standard (2011).Global Organic Textile Standard (GOTS) Version 3.0,http://tilth.org/files/certification/GOTSStandard.pdfGrandjean P, Andersen EW, Budtz-Jørgensen E, Nielsen F,Mølbak K, Weihe P, Heilmann C. (2012).Serum vaccine antibody concentrations in children exposed toperfluorinated compounds. JAMA. 307(4):391-7.Greenpeace (2011). Dirty Laundry.Unraveling the corporate connections to toxic water pollution inChina. Greenpeace International, 2011. http://www. greenpeace.org/dirtylaundryreportGreenpeace (2011). Dirty Laundry 2.Hung Out to Dry. Unravelling the toxic trail from pipes to products.Greenpeace International, 2011. http://www.greenpeace.org/international/en/publications/reports/Dirty-Laundry-2Greenpeace (2012). Dirty Laundry.Reloaded How big brands are making consumers unwitting accomplicesin the toxic water cycle. Greenpeace International,2012. http://www.greenpeace.org/international/en/publications/Campaign-reports/Toxics-reports/Dirty-Laundry-ReloadedJensen A & Leffers H (2008).Emerging endocrine disrupters: perfluoroalkyaled substances.International Journal of Andrology 31: 161-169.Langer V, Dreyer A, Ebinghaus R (2010).Polyfluorinated compounds in residential and nonresidentialindoor air. 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